CN105778458A - Plastic composition and plastic substrate, application thereof, and plastic surface selective metallization method - Google Patents
Plastic composition and plastic substrate, application thereof, and plastic surface selective metallization method Download PDFInfo
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- CN105778458A CN105778458A CN201410815182.8A CN201410815182A CN105778458A CN 105778458 A CN105778458 A CN 105778458A CN 201410815182 A CN201410815182 A CN 201410815182A CN 105778458 A CN105778458 A CN 105778458A
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Abstract
The present invention provides a plastic composition and a plastic substrate, application thereof, and a plastic surface selective metallization method. The plastic composition comprises a plastic component and a metal compound; the metal compound has a general formula of ACuPO4 and / or A2CuP2O7, wherein A is at least one selected from IA family in the elements periodic table. Surface metallization on the plastic composition and / or plastic substrate containing a specific compound can obtain a high plating rate, and the obtained plastic product has high whiteness.
Description
Technical field
A kind of method that the present invention relates to the application in selective metallization of plastic surface of a kind of plastics composite, described the plastics composite plastic basis material prepared, described plastics composite and/or plastic basis material and selective metallization of plastic surface.
Background technology
Metal level is formed, it is possible to as the path of electromagnetic signal conduction, be currently widely used for the fields such as automobile, industry, computer, communication at frosting.It is the core link that such plastic manufactures that frosting is formed selectively metal level.Metallization of plastic surface produces circuit multiple diverse ways, and in prior art, main employing first forms metal core as chemical plating catalytic active center on plastic basis material surface, then carries out chemical plating.Specifically, in the preparation process of plastic basis material, directly chemical plating catalyst and plastic fraction are prepared plastic basis material by the mode of injection mo(u)lding, so that chemical plating catalyst is preset in plastic basis material, before carrying out chemical plating, the method first adopting such as laser-induced thermal etching removes the plastic fraction in the selection area of described plastic basis material surface, to expose chemical plating catalyst in this region, then on the region that this is exposed, chemical plating is carried out, thus forming metal level on the surface of this insulated plastic base material.
Currently used chemical plating catalyst essentially inorganic compound particle.Such as, US2004/0241422A1 discloses the inorganic compound powder adding spinel structure in polymeric matrix, these inorganic compound contain the elements such as copper, nickel, cobalt, chromium, ferrum, then activate with Ultra-Violet Laser (wavelength is 248nm, 308nm and 355nm) and iraser (wavelength is 1064nm and 10600nm).US2004/0241422A1 it should be particularly mentioned the oxide with spinel structure can restore metal simple-substance under laser action, using metal simple-substance as nucleus, induction-chemical deposition metal, forms metal level.But, the realization of said process needs strict technology controlling and process, needing to irradiate higher laser energy could be metal simple-substance by the Reduction of Oxide of spinel structure, thus obtaining the effect of intended induction-chemical deposition metal, the requirement of equipment and technique is all higher.
In order to overcome the problems referred to above, researcher develops a kind of new chemical plating catalyst alkaline-earth metal (Jiao) cupric phosphate, i.e. the compound substituted with alkaline-earth metal by the part copper atom in (Jiao) cupric phosphate.Research shows, alkaline-earth metal (Jiao) cupric phosphate can be used as chemical plating catalyst without restoring metal simple-substance, therefore, plastic basis material surface only need to can be carried out selective metallization by chemical plating by surface selectivity roughening by corresponding plastic basis material, and when adopting laser selective irradiated plastics substrate surface to realize surface roughening, without too high energy, alkaline-earth metal (Jiao) cupric phosphate is reduced into metal simple-substance, and plastic fraction gasification only need to be made to expose alkaline-earth metal (Jiao) cupric phosphate, chemical plating can be made directly, realize plastic basis material surface selective metallization, technique is simple, energy requirement is low.But, although adopting alkaline-earth metal (Jiao) cupric phosphate can reduce the requirement to energy as chemical plating catalyst, and the primary colours of the plastic obtained can be improved to a certain extent, but the activity of alkaline-earth metal (Jiao) cupric phosphate is relatively low, therefore the plating speed in later stage metallization processes is relatively low.
Summary of the invention
A kind of method that the invention aims to provide the application in selective metallization of plastic surface of a kind of new plastics composite, described the plastics composite plastic basis material prepared, described plastics composite and/or plastic basis material and selective metallization of plastic surface.
The present inventor finds after further investigation, existing alkaline-earth metal (Jiao) cupric phosphate chemical plating catalyst is to utilize alkaline-earth metal to substitute the part copper atom in (Jiao) cupric phosphate and obtain, belong to the simple replacement of iso-valence metal atom, the introducing of alkaline-earth metal does not substantially change the structure of (Jiao) cupric phosphate, after adopting alkaline-earth metal to substitute the part copper atom in (Jiao) cupric phosphate, although the alkaline-earth metal obtained (Jiao) cupric phosphate is of light color, thus the plastic obtained also can present light color, but catalysis activity is not improved.In addition, the present inventor stumbles on, the less alkali metal of valence state is adopted to substitute the part copper atom in (Jiao) cupric phosphate, alkali metal at a low price could alter that the structure of (Jiao) cupric phosphate, primary colours can not only be reduced, but also its catalysis activity can be improved, therefore, there is during using alkali metal (Jiao) cupric phosphate as chemical plating catalyst more excellent catalytic performance, and the plastic of gained has whiter whiteness.Based on above-mentioned discovery, complete the present invention.
Specifically, the invention provides a kind of plastics composite, described plastics composite contains plastic fraction and metallic compound, and wherein, the formula of described metallic compound is ACuPO4And/or A2CuP2O7, A is at least one in the periodic table of elements in the Ith A race metallic element.
Present invention also offers the plastic basis material prepared by above-mentioned plastics composite.
Present invention also offers the application in selective metallization of plastic surface of above-mentioned plastics composite and/or plastic basis material.
In addition, a kind of method that present invention also offers selective metallization of plastic surface, the method includes plastics composite mix homogeneously injection mo(u)lding, obtain plastic basis material, then pass through energetic beam illumination remove the plastic fraction in the selection area of described plastic basis material surface and expose metallic compound, then carrying out chemical plating on this exposed region, wherein, described plastics composite is above-mentioned plastics composite.
By provided by the invention be ACuPO containing formula4And/or A2CuP2O7(wherein, A is at least one metallic element in the periodic table of elements in the Ith A race) the plastics composite of metallic compound and/or plastic basis material when carrying out surface metalation, it is obtained in that higher plating speed, and the plastic finally given has whiter whiteness.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
Plastics composite provided by the invention contains plastic fraction and metallic compound, and wherein, the formula of described metallic compound is ACuPO4And/or A2CuP2O7, A is at least one in the periodic table of elements in the Ith A race metallic element, it is preferred at least one in Li, Na, K, Rb and Cs.
The instantiation of described metallic compound can include but not limited to: LiCuPO4、NaCuPO4、KCuPO4、RbCuPO4、CsCuPO4、Li2CuP2O7、Na2CuP2O7、K2CuP2O7、Rb2CuP2O7、Cs2CuP2O7、LiNaCuP2O7、LiKCuP2O7And NaKCuP2O7In at least one.
Metallic compound provided by the invention can be commercially available, it is also possible to preparing according to existing various methods, this is as well known to those skilled in the art, and therefore not to repeat here.
Described metallic compound generally exists in the form of granules.The size of described metallic compound is not particularly limited by the present invention, and it generally can select according to the method for molding, and the plastic basis material can form densification is as the criterion.Preferably, the volume average particle size of described metallic compound is 0.1-5 μm, more preferably 0.1-2 μm, it is most preferred that for 0.1-0.5 μm, is so possible not only to obtain higher catalysis activity, but also can form the plastic basis material of densification.
The content of metallic compound in described plastics composite is not particularly limited by the present invention, for instance, with the gross weight of described plastics composite for benchmark, the content of described metallic compound can be 1-40 weight %, it is preferred to 4.5-20 weight %.Additionally, with the gross weight of described plastics composite for benchmark, the content of described plastic fraction can be 60-99 weight %, it is preferred to 80-95.5 weight %.
Described plastic fraction can be thermoplastic, it is also possible to for thermosetting plastics, it is also possible to for the mixture of thermoplastic and thermosetting plastics.Wherein, described thermoplastic can be at least one in polyolefin, Merlon (PC), polyester, polyamide, polyarylether, polyesterimide, Merlon/(acrylonitrile-butadiene-styrene (ABS)) alloy (PC/ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimides (PI), polysulfones (PSU), polyether-ether-ketone (PEEK) and polybenzimidazoles (PBI).Wherein, " alloy " in described Merlon/(acrylonitrile-butadiene-styrene (ABS)) alloy is not general metal alloy but polymer alloy, polymer alloy generally refers to the polymer mixture by blended two or more polymer waiting physical method to obtain after processing, and described Merlon/(acrylonitrile-butadiene-styrene (ABS)) alloy refers to the mixture of Merlon and acrylonitrile-butadiene-styrene (ABS).Specifically, described polyolefin can be at least one in polystyrene (PS), polypropylene (PP), polymethyl methacrylate and poly-(acrylonitrile-butadiene-styrene (ABS))；Described polyester can be at least one in diformazan alcohol ester (PCT), PDAIP (PDAIP), poly terephthalic acid diallyl (PDAP), PBN (PBN), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) (PBT) selected from polycyclohexylene；Described polyamide can be selected from polyhexamethylene adipamide (PA-66), poly-hexamethylene azelamide (PA-69), polybutadiene acyl hexamethylene diamine (PA-64), nylon 612 (PA-612), polyhexamethylene sebacamide (PA-610), nylon 1010 (PA-1010), nylon 11 (PA-11), poly-lauramide (PA-12), poly-caprylamide (PA-8), poly-9 aminononanoic acid (PA-9), polycaprolactam (PA-6), poly-paraphenylene terephthalamide's phenylenediamine (PPTA), poly-6I hexamethylene isoterephalamide (MXD6), at least one in poly-hexamethylene terephthalamide (PA6T) and poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T).Described thermosetting plastics can be at least one in phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, alkyd resin and polyurethane.
Additionally, in order to improve the performance of described plastics composite or give described plastics composite with new performance, plastics composite provided by the invention can also contain at least one auxiliary agent in filler, antioxidant, light stabilizer and lubricant.The content of above-mentioned auxiliary agent can be all the conventional selection of this area.Such as, when in described plastics composite containing filler, relative to plastic fraction described in 100 weight portions, the content of described filler can be 1-40 weight portion.When in described plastics composite containing antioxidant, relative to plastic fraction described in 100 weight portions, the content of described antioxidant can be 0.01-1 weight portion.When in described plastics composite containing light stabilizer, the content of described light stabilizer can be 0.01-1 weight portion.When in described plastics composite containing lubricant, the content of described lubricant can be 0.01-1 weight portion.
Described filler can be the physics filler that laser does not rise any physics or chemical action, for instance, Pulvis Talci and calcium carbonate.Although glass fibre is insensitive to laser, but add the degree of depth that after glass fibre can deepen laser activation significantly, plastic substrate caves in, be conducive to the adhesion of copper in electroless copper.Described filler can also is that the inorganic filler that laser is played a role, for instance, stannum oxide especially nano tin dioxide can increase the iraser capacity usage ratio when peeling off frosting.Functional filler also has white carbon black, and it can also increase plastics to infrared absorption, increases the extent of exfoliation of plastics.Described filler does not preferably contain the elements that environment and human body is harmful such as Cr.Described filler can also be at least one in glass microballoon, calcium sulfate, barium sulfate, titanium dioxide, pearl essence, wollastonite, kieselguhr, Kaolin, coal dust, potter's clay, Muscovitum, kerosene shale ash, aluminium silicate, aluminium oxide, carbon fiber, silicon dioxide, zinc oxide etc..
Described antioxidant can improve the antioxygenic property of described plastics composite, thus improving the service life of the product finally given.Described antioxidant has been conventionally known to one of skill in the art, for instance can be hindered phenol type antioxidant and/or phosphite type antioxidant.The example of described hindered phenol type antioxidant includes antioxidant 1098 and 1010 (antioxidant that Ciba company produces); wherein antioxidant 1098 be mainly composed of N; N '-bis--(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine; antioxidant 1010 be mainly composed of four [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane.The example of described phosphite type antioxidant has irgasfos 168 (Ciba company produce antioxidant), it be mainly composed of three (2,4-di-tert-butyl-phenyl) phosphite ester.
Described light stabilizer can provide light stability for described plastics composite, thus improving the service life of the product finally given.Described light stabilizer can be various known light stabilizer, for instance hindered amine type light stabilizer.The example of hindered amine type light stabilizer has bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate.
Plastics composite can be made to have better mobility for described lubricant so that plastics composite is mixed to get evenly, it can be various known lubricant, for instance can be at least one in the copolymerization wax (EVA wax) selected from ethylene/vinyl acetate, Tissuemat E (PE wax) and stearate.
Present invention also offers the plastic basis material prepared by above-mentioned plastics composite.
Present invention also offers the application in selective metallization of plastic surface of described plastics composite and/or plastic basis material.
In addition, the method of selective metallization of plastic surface provided by the invention includes plastics composite mix homogeneously injection mo(u)lding, obtain plastic basis material, then pass through energetic beam illumination remove the plastic fraction in the selection area of described plastic basis material surface and expose metallic compound, then on this exposed region, carry out chemical plating, wherein, described plastics composite is above-mentioned plastics composite.
The method of injection mo(u)lding is had no particular limits by the present invention, the method that can use the injection mo(u)lding of routine, such as first described plastics composite can being put into extruding pelletization in extruder, then placing into injection mo(u)lding in injection moulding machine is the plastic sample needing shape.
Described energy beam can for the various energy beams that can make plastic fraction gasification stripping and expose described metallic compound, for instance, it is possible to for laser, electron beam or ion beam, it is preferred to laser.Wherein, when described energy beam is laser, the wavelength of described laser can be 157nm to 10.6 μm, it is preferred to 532nm-1064nm；The power of described laser can be 3-20W, it is preferred to 3-10W；Scanning speed can be 500-8000mm/s, it is preferred to 4000-6000mm/s.
The condition of described energetic beam illumination exposes described metallic compound and is as the criterion so that the plastic fraction on plastic basis material surface can be made to gasify, it is possible to select according to the difference of the kind of plastic fraction and the type of energy beam.When with energy beam elective irradiation plastic basis material surface, without too high energy, metallic compound is reduced into metal simple-substance, and plastic fraction gasification only need to be made to expose metallic compound, chemical plating can be made directly, realize plastic basis material surface selective metallization, technique is simple, and energy requirement is low.
Usually, when adopting laser as energy beam, step-length can be 3-20 μm, and time delay can be 20-100 μ s, and frequency can be 10-400kHz, and filling spacing can be 10-50 μm.The thickness of general plastic basis material is typically at least 1 micron, by irradiating such laser, the thickness of the plastics generally etched away is several microns to tens microns, so that the metal compound particles in plastic basis material comes out, plastic basis material is formed as on microcosmic as having the rough surface structure in rugged space.When follow-up chemical plating, coated metal can be embedded in the hole of rough surface, thus and forming very strong adhesion between plastic basis material.
Mainly the theing improvement is that of the method for selective metallization of plastic surface provided by the invention have employed a kind of containing special metal compound as chemical plating catalyst to prepare plastic basis material, and the concrete grammar of the metal species plated in follow-up plating process and chemical plating and condition can be all the conventional selection of this area.For example, it is possible to carry out electroless copper, chemical nickel plating, chemical gilding etc. on described exposed region.
Wherein, the method for described electroless copper can carry out according to existing various methods, for instance, it is possible to the plastic basis material after laser-induced thermal etching is contacted with copper electrolyte.Described copper electrolyte contains mantoquita and reducing agent, and pH value is 12-13.Copper ion in mantoquita can be reduced to copper simple substance by described reducing agent, for instance can be at least one in glyoxalic acid, hydrazine and sodium hypophosphite." sufacing " (within 2002, December the 31st volume the 6th is interim) discloses basic composition is of a kind of typical copper electrolyte: CuSO4·5H2O0.12mol/L、Na2EDTA·2H2O0.14mol/L, potassium ferrocyanide 10mg/L, 2,2 '-bipyridyl 10mg/L, glyoxalic acid (HOCCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value regulating plating solution is 12.5-13.If additionally, the thickness of copper is not enough after electroless copper, then can also continue to carry out again or repeatedly electro-coppering.
The method of described chemical nickel plating can carry out according to existing various methods, for instance, it is possible to the plastic basis material after laser-induced thermal etching is contacted with nickel plating bath.A kind of typical case of described nickel plating bath consists of: nickel sulfate 23g/L, sodium hypophosphite 18g/L, lactic acid 20g/L, malic acid 15g/L, regulates its pH value to 5.2 with NaOH.The thickness of the nickel dam obtained after chemical nickel plating has no particular limits, for instance, it is possible to for 0.5-1 μm.
The method of described chemical gilding can adopt the method for flash to carry out, and is specially as well known to those skilled in the art, and therefore not to repeat here.Wherein, the golden liquid used by described flash such as can create the BG-24 neutrality gold plating liquid of chemical company for Shenzhen lappingout.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example, volume average particle size is to adopt the laser particle analyzer commercially available from Jingxin Power Testing Apparatus Co., Ltd., Chengdu to measure.
Embodiment 1
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
By the KCuPO that 50g volume average particle size is 100 nanometers4Join in the Merlon (supporting company purchased from three, the trade mark is 3025PJ, lower same) of 1000g with the Pulvis Talci of 10g, high-speed stirred mix homogeneously, obtain plastics composite.Then this plastics composite is proceeded to extruding pelletization in extruder, then proceeded in injection moulding machine the plastic basis material being injection molded into 2 millimeters thick again.The hexadecimal color code (that is, HEX form) of this plastic basis material is #66FF66, and rgb color pattern (that is, rgb format) is 102,255,102.
This plastic basis material is placed on laser instrument sample stage, by laser focusing, computer program controls the movement of light beam or sample stage, and laser instrument used is big nation YLP-20 type laser instrument, and laser parameter is: wavelength 1064nm, scanning speed 1000mm/s, step-length 9 μm, time delay 30 μ s, frequency 40KHz, power 3W, fills spacing 50 μm.After laser ablation, plastic basis material is carried out abatement processes, is subsequently placed in and consists of CuSO4·5H2O0.12mol/L、Na2EDTA·2H2O0.14mol/L, potassium ferrocyanide 10mg/L, 2, in the plating solution of 2 '-bipyridyl 10mg/L and glyoxalic acid (HOCCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value regulating plating solution is 12.5 carry out electroless copper.After tested, copper plating rate is 4 μm/h.
Embodiment 2
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
By the LiNaCuP that 100g volume average particle size is 500 nanometers2O7With in the Merlon that the Pulvis Talci of 10g joins 1000g, high-speed stirred mix homogeneously, obtain plastics composite.Then this plastics composite is proceeded to extruding pelletization in extruder, then proceeded in injection moulding machine the plastic basis material being injection molded into 2 millimeters thick again.The hexadecimal color code (that is, HEX form) of this plastic basis material is #99FFFF, and rgb color pattern (that is, rgb format) is 153,255,255.
This plastic basis material is placed on laser instrument sample stage, by laser focusing, computer program controls the movement of light beam or sample stage, and laser instrument used is big nation YLP-20 type laser instrument, and laser parameter is: wavelength 1064nm, scanning speed 1000mm/s, step-length 9 μm, time delay 30 μ s, frequency 40KHz, power 3W, fills spacing 50 μm.After laser ablation, plastic basis material is carried out abatement processes, is subsequently placed in and consists of CuSO4·5H2O0.12mol/L、Na2EDTA·2H2O0.14mol/L, potassium ferrocyanide 10mg/L, 2, in the plating solution of 2 '-bipyridyl 10mg/L and glyoxalic acid (HOCCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value regulating plating solution is 12.5 carry out electroless copper.After tested, copper plating rate is 5 μm/h.
Comparative example 1
This comparative example is for illustrating the plastics composite of reference and the method for plastic basis material and application and selective metallization of plastic surface.
Prepare plastics composite, plastic basis material according to the method for embodiment 2 and carry out selective metallization of plastic surface, the difference is that, by LiNaCuP2O7With identical weight part and CaCuP that volume average particle size is identical2O7Substitute.It is shown that the hexadecimal color code (that is, HEX form) of plastic basis material is #33CCCC, rgb color pattern (that is, rgb format) is 51,204,204.After tested, copper plating rate is 3 μm/h.
Comparative example 2
This comparative example is for illustrating the plastics composite of reference and the method for plastic basis material and application and selective metallization of plastic surface.
Prepare plastics composite, plastic basis material according to the method for embodiment 2 and carry out selective metallization of plastic surface, the difference is that, when carrying out selective metallization of plastic surface, do not adopt laser-induced thermal etching, but adopt the method for chemical etching that plastic basis material surface is etched.Wherein, the condition of chemical etching is: corroding sample surfaces with the sodium hydroxide solution of 5 weight %, etching time is 30 minutes.After tested, copper plating rate is 1 μm/h.
Embodiment 3
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
By the K that 200g volume average particle size is 300 nanometers2CuP2O7With in the Merlon that the Pulvis Talci of 10g joins 1000g, high-speed stirred mix homogeneously, obtain plastics composite.Then this plastics composite is proceeded to extruding pelletization in extruder, then proceeded in injection moulding machine the plastic basis material being injection molded into 2 millimeters thick again.The hexadecimal color code (that is, HEX form) of this plastic basis material is #66FFFF, and rgb color pattern (that is, rgb format) is 102,255,255.
This plastic basis material is placed on laser instrument sample stage, by laser focusing, computer program controls the movement of light beam or sample stage, and laser instrument used is big nation YLP-20 type laser instrument, and laser parameter is: wavelength 1064nm, scanning speed 1000mm/s, step-length 9 μm, time delay 30 μ s, frequency 40KHz, power 3W, fills spacing 50 μm.After laser ablation, plastic basis material is carried out abatement processes, is subsequently placed in and consists of CuSO4·5H2O0.12mol/L、Na2EDTA·2H2O0.14mol/L, potassium ferrocyanide 10mg/L, 2, in the plating solution of 2 '-bipyridyl 10mg/L and glyoxalic acid (HOCCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value regulating plating solution is 12.5 carry out electroless copper.After tested, copper plating rate is 6 μm/h.
Embodiment 4
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
Prepare plastics composite, plastic basis material according to the method for embodiment 1 and carry out selective metallization of plastic surface, the difference is that, by the KCuPO that 50g volume average particle size is 100 nanometers4With the RbCuPO that 20g volume average particle size is 100 nanometers4, 20g volume average particle size be the LiNaCuP of 100 nanometers2O7With the Rb that 10g volume average particle size is 100 nanometers2CuP2O7Mixture replacing, and the poly-hexamethylene terephthalamide of Merlon identical weight part (purchased from BASF Aktiengesellschaft, the trade mark is TKR4350, lower with) is substituted, obtains plastics composite and plastic basis material.The hexadecimal color code (that is, HEX form) of this plastic basis material is #66FFFF, and rgb color pattern (that is, rgb format) is 102,255,255.
Compound copper facing is carried out on above-mentioned plastic basis material surface according to the method for embodiment 1.After tested, copper plating rate is 5 μm/h.
Embodiment 5
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
Prepare plastics composite, plastic basis material according to the method for embodiment 1 and carry out selective metallization of plastic surface, the difference is that, metallic compound KCuPO4Consumption be 400g, obtain plastics composite and plastic basis material.The hexadecimal color code (that is, HEX form) of this plastic basis material is #006400, and rgb color pattern (that is, rgb format) is 0,100,0.
Compound copper facing is carried out on above-mentioned plastic basis material surface according to the method for embodiment 1.After tested, copper plating rate is 4.5 μm/h.
Embodiment 6
This embodiment method for plastics composite provided by the invention and plastic basis material and application thereof and selective metallization of plastic surface are described.
Prepare plastics composite, plastic basis material according to the method for embodiment 1 and carry out selective metallization of plastic surface, the difference is that, in the preparation process of plastics composite, by the Merlon of Merlon identical weight with acrylonitrile-butadiene-styrene copolymer (purchased from Qi Mei company, the trade mark is 747, lower same) replace according to the mixture of weight ratio 1:1, obtain plastics composite and plastic basis material.The hexadecimal color code (that is, HEX form) of the plastic basis material that employing the method obtains is #66FF66, and rgb color pattern (that is, rgb format) is 102,255,102.
Compound copper facing is carried out on above-mentioned plastic basis material surface according to the method for embodiment 1.After tested, copper plating rate is 5 μm/h.
Comparative example 3
This comparative example is for illustrating the plastics composite of reference and the method for plastic basis material and application and selective metallization of plastic surface.
By the Ca that 100g volume average particle size is 1.5 microns0.5CuPO4With in the Merlon that the Pulvis Talci of 10g joins 1000g, high-speed stirred mix homogeneously, obtain plastics composite.Then this plastics composite is proceeded to extruding pelletization in extruder, then proceeded in injection moulding machine the plastic basis material being injection molded into 2 millimeters thick again.The hexadecimal color code (that is, HEX form) of this plastic basis material is #33FF33, and rgb color pattern (that is, rgb format) is 51,255,51.
This plastic basis material is placed on laser instrument sample stage, by laser focusing, computer program controls the movement of light beam or sample stage, and laser instrument used is big nation YLP-20 type laser instrument, and laser parameter is: wavelength 1064nm, scanning speed 1000mm/s, step-length 9 μm, time delay 30 μ s, frequency 40KHz, power 3W, fills spacing 50 μm.After laser ablation, plastic basis material is carried out abatement processes, is subsequently placed in and consists of CuSO4·5H2O0.12mol/L、Na2EDTA·2H2O0.14mol/L, potassium ferrocyanide 10mg/L, 2, in the plating solution of 2 '-bipyridyl 10mg/L and glyoxalic acid (HOCCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value regulating plating solution is 12.5 carry out electroless copper.After tested, copper plating rate is 3.5 μm/h.
As can be seen from the above results, when plastics composite containing specific metallic compound provided by the invention and/or plastic basis material are carried out surface metalation, it is obtained in that higher plating speed, and the plastic basis material obtained has whiter whiteness, thereby it is assumed that the plastic finally given also has whiter whiteness, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a plastics composite, described plastics composite contains plastic fraction and metallic compound, it is characterised in that the formula of described metallic compound is ACuPO4And/or A2CuP2O7, A is at least one in the periodic table of elements in the Ith A race metallic element.
2. plastics composite according to claim 1, wherein, with the gross weight of described plastics composite for benchmark, the content of described metallic compound is 1-40 weight %.
3. plastics composite according to claim 2, wherein, with the gross weight of described plastics composite for benchmark, the content of described metallic compound is 4.5-20 weight %.
4. the plastics composite according to any one in claim 1-3, wherein, A is at least one in Li, Na, K, Rb and Cs.
5. plastics composite according to claim 4, wherein, described metallic compound is LiCuPO4、NaCuPO4、KCuPO4、RbCuPO4、CsCuPO4、Li2CuP2O7、Na2CuP2O7、K2CuP2O7、Rb2CuP2O7、Cs2CuP2O7、LiNaCuP2O7、LiKCuP2O7And NaKCuP2O7In at least one.
6. the plastics composite according to any one in claim 1-3, wherein, described metallic compound exists in the form of granules, and the volume average particle size of described metallic compound is 0.1-5 μm.
7. the plastics composite according to any one in claim 1-3, wherein, described plastic fraction is thermoplastic and/or thermosetting plastics；Described thermoplastic is at least one in polyolefin, Merlon, polyester, polyamide, polyarylether, polyesterimide, Merlon/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene oxide, polyphenylene sulfide, polyimides, polysulfones, polyether-ether-ketone and polybenzimidazoles, and described thermosetting plastics is at least one in phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, alkyd resin and polyurethane.
8. the plastics composite according to any one in claim 1-3, wherein, described plastics composite is possibly together with at least one in filler, antioxidant, light stabilizer and lubricant.
9. the plastic basis material that the plastics composite described in any one in claim 1-8 prepares.
10. the plastics composite described in any one and/or the plastic basis material described in claim 9 application in selective metallization of plastic surface in claim 1-8.
11. the method for a selective metallization of plastic surface, the method includes plastics composite mix homogeneously injection mo(u)lding, obtain plastic basis material, then pass through energetic beam illumination remove the plastic fraction in the selection area of described plastic basis material surface and expose metallic compound, then on this exposed region, carry out chemical plating, it is characterized in that, described plastics composite is the plastics composite in claim 1-8 described in any one.
12. method according to claim 11, wherein, described energy beam is laser.
13. method according to claim 12, wherein, the wavelength of described laser is 157nm to 10.6 μm, and the power of described laser is 3-20W, and scanning speed is 500-8000mm/s.
14. the method according to any one in claim 11-13, wherein, when energy beam is laser, step-length is 3-20 μm, and time delay is 20-100 μ s, and frequency is 10-400kHz, fills spacing and is 10-50 μm.
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| CN102575142A (en) * | 2009-09-30 | 2012-07-11 | 旭硝子株式会社 | Near-infrared-absorbing particles, process for producing same, dispersion, and article thereof |
| CN103774123A (en) * | 2014-01-27 | 2014-05-07 | 比亚迪股份有限公司 | Selective metallization method for surface of polymer substrate, and polymer substrate with metallized patterns on surface obtained by same |
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| CN102575142A (en) * | 2009-09-30 | 2012-07-11 | 旭硝子株式会社 | Near-infrared-absorbing particles, process for producing same, dispersion, and article thereof |
| CN103774123A (en) * | 2014-01-27 | 2014-05-07 | 比亚迪股份有限公司 | Selective metallization method for surface of polymer substrate, and polymer substrate with metallized patterns on surface obtained by same |
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