CN106967965B - The method of plastic products and plastic basis material surface selective metallization - Google Patents

The method of plastic products and plastic basis material surface selective metallization Download PDF

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CN106967965B
CN106967965B CN201610023290.0A CN201610023290A CN106967965B CN 106967965 B CN106967965 B CN 106967965B CN 201610023290 A CN201610023290 A CN 201610023290A CN 106967965 B CN106967965 B CN 106967965B
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cusb
powder
plastic
basis material
chemical plating
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CN106967965A (en
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周芳享
黄江
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BYD Co Ltd
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

The invention discloses a kind of methods of plastic products and plastic basis material surface selective metallization.The plastic products include plastic basis material and the coat of metal that is attached on at least partly surface of the plastic basis material, the plastic basis material surface for being attached with the coat of metal is formed by a kind of plastics composite, the plastics composite contains substrate resin and at least one chemical plating activator, which includes CuSb2O6Powder.Plastic products of the present invention are by using CuSb2O6Powder utilizes this CuSb as chemical plating activator2O6Powder has preferable chemical plating catalytic effect, and the feature relatively small to the degradation of plastics, advantageously reduces as the degree of degradation of the plastic products prepared by it, and improve the impact strength of the plastic products.

Description

The method of plastic products and plastic basis material surface selective metallization
Technical field
The present invention relates to insulating properties base material surface metalation fields, in particular it relates to a kind of plastic products and modeling Expect the method for substrate surface selective metallization.
Background technique
In insulating properties base material forming metal layer on surface, as the access of electromagnetic signal conduction, be widely used in automobile, industry, The fields such as computer, communication.How the surface of insulating properties base material be formed selectively metal layer be the based article manufacture one A core link.In the prior art, many in the method for insulating properties base material forming metal layer on surface, these methods are usually all Metal core (chemical plating activator, SBID powder) first is formed on insulating properties base material surface and is used as chemical plating catalytic active center, so After carry out chemical plating.
Currently, existing SBID powder has metallo-chelate (as described in patent application CN101851431A on the market Raw material), the ABO with delafossite structure2Type composite oxides (the original as described in patent application CN102391633A Material), copper chromite, chromous acid it is cuprous etc..
However, above-mentioned SBID powder (active material) partially exists, structure is complicated, and synthesis difficulty is big, synthesis cost is high asks It inscribes (such as metallo-chelate)；Part cannot actually use and activity is low, at high cost etc. asks in the presence of that may promote plastic degradation Topic；It is relatively deep (mainly copper-bearing materials, usually dark or black) that there are colors for part, makes it difficult to meet light color or even white Plastic products, the problem of limiting application.
Summary of the invention
The object of the present invention is to provide a kind of methods of plastic products and plastic basis material surface selective metallization, to reduce The degree of degradation of plastic products.
To achieve the goals above, according to the first aspect of the invention, a kind of plastic products are provided, the plastic products Including plastic basis material and the coat of metal being attached on at least partly surface of the plastic basis material, it is attached with the metal-plated The plastic basis material surface of layer is formed by a kind of plastics composite, and the plastics composite contains substrate resin and at least one chemistry Activator is plated, which includes CuSb2O6Powder.
According to the second aspect of the invention, a kind of method of plastic basis material surface selective metallization, the party are provided Method includes: so that illuminated surface is gasified with the surface of energetic beam illumination plastic basis material metallize；And it will shine Plastic basis material after penetrating carries out chemical plating, and the surface of the plastic basis material metallize is by a kind of plastics composite shape At the plastics composite contains substrate resin and at least one chemical plating activator, and the chemical plating activator includes CuSb2O6Powder.
According to the third aspect of the present invention, a kind of side by plastic basis material surface selective metallization of the present invention is provided The plastic products of method preparation.
The method of plastic products and plastic basis material surface selective metallization provided by the present invention is above-mentioned, utilization are this CuSb2O6Powder has preferable chemical plating catalytic effect, and the feature relatively small to the degradation of plastics, is conducive to It reduces as the degree of degradation of the plastic products prepared by it, and improves the plastic products impact strength；In addition, this CuSb2O6Powder Originally as chartreuse, the color using the plastic products of its production is shallower at end, it might even be possible to for white.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Be directed to described in background technology part " existing chemical plating activator usually exist plastic degradation is acted on it is bright It is aobvious " the technical issues of.A kind of plastic products are provided in the present invention, which includes plastic basis material and be attached to institute The coat of metal for stating at least partly surface of plastic basis material is attached with the plastic basis material surface of the coat of metal by a kind of plastics Composition is formed, and the plastics composite contains substrate resin and at least one chemical plating activator, the chemical plating activator packet Include (for) CuSb2O6Powder.
Plastic products provided by the present invention are by using CuSb2O6For powder as chemical plating activator, utilization is this CuSb2O6Powder has preferable chemical plating catalytic effect, and the feature relatively small to the degradation of plastics, can drop The low degree of degradation as the plastic products prepared by it, and improve the plastic products impact strength；In addition, this CuSb2O6Powder , as chartreuse, the color using the plastic products of its production is shallower for this, it might even be possible to for white.
Provided plastic products according to the present invention, for wherein chemical plating activator content there is no particular/special requirement, Its conventional amount used for being referred to chemical plating activator in this field.Such as the substrate resin relative to 100 parts by weight, institute The content for stating chemical plating activator is 1-20 parts by weight.
Provided plastic products according to the present invention, the chemical plating activator (CuSb2O6Powder) partial size can basis Its concrete application occasion makes appropriate choice.Generally, the chemical plating activator (CuSb2O6Powder) partial size D50It can be with It is 100nm to 10 μm, preferably 300nm to 5 μm, more preferably 1-3.5 μm.The partial size D50For volume average particle size, it is By liquid phase method using laser particle analyzer measurement.
The substrate resin can be thermoplastic resin, or thermosetting resin.The specific reality of the substrate resin Example can include but is not limited to: polyolefin (such as polystyrene, polypropylene, polymethyl methacrylate and poly- (acrylic nitrile-butadiene two Alkene-styrene)), polycarbonate, (such as polycyclohexylene is to diformazan alcohol ester, two allyl of poly- M-phthalic acid for polyester Ester, poly terephthalic acid diallyl, polybutylene naphthalate, polyethylene terephthalate and poly terephthalic acid fourth two Alcohol ester), polyamide (such as polyhexamethylene adipamide, poly-hexamethylene azelamide, polybutadiene acyl hexamethylene diamine, two acyl of poly- dodecane oneself two Amine, polyhexamethylene sebacamide, nylon 1010, nylon 11, poly-lauramide, poly-caprylamide, poly- 9 aminononanoic acid, Polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly-6I hexamethylene isoterephalamide, poly- hexamethylene terephthalamide and poly- to benzene two Formyl nonamethylene diamine), polyarylether, polyetherimide, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene oxide, polyphenyl Thioether, polyimides, polysulfones, polyether-ether-ketone, polybenzimidazoles, phenolic resin, Lauxite, melamine formaldehyde resin, ring One or more of oxygen resin, alkyd resin and polyurethane.
The auxiliary agent can be that can improve the performance of plastic products or assign plastic products with the substance of new performance, Such as filler, antioxidant and light stabilizer.It is appropriate that the content of the auxiliary agent can be carried out according to its type and specifically used requirement Selection, be not particularly limited.Generally, relative to resin base material described in 100 parts by weight, the content of the filler can be 1- 40 parts by weight, the content of the antioxidant can be 0.01-1 parts by weight, and the content of the light stabilizer can be 0.01-1 weight Part is measured, the content of the lubricant can be 0.01-1 parts by weight.
The filler can be the filler for not playing any physics or chemical action to laser, for example, talcum powder and carbonic acid Calcium.Although glass fibre is insensitive to laser, plastic substrate is recessed after addition glass fibre can deepen significantly laser activation Sunken depth is conducive to the adherency of copper in electroless copper.The inorganic filler can also be the nothing to play a role to laser Machine filler, for example, the filler can also be glass microballoon, calcium sulfate, barium sulfate, titanium dioxide, pearl powder, wollastonite, silicon One of diatomaceous earth, kaolin, clay, mica, kerosene shale ash, alumina silicate, aluminium oxide, silica and zinc oxide are a variety of.
The antioxygenic property for the plastic products that plastics composite of the invention obtains can be improved in the antioxidant, to mention The service life of high product.The antioxidant can be various antioxidant common in plastic applications, such as can be containing main anti- Oxygen agent and auxiliary antioxidant.Relative usage between the primary antioxidant and the auxiliary antioxidant can be fitted according to type When selection.Generally, the weight ratio of the primary antioxidant and the auxiliary antioxidant can be 1:1-4.The primary antioxidant It can be hindered phenol type antioxidant, specific example can include but is not limited to antioxidant 1098 and antioxidant 1010, wherein anti- The main component of oxygen agent 1098 is N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, and antioxidant 1010 main component is four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites.The auxiliary antioxidant can Think phosphite type antioxidant, specific example can include but is not limited to irgasfos 168, and main component is three (2,4- Di-tert-butyl-phenyl) phosphite ester.
The light stabilizer can be well known various light stabilizers, such as hindered amine type light stabilizer, specific example It can include but is not limited to bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate.
The lubricant can be the substance of the various mobility that can improve plastic melt, such as can be for selected from second One or more of alkene/vinyl acetate copolymerization wax (EVA wax), polyethylene wax (PE wax) and stearate.
The content of the auxiliary agent can make appropriate choice according to the function and type of auxiliary agent.Generally, relative to The content of the substrate resin of 100 parts by weight, the filler can be 1-40 parts by weight, and the content of the antioxidant can be The content of 0.1-10 parts by weight, the light stabilizer can be 0.1-10 parts by weight, and the content of the lubricant can be 0.1- 10 parts by weight.
Plastic products according to the present invention, the plastic basis material can only be attached with the surface of the coat of metal by the plastics Composition is formed, and can also integrally be formed by the plastics composite, i.e., the described plastic basis material is by the plastics composite shape At.When the size of plastic basis material is larger, from the angle for reducing cost, only the coat of metal can be attached with by plastic basis material Surface is formed by the plastics composite；It, can be integrally by the plastics composite shape when the size of plastic basis material is little At.
The specific size of the plastic basis material can be selected according to expected use occasion, be not particularly limited.Institute State plastic basis material also can have various shape according to specific needs.The plastic basis material can be prepared using conventional method, example Such as extrusion molding process, injection molding process.
The thickness of plastic products according to the present invention, the coat of metal can not have depending on specifically used requirement It is particularly limited to, generally can be 0.1-10 μm.According to specifically used requirement, the coat of metal can have various shape.Example Such as: in the plastic products for when making wiring board, the metal layer can to form line pattern.
Meanwhile a kind of method of plastic basis material surface selective metallization is additionally provided in the present invention, this method comprises: With the surface of energetic beam illumination plastic basis material metallize, illuminated surface is made to gasify；And it will be after irradiation Plastic basis material carries out chemical plating, and the surface of the plastic basis material metallize is formed by a kind of plastics composite, described Plastics composite contains substrate resin and at least one chemical plating activator, and the chemical plating activator includes (for) CuSb2O6Powder End.
Plastic basis material surface selective metallization method provided by the present invention is above-mentioned, by using CuSb2O6As chemistry Activator is plated, this CuSb is utilized2O6Mealy structure is simple, is readily synthesized, and the feature that cost of material is relatively low, is conducive to Reduce the preparation cost of plastic products；This CuSb is utilized simultaneously2O6Powder has preferable chemical plating catalytic effect and right The relatively small feature of the degradation of plastics is advantageously reduced as the degree of degradation of the plastic products prepared by it, and improving should Plastic products impact strength；In addition, this CuSb2O6Powder sheet is as chartreuse, using the face of the plastic products of its production Color is shallower, it might even be possible to for white.
The method of plastic basis material surface selective metallization according to the present invention, for chemical plating activator in plastics composite Content there is no particular/special requirement, be referred to the conventional amount used of chemical plating activator in this field.Such as relative to 100 weights The substrate resin of part is measured, the content of the chemical plating activator is 1-20 parts by weight.
Plastic basis material surface selective metallization method according to the present invention, wherein CuSb employed in plastics composite2O6 Powder can be commercial product, be also possible to made products.The CuSb2O6The preparation method of powder may comprise steps of: will Copper oxide (CuO) and antimony pentoxide (Sb2O5) ground and mixed in dispersing agent, form mixture；Under sintering condition, sintering The mixture is handled, the active material CuSb is obtained2O6Powder.
In above-mentioned CuSb2O6It is not special for the mixed proportion of copper oxide and antimony pentoxide in the preparation method of powder It is different to require, as long as being capable of forming CuSb2O6Powder.Preferably copper oxide and antimony pentoxide are ground in dispersing agent mixed In the step of conjunction, the molar ratio of copper oxide and antimony pentoxide is 1:(1-1.05).Preferably, the partial size D of copper oxide50For 10nm-10 μm, the partial size D of antimony pentoxide50It is 10nm-10 μm.The step of grinding is wet grinding, and grinding revolving speed is 300-800rpm, milling time 2-10h, the partial size D of mixture after grinding50It is 10nm-10 μm.
Preferably, the process of grinding is added dispersing agent and carries out wet grinding, and the dispersing agent is water or C1-C5Alcohol, more preferably Ground, the dispersing agent are water and/or C1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be methanol, ethyl alcohol, normal propyl alcohol, 2- third Alcohol, n-butanol, 2- butanol, 2- methyl-1-propyl alcohol, 2- methyl-2-propanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-fourth Alcohol, 2- methyl -2- butanol, 3- methyl -2- butanol and 2, one of 2- dimethyl -1- propyl alcohol or a variety of, preferably ethyl alcohol.
In above-mentioned CuSb2O6In the preparation method of powder, for sintering condition, there is no particular/special requirements, are referred to ability Domain is sintered copper oxide and antimony pentoxide to form CuSb2O6The normal condition of powder, in the present invention preferably the sintering condition It include: to be sintered 2-10h at a temperature of 800-950 DEG C.It is highly preferred that the sintering condition includes: that temperature is first risen to 550-650 DEG C, it is sintered 1-3h, then temperature is risen to 800-950 DEG C, is sintered 8-10h.
In above-mentioned CuSb2O6In the preparation method of powder, the step of the mixture described in sintering processes before further include dry institute The step of stating mixture, by the dispersing agent in dry step elimination reaction system, so that copper oxide and antimony pentoxide are mixed That closes is closer, is more advantageous to form CuSb2O6Powder.It is preferred that in the drying mixture the step of, drying temperature 80- 150 DEG C, drying time 1-10h.
The method of plastic basis material surface selective metallization according to the present invention, the energy beam can be laser, electronics Beam or ion beam, preferably laser.The laser can be obtained by various well known approach, preferably be swashed by laser Light.
The method of plastic basis material surface selective metallization according to the present invention, the condition of the energetic beam illumination is with can So that illuminated surface of plastic products gasifies, chemical plating activator (CuSb is exposed2O6) subject to.Specifically, in the energy When beam is laser, the wavelength of the laser can be 157-10600nm, and scanning speed can be 500-8000mm/s, and step-length can Think 3-9 μm, delay can be 30-100 μ s, and frequency can be 30-40kHz, and power can be 3-4kW, and filling spacing can be with It is 10-50 μm.By irradiating such laser, the plastics generally etched away with a thickness of several microns to more than ten microns, to make The chemical plating activator that must be dispersed in plastic products is exposed, and is formed on microcosmic on at least partly surface of plastic products For the rough surface structure with rugged gap；In subsequent chemical plating, metallic particles is just embedded into rough surface Hole in, to form very strong binding force between plastic sample.Plastic products through energetic beam illumination are carrying out chemistry It before plating, is preferably cleaned, with clean surface.Such as water can be used as cleaning agent to the plastic products through energetic beam illumination It is cleaned.
The method for carrying out chemical plating to the plastic products after irradiation is known to those skilled in the art.For example, into When row electroless copper, this method may include contacting the plastic products after irradiation with copper electrolyte, and the copper electrolyte contains mantoquita And copper ion in mantoquita can be reduced to copper simple substance, such as the reducing agent by reducing agent, pH value 12-13, the reducing agent It can be one of glyoxalic acid, hydrazine and sodium hypophosphite or a variety of.
After carrying out chemical plating, it can also then carry out being electroplated or carry out one or many chemical platings again, with into one Step increases the thickness of coating or forms other coats of metal on chemical deposit.For example, after electroless copper, Ke Yizai Chemical plating one layer of nickel prevents copper coating surface to be oxidized.
Mainly theing improvement is that for the preparation method of plastic products provided by the invention contains CuSb using one kind2O6 The plastic basis material composition of powder prepares plastic basis material, and the metal species plated in subsequent plating process and chemical plating Specific method and condition all can be this field conventional selection.
A kind of specific embodiment according to the present invention, the method for the chemical plating include on the exposed region successively Carry out electroless copper, chemical nickel plating and chemical gilding.The method of the chemical gilding can be carried out using the method for flash, specifically It is known to the skilled person, therefore not to repeat here.
Wherein, the method for the electroless copper can be carried out according to existing various methods, for example, can be by laser-induced thermal etching Plastic basis material afterwards is contacted with copper electrolyte.The copper electrolyte contains mantoquita and reducing agent, pH value 12-13.The reducing agent energy It is enough that copper ion in mantoquita is reduced to copper simple substance, such as can be at least one of glyoxalic acid, hydrazine and sodium hypophosphite.Example Such as, interim a kind of basic composition is for typical copper electrolyte is disclosed " sufacing " in December, 2002 volume 31 the 6th: CuSO4·5H2O:0.12mol/L, Na2EDTA·2H2O:0.14mol/L, potassium ferrocyanide: 10mg/L, 2,2 '-bipyridyls: 10mg/L, glyoxalic acid (HOCCOOH): 0.10mol/L, and with NaOH and H2SO4The pH value for adjusting plating solution is 12.5-13.In addition, If feeling copper thickness deficiency after electroless copper, electro-coppering can also be carried out.
The method of the chemical nickel plating can be carried out according to existing various methods, for example, can will be after electroless copper Plastic sample is contacted with nickel plating bath.A kind of typical composition of the nickel plating bath are as follows: nickel sulfate: 23g/L, sodium hypophosphite: 18g/ L, lactic acid: 20g/L, malic acid: its pH value is adjusted to 5.2 with NaOH by 15g/L.It is not special to the thickness of chemical Ni-plating layer Limitation, such as can be 0.5-1 μm.
According to the method for the present invention, chemical plating formed the coat of metal thickness can depending on specifically used requirement, It is not particularly limited, generally can be 0.1-10 μm.
According to specifically used requirement, the metal layer can have various shape.Such as: when being used to make wiring board, The metal layer can form line pattern.
In addition, additionally providing a kind of plastic products in the present invention, plastics preparation is by plastic basis material surface of the present invention Selective metallization method is prepared.
The present invention will be described in detail with comparative example with reference to embodiments.
In following embodiment and comparative example, chemical plating is measured using inductively coupled plasma emission spectrography (ICP) The composition of activator.
In following embodiment and comparative example, using the laser particle size for being commercially available from Jingxin Power Testing Apparatus Co., Ltd., Chengdu Tester measures the volume average particle size D of chemical plating activator50And D90。
Embodiment 1
Method for illustrating plastic products and plastic basis material surface selective metallization of the present invention
(1) chemical plating activator CuSb2O6The preparation of powder
CuO powder (the commercially available Chemical Co., Ltd. of Gansu Province westerly, purity 99.5%, partial size D are taken respectively50Less than 1.5 μm, D90 Less than 3 μm) and Sb2O5Powder (the commercially available Chemical Co., Ltd. of Gansu Province westerly, purity 99%, partial size D50Less than 1.6 μm, D90It is less than 2.9 μm), CuO and Sb2O5Molar ratio 1:1, using deionized water as dispersing agent, by CuO powder and Sb2O5Powder carries out mixing ball Mill.Wherein, relative to 100 parts by weight mixtures, with the dosage of deionized water for 150 parts by weight.Revolving speed when grinding is 500 Rev/min, the time is 5 hours, the partial size D of mixture after grinding50Less than 1.2 μm.The powder that grinding obtains is placed in baking oven, It is dried in air atmosphere, dry temperature is 95 DEG C, and the time is 2 hours.
Powder after drying is placed in Muffle furnace and is sintered, the temperature of sintering is 945 DEG C, and the time is 2 hours.It will burn It ties object and carries out dry grinding, obtain volume average particle size D50Chartreuse metallic compound less than 2 μm.Through detecting, the metal Compound is CuSb2O6Powder is denoted as P1.
(2) preparation method of plastic products
By polycarbonate (being commercially available from three feeding engineering plastics Co., Ltds), antioxidant 1098 (being commercially available from Ciba company), profit The chemical plating activator CuSb of lubrication prescription PE wax (being commercially available from Clariant chemical industry (Clariant) Co., Ltd) and step (1) preparation2O6 Powder P1 mixing, wherein relative to 100 weight part polycarbonates, chemical plating activator level is 20 parts by weight, the use of antioxidant Amount is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, it is sent into injection molding machine and is molded Molding, obtains the plastic sheet with a thickness of 2mm.
Aforementioned obtained plastic sheet is placed on laser sample stage, laser is focused, computer program control light beam or The movement of sample stage, laser used are big nation YLP-20 type laser, laser parameter are as follows: wavelength 1064nm, scanning speed For 1000mm/s, step-length is 6 μm, is delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing is 20 μm.Laser ablation Afterwards, abatement processes, ultrasonic cleaning (28kHz cleans 5mins) the plastic sheet surface are carried out to plastic sample.
Plastic carrier after cleaning, which is integrally immersed 4 hours formation copper plates, chemical bronze plating liquid in chemical bronze plating liquid, includes CuSO4·5H2O 0.12mol/L, Na2EDTA·2H2O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2 '-bipyridyls 10mg/L, glyoxalic acid (HCOCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value for adjusting plating solution is 12.5-13；
10 minutes formation nickel coatings of chemical nickel-plating liquid are immersed again, chemical nickel-plating liquid: nickel sulfate: 23g/l, sodium hypophosphite: 18g/l, lactic acid: 20g/l, malic acid: 15g/l, adjusting pH with NaOH is 5.2.
It finally immerses again and dodges 20 minutes formation Gold plated Layers of gold plating liquid, dodge gold plating liquid using Shenzhen lappingout and create company, chemical company BG-24 neutrality gold plating liquid.
Embodiment 2
Method for illustrating plastic products and plastic basis material surface selective metallization of the present invention
(1) chemical plating activator CuSb2O6The preparation of powder: referring to step (1) in embodiment 1, difference is: 1. CuO with Sb2O5Molar ratio 1:1.05；It is sintered 2. the powder after drying is placed in Muffle furnace, first in 550 DEG C of pre-sintering 2h, so Temperature rises to 800 DEG C of sintering 10h afterwards；
Sinter is subjected to dry grinding, obtains volume average particle size D50Chartreuse metallic compound less than 1.2 μm. Through detecting, the chemical formula of the metallic compound is CuSb2O6Powder is denoted as P2.
(2) preparation method of plastic products: referring to step (2) in embodiment 1, difference is, using 2 step of embodiment (1) the chemical plating activator CuSb prepared2O6Powder P2 replaces the chemical plating activator CuSb of 1 step of embodiment (1) preparation2O6 Powder.
Embodiment 3
Method for illustrating plastic products and plastic basis material surface selective metallization of the present invention
(1) chemical plating activator CuSb2O6The preparation of powder: referring to step (1) in embodiment 1, difference is: will dry Powder afterwards, which is placed in Muffle furnace, to be sintered, and first in 650 DEG C of pre-sintering 1h, then temperature rises to 950 DEG C of sintering 8h；
Sinter is subjected to dry grinding, obtains volume average particle size D50Chartreuse metallic compound less than 1.2 μm. Through detecting, the chemical formula of the metallic compound is CuSb2O6Powder is denoted as P3.
(2) preparation method of plastic products: referring to step (2) in embodiment 1, difference is, using 3 step of embodiment (1) the chemical plating activator CuSb prepared2O6Powder P3 replaces the chemical plating activator CuSb of 1 step of embodiment (1) preparation2O6 Powder.
Comparative example 1
Method for comparative illustration plastic products of the present invention and plastic basis material surface selective metallization
(1) chemical plating activator CuCr2O4Preparation.
By CuO and Cr2O3It is uniformly mixed, wherein Cu2O and Cr2O3Molar ratio be 1:1.Obtained mixture is ground Machine carries out wet grinding, wherein dispersing agent is water, and relative to 100 parts by weight mixtures, the dosage of water is 150 parts by weight.Grinding When revolving speed be 500 revs/min, the time be 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 100 DEG C, when Between be 12 hours.
Powder after drying is placed in Muffle furnace and is sintered, the temperature of sintering is 950 DEG C, and the time is 10 hours.It will Sinter carries out dry grinding, obtains volume average particle size D50Ferrous metal compound less than 2 μm.Through detecting, the metallization The chemical formula for closing object is CuCr2O4, it is denoted as DP1.
(2) preparation method of plastic products: referring to step (2) in embodiment 1, difference is, using 1 step of comparative example (1) the chemical plating activator CuCr prepared2O4Powder DP1 replaces the chemical plating activator CuSb of 1 step of embodiment (1) preparation2O6 Powder.
Comparative example 2
Method for comparative illustration plastic products of the present invention and plastic basis material surface selective metallization
(1) chemical plating activator Cu2(PO4) (OH): it is commercially available from Shanghai Ao highland barley Industrial Co., Ltd., for shallow white green, is denoted as DP2。
(2) preparation method of plastic products: referring to step (2) in embodiment 1, difference is, using 2 step of comparative example (1) chemical plating activator Cu in2(PO4) (OH) powder DP2 replace 1 step of embodiment (1) preparation chemical plating activator CuSb2O6Powder.
It tests (one)
It takes plastic products prepared by embodiment 1-3 and comparative example 1-2, following survey is carried out to these plastic products respectively Examination:
The measurement of thickness of coating: testing film thickness using x-ray method, is directly tested using film thickness instrument test (X-ray).
The measurement of adhesive force: the adhesive force of the metal layer formed in substrate surface is measured using cross-cut tester method.It is specific to survey Method for testing are as follows: draw the small grid of 10 × 10 1mm × 1mm, each scribing line depth and metal on sample to be tested surface with cross-cut tester The bottom of layer, after being cleaned down the fragment of test zone with hairbrush, clings tested small net with adhesive tape (3M600 gummed paper) Lattice hold adhesive tape one end, shut down gummed paper rapidly in vertical direction, 2 same tests are carried out in same position, according to following Standard determines adhesive force grade:
ISO grade 0: scribing edge is smooth, at the edge and intersection of scribing line without peeling paint；
ISO grade 1: there is the peeling paint of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
ISO grade 2: there is the peeling paint of small pieces at the edge and intersection of scribing line, and the gross area that falls off is in 5-15% Between；
ISO grade 3: there is sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is in 15-35% Between；
ISO class 4: there is sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is in 35-65% Between；
ISO class 5: having sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Test result: as shown in table 1.
Table 1.
It can be to use CuSb in 1-3 of the embodiment of the present invention by data in table 12O6Powder is made as chemical plating activator The adhesive force of standby plastic products can reach with plastic products phase same level prepared by comparative example 1 and 2, and each thickness of coating connects The closely plastic products as prepared by comparative example 1 and 2, it can be seen that CuSb2O6Powder is as chemical plating activator in use, it is chemical Plating activity can reach the level of the chemical plating activator employed in comparative example 1 and 2.
It tests (two)
It takes plastic products prepared by embodiment 1-3 and comparative example 1-2, following survey is carried out to these plastic products respectively Examination:
Coloration test: the color difference meter test sample of the SP60 model produced using X-rite company is in CIELAB color space In L, a, b value, and with carbon black black standard sample compare.
Degree of degradation (%): 300 DEG C at a temperature of, apply the load of 11.76N, respectively measurement without containing chemical plating activate The melt flow rate (MFR) of the plastic products of agent and the plastic products containing chemical plating activator, is calculated using the following equation plastics system The degree of degradation of product,
Degree of degradation (%)=[| MI0- MI1︱/MI0] × 100%,
Wherein, MI0For the melt flow rate (MFR) of resin matrix, in terms of g/min,
MI1For the melt flow rate (MFR) of the resin sheet containing chemical plating activator, in terms of g/min.
Impact strength: method disclosed in the test method using ASTM-D256 measurement plastics cantilever beam impact strength The test of beam type notch impact strength is carried out to sample, standard sample specification is 64mm × 12.7mm × 3.2mm, sample break Depth be 10.2mm, each test result is the average value of 5 groups of same samples.Acquired results are as shown in table 2.
Test result: as shown in table 2.
Table 2.
As data in table 2 it is found that modeling prepared by the plastic products as prepared by preparation example 1-3 of the present invention and comparative example 1-2 Material products are compared, and the degree of degradation of plastic products is relatively low, and impact strength (mechanical property) is opposite to be improved；And it is made by the present invention The paler colour of plastic products prepared by standby example 1-3, can consumer for light plastic products demand.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of method of plastic basis material surface selective metallization, this method comprises:
With the surface of energetic beam illumination plastic basis material metallize, illuminated surface is made to gasify；And it will irradiation Plastic basis material afterwards carries out chemical plating,
It is characterized in that, the surface of the plastic basis material metallize is formed by a kind of plastics composite, the modeling Feed composition contains substrate resin and at least one chemical plating activator, and the chemical plating activator is CuSb2O6Powder；
The energy beam is laser, and the wavelength of the laser is 1064nm to 10.6 μm, scanning speed 500-8000mm/s, step It a length of 3-9 μm, is delayed as 30-100 μ s, frequency 30-40kHz, power 3-4kW, filling spacing is 10-50 μm.
2. according to the method described in claim 1, wherein, relative to the substrate of 100 parts by weight in the plastics composite Resin, the content of the chemical plating activator are 1-20 parts by weight.
3. according to the method described in claim 1, wherein, the CuSb2O6The partial size D of powder50It is 100nm-10 μm.
4. according to the method described in claim 1, wherein, the CuSb2O6The preparation method of powder includes: by copper oxide and five Two antimony ground and mixed in dispersing agent is aoxidized, mixture is formed；Under sintering condition, mixture described in sintering processes obtains institute State active material CuSb2O6Powder.
5. according to the method described in claim 4, wherein, the CuSb2O6In the preparation method of powder, copper oxide and five oxidations The molar ratio of two antimony is 1:(1-1.05).
6. according to the method described in claim 5, wherein, the partial size D of the copper oxide50It is 100nm-10 μm, five oxidation The partial size D of two antimony50It is 100nm-10 μm, the partial size D of the mixture50It is 100nm-10 μm.
7. according to the method described in claim 4, wherein, the CuSb2O6Sintering condition in the preparation method of powder includes: 2-10h is sintered at a temperature of 800-950 DEG C.
8. according to the method described in claim 7, wherein, the CuSb2O6Sintering condition in the preparation method of powder includes: Temperature is first risen to 550-650 DEG C, 1-3h is sintered, then temperature is risen to 800-950 DEG C, is sintered 8-10h.
9. according to the method described in claim 1, wherein, the substrate resin be polyolefin, polycarbonate, polyester, polyamide, Polyarylether, polyetherimide, polyphenylene oxide, polyphenylene sulfide, polyimides, polysulfones, polyether-ether-ketone, polybenzimidazoles, phenolic resin, One or more of Lauxite, melamine formaldehyde resin, epoxy resin, alkyd resin and polyurethane.
10. a kind of plastic products of the preparation of the method as described in any one of claim 1 to 9.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295499A (en) * 1998-04-06 2001-05-16 巴斯福股份公司 Multi-metal oxide compounds
CN101654564A (en) * 2008-08-23 2010-02-24 比亚迪股份有限公司 Plastic composition and surface selective metallization process thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295499A (en) * 1998-04-06 2001-05-16 巴斯福股份公司 Multi-metal oxide compounds
CN101654564A (en) * 2008-08-23 2010-02-24 比亚迪股份有限公司 Plastic composition and surface selective metallization process thereof

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