CN106967965A - 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

Info

Publication number
CN106967965A
CN106967965A CN201610023290.0A CN201610023290A CN106967965A CN 106967965 A CN106967965 A CN 106967965A CN 201610023290 A CN201610023290 A CN 201610023290A CN 106967965 A CN106967965 A CN 106967965A
Authority
CN
China
Prior art keywords
powder
plastic
cusb
chemical plating
basis material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610023290.0A
Other languages
Chinese (zh)
Other versions
CN106967965B (en
Inventor
周芳享
黄江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BYD Co Ltd filed Critical BYD Co Ltd
Priority to CN201610023290.0A priority Critical patent/CN106967965B/en
Publication of CN106967965A publication Critical patent/CN106967965A/en
Application granted granted Critical
Publication of CN106967965B publication Critical patent/CN106967965B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

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

Abstract

The invention discloses a kind of method of plastic products and plastic basis material surface selective metallization.The plastic products include plastic basis material and the coat of metal being attached at least part 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, and the chemical plating activator includes CuSb2O6Powder.Plastic products of the present invention are by using CuSb2O6Powder utilizes this CuSb as chemical plating activator2O6Powder has a preferable chemical plating catalytic effect, and to the degradation of plastics it is relatively small the characteristics of, advantageously reduce 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 field, in particular it relates to a kind of plastics The method of product and plastic basis material surface selective metallization.
Background technology
In insulating properties base material forming metal layer on surface, the path conducted as electromagnetic signal is widely used in vapour The fields such as car, industry, computer, communication.How gold is formed selectively on the surface of insulating properties base material Category layer is a core link of based article manufacture.In the prior art, in insulating properties base material surface shape Method into metal level is a lot, and these methods are generally all first to form metal core on insulating properties base material surface Then (chemical plating activator, SBID powder) carry out chemical plating as chemical plating catalytic active center.
At present, existing SBID powder has metallo-chelate (such as patent application on the market Raw material described in CN101851431A), the ABO with delafossite structure2Type composite oxides (raw material as described in patent application CN102391633A), copper chromite, chromous acid are cuprous etc..
However, above-mentioned SBID powder (active material) partly exists complicated, synthesis difficulty is big, Synthesize the problem of cost is high (such as metallo-chelate)；Part presence may promote plastic degradation and can not Actual use and activity it is low, the problems such as cost is high；Part exist color it is relatively deep (mainly copper-bearing materials, Usually dark or black), making it difficult to the plastic products of light color or even white are met, application is limited The problem of.
The content of the invention
It is an object of the invention to provide the side of a kind of plastic products and plastic basis material surface selective metallization Method, to reduce the degree of degradation of plastic products.
To achieve these goals, according to the first aspect of the invention there is provided a kind of plastic products, The plastic products include plastic basis material and the gold being attached at least part surface of the plastic basis material Belong to coating, the plastic basis material surface for being attached with the coat of metal 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 CuSb2O6Powder.
There is provided a kind of side of plastic basis material surface selective metallization according to the second aspect of the invention Method, this method includes：With the surface metallized the need for energetic beam illumination plastic basis material, make to be shone The surface gasification penetrated；And the plastic basis material after irradiation is subjected to chemical plating, enter the need for the plastic basis material The surface of row metal is formed by a kind of plastics composite, and the plastics composite contains substrate resin and extremely A kind of few chemical plating activator, the chemical plating activator includes CuSb2O6Powder.
According to the third aspect of the present invention there is provided one kind by plastic basis material surface of the present invention selectivity gold Plastic products prepared by the method for categoryization.
The method of above-mentioned the provided plastic products of the present invention and plastic basis material surface selective metallization, profit Use this CuSb2O6Powder has preferable chemical plating catalytic effect, and to the degradation phase of plastics To less feature, advantageously reduce as the degree of degradation of the plastic products prepared by it, and improve the plastics Product impact strength；In addition, this CuSb2O6Powder sheet is as chartreuse, using its making The color of plastic products is shallower, it might even be possible to for white.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Be directed to described by background section " existing chemical plating activator generally exist to plastics drop Solution effect is obvious " technical problem.A kind of plastic products, the plastic products bag are provided in the present invention Include plastic basis material and be attached to the coat of metal at least part surface of the plastic basis material, attachment is The plastic basis material surface for stating the coat of metal is formed by a kind of plastics composite, and the plastics composite contains base Material resin and at least one chemical plating activator, the chemical plating activator include (being) CuSb2O6Powder.
Plastic products provided by the present invention are by using CuSb2O6Powder is used as chemical plating activator, profit Use this CuSb2O6Powder has preferable chemical plating catalytic effect, and to the degradation phase of plastics To less feature, it can reduce as the degree of degradation of the plastic products prepared by it, and improve the plastics system Product impact strength；In addition, this CuSb2O6Powder sheet is as chartreuse, using the modeling of its making The color of material products is shallower, it might even be possible to for white.
According to plastic products provided by the present invention, do not have spy for the content of wherein chemical plating activator Different to require, it is referred to the conventional amount used of chemical plating activator in this area.For example relative to 100 weights The substrate resin of part is measured, the content of the chemical plating activator is 1-20 parts by weight.
According to plastic products provided by the present invention, the chemical plating activator (CuSb2O6Powder) Particle diameter can carry out appropriate selection according to its concrete application occasion.Usually, the chemical plating activator (CuSb2O6Powder) particle diameter D50Can be 100nm to 10 μm, preferably 300nm to 5 μm, More preferably 1-3.5 μm.The particle diameter D50For volume average particle size, it is using sharp by liquid phase method Light particle size analyzer determination.
The substrate resin can be thermoplastic resin, or thermosetting resin.The substrate resin Instantiation can include but is not limited to：Polyolefin (such as polystyrene, polypropylene, polymethyl Sour methyl esters and poly- (acrylonitrile-butadiene-styrene (ABS))), makrolon, polyester (such as poly terephthalic acid ring Hexane is to diformazan alcohol ester, PDAIP, poly terephthalic acid diallyl, poly- naphthalene two Sour butyl alcohol ester, polyethylene terephthalate and polybutylene terephthalate (PBT)), polyamide (such as Polyhexamethylene adipamide, poly-hexamethylene azelamide, polybutadiene acyl hexamethylene diamine, nylon 612, 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-paraphenylene terephthalamide's nonamethylene diamine), polyarylether, PEI, poly- carbon Acid esters/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene oxide, polyphenylene sulfide, polyimides, polysulfones, Polyether-ether-ketone, polybenzimidazoles, phenolic resin, Lauxite, melamine formaldehyde resin, epoxy It is more than one or both of resin, alkyd resin and polyurethane.
The auxiliary agent can be that can improve the performance of plastic products or assign plastic products with new property The material of energy, such as filler, antioxidant and light stabilizer.The content of the auxiliary agent can be according to its species Require to carry out appropriate selection with specifically used, be not particularly limited.Usually, relative to 100 weight Part resin base material, 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, the content of the light stabilizer can be 0.01-1 parts by weight, the lubrication The content of agent can be 0.01-1 parts by weight.
The filler can not play any physics or the filler of chemical action to laser, for example, talcum Powder and calcium carbonate.Although glass fibre is insensitive to laser, adding glass fibre can deepen significantly The depth that plastic substrate is recessed after laser activation, is conducive to the adhesion of copper in electroless copper.It is described inorganic to fill out Material can also be the inorganic filler played a role to laser, for example, the filler can also be glass Microballon, calcium sulfate, barium sulfate, titanium dioxide, pearl essence, wollastonite, diatomite, kaolin, pottery One or more in soil, mica, kerosene shale ash, alumina silicate, aluminum oxide, silica and zinc oxide.
The inoxidizability for the plastic products that the plastics composite that the antioxidant can improve the present invention is obtained Can, so as to improve the service life of product.The antioxidant can be various anti-for what is commonly used in plastic applications Oxygen agent, for example, can contain primary antioxidant and auxiliary antioxidant.The primary antioxidant and the auxiliary antioxygen Relative usage between agent can carry out appropriate selection according to species.Usually, the primary antioxidant with The weight ratio of the auxiliary antioxidant can be 1：1-4.The primary antioxidant can be hindered phenol type antioxygen Agent, its instantiation can include but is not limited to antioxidant 1098 and antioxidant 1010, wherein, antioxygen The main component of agent 1098 be N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, The main component of antioxidant 1010 is four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites. The auxiliary antioxidant can be phosphite type antioxidant, and its instantiation can include but is not limited to anti- Oxygen agent 168, its main component is three (2,4- di-tert-butyl-phenyl) phosphite esters.
The light stabilizer can be known various light stabilizers, such as hindered amine type light stabilizer, its Instantiation can include but is not limited to bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate.
The lubricant can be the material of the various mobility that can improve plastic melt, for example, can be Copolymerization wax (EVA waxes), Tissuemat E (PE waxes) and stearate selected from ethylene/vinyl acetate One or both of more than.
The content of the auxiliary agent can carry out appropriate selection according to the function and species of auxiliary agent.Usually, Relative to the substrate resin of 100 parts by weight, the content of the filler can be 1-40 parts by weight, The content of the antioxidant can be 0.1-10 parts by weight, and the content of the light stabilizer can be 0.1-10 Parts by weight, the content of the lubricant can be 0.1-10 parts by weight.
According to the plastic products of the present invention, the plastic basis material can only be attached with the surface of the coat of metal by The plastics composite is formed, and integrally can also be formed by the plastics composite, i.e., described plastics base Material is formed by the plastics composite.When the size of plastic basis material is larger, go out from the angle for reducing cost Hair, only plastic basis material can be attached with the surface of the coat of metal and formed by the plastics composite；In plastics When the size of base material is little, integrally it can be formed by the plastics composite.
The specific size of the plastic basis material can be selected according to expected use occasion, without special Limit.The plastic basis material can also have variously-shaped according to specific needs.The plastic basis material can be with Prepared using conventional method, for example extruding-out process, injection molding process.
According to the plastic products of the present invention, the thickness of the coat of metal can be according to specifically used requirement It is fixed, it is not particularly limited, typically can is 0.1-10 μm.Required according to specifically used, the metal-plated Layer can have variously-shaped.For example：When the plastic products are used to make wiring board, the metal Layer can form line pattern.
Meanwhile, a kind of method of plastic basis material surface selective metallization is additionally provided in the present invention, should Method includes：With the surface metallized the need for energetic beam illumination plastic basis material, make illuminated table Gasify in face；And the plastic basis material after irradiation is subjected to chemical plating, enter row metal the need for the plastic basis material The surface of change is formed by a kind of plastics composite, and the plastics composite contains substrate resin and at least one Chemical plating activator, the chemical plating activator includes (being) CuSb2O6Powder.
Above-mentioned the provided plastic basis material surface selective metallization method of the present invention, by using CuSb2O6As chemical plating activator, this CuSb is utilized2O6Mealy structure is simple, is readily synthesized, And cost of material it is relatively low the characteristics of, advantageously reduce the preparation cost of plastic products；Utilize this simultaneously Plant CuSb2O6Powder has a preferable chemical plating catalytic effect, and to the degradations of plastics relatively Small the characteristics of, advantageously reduce as the degree of degradation of the plastic products prepared by it, and improve the plastic products Impact strength；In addition, this CuSb2O6Powder sheet is as chartreuse, using the plastics of its making The color of product is shallower, it might even be possible to for white.
According to the method for plastic basis material surface selective metallization of the present invention, for chemical in plastics composite The content of plating activator does not have particular/special requirement, and it is referred to the routine of chemical plating activator in this area Consumption.For example relative to the substrate resin of 100 parts by weight, the content of the chemical plating activator is 1-20 parts by weight.
According to plastic basis material surface selective metallization method of the present invention, wherein employed in plastics composite CuSb2O6Powder can be commercially available prod or made products.The CuSb2O6The system of powder Preparation Method may comprise steps of：By cupric oxide (CuO) and antimony pentoxide (Sb2O5) dividing Ground and mixed in powder, forms mixture；Under sintering condition, mixture described in sintering processes is obtained The active material CuSb2O6Powder.
In above-mentioned CuSb2O6In the preparation method of powder, for the mixing ratio of cupric oxide and antimony pentoxide Example does not have particular/special requirement, as long as CuSb can be formed2O6Powder.Preferably by cupric oxide and five Aoxidize two antimony in dispersant the step of ground and mixed in, the mol ratio of cupric oxide and antimony pentoxide is 1： (1-1.05).Preferably, the particle diameter D of cupric oxide50For 10nm-10 μm, the particle diameter of antimony pentoxide D50For 10nm-10 μm.The step of grinding is wet grinding, and grinding rotating speed is 300-800rpm, Milling time is the particle diameter D of mixture after 2-10h, grinding50For 10nm-10 μm.
Preferably, the process of grinding adds dispersant and carries out wet grinding, and the dispersant is water or C1-C5 Alcohol, it is highly preferred that the dispersant is water and/or C1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be with For methanol, ethanol, normal propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, 2- methyl isophthalic acids-propyl alcohol, 2- methyl - 2- propyl alcohol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanols, 2- methyl -2- butanol, 3- methyl -2- One or more in butanol and 2,2- dimethyl -1- propyl alcohol, preferably ethanol.
In above-mentioned CuSb2O6In the preparation method of powder, do not have particular/special requirement for sintering condition, can So that cupric oxide and antimony pentoxide to be sintered to form CuSb with reference to this area2O6The normal condition of powder, The preferred sintering condition includes in the present invention：2-10h is sintered at a temperature of 800-950 DEG C.It is highly preferred that The sintering condition includes：Temperature is first risen to 550-650 DEG C, 1-3h is sintered, then temperature is risen to 800-950 DEG C, sinter 8-10h.
In above-mentioned CuSb2O6In the preparation method of powder, the step of mixture described in sintering processes before also The step of including drying the mixture, by the dispersant in dry step elimination reaction system, make Cupric oxide and antimony pentoxide mixing it is closer, be more beneficial for forming CuSb2O6Powder.It is preferred that In the step of drying the mixture, drying temperature is 80-150 DEG C, and drying time is 1-10h.
According to the method for the plastic basis material surface selective metallization of the present invention, the energy beam can be sharp Light, electron beam or ion beam, preferably laser.The laser can be obtained by various known approach, It is preferred that obtaining laser by laser.
According to the method for the plastic basis material surface selective metallization of the present invention, the bar of the energetic beam illumination Part exposes chemical plating activator (CuSb to enable to illuminated surface of plastic products to gasify2O6) It is defined.Specifically, when the energy beam is laser, the wavelength of the laser can be 157-10600nm, Sweep speed can be 500-8000mm/s, and step-length can be 3-9 μm, and delay can be 30-100 μ s, Frequency can be 30-40kHz, and power can be 3-4kW, and filling spacing can be 10-50 μm.Pass through The such laser of irradiation, the thickness of the plastics typically etched away is several microns to more than ten microns, so that The chemical plating activator being dispersed in plastic products is exposed, at least part surface of plastic products Form microcosmic upper for the rough surface structure with rugged space；In follow-up chemical plating, gold Metal particles are just embedded into the hole of rough surface, so as to form very strong adhesion between plastic sample. Plastic products through energetic beam illumination are preferably cleaned, with clean surface before chemical plating is carried out. The plastic products through energetic beam illumination can for example be cleaned as cleaning agent with water.
The method for carrying out chemical plating to the plastic products after irradiation is known to those skilled in the art. For example, when carrying out electroless copper, this method can include contacting the plastic products after irradiation with copper electrolyte, The copper electrolyte contains mantoquita and reducing agent, and pH value is 12-13, and the reducing agent can be by copper in mantoquita Ion reduction is copper simple substance, such as described reducing agent can be one in glyoxalic acid, hydrazine and sodium hypophosphite Plant or a variety of.
After chemical plating is carried out, it can also then be electroplated or carry out one or many chemical platings again, Further to increase the thickness of coating or other coats of metal formed on chemical deposit.For example, changing Learn after copper facing terminates, copper coating surface can be prevented to be oxidized by one layer of nickel of chemical plating again.
The main of the preparation method for the plastic products that the present invention is provided thes improvement is that employing one kind contains There is CuSb2O6The plastic basis material composition of powder prepares plastic basis material, and is plated in follow-up plating process Metal species and chemical plating specific method and condition can be this area conventional selection.
According to a kind of embodiment of the present invention, the method for the chemical plating is included in the exposed area Electroless copper, chemical nickel plating and chemical gilding are carried out on domain successively.The method of the chemical gilding can be adopted Carried out, be specifically known to the skilled person, therefore not to repeat here with the method for flash.
Wherein, the method for the electroless copper can be carried out according to existing various methods, for example, can be with Plastic basis material after laser-induced thermal etching is contacted with copper electrolyte.The copper electrolyte contains mantoquita and reducing agent, pH It is worth for 12-13.Copper ion in mantoquita can be reduced to copper simple substance by the reducing agent, for example, can be second At least one of aldehydic acid, hydrazine and sodium hypophosphite.For example,《Sufacing》December in 2002 Volume 31 the 6th be interim to disclose a kind of basic composition is for typical copper electrolyte：CuSO4·5H2O： 0.12mol/L, Na2EDTA·2H2O：0.14mol/L, potassium ferrocyanide：10mg/L, 2,2 '-bipyridyl： 10mg/L, glyoxalic acid (HOCCOOH)：0.10mol/L, and with NaOH and H2SO4Adjust plating solution PH value is 12.5-13.In addition, can also be electroplated after electroless copper if thinking that copper thickness is not enough Copper.
The method of the chemical nickel plating can be carried out according to existing various methods, for example, can be by chemistry Plastic sample after copper facing is contacted with nickel plating bath.One kind typical case of the nickel plating bath, which constitutes, is：Nickel sulfate： 23g/L, sodium hypophosphite：18g/L, lactic acid：20g/L, malic acid：15g/L, with NaOH by its PH value is adjusted to 5.2.The thickness of chemical Ni-plating layer is had no particular limits, for example, can be 0.5-1 μm.
The method according to the invention, the thickness of the coat of metal of chemical plating formation can be wanted according to specifically used Depending on asking, it is not particularly limited, typically can is 0.1-10 μm.
Required according to specifically used, the metal level can have variously-shaped.For example：For making During wiring board, the metal level can form line pattern.
In addition, additionally providing a kind of plastic products in the present invention, prepared by the plastics is by plastics of the present invention Substrate surface selective metallization method is prepared from.
With reference to embodiments the present invention is described in detail with comparative example.
In following examples and comparative example, using inductively coupled plasma emission spectrography (ICP) come Determine the composition of chemical plating activator.
In following examples and comparative example, using commercially available from Jingxin Power Testing Apparatus Co., Ltd., Chengdu Laser particle analyzer determines the volume average particle size D of chemical plating activator50And D90。
Embodiment 1
Method for illustrating plastic products of the present invention and plastic basis material surface selective metallization
(1) chemical plating activator CuSb2O6The preparation of powder
Taking CuO powder respectively, (the commercially available Chemical Co., Ltd. of Gansu Province westerly, purity are 99.5%, particle diameter D50 Less than 1.5 μm, D90Less than 3 μm) and Sb2O5Powder (the commercially available Chemical Co., Ltd. of Gansu Province westerly, purity For 99%, particle diameter D50Less than 1.6 μm, D90Less than 2.9 μm), CuO and Sb2O5Mol ratio 1： 1, using deionized water as dispersant, by CuO powder and Sb2O5Powder carries out mixing and ball milling.Wherein, Relative to 100 parts by weight mixtures, using the consumption of deionized water as 150 parts by weight.Rotating speed during grinding For 500 revs/min, the time is 5 hours, the particle diameter D of mixture after grinding50Less than 1.2 μm.Will grinding Obtained powder is placed in baking oven, is dried in air atmosphere, and dry temperature is 95 DEG C, time For 2 hours.
Dried powder is placed in Muffle furnace and is sintered, the temperature of sintering is 945 DEG C, the time is 2 hours.Sinter is subjected to dry grinding, volume average particle size D is obtained50Light yellow green less than 2 μm Non-ferrous metal compound.After testing, the metallic compound is CuSb2O6Powder, is designated as P1.
(2) preparation method of plastic products
By makrolon (supporting engineering plastics Co., Ltd commercially available from three), antioxidant 1098 (commercially available from Ciba Company), lubricant PE waxes (commercially available from Clariant chemical industry (Clariant) Co., Ltd) and step (1) The chemical plating activator CuSb of preparation2O6Powder P1 is mixed, wherein, relative to the poly- carbon of 100 parts by weight Acid esters, chemical plating activator level is 20 parts by weight, and the consumption of antioxidant is 0.05 parts by weight, lubrication The consumption of agent is 0.04 parts by weight.After obtained mixture pelleting, injection molding in feeding injection machine, Obtain the plastic sheet that thickness is 2mm.
Foregoing obtained plastic sheet is placed on laser sample stage, by Laser Focusing, computer program control The movement of light beam or sample stage processed, laser used is big nation YLP-20 type lasers, and laser parameter is： Wavelength is 1064nm, and sweep speed is 1000mm/s, and step-length is 6 μm, is delayed as 50 μ s, frequency For 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, plastic sample is carried out Abatement processes, are cleaned by ultrasonic (28kHz cleans 5mins) the plastic sheet surface.
Plastic carrier after cleaning is integrally immersed 4 hours in chemical bronze plating liquid and forms copper plate, chemical plating Copper liquid includes CuSO4·5H2O 0.12mol/L, Na2EDTA·2H2O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2 '-bipyridyl 10mg/L, glyoxalic acid (HCOCOOH) 0.10mol/L, and use NaOH And H2SO4The pH value for adjusting plating solution is 12.5-13；
Chemical nickel-plating liquid is immersed again forms nickel coating, chemical nickel-plating liquid within 10 minutes：Nickel sulfate：23g/l, Sodium hypophosphite：18g/l, lactic acid：20g/l, malic acid：15g/l, is 5.2 with NaOH regulations pH.
The last sudden strain of a muscle gold plating liquid that immerses again forms Gold plated Layer in 20 minutes, dodges gold plating liquid and uses Shenzhen lappingout woundization The neutral gold plating liquids of the BG-24 of company of work company.
Embodiment 2
Method for illustrating plastic products of the present invention and plastic basis material surface selective metallization
(1) chemical plating activator CuSb2O6The preparation of powder：With reference to step (1) in embodiment 1, Difference is：1. CuO and Sb2O5Mol ratio 1：1.05；2. dried powder is placed in Muffle It is sintered in stove, first in 550 DEG C of pre-sintering 2h, then temperature rises to 800 DEG C of sintering 10h；
Sinter is subjected to dry grinding, volume average particle size D is obtained50Chartreuse less than 1.2 μm Metallic compound.After testing, the chemical formula of the metallic compound is CuSb2O6Powder, is designated as P2.
(2) preparation method of plastic products：With reference to step (2) in embodiment 1, difference is, adopts The chemical plating activator CuSb prepared with the step of embodiment 2 (1)2O6Powder P2 replaces the step of embodiment 1 Suddenly the chemical plating activator CuSb that prepared by (1)2O6Powder.
Embodiment 3
Method for illustrating plastic products of the present invention and plastic basis material surface selective metallization
(1) chemical plating activator CuSb2O6The preparation of powder：With reference to step (1) in embodiment 1, Difference is：Dried powder is placed in Muffle furnace and is sintered, 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, volume average particle size D is obtained50Chartreuse less than 1.2 μm Metallic compound.After testing, the chemical formula of the metallic compound is CuSb2O6Powder, is designated as P3.
(2) preparation method of plastic products：With reference to step (2) in embodiment 1, difference is, adopts The chemical plating activator CuSb prepared with the step of embodiment 3 (1)2O6Powder P3 replaces the step of embodiment 1 Suddenly the chemical plating activator CuSb that prepared by (1)2O6Powder.
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 well mixed, wherein, Cu2O and Cr2O3Mol ratio be 1：1.Will Obtained mixture carries out wet grinding with grinder, wherein, dispersant is water, relative to 100 weight Part mixture, the consumption of water is 150 parts by weight.Rotating speed during grinding is 500 revs/min, and the time is 5 Hour.
The powder that grinding is obtained is placed in baking oven, is dried in air atmosphere, dry temperature is 100 DEG C, the time is 12 hours.
Dried powder is placed in Muffle furnace and is sintered, the temperature of sintering is 950 DEG C, the time is 10 hours.Sinter is subjected to dry grinding, volume average particle size D is obtained50Black less than 2 μm Metallic compound.After testing, the chemical formula of the metallic compound is CuCr2O4, it is designated as DP1.
(2) preparation method of plastic products：With reference to step (2) in embodiment 1, difference is, adopts The chemical plating activator CuCr prepared with the step of comparative example 1 (1)2O4Powder DP1 replaces embodiment 1 Chemical plating activator CuSb prepared by step (1)2O6Powder.
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)：Commercially available from Shanghai Ao highland barleys Industrial Co., Ltd., it is Shallow white green, is designated as DP2.
(2) preparation method of plastic products：With reference to step (2) in embodiment 1, difference is, adopts With chemical plating activator Cu in the step of comparative example 2 (1)2(PO4) (OH) powder DP2 replace embodiment 1 Chemical plating activator CuSb prepared by step (1)2O6Powder.
Test (one)
Take plastic products prepared by embodiment 1-3 and comparative example 1-2, these plastic products are entered respectively Row is following to be tested：
The measurement of thickness of coating：Thickness is tested using x-ray method, tests that (X is penetrated using film thickness instrument Line) directly test.
The measurement of adhesive force：The adhesive force in the metal level of substrate surface formation is determined using cross-cut tester method. Specifically method of testing is：With cross-cut tester 10 × 10 1mm × 1mm small net is drawn on testing sample surface The bottom of lattice, each line depth and metal level, after with hairbrush, the fragment of test zone is cleaned down, Tested small grid is clung with adhesive tape (3M600 gummed papers), adhesive tape one end is held, vertical Gummed paper is shut down rapidly in direction, and 2 same tests are carried out in same position, determines to adhere to according to following standard Power grade：
ISO grades 0：Scribing edge is smooth, at the edge and intersection of line without peeling paint；
ISO grades 1：There is the peeling paint of small pieces in the intersection of line, and the gross area that comes off is less than 5%；
ISO grades 2：There is the peeling paint of small pieces at the edge and intersection of line, and total face that comes off Product is between 5-15%；
ISO grades 3：There are sheet of peeling paint, and total face that comes off at the edge and intersection of line Product is between 15-35%；
ISO class 4s：There are sheet of peeling paint, and total face that comes off at the edge and intersection of line Product is between 35-65%；
ISO class 5s：There are sheet of peeling paint, and total face that comes off at the edge and intersection of line Product is more than 65%.
Test result：As shown in table 1.
Table 1.
Data can be with using CuSb in 1-3 of the embodiment of the present invention in table 12O6Powder is used as chemistry The adhesive force of plastic products prepared by plating activator can reach and plastics system prepared by comparative example 1 and 2 Condition same level, and the close plastic products as prepared by comparative example 1 and 2 of each thickness of coating, it can be seen that CuSb2O6Powder is as chemical plating activator in use, its chemical plating activity can be reached in comparative example 1 With 2 employed in chemical plating activator level.
Test (two)
Take plastic products prepared by embodiment 1-3 and comparative example 1-2, these plastic products are entered respectively Row is following to be tested：
Colourity is tested：The color difference meter test sample of the SP60 models produced using X-rite companies is existed L in CIELAB color spaces, a, b value, and contrasted with the standard sample of carbon black nigrescence.
Degree of degradation (%)：At a temperature of 300 DEG C, apply 11.76N load, determine be free of respectively There is the melt flows speed of the plastic products of chemical plating activator and the plastic products containing chemical plating activator Rate, the degree of degradation of plastic products is calculated using below equation,
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：In the test method that plastics cantilever beam impact strength is determined using ASTM-D256 Disclosed method carries out beam type notch impact strength test to sample, and standard specimen specification is 64mm × 12.7mm × 3.2mm, the depth of sample break is 10.2mm, and each result of the test is 5 groups of phases With the average value of sample.Acquired results are as shown in table 2.
Test result：As shown in table 2.
Table 2.
The data in table 2, plastic products and comparative example 1-2 as prepared by preparation example 1-3 of the present invention Prepared plastic products are compared, and the degree of degradation of plastic products is relatively low, impact strength (mechanical property Can) relative raising；And as prepared by preparation example 1-3 of the present invention plastic products paler colour, can disappear Demand of the person of expense for light plastic products.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, In the case of reconcilable, it can be combined by any suitable means.In order to avoid unnecessary Repeat, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.

Claims (13)

1. a kind of plastic products, the plastic products include plastic basis material and are attached to the plastic basis material At least part surface on the coat of metal, be attached with the plastic basis material surface of the coat of metal by one kind Plastics composite is formed, and the plastics composite contains substrate resin and at least one chemical plating activator, Characterized in that, the chemical plating activator includes CuSb2O6Powder.
2. plastic products according to claim 1, wherein, relative to 100 in plastics composite The substrate resin of parts by weight, the content of the chemical plating activator is 1-20 parts by weight.
3. plastic products according to claim 1, wherein, the CuSb2O6The particle diameter of powder D50For 100nm-10 μm.
4. plastic products as claimed in any of claims 1 to 3, wherein, the base material Resin be polyolefin, makrolon, polyester, polyamide, polyarylether, PEI, polyphenylene oxide, Polyphenylene sulfide, polyimides, polysulfones, polyether-ether-ketone, polybenzimidazoles, phenolic resin, Lauxite, It is more than one or both of melamine formaldehyde resin, epoxy resin, alkyd resin and polyurethane.
5. a kind of method of plastic basis material surface selective metallization, this method includes：
With the surface metallized the need for energetic beam illumination plastic basis material, illuminated surface is set to gasify； And the plastic basis material after irradiation is subjected to chemical plating,
Characterized in that, the surface metallized the need for the plastic basis material is by a kind of plastics composite Formed, the plastics composite contains substrate resin and at least one chemical plating activator, the chemical plating Activator includes CuSb2O6Powder.
6. method according to claim 5, wherein, relative to 100 in the plastics composite The substrate resin of parts by weight, the content of the chemical plating activator is 1-20 parts by weight.
7. method according to claim 5, wherein, the CuSb2O6The particle diameter D of powder50 For 100nm-10 μm.
8. method according to claim 5, wherein, the CuSb2O6The preparation method of powder Including：By cupric oxide and antimony pentoxide in dispersant ground and mixed, formed mixture；In sintered bar Under part, mixture described in sintering processes obtains the active material CuSb2O6Powder.
9. method according to claim 8, wherein, the CuSb2O6The preparation method of powder In, the mol ratio of cupric oxide and antimony pentoxide is 1：(1-1.05),
Preferably, the particle diameter D of the cupric oxide50For 100nm-10 μm, the grain of the antimony pentoxide Footpath D50For 100nm-10 μm, the particle diameter D of the mixture50For 100nm-10 μm.
10. method according to claim 8, wherein, the CuSb2O6The preparation method of powder In sintering condition include：2-10h is sintered at a temperature of 800-950 DEG C, is preferably included：First by temperature liter To 550-650 DEG C, 1-3h is sintered, then temperature is risen to 800-950 DEG C, 8-10h is sintered.
11. method according to claim 5, wherein, the substrate resin is polyolefin, poly- carbon Acid esters, polyester, polyamide, polyarylether, PEI, polyphenylene oxide, polyphenylene sulfide, polyimides, Polysulfones, polyether-ether-ketone, polybenzimidazoles, phenolic resin, Lauxite, melamine formaldehyde resin, It is more than one or both of epoxy resin, alkyd resin and polyurethane.
12. method according to claim 5, wherein, the energy beam is laser, preferably described The wavelength of laser is 157nm to 10.6 μm, and sweep speed is 500-8000mm/s, and step-length is 3-9 μm, It is delayed as 30-100 μ s, frequency is 30-40kHz, and power is 3-4kW, filling spacing is 10-50 μm.
13. plastic products prepared by a kind of method as described in any one in claim 5 to 12.
CN201610023290.0A 2016-01-13 2016-01-13 The method of plastic products and plastic basis material surface selective metallization Active CN106967965B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610023290.0A CN106967965B (en) 2016-01-13 2016-01-13 The method of plastic products and plastic basis material surface selective metallization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610023290.0A CN106967965B (en) 2016-01-13 2016-01-13 The method of plastic products and plastic basis material surface selective metallization

Publications (2)

Publication Number Publication Date
CN106967965A true CN106967965A (en) 2017-07-21
CN106967965B CN106967965B (en) 2019-10-11

Family

ID=59334492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610023290.0A Active CN106967965B (en) 2016-01-13 2016-01-13 The method of plastic products and plastic basis material surface selective metallization

Country Status (1)

Country Link
CN (1) CN106967965B (en)

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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
阚伟等: "《物理化学理论与应用研究》", 31 January 2014, 北京：中国水利水电出版社 *

Also Published As

Publication number Publication date
CN106967965B (en) 2019-10-11

Similar Documents

Publication Publication Date Title
CN102071424B (en) Plastic product and preparation method thereof
CN102071411B (en) Plastic product and preparation method thereof
CN102071421B (en) Plastic product and preparation method thereof
CN101747650B (en) Plastic compound, application thereof and method of selective metallization of plastic surface
CN103773143B (en) White paint composition, selective metallization of surface of insulation base material and composite product
CN102071423B (en) Preparation method of plastic product and plastic product
CN103741125B (en) Selective surface metallization method of polymer base material and polymer base material with metallized pattern on surface obtained by method
CN102492940B (en) Preparation method of plastic product and plastic product
CN104275886B (en) A kind of polymer product and a kind of surface of polymer substrates selective metallization method
CN106555179B (en) Alkali formula cupric phosphate coats diatomite composite material and plastics composite and plastic products and their preparation method comprising it
TW201445006A (en) A method of selective metallizing a surface of a polymer article and a polymer article obtained thereof
CN102409319A (en) Preparation method of plastic product and plastic product
CN104448752B (en) Polymer product, printing ink composition and surface selective metallization method
CN105568266B (en) Plastic products and plastic basis material surface selective metallization method
CN106967965A (en) The method of plastic products and plastic basis material surface selective metallization
CN106929836B (en) The surface treatment method and chemical plating activator and polymer product and surfaces of polymeric articles selective metallization method of inorganic particle
Hou et al. Fabrication of adhesion-enhanced and highly reliable copper circuits onto flexible substrates via a scribing–seeding–plating process
CN102391633A (en) Plastic composition and application thereof, and plastic surface selective metallization method
CN107557763B (en) The method of plastic products and plastic basis material surface selective metallization
CN108018542A (en) The method of plastic products and plastic basis material surface selective metallization
CN102277569A (en) Plastic product preparation method and plastic product
CN106893291A (en) Plastics composite and plastic products and plastic basis material surface selective metallization method
CN104178751A (en) Selective metallization method for surface of polymer product and polymer product
CN104311873B (en) The application of stannic oxide of doping and polymer composition and formed body and ink composite and method for surface metallation
CN104176769B (en) The stannum oxide of doping and preparation method and polymer product and preparation method and ink composite and surface selective metallization method

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant