CN102345123B - Preparation method of a plastic product and a plastic product - Google Patents

Abstract

The invention provides a method for producing a plastic product and the plastic product. The production method comprises the following steps: 1) forming a plastic substrate, wherein the plastic substrate comprises a chemical plating enhancer which is one or more selected from Ni2O3, Co2O3, CuSiO3, CuC2O4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide, Cu/Fe/Al/Mn quaternary co-sintering oxide; 2) laser gasificating the surface of the plastic substrate, exposing the chemical plating enhancer; 3) performing chemical copper plating or chemical nickel plating, continuously carrying out a chemical plating and/or electroplating, forming a metal layer on the surface of the plastic substrate. The method of the invention has the advantages of simple process, low energy requirement and low cost; in addition, the chemical plating enhancer is distributed in the plastic substrate, thereby a plating layer formed by chemical plating has high binding force with the plastic substrate.

Description

Preparation method of a plastic product and a plastic product

related application

This application is a divisional application of the Chinese invention patent application with the application number 200910238957.9, the application date is December 30, 2009, and the invention title is "a preparation method of a plastic product and a plastic product".

technical field

The invention belongs to the field of surface metallization of non-metallic materials, and in particular relates to a preparation method of a plastic product and a plastic product.

Background technique

A metal layer is formed on the surface of the plastic, which is used as a channel for electromagnetic signal transmission, and is widely used in automobiles, industries, computers, communications and other fields. The selective formation of a metal layer on the plastic surface is a core link in the manufacture of such plastic products. There are many methods for plastic surface metallization production lines. In the prior art, metal nuclei are first formed on the surface of the plastic substrate as the electroless plating catalytic active center, and then electroless plating is performed.

For example, US2003031803A1 discloses the use of metal oxide particles such as ZnO, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , CeO _2, etc. to coat the surface of a plastic substrate, and then reduce it to a simple metal with an ultraviolet laser, as a catalyst for electroless copper plating. Then the copper plating process is performed. Among them, the maximum speed of ultraviolet laser movement is 100 mm/s, and there is no selectivity to the generation of patterns, and the metal oxide particles are coated on the surface of the plastic substrate, so the adhesion to the plastic substrate is poor, so that the final formed coating is incompatible with the plastic substrate. Substrate adhesion is poor.

US7060421 discloses a method for plastic surface metallization, by adding metal oxides of spinel structure in the plastic matrix, wherein the metal elements can be selected from copper, nickel, cobalt, chromium, iron, etc., and then use ultraviolet laser (wavelength Activation of 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength of 1064nm and 10600nm) to decompose metal oxides and release metal elements, which serve as catalysts for subsequent electroless plating, so that electroless plating can be performed. In this method, a metal oxide with a spinel structure is used to induce chemical deposition of a metal layer after reducing the metal element under the action of a laser. The process is complicated, the energy requirement is high, and the requirements for equipment and technology are relatively high.

Contents of the invention

The invention aims to solve the technical problems of complex plastic surface metallization process, high energy requirement and poor adhesion between the plating layer and the plastic base material existing in the prior art.

The invention provides a kind of preparation method of plastic product, comprises the following steps:

1) Forming a plastic substrate; the plastic substrate is a thermoplastic or thermosetting plastic containing an electroless plating accelerator, and the electroless plating accelerator is evenly distributed in the thermoplastic or thermosetting plastic; the electroless plating accelerator is Ni ₂ O ₃ , Co ₂ O _3. One or more of CuSiO ₃ , CuC ₂ O ₄ , Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxide, Cu/Fe/Al/Mn quaternary co-sintered oxide;

2) Laser vaporizes the surface of the plastic substrate, exposing the electroless plating accelerator;

3) Electroless copper or electroless nickel plating is performed on the surface of the electroless plating accelerator in step 2), and at least one electroless plating and/or electroplating is continued to form a metal layer on the surface of the plastic substrate.

The invention also provides a plastic product, which comprises a plastic base and a metal layer on the surface of the plastic base; the plastic product is prepared by the method provided by the invention.

The inventors of the present invention have found through a large number of experiments that Ni ₂ O ₃ , Co ₂ O ₃ , CuSiO ₃ , CuC ₂ O ₄ , Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxides, Cu /Fe/ Al/Mn quaternary co-sintered oxide can be directly used as an electroless plating accelerator without reducing the metal element, and selective electroless plating can be directly performed on the surface of the electroless plating accelerator, and the electroless plating accelerator will not cause plastic degradation . In the preparation method of plastic products provided by the present invention, the electroless plating accelerator is evenly distributed in the plastic matrix, and the laser selectively irradiates the surface of the plastic matrix, so that the electroless plating accelerator is reduced to metal simple substance without excessive energy, and only The electroless copper plating or electroless nickel plating can be carried out directly after the plastic is vaporized to expose the electroless plating accelerator, and the selective metallization of the plastic surface is realized. The process is simple, the energy requirement is low, and the cost is low; in addition, the electroless plating accelerator is distributed in In the plastic matrix, the bonding force between the coating formed after electroless plating and the plastic matrix is very high.

Detailed ways

The invention provides a kind of preparation method of plastic product, comprises the following steps:

1) Forming a plastic substrate; the plastic substrate is a thermoplastic or thermosetting plastic containing an electroless plating accelerator, and the electroless plating accelerator is evenly distributed in the thermoplastic or thermosetting plastic; the electroless plating accelerator is Ni ₂ O ₃ , Co ₂ O _3. One or more of CuSiO ₃ , CuC ₂ O ₄ , Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxide, Cu/Fe/Al/Mn quaternary co-sintered oxide;

2) Laser vaporizes the surface of the plastic substrate, exposing the electroless plating accelerator;

3) Electroless copper or electroless nickel plating is performed on the surface of the electroless plating accelerator in step 2), and at least one electroless plating and/or electroplating is continued to form a metal layer on the surface of the plastic substrate.

The inventors of the present invention found that, except that simple metals such as copper and palladium can be used as crystal nuclei for electroless plating, nano-copper oxide can greatly increase the deposition rate of metal atoms in the electroless plating solution on the surface of the carrier. The inventors of the present invention conducted the following experiment: the nano-copper oxide (particle size 40nm) of Aladdin Reagent Company was directly placed in a common electroless copper plating solution, a large amount of simple copper was quickly deposited on the surface of the nano-copper oxide, and it was coated . Therefore, copper oxide with a certain particle size, especially nano-particle size, can promote electroless copper plating. However, nano-copper oxide is easy to cause degradation of plastics in plastics. The inventor found through a large number of experiments that Ni ₂ O ₃ , Co ₂ O ₃ , CuSiO ₃ , CuC ₂ O ₄ , Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxides, Cu/Fe/Al/Mn One or more of the quaternary co-sintered oxides can be used as an electroless plating accelerator, and the electroless copper/nickel plating can be directly performed on the surface, and these substances will not cause degradation of the plastic if they exist in the plastic for a long time.

In the present invention, the plastic base is formed first. The plastic matrix is a thermoplastic or thermosetting plastic containing an electroless plating accelerator, wherein the electroless plating accelerator is uniformly distributed in the thermoplastic or thermosetting plastic. The electroless plating accelerator is Ni ₂ O ₃ , Co ₂ O ₃ , CuSiO ₃ , CuC ₂ O ₄ , Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxide, Cu/Fe/Al/Mn One or more kinds of quaternary co-sintered oxides.

The electroless plating accelerator used in the present invention has a particle size of 20nm-100μm, preferably 50nm-10μm, more preferably 200nm-4μm. Among the electroless plating accelerators used, Ni ₂ O ₃ , Co ₂ O ₃ , CuSiO ₃ , CuC ₂ O ₄ can be commercially available products, and then ball milled to a suitable particle size; while Cu/Fe/Mn or Cu/Fe /Al ternary co-sintered oxides and Cu/Fe/Al/Mn quaternary co-sintered oxides can be prepared by the following method: purchase the corresponding metal oxides, mix them by ball milling, and place them in a vacuum atmosphere furnace at 700-1500 degrees Sintered and then ball milled to a suitable particle size. The molecular formula of the Cu/Fe/Mn ternary co-sintered oxide is CuFe _x Mn _y O _z , where x=0.01-2, y=0.01-2, z=2-4; the Cu/Fe/Al three The molecular formula of the elementary co-sintered oxide is CuFe _m Al _n O _l , where m=0.01-2, n=0.01-2, l=2-4; the Cu/Fe/Al/Mn quaternary co-sintered oxide The molecular formula is CuFe _a Al _b Mn _c O _d , where a=0.01-2, b=0.01-2, c=0.01-2, d=2-4.

The thermoplastic/thermosetting plastics are well known to those skilled in the art. For example, thermoplastics can be selected from polyolefins, polyesters, polyamides, polyarylene ethers, polyesterimides, polycarbonate (PC), polycarbonate/ (Acrylonitrile-butadiene-styrene) alloy (PC/ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfone (PSU), polyether ether One or more of ketone (PEEK), polybenzimidazole (PBI) or liquid crystal polymer (LCP). Wherein, the polyolefin may be polystyrene (PS), polypropylene (PP), polymethyl methacrylate or poly(acrylonitrile-butadiene-styrene). The polyester can be polycyclohexane-p-dimethylene terephthalate (PCT), polydiallyl isophthalate (PDAIP), polydiallyl terephthalate (PDAP), polynaphthalate Butanol ester (PBN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT). The polyamide can be polyhexamethylene adipamide (PA-66), polyhexamethylene azelamide (PA-69), polyhexamethylene succinamide (PA-64), polydodecanediamide adipamide Diamine (PA-612), polyhexamethylene sebacamide (PA-610), polydecanediamide (PA-1010), polyundecamide (PA-11), polydodecamide (PA -12), polyoctylamide (PA-8), poly-9-aminononanoic acid (PA-9), polycaprolactam (PA-6), polyphenylene terephthalamide (PPTA), polyisophthalamide Formamide hexamethylene diamide (MXD6), polyhexamethylene terephthalamide (PA6T) or polynonanediamide terephthalamide (PA9T). Liquid crystal polymer is a polymer material known to those skilled in the art that is composed of rigid molecular chains and has both liquid fluidity and anisotropic state of crystal physical properties (ie, liquid crystal state) under certain physical conditions. The thermosetting plastic may be selected from one or more of phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin, alkyd resin, and polyurethane.

The molding method can adopt various molding methods in the prior art. First, mix the electroless plating accelerator and thermoplastic/thermosetting plastic polymer resin evenly, and use an internal mixer, a single-screw or twin-screw extruder, a mixer, etc. Plastic compounding machines are commonly used to prepare plastic compositions, and then pass through injection molding, blow molding, extrusion or hot pressing extrusion equipment to produce plastic substrates of various desired shapes.

In the present invention, since CuC ₂ O ₄ is easy to decompose, it will degrade the plastic matrix, thereby reducing the mechanical properties of the plastic matrix. Therefore, as the common knowledge of those skilled in the art, the temperature of the molding plastic substrate is generally lower than 300°C. Therefore, if the electroless plating accelerator contains CuC ₂ O ₄ in the present invention, CuC ₂ O ₄ will not occur during molding. break down.

Based on the mass of the plastic substrate, the content of the electroless plating accelerator is 1-40%, preferably 1-30%, more preferably 2-15%.

In order to improve various performances of the plastic matrix used in the present invention, the plastic matrix may also contain antioxidants, light stabilizers, lubricants, and inorganic fillers. The antioxidants, light stabilizers, lubricants, and inorganic fillers are all well known to those skilled in the art, and commercially available products can be directly used. In the present invention, after uniformly mixing the antioxidant, light stabilizer, lubricant, inorganic filler, electroless plating accelerator and thermoplastic/thermosetting plastic polymer resin, they are molded together to obtain a plastic matrix.

Based on the quality of the plastic matrix, the content of the antioxidant can be 0.01-2%, the content of the light stabilizer can be 0.01-2%, the content of the lubricant can be 0.01-2%, and the content of the inorganic filler is 1-70%.

Antioxidants can improve the oxidation resistance of plastic substrates. The antioxidant is well known to those skilled in the art, for example, it can be selected from the antioxidants 1098, 1076, 1010, and 168 of Ciba Company. Light stabilizers can improve the light stability of the plastic matrix. The light stabilizer may be various known light stabilizers, preferably a hindered amine light stabilizer, such as light stabilizer 944 from Ciba Company.

The lubricant can improve the fluidity of the plastic, so that the plastic matrix can be mixed more uniformly. The lubricant may be selected from one or more of methyl polysiloxane, ethylene/vinyl acetate copolymer wax (EVA wax), polyethylene wax and stearate.

The inorganic filler can be talcum powder, calcium carbonate, glass fiber, calcium silicate fiber, tin oxide or carbon black. Among them, glass fiber can deepen the depression depth of plastic substrate after laser vaporization, which is beneficial to the adhesion of copper in electroless copper plating; tin oxide, especially nano tin oxide or carbon black, can increase the energy utilization rate of laser. The inorganic filler can also be glass microspheres, calcium sulfate, barium sulfate, titanium dioxide, pearl powder, wollastonite, diatomaceous earth, kaolin, coal powder, clay, mica, oil shale ash, aluminum silicate, alumina , carbon fiber, silica or zinc oxide. The inorganic filler preferably does not contain elements harmful to the environment and human body such as Cr.

In the present invention, the electroless plating accelerator is evenly distributed in the plastic matrix, so the adhesion between the electroless plating accelerator and the plastic matrix is very high, and the subsequent electroless plating is directly carried out on the surface of the electroless plating accelerator, so that the final formed Adhesion of the metal coating to the plastic substrate is also very high.

According to the preparation method provided by the invention, the surface of the plastic substrate is vaporized by laser, and patterns are formed on the surface of the plastic substrate through laser gasification. In the laser-irradiated area, the polymer resin in the plastic matrix vaporizes, exposing the electroless plating promoter. The laser equipment used can be a general-purpose infrared laser, such as a _CO2 laser marking machine. The wavelength of the laser is 157nm-10.6μm, the scanning speed is 500-8000mm/s, the step size is 3-9μm, the delay is 30-100μs, the frequency is 30-40 KHz, the power is 3-4 W, and the filling space 10-50μm. In the present invention, the energy requirements of the laser are relatively low, and it is only necessary to vaporize the surface of the plastic substrate to expose the electroless plating accelerator, without reducing the electroless plating accelerator to a simple metal substance.

Generally, the thickness of the formed plastic substrate is more than 500 μm, and the thickness of the etched plastic substrate during laser gasification is generally several microns to more than ten microns, so that the electroless plating accelerator in the plastic substrate is exposed, and the surface of the plastic substrate is formed. Above is a rough surface structure with uneven voids. During the subsequent electroless copper/nickel plating, the copper/nickel is embedded into the pores of the rough surface, thus forming a strong bond with the plastic sample.

In the present invention, in the laser irradiated area of the plastic substrate, the plastic is gasified to produce smoke. In order to prevent the smoke from falling down and covering the electroless plating catalyst, the laser can be equipped with an exhaust device to extract the smoke as much as possible, and the plastic substrate can also be ultrasonically cleaned after the laser gasification is completed.

According to the preparation method provided by the present invention, after laser gasification, the plastic substrate in the laser irradiation area is exposed to the electroless plating accelerator, and then the electroless copper plating or electroless nickel plating is performed on the surface of the electroless plating accelerator. The method for performing electroless copper plating or electroless nickel plating is an electroless plating method commonly used by those skilled in the art, for example, the laser vaporized plastic substrate can be contacted with an electroless copper plating solution or an electroless nickel plating solution.

The electroless plating accelerator exposed in the plastic matrix, after contacting the electroless copper plating solution or the electroless nickel plating solution, the electroless plating accelerator can promote the reduction reaction of copper ions or nickel ions in the electroless plating solution to generate metallic copper or nickel particles , wrapped on the surface of the electroless plating accelerator, and interconnected to form a dense layer of copper or nickel plating, so as to quickly form the first layer of plating in the laser irradiation area.

In order to improve the surface decoration, practicability and corrosion resistance of the plating layer, at least one electroless plating and/or electroplating can be continued on the surface of the copper plating layer or nickel plating layer to finally obtain the metal layer.

For example, electroless nickel plating is performed on the surface of the electroless plating accelerator, and after the nickel coating is formed in the laser vaporization area of the plastic substrate, other metal coatings can be continued to be formed on the nickel coating by conventional methods in the prior art. The conventional methods in the prior art include electroless plating and electroplating. Preferably, electroless copper plating can be continued on the surface of the nickel coating to form a copper coating on the surface of the nickel coating; another electroless nickel plating is performed to obtain a composite metal layer, which has Ni-Cu-Ni from the inside out. structure. More preferably, a gold layer is flash-plated on the surface of the composite metal layer so that the metal layer on the surface of the plastic substrate has a Ni-Cu-Ni-Au structure from inside to outside.

Electroless copper plating is carried out on the surface of the electroless plating accelerator, and after the copper coating is formed in the laser gasification area of the plastic substrate, other metal coatings can also be continued to be formed on the copper coating by conventional methods in the prior art. Preferably, in order to prevent the copper plating on the surface of the plastic substrate from being oxidized, an electroless nickel plating can be continued to form a layer of nickel plating on the surface of the copper plating, and the metal layer on the surface of the obtained plastic substrate has a Cu-Ni structure from the inside out . More preferably, a gold layer is flash-plated on the surface of the Cu-Ni metal layer so that the metal layer on the surface of the plastic substrate has a Cu-Ni-Au structure from inside to outside.

In the present invention, in the metal layer with Ni-Cu-Ni, Ni-Cu-Ni-Au, Cu-Ni or Cu-Ni-Au structure, the thickness of various Ni layers is 0.1-50 μm, preferably 1-10 μm , more preferably 2-3 μm; the thickness of the copper layer is 0.1-100 μm, preferably 1-50 μm, more preferably 5-30 μm; the thickness of the Au layer is 0.01-10 μm, preferably 0.01-2 μm, more preferably 0.1-1 μm .

Wherein, the adopted electroless copper plating solution, electroless nickel plating solution, electroplating solution copper solution or electroplating nickel solution, and the gold plating solution adopted by the flash gold layer all adopt various plating solutions commonly used by those skilled in the art. For example, the electroless copper plating solution contains copper salt and a reducing agent, and the pH value is 12-13. The reducing agent can reduce copper ions in the copper salt to simple copper. One or several kinds of sodium phosphate. The electroless copper plating can also directly adopt the copper plating solution disclosed in the prior art, such as "Surface Technology" in December 2002, a kind of plating solution disclosed in the 6th issue of volume 31: CuSO ₄ 5H ₂ O 0.12 mol/L, Na ₂ EDTA·2H ₂ O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridyl 10mg/L, glyoxylic acid (HCOCOOH) 0.10mol/L, and use NaOH and H ₂ SO ₄ adjusts the pH value of the plating solution to 12.5-13. In addition, if you feel that the thickness of the copper coating is not enough after electroless copper plating, you can also perform copper electroplating. Electroless nickel plating also can adopt the nickel plating solution in the prior art, for example it is composed of: nickel sulfate: 23g/l, sodium hypophosphite: 18g/l, lactic acid: 20g/l, malic acid: 15g/l, with NaOH adjusts pH to 5.2, temperature: 85-90°C.

In the present invention, the time for performing electroless copper plating or electroless nickel plating on the surface of the electroless plating accelerator is not limited. Preferably, the time for electroless copper plating on the surface of the electroless plating accelerator is 10-240 minutes; the time for electroless nickel plating on the surface of the electroless plating accelerator is 8-15 minutes.

The method of flash-plating a gold layer on the nickel plating layer is also known to those skilled in the art, and will not be repeated in the present invention. Among them, the gold plating solution used in the flash gold layer can directly use the BG-24 neutral gold plating solution of Shenzhen Jingyan Chuang Chemical Company.

In the area of the plastic substrate surface that is not irradiated by the laser, there is no electroless plating accelerator, and its surface is far less rough than the surface of the laser irradiated area, so the metal chemical deposition speed is very slow and the adhesion is very low, and there is basically no metal deposition during electroless plating , if there is a small part of deposition but can be easily wiped off, so as to achieve the purpose of selective metallization directly on the plastic surface of the present invention, and obtain the plastic product provided by the present invention.

The plastic product includes a plastic base and a patterned metal layer on the surface of the plastic base. The metal layer is Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or Cu-Ni-Au layer from inside to outside.

The present invention will be described in more detail below in conjunction with examples. The raw materials used in Examples and Comparative Examples are all commercially available.

Example 1

(1) Vacuum-dry CuC ₂ O ₄ 2H ₂ O to decrystallize water, ball mill until D50 is less than 1 μm, and dry; PP resin, CuC ₂ O ₄ , talcum powder and antioxidant 1010 are 100 by mass ratio: 15:10:0.2 After mixing with a high-speed mixer, extrude into pipes with a single-screw extruder (Nanjing Rubber and Plastic Machinery Factory), and the extrusion temperature is 180°C.

(2) Use an infrared laser (Tide, DPF-M12) to irradiate the outer surface of the entire pipe. The laser parameters are: wavelength 1064nm, scanning speed 1000mm/s, step size 9μm, delay 30μs, frequency 40KHz, power 3W, filling spacing 50μm; clean the surface of the pipe. the

(3) Immerse in the electroless copper plating solution for 3 hours to form a copper layer with a thickness of 10 μm, and immerse in the electroless nickel plating solution for 10 minutes to form a nickel layer with a thickness of 3 μm on the outside of the copper layer; electroless copper plating solution: CuSO ₄ 5H ₂ O 0.12mol/L, Na ₂ EDTA·2H ₂ O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridine 10mg/L, glyoxylic acid (HCOCOOH) 0.10mol/L, and use NaOH and H ₂ SO ₄ to adjust the pH value of the plating solution to 12.5-13; electroless nickel plating solution: nickel sulfate: 23g/l, sodium hypophosphite: 18g/l, lactic acid: 20g/l, malic acid: 15g/l, The pH was adjusted to 5.2 with NaOH.

Through the above steps, the plastic product used as a pipe in this embodiment is obtained.

Example 2

Adopt the method identical with embodiment 1 to prepare the plastic product of the present embodiment, difference is:

In step (1), ball mill CuSiO ₃ until D50 is less than 2 μm, and dry; mix PC resin, CuSiO ₃ , antioxidant 168, and EVA wax at a mass ratio of 100:20:0.2:0.1, extrude and granulate Injection molding for electrical enclosures;

In step (2), the infrared laser is used to print the metal circuit pattern on the electrical casing; after the laser vaporization is completed, the electrical casing is ultrasonically cleaned;

In step (3), the sequence of electroless plating is: first electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, then electroless copper plating for 3 hours to form an 11 μm thick copper layer, and finally electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer. the

Through the above-mentioned steps, the plastic product used as an electrical appliance housing in this embodiment is obtained.

Example 3

Adopt the method identical with embodiment 2 to prepare the plastic product of the present embodiment, difference is:

In step (1), Co ₂ O ₃ is ball milled until the D50 is less than 5 μm, and dried; the mass ratio of PBT resin, Co ₂ O ₃ , glass fiber and light stabilizer 944 is 100:15:35:0.2 directly with twin-screw Extruder (Nanjing Rubber and Plastic Machinery Factory) compounding, granulation, injection molding into automotive connector housing;

In step (3), the electroless plating sequence is as follows: first electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, then electroless copper plating for 2 hours to form a 6 μm thick copper layer, and finally electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, Finally, a gold layer with a thickness of 0.03 micron is flash-plated, and the flash-plating liquid adopts the BG-24 neutral gold-plating liquid of Shenzhen Jingyan Chuang Chemical Co., Ltd. the

Through the above steps, the plastic product used as the automobile connector housing of this embodiment is obtained.

Example 4

Adopt the method identical with embodiment 2 to prepare the plastic product of the present embodiment, difference is:

In step (1), Ni ₂ O ₃ is ball milled until the D50 is less than 10 μm, and then dried; after mixing PC resin, Ni ₂ O ₃ , antioxidant 1076 and polyethylene wax in a mass ratio of 100:10:0.2:0.1, Extrusion granulation, hollow blow molding the casing of automotive electronic components;

In step (3), the order of electroless plating is: first electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, then electroless copper plating for 2 hours to form a 6 μm thick copper metal layer, and finally electroless nickel plating for 12 minutes to form a 4 μm thick protective layer The metal nickel layer used. the

Through the above-mentioned steps, the plastic product used as the housing of the automotive electronic parts of this embodiment is obtained.

Example 5

(1) Mix 54.1g CuO (0.68mol), 27.13g Fe ₂ O ₃ (0.17mol) and 26.87g Mn ₂ O ₃ (0.17mol) evenly, roast in air at 1000°C for 2 hours, and grind to the powder uniformity by high-speed ball milling The particle size is 0.8 μm, and the composition of the product is CuFe _0.5 Mn _0.5 O _2.5 analyzed by means of analysis such as XPS.

(2) Mix PPO resin, CuFe _0.5 Mn _0.5 O _2.5 , calcium silicate fiber, antioxidant 1076 and polyethylene wax in a mass ratio of 100:10:10:0.2:0.1 with a high-speed mixer, and then extrude with a twin-screw Extrude the machine to granulate, and then through injection molding, make the solar cell outdoor connector shell.

(3) Use the same method as step (2) in Example 2 to print metal circuit patterns on the solar cell outdoor connector shell. the

(4) Electroless plating sequence: first electroless nickel plating for 8 minutes to form a 2 μm thick nickel layer, then electroless copper plating for 4 hours to form a 15 μm thick copper layer, then electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, and finally flash plating 0.03 μm thick gold layer. the

Through the above steps, the plastic product used as the solar cell outdoor connector shell of this embodiment is obtained.

Example 6

Adopt the method identical with embodiment 5 to prepare the plastic product of the present embodiment, difference is:

In step (1), 54.1g CuO (0.68mol), 27.13g Fe ₂ O ₃ (0.17mol), 17.33g Al ₂ O ₃ (0.17mol) were mixed uniformly, roasted in air at 1000°C for 2h, and passed high-speed ball milling Until the average particle size of the powder is 0.5 μm, the composition of the product is analyzed by means of analysis such as XPS to be CuFe _0.5 Al _0.5 O _2.5 ;

In step (2), mix PA6T resin, CuFe _0.5 Al _0.5 O _2.5 , antioxidant 1076 and polyethylene wax in a mass ratio of 100:10:0.2:0.1, extrude and granulate, and make an automobile engine by injection molding electronic connector housing;

In step (4), the electroless plating sequence: first electroless nickel plating for 8 minutes to form a 2 μm thick nickel layer, then electroless copper plating for 4 hours to form a 15 μm thick copper metal layer, and then electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer, Finally, a gold layer with a thickness of 0.03 μm is flash-plated. the

Through the above steps, the plastic product used as the housing of the electronic connector of the automobile engine in this embodiment is obtained.

Example 7

This adopts the method identical with embodiment 5 to prepare the plastic product of the present embodiment, difference is:

In step (1), 54.1g CuO (0.68mol), 13.56g Fe ₂ O ₃ (0.085mol), 8.67g Al ₂ O ₃ (0.085mol) and 26.87g Mn ₂ O ₃ (0.17mol) were mixed evenly, Calcined in the air at 1000°C for 2 hours, then subjected to high-speed ball milling until the average particle size of the powder was 1.0 μm, and the composition of the product was analyzed by XPS and other analytical means to be CuFe _0.25 Al _0.25 Mn _0.5 O _2.5 ;

In step (2), mix PPS resin, CuFe _0.25 Al _0.25 Mn _0.5 O _2.5 , antioxidant 1076 and polyethylene wax in a mass ratio of 100:10:0.2:0.1, extrude and granulate, and make Housings for electronic connectors;

In step (4), the sequence of electroless plating: first electroless copper plating for 3 hours to form a 12 μm thick copper layer, and then electroless nickel plating for 10 minutes to form a 3 μm thick nickel layer. 

Through the above steps, the plastic product of the electronic connector housing of this embodiment is obtained.

Claims (12)

1. the preparation method of plastics may further comprise the steps:

1) moulding plastics matrix; Described plastic substrate is thermoplasticity or the thermosetting resin that contains electroless plating promotor, and electroless plating promotor is uniformly distributed in thermoplasticity or the thermosetting resin; Described electroless plating promotor is Ni ₂O ₃, Co ₂O ₃, CuSiO ₃, CuC ₂O ₄, Cu/Fe/Mn ternary co-sintering oxide compound, Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more;

2) laser gasification surface of plastic matrix exposes electroless plating promotor;

3) in step 2) electroless plating promotor Electroless copper or chemical nickel plating, proceed at least electroless plating and/or plating, form metal level at surface of plastic matrix,

Wherein, take the quality of plastic substrate as benchmark, the content of chemical plating catalyst is 1-40%.

2. preparation method according to claim 1 is characterized in that, the mode of moulding is injection moulding, blowing, extrudes or hot pressing in the step 1).

3. preparation method according to claim 1, it is characterized in that, step 2) condition of laser gasification comprises in: the wavelength of laser is 157nm-10.6 μ m, sweep velocity is 500-8000mm/s, step-length is 3-9 μ m, delays time to be 30-100 μ s, and frequency is 30-40 KHz, power is 3-4 W, and filling spacing is 10-50 μ m.

4. preparation method according to claim 1 is characterized in that, behind electroless plating promotor chemical nickel plating on surface, continues electroless plating or/and electroplate in the step 3), forms Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer at surface of plastic matrix; Or after electroless plating promotor Electroless copper, continue electroless plating or/and electroplate, form Cu-Ni layer or Cu-Ni-Au layer at surface of plastic matrix.

5. preparation method according to claim 4, it is characterized in that, the thickness of various Ni layers is 0.1-50 μ m in described Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or the Cu-Ni-Au layer, and the thickness of Cu layer is 0.1-100 μ m, and the thickness of Au layer is 0.01-10 μ m.

6. preparation method according to claim 1 is characterized in that, the median size of described electroless plating promotor is 20nm-100 μ m.

7. according to claim 1 or 6 described preparation methods, it is characterized in that the molecular formula of described Cu/Fe/Mn ternary co-sintering oxide compound is CuFe _xMn _yO _z, x=0.01-2 wherein, y=0.01-2, z=2-4; The molecular formula of described Cu/Fe/Al ternary co-sintering oxide compound is CuFe _mAl _nO _l, m=0.01-2 wherein, n=0.01-2, l=2-4; The molecular formula of described Cu/Fe/Al/Mn quaternary co-sintering oxide compound is CuFe _aAl _bMn _cO _d, a=0.01-2 wherein, b=0.01-2, c=0.01-2, d=2-4.

8. preparation method according to claim 1, it is characterized in that described thermoplastics is selected from one or more of polyolefine, polyester, polymeric amide, polyarylether, polyester-imide, polyphenylene sulfide, polyimide, polysulfones, polyether-ether-ketone, polybenzimidazole, liquid crystalline polymers; Described thermosetting resin is selected from one or more of resol, urea-formaldehyde resin, melamine formaldehyde resin, Resins, epoxy, Synolac, urethane.

9. preparation method according to claim 1 is characterized in that, take the quality of plastic substrate as benchmark, wherein the content of electroless plating promotor is 1-40%.

10. preparation method according to claim 1 is characterized in that, also contains antioxidant, photostabilizer, lubricant, mineral filler in the described plastic substrate.

11. plastics, described plastics comprise plastic substrate and are positioned at the metal level of surface of plastic matrix; Described plastics are prepared by method claimed in claim 1.

12. plastics according to claim 11 is characterized in that, described metal level is Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or Cu-Ni-Au layer from the inside to surface.