JP2001329394A - Metal-plastic composite article and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a metal-plastic composite article from which nickel as a metallic component is efficiently recovered when charging the waste metal-plastic composite article into a feedstock recycle, for example, and recovering a metal to form a metallic plating from the composite article for recycling. SOLUTION: The plating or conductive coating material-containing material to impart conductivity to an electrically nonconductive plastic formed article 12 is limited to nickel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal / plastic composite article and a method for producing the same, and more particularly, to
In producing a metal / plastic composite product by applying metal plating to a plastic molded product, by using only nickel as the metal, the lightness and high rigidity required for the metal / plastic composite product are impaired. A metal-plastic composite product that can greatly facilitate the recovery of the nickel when the composite product is recycled, and
It relates to a method for producing the same.

[0002]

2. Description of the Related Art Generally, lightweight and high rigidity are required for housing parts and portable precision mechanism parts of notebook personal computers. For this reason, as the material of these members, instead of using heavy iron-based materials, high-rigidity plastic molded products with fiber reinforcement, aluminum die-cast products, magnesium alloy die-cast products, and other thixomolded products are suitably used. Have been.

However, the above-mentioned molded articles have the following problems. About conductive fiber-containing plastic molded articles When a large amount of fiber filler is mixed into plastic, fluidity is reduced and thin-wall molding becomes difficult. For this reason, the filling amount of the conductive filler is limited, and it is difficult to achieve compatibility with the originally required high elastic modulus. Further, since the filler to be filled is easily oriented, the impact strength is reduced. Aluminum die-cast products Although mechanical strength against impact and the like can be sufficiently ensured, the weight is easily increased due to its higher density than plastic molded products and magnesium-containing molded products. In addition, the work required for post-processing such as finishing is complicated. Magnesium alloy die cast, etc. The density is slightly heavier than plastic and has a higher elastic modulus, but burrs are likely to occur during molding. In addition, since the smoothness of the surface of the molded product is not good, post-processing such as filling with putty or sanding takes time, and the total cost increases. Magnesium is inherently high in activity, and therefore requires sufficient care in handling and operating molding equipment.

In order to avoid such drawbacks, the inventor of the present application has applied a conductive treatment to the front and back surfaces of a plastic molded product, and applied a metal layer having an elastic modulus of 150 GPa or more to the treated surface in a thickness of 10 to 50 μm. By plating, a metal-plastic composite product that can achieve both lightness and high rigidity was devised.
No. 4 filed a patent application. Invention according to this already filed application
(Hereinafter referred to as "the prior invention"), as a procedure for conducting a conductive treatment on the surface of a plastic molded product, the surface of the plastic molded product is chemically roughened with a chemical such as a chromic acid or permanganate solution. Pre-treatment, followed by electroless plating and electrolytic plating with a metal suitable for the application.

Looking at the constituent metals of the metal plating layer in the metal / plastic composite article of the prior application described above, the metal forming the surface electrolytic metal plating layer exhibiting high rigidity has an elastic modulus of 150 GPa or more. Nickel, iron or a nickel-based alloy which is industrially easy to use is preferably used. As a metal for forming the electroless metal plating layer for depositing the electrolytic metal plating layer on a required surface of a plastic molded product, inexpensive and easily plated copper or the like is suitably used.

[0006]

The thickness of the electrolytic metal plating layer applied in the above-mentioned prior application is set to about 10 to 50 μm in order to achieve both lightweight and high rigidity.
Therefore, when nickel is adopted as a metal to be used for electrolytic plating and is deposited with a thickness of, for example, 30 μm, about 65 g of nickel is used in an A4 size notebook computer. Since nickel is a rare metal, an effective method of reclaiming and recovering after disposal of a personal computer or the like using the nickel as a metal for electrolytic plating is being sought. Regarding this point, the “Household Appliance Recycling Law” is scheduled to be enforced in April 2001, and from the viewpoint of increasing the disposal costs of various industrial wastes and requesting the effective use of global resources, the recycling of all industrial products is Suitability for use and recycling is required. From such a social background, there is a strong demand for the recycling and recovery of nickel and the like described above.

However, the metal / plastic composite product of the invention of the prior application described above is a composite of the electroless metal plating layer, the electrolytic metal plating layer provided thereon, and the plastic molded part serving as the base material. And cannot be easily separated. Therefore, if the recycling process is not properly performed, not only the plastic molded product but also the metal forming the metal plating layer will be lost, resulting in a large loss in resources. In relation to this, typical recycling methods include “material recycling”, which recycles used waste molded products as recycled pellets and uses them as raw materials for molded products.
"Thermal recycling" to recover heat by burning waste molded products, "Feedstock recycling" to obtain alternative products such as blast furnace reducing agent by thermally or chemically decomposing waste molded products
In addition, "chemical recycling" in which waste molded articles are thermally or chemically decomposed and used as oil or resin raw materials is known.

[0008] Among these recycling methods, the "material recycling" refers to a method in which a waste molded article is pulverized and then melted. Is not suitable for reuse because it becomes a foreign substance and is mixed into the plastic, and the strength and appearance are reduced. In "thermal recycling", it is not possible to recycle and recover waste products because they only burn and recover heat. Furthermore, the above-mentioned “chemical recycling”
Is currently too costly and impractical. However, in the above-mentioned "feedstock recycling", waste treatment in a gasification melting furnace, a blast furnace for steelmaking and other mini-blast furnaces has reached the stage of practical use, and it is considered promising to use this.

According to the above-mentioned "feedstock recycling", a plastic molded article as a base material of a metal / plastic composite article can be used as a reducing gas or a heat source, and the metal plated on the molded article is a molten material. It is suitable as a recycling means because it can be collected with high efficiency. However, since the metal plating layer of the metal / plastic composite product according to the prior application invention is composed of two layers, an electroless metal plating layer and an electrolytic metal plating layer, for example, when one metal is copper and the other metal is nickel, However, it is pointed out that even if the recycling method based on the above "feedstock recycling" is carried out, these metals are melted and alloyed at the time of recovery, making it difficult to recover or reuse the metal as a single substance.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned problem that appears when a metal / plastic composite product that has been discarded is thrown into, for example, feedstock recycling, and a metal that forms a metal plating layer is recovered from the composite product. It is an object of the present invention to provide a metal / plastic composite article capable of recovering nickel as a metal component with high efficiency when the recycling is performed, and a method for producing the same. I do.

[0011]

SUMMARY OF THE INVENTION In order to overcome the above-mentioned problems and achieve the intended object, a metal-plastic composite product according to the present invention comprises a plastic molded product molded from an electrically non-conductive plastic raw material. An electroless nickel plating layer provided on a required surface of the plastic molded article, and an electrolytic nickel plating layer deposited on the electroless nickel plating layer, wherein the thickness of the electrolytic nickel plating layer is 10
５０50 μm.

[0012] In order to overcome the above-mentioned problems and achieve the intended object, a metal-plastic composite product according to still another invention of the present application comprises a plastic molded product molded from an electrically non-conductive plastic raw material, A plastic layer provided on a required surface of the plastic molded article and containing a nickel filler; and an electrolytic nickel plating layer deposited on the polymer layer, wherein the thickness of the electrolytic nickel plating layer is 1
It is characterized by being in the range of 0 to 50 μm.

[0013] In order to overcome the above-mentioned problems and achieve the intended object, a method for producing a metal-plastic composite product according to another invention of the present application is a plastic molded product having a required shape made of an electrically non-conductive plastic raw material. The surface of the plastic molded article to be plated is chemically roughened, and then the plastic molded article is subjected to electroless plating to form an electroless nickel plating layer. Then, electrolytic plating was performed with the same nickel as the nickel used for the electroless plating to deposit an electrolytic nickel plating layer on the electroless nickel plating layer (15) in a thickness of 10 to 50 μm. It is characterized by the following.

[0014] In order to overcome the above-mentioned problems and achieve the intended object, a method for producing a metal / plastic composite product according to still another invention of the present application is a method for manufacturing a plastic having a required shape using an electrically non-conductive plastic raw material. A molded article is molded, a polymer compound containing a nickel filler is applied to a required surface of the plastic molded article to be plated, and the polymer compound is dried to form a polymer layer. Is subjected to electrolytic plating of nickel to form an electrolytic nickel plating layer of nickel having a thickness of 10 to 50 μm.
Characterized in that they are precipitated in the range of

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, a metal / plastic composite article and a method of manufacturing the same according to the present invention will be described below with reference to the accompanying drawings by way of preferred embodiments. The inventor of the present application has developed an electrolytic metal plating layer that expresses high rigidity in a metal-plastic composite, imparts conductivity to the surface of a plastic molded product, and deposits the electrolytic metal plating layer on the surface of the plastic molded product in close contact. By forming the electroless metal plating layer with nickel of the same metal, it has been found that metals and plastics after disposal can be easily recycled and recovered.

In this embodiment, the reason why nickel was selected as a metal component of electroless plating, electrolytic plating, and a conductive paint component described later is that an electroless plating method capable of applying plastic materials at a low temperature has been established, This is because it is a metal element that can be electroplated on the obtained electroless plating layer and has an elastic modulus of 150 GPa or more (nickel is 200 GPa). In the case of iron, cobalt, chromium, manganese, molybdenum or tungsten, electroless plating cannot be performed or electroless plating at low temperatures cannot be performed. Copper, silver or gold can be subjected to electroless plating at a low temperature of 60 ° C. or lower, but cannot have high rigidity because the elastic modulus is less than 150 GPa. Cannot be used.

As shown in FIGS. 1 and 2, a metal / plastic composite article (hereinafter, referred to as a "composite article") 10 according to a preferred embodiment of the present invention is a plastic molded article molded as, for example, a notebook personal computer housing. An article 12 and a metal plating layer 14 deposited on required surfaces on the front and back of the plastic molded article 12. The metal plating layer 14,
It comprises an electroless nickel plating layer 15 formed by electroless nickel plating and an electrolytic nickel plating layer 16 deposited by electrolytic nickel plating. In addition, the plastic molded article 12 is made of a suitable inorganic or organic reinforcing fiber 1 for improving mechanical strength and reducing costs.
8 may be mixed in a predetermined amount.

As shown in FIG. 3, the metal / plastic composite article 10 is formed into a molding step S1 of a plastic molded article 12.
1. It is manufactured by passing through a physical roughening step S12, a chemical roughening step S13, an electroless nickel plating step S14, an electrolytic nickel plating step S15, and a final step S16.

The molding step S11 is a step of producing a plastic molded product 12 having a required shape, and includes a generally known injection molding, extrusion molding, blow molding, vacuum molding, press molding, transfer molding or other molding method. Any of them can be adopted, and is appropriately selected as appropriate. In particular, in the case of the present invention, injection molding, which has high mass productivity and can cope with high molding precision required for casing molding or the like, is preferable.

The plastic molding 12 used here
For example, ABS or an ABS alloy raw material, which is easy to form and is easily subjected to a chemical roughening step S13 described later, that is, an etching process using chromic acid, is suitable as a raw material for forming. In addition, other raw materials such as polycarbonate which can be etched with chromic acid by various pretreatments, nylon which can be etched with hydrochloric acid other than chromic acid, and the like can also be used.

The physical roughening step S21 is a step which is selectively performed only when the reinforcing fibers 18 are mixed with the plastic molded article 12, and the reinforcement projecting to a required surface of the molded article 12 This is for shaving the fibers 18 and adjusting the surface roughness of the surface portion. As a specific means, a method in which an operator polishes using abrasive paper, a sand blast method in which hard abrasive particles are directly blown onto a plastic molded article 12 as a roughened object at a high speed, and hard abrasive particles are dispersed in a solvent such as water. Then, a liquid honing method or the like in which this dispersion is sprayed at a high speed onto the plastic molded article 12 as a roughened object is used. In particular, in the liquid honing method, the angle of incidence of abrasive particles with respect to the plastic molded article 12 that is the object of physical roughening can be set finely, and the heat generated during the roughening is cooled by water as a solvent, and the molded article due to the generated heat is cooled. Twelve is preferably used to prevent deformation and the like. In this embodiment, since the reinforcing fibers 18 for reinforcing the mechanical strength are mixed in the plastic molded body 12,
Although the physical roughening step S12 is performed, if the fibers 18 are not mixed, the physical roughening step S12 is not required. As the reinforcing fibers 18, various organic fillers, carbon fibers, glass fibers, or the like are appropriately and selectively employed.

The hard abrasive particles have a hardness higher than the surface hardness of the plastic molded product 12 and the hardness of the reinforcing fibers 18 contained therein.
Any material can be used as long as it has a function of scraping the surface upon collision with the material.

The chemical roughening step S13 is one of the conductive treatment steps for performing an electrolytic plating step S5 described later, and any conventionally known method can be adopted depending on the material of the plastic molded article 12. Generally, a mixture of chromic acid and sulfuric acid is suitably used for a raw material having an oxidized and easily meltable polymer component such as ABS as a dispersed phase, and a hydrochloric acid or the like is suitably used for a polyamide-based raw material. .

In the electroless nickel plating step S14,
This is a conductive treatment step for performing the electrolytic nickel plating step S15 in the same manner as the chemical roughening step S3, and the plastic molded product 1 physically and chemically roughened.
(2) a catalyst adsorbing step S141 for adsorbing a catalytic metal containing desired metal fine particles exhibiting catalytic activity with respect to electroless nickel plating on the required surface, and immersing in an appropriately selected plating bath for electroless nickel plating Then, a plating step S42 of forming the electroless nickel plating layer 15 is performed.

In the catalyst adsorption step S141, each material (ABS resin, PPO resin,
Various types of polymer alloys such as PC resin, PP resin, PA resin, PBT resin, PEI resin, PES resin, and PC / ABS resin have been established, and the established known methods are suitably used. Taking a typical ABS-based raw material as an example, neutralization, washing and removal of chromic acid and the like used in the above-described chemical roughening step S3, immersion in a surfactant solution (accelerator treatment), catalytic metal Immersion and application in an aqueous solution of a palladium-tin complex compound, washing with water, and activation of a catalytic metal.

In the catalyst adsorbing step S141, the primer containing the catalyst metal is mixed with the plastic molded article 1
The catalyst metal may be applied by applying to the required surface of No. 2. Examples of the primer include a silicone-based material and various latexes, which are appropriately selected depending on the material of the plastic molded product 12.

The plating step S142 is a step in which electroless nickel plating is performed on a required surface of the plastic molded article 12 to which a predetermined catalytic metal is applied, and the thickness of the electroless nickel plating layer 15 is about 0.1 μm. It is applied to become. If the plating thickness is too small, the efficiency of electrolytic nickel plating in the later-described electrolytic nickel plating step S15 decreases, and if the plating thickness is too large, the manufacturing cost increases.

In the plating step S142, a phosphorus compound such as sodium hypophosphite and a boron compound such as sodium tetrahydroborate or dimethylaminoborane are used as a reducing agent to form the electroless nickel plating layer 15. These reducing agents simultaneously precipitate phosphorus or boron by an oxidation-reduction reaction during the formation reaction of the electroless nickel plating layer 15. This phosphorus or boron is alloyed with the nickel forming the electroless nickel plating layer 15 to form a nickel-phosphorus alloy or a nickel-phosphorus alloy, respectively.
It becomes a boron alloy and becomes an impurity in the nickel. However, the formation of the electroless nickel plating layer 15 in the main plating step S142 is for forming an electrical underlayer for electrolytic nickel plating, that is, a so-called conductive process. Therefore, the electroless nickel plating layer 1
5 is about 0.1 to 0.5 μm at most, and is 1 to 0.001 with respect to the electrolytic nickel plating thickness of 10 to 50 μm.
%. That is, the content of the phosphorus or boron which is only a trace impurity in the electroless nickel plating layer 15 is a very small amount of 0.001 to 1% by weight or less. Has no effect.

When the electroless nickel plating layer 15 is formed, various metals such as phosphorus, manganese or palladium, or fillers such as silicon carbide or alumina are intentionally contained and are co-deposited with nickel to improve heat resistance and wear resistance. There are known ways to improve it. However, the metal-plastic composite article according to the present invention is not only unnecessary, but also requires caution as it is a bad factor that lowers the purity of nickel metal at the time of recovery.

In the electrolytic nickel plating step S15, the electrolytic nickel plating is carried out to provide a required surface of the electroless nickel-plated plastic molded product 12 with sufficient conductivity and sufficient rigidity to exhibit EMI shielding and the like. This is performed to deposit the plating layer 16.

The nickel forming the electrolytic nickel plating layer 16 has an elastic modulus of 200 GPa or 150 GPa.
It is a metal having a value of a or more, and can suitably exhibit various physical properties such as light weight and high rigidity. The thickness of the electrolytic nickel plating layer 16 applied by the electrolytic nickel plating is 10 μm
Below, a sufficient rigidity value cannot be obtained, and when it exceeds 50 μm, the weight exceeds the weight of the magnesium alloy housing, and the weight cannot be reduced, so that 10 to 50 μm is required.
About m is preferable.

Since the electrolytic nickel plating layer 16 has high elasticity, it is necessary to control the electrolytic nickel plating conditions at the time of deposition of the electrolytic nickel plating layer 16 so that the electrodeposition stress generated at the time of deposition becomes a slight tensile stress. preferable. It is important that the electrolytic nickel plating layer 16 is deposited on the required front and back surfaces of the plastic molded product 12 at substantially the same speed and thickness. By controlling the deposition of the electrolytic nickel plating layer 16 in this manner, the stresses applied to the front and back of the plastic molded product 12 are offset, thereby preventing peeling during plating and deformation of the composite product, and preventing the deposition of the deposited metal layer. Can be made uniform to improve rigidity.
At this time, the difference between the thickness of the front surface and the thickness of the back surface is allowed up to 20% without adversely affecting the lightness and high rigidity.

The electrolytic nickel plating step S15 is carried out by immersing the plastic molded product 12 made conductive in the preceding step in a plating bath in which nickel for electrolytic plating is ionized. At this time, the plastic molded article 12 is used as a cathode, and a required soluble electrode material is used as an anode. As the electrolytic nickel plating bath, a sulfamic acid bath, a Watt bath, a chloride bath, or the like is suitably used.

In order to obtain the above-mentioned electrolytic nickel plating layer 16 having a thickness of 10 to 50 μm, a plating bath which can set a high current density and has a very low electrodeposition stress is preferable. When a high current density is set, the required electrolytic nickel plating layer 16 can be deposited in a short period of time and productivity can be improved, and when the electrodeposition stress is low, the electrolytic deposition caused by the high stress is generated. Cracking and peeling of the nickel plating layer 16 or deformation of the plastic molded product 12 can be prevented. Generally, the sulfamic acid bath is preferably used because it is greatly superior in these points.

In some cases, the nickel plating layer 1
4 may not be applied to the entire molded product 12 in order to give priority to the insulating property of the electronic device and the like disposed in the plastic molded product 12. However, the nickel plating layer 14
No problem arises because sufficient rigidity can be secured by covering about 80% or more of the entire surface of the plastic molded article 12. The masking of the nickel plating layer 14 is performed by applying an etching resist in advance to a corresponding portion in the case of performing etching with chromic acid or the like using an ABS-based material, or by applying a primer in the case of using other special materials. The formation of the nickel plating layer 14 is performed by not applying the primer coating.

The metal / plastic composite product obtained by completing the above steps is completed through a final step S16 of performing final cleaning, processing and inspection.

[0037]

Another Embodiment In the above embodiment, the electroless nickel plating layer 15 was formed as a conductive treatment for depositing the electrolytic nickel plating layer 16, but the present invention is not limited to this. The conductive treatment may be performed by applying a conductive paint.

A metal / plastic composite product (hereinafter, referred to as a composite product) 30 manufactured by the method according to another embodiment includes:
As shown in FIGS. 4 and 5, it is basically composed of a plastic molded product 12 similar to those of the above-described embodiments and an electrolytic nickel plating layer 16 deposited on a required surface of the plastic molded product 12 by electrolytic nickel plating. You. In order to deposit the electrolytic nickel plating layer 16, a polymer layer 20 formed of a conductive polymer compound containing a nickel filler or the like is provided on the surface of the plastic molded product 12 in advance. ing.

As shown in FIG. 6, the composite product 30 is manufactured through a molding step S21 of the plastic molded article 12, a polymer layer providing step S22, an electrolytic nickel plating step S23, and a final step S24.

The molding step S21 is the same as the molding step S
11 is omitted, but as a raw material for forming the plastic molded product 22 used in this step S21, a material that can be easily subjected to a polymer layer providing step S22 described later, that is, generally has a high adhesion to paint. ABS or PC with a high content is preferred, and a wide range of other raw materials such as PPE or PPS can be employed. Even when a material having low adhesion to a paint such as a polypropylene resin or a polyacetal resin is used as a raw material of the plastic molded product 22, an appropriate primer such as silicone or latex may be applied as a base of the polymer layer 20. Good adhesion can be ensured by employing a surface activation method using flame, plasma, or the like.

The polymer layer applying step S22 is a step of imparting conductivity so that a required surface of the plastic molded article 12 can be subjected to electrolytic nickel plating described later. Specifically, a conductive polymer compound obtained by dispersing a nickel filler imparting conductivity in a polymer compound is applied to the surface of the plastic molded product 12 by a method such as spray coating or brush coating. Will be implemented. The applied polymer layer 20 adheres to the surface of the plastic molded article 12 by drying. At this time, in order to enhance the deposition property and adhesion of the electrolytic nickel plating described later, the polymer layer 20 is used.
May be immersed in an acid or alkali solution or subjected to a physical treatment such as sanding so that the nickel filler protrudes from the surface of the polymer layer 20.

As the polymer compound containing the nickel filler, paints such as polyurethane resin, epoxy resin, polyester resin, melamine resin, phenol resin, silicone resin, styrene resin, polyvinylidene fluoride resin and acrylic resin are preferably used. Can be adopted.

The electrolytic nickel plating step S23 comprises an electrolytic nickel plating step for imparting sufficient conductivity and sufficient rigidity to exhibit EMI shielding and the like to the required surface of the plastic molded article 12 provided with the polymer layer 20. Plating layer 1
6 is performed. The procedure for performing the electrolytic nickel plating step S23 is the same as that of the electrolytic nickel plating step S15 in the above-described embodiment.

The metal / plastic composite product obtained by completing the above steps is completed through a final washing, processing and inspection step S24.

[0045]

[Experimental Examples] Hereinafter, a method of manufacturing a metal / plastic composite article according to an embodiment and an experimental example of the obtained metal / plastic composite article will be described. Using the raw materials described in each experimental example below, for the metal-plastic composite product obtained through each step, visually or using various measuring instruments, metal plating layer thickness (μm), adhesion , Stiffness (Nm) and specific gravity (g / cm ³ ) were observed and measured. Here the adhesion is
By a peel test to a cross cut with an adhesive tape, the bending stiffness was defined as I × E (where I is the moment of inertia of the specimen and E is the apparent elastic modulus), and these were I, E, and The bending stiffness was calculated from the relational expression (V = W × L ³ / (48 × E × I)) between the measured deflection V and the applied load W (L: length between the fulcrums of the sample (load applied) Distance between two points supporting the sample).

(Experimental Example 1) In the case of conducting treatment by electroless nickel plating. Molding step S11: A PC / ASA material (trade name: FA420CA; manufactured by Mitsubishi Rayon) was used as a raw material of a plastic molded product. A carbon fiber of 10 wt% is added as a conductive fiber, and the size is 210 × by injection molding.
A box-shaped molded product having a size of 260 × 20 and a thickness of 1.2 mm and opened upward was obtained. -Physical roughening step S12: A liquid honing device (trade name: LH-5 type; non-abrasive particle FRB220, 85% passing particle size: 74 μm) was used as the polishing particles, and water was used as the dispersion medium. The volume fraction (volume occupied by the bulk volume of the abrasive particles / volume of the mixture of the dispersion medium and the particles) is 15%, the air is 0.4 MPa, and the material is physically roughened under the conditions of 1 minute by Niseiki Seisakusho. Was performed. After the physical roughening, the entire surface of the plastic molded article became dull, and became white after moisture drying. At this time, the surface roughness (Ra) was about 5 μm.・ Chemical roughening step S13: Sodium sulfate 20g / L
And degreased by immersion in a degreasing solution containing sodium phosphate and 20 g / L at a temperature of 50 ° C. for 4 minutes.
An etching solution consisting of 400 g / L of sulfuric acid at a temperature of 68 ° C. was immersed for 1 minute to perform etching. Subsequently, after sufficient washing with water, neutralization was carried out by immersion in a room temperature neutralizing solution of 35% hydrochloric acid 50 ml / L for 1 minute. -Electroless nickel plating step S14: catalyst adsorption step S1
41: After rinsing with water and immersing in 180 ml / L of 35% hydrochloric acid in a pre-dip tank, a catalyst (palladium
(Tin catalyst; manufactured by Okuno Pharmaceutical Co., Ltd.) In a catalyst bath composed of 30 ml / L and 35% hydrochloric acid 200 ml / L, a temperature of 35
C. for 2 minutes. Then, it is washed with water, and a surface activator (trade name: Accelerator X; manufactured by Okuno Pharmaceutical)
Immersing in an accelerator bath consisting of 0.5 g / L and 98% sulfuric acid 100 ml / L to sufficiently apply palladium as a catalyst metal to the surface of the plastic molded article;
Finally, it was further washed with water. Plating step S142:
Then, it was immersed in an electroless nickel plating bath (trade name: Chemical Nickel HR-T Standard Formula; manufactured by Okuno Pharmaceutical Co., Ltd.) at a temperature of 35 ° C. for 10 minutes to deposit an electroless nickel plating layer.・ Electrolytic nickel plating step S5: After washing with water, nickel sulfamate 450 g / L, nickel chloride 5 g / L, boric acid 40 g / L and bit preventing agent (trade name: Bitless-
S: manufactured by Nihon Kagaku Sangyo). Nickel sulfamate of 5 ml / L was subjected to electrolytic nickel plating using depolarized nickel as an anode at a temperature of 40 ° C., a current density of 4 A / dm ² and for 25 minutes. did.

Result: Each physical property of the produced metal / plastic composite product The metal plating layer thickness was 20 μm, and the precipitation on both sides of the plastic molded product was almost the same. Adhesion: No peeling occurred and adhesion was sufficient. Bending stiffness: A three-point bending test was performed, and a value of 4.0 Nm was obtained. Specific gravity of molded product: 1.48 g / cm ³

After completion of each of the above measurements, the produced metal / plastic composite was pulverized, and 1 g of the pulverized product was obtained.
Was thermally decomposed in an alumina crucible simulating a gasification melting furnace under a nitrogen atmosphere at a temperature of 800 ° C. for 1 hour. The residue obtained by this thermal decomposition was subjected to weight measurement and elemental analysis by EPDM.

Result: recovery rate of nickel from metal / plastic composite during pyrolysis Residue weight: 1.9 g Elemental analysis: nickel as main component, 0.1 to 1% phosphorus

(Experimental Example 2) In the case of conducting treatment with a conductive paint. Molding step S21: A polyphenylene ether resin material (trade name: Noryl N) was used as a raw material of a plastic molded product.
C120 (manufactured by Nippon GE Plastics Co., Ltd.), into which 20 wt% of carbon fibers were added as conductive fibers, and which was injection-molded to a size of 210 × 260 × 20 and a thickness of 1.
A box-shaped molded product opened upward by 2 mm was obtained. Polymer layer providing step S22: Using a conductive paint containing nickel metal powder (trade name: E-3603; manufactured by Shinto Paint Co., Ltd.), dry thickness is applied on the required front and back surfaces of the plastic molded article. It was applied so as to have a thickness of about 20 μm, and was dried by a hot air drier at a temperature of 60 ° C. for 1 hour.・ Electrolytic nickel plating step S23: The plastic molded article, which has been made conductive, is surface-activated (trade name)
Top sun; manufactured by Okuno Pharmaceutical) 100 g / L, temperature 35 ° C,
The surface is activated by immersion for 3 minutes, followed by 450 g / L nickel sulfamate and 5 g / nickel chloride.
L, nickel sulfamate consisting of 40 g / L of boric acid and 5 ml / L of a bit inhibitor (trade name: Bitless-S; manufactured by Nippon Chemical Industry Co., Ltd.). Current density 4A / dm ² , 2
Electroplating was performed for 5 minutes.

Result: Various physical properties of the produced metal / plastic composite product The metal plating layer thickness was 20 μm, and the precipitation on both sides of the plastic molded product was substantially the same. Adhesion: No peeling occurred and adhesion was sufficient. Bending stiffness: A three-point bending test was performed, and a value of 3.8 Nm was obtained. Specific gravity of molded product: 1.50 g / cm ³

Result: recovery rate of nickel from metal-plastic composite during pyrolysis Residue weight: 1.9 g Elemental analysis: nickel as main component, 0.1 to 1% phosphorus

Based on the facts of Experimental Examples 1 and 2, the metal / plastic composite article manufactured by the manufacturing method according to the example obtained from each of the experimental examples is a magnesium alloy (AZ91D (bending stiffness: 1 mm) having a thickness of 1 mm. 3.75Nm, specific gravity is 1.
As compared with 81 g / cm ³ )), it was confirmed that the bending stiffness was lighter than the above.

In the residue after the heat treatment, components other than nickel can hardly be specified, and other plastic components remaining as carbon and fillers remaining as metal oxides can also be reduced by controlling the amount of oxygen supplied during the heat treatment. Alternatively, it was confirmed that complete separation was possible and that nickel metal with high purity could be recovered.

(Comparative Example 1) As in Example 1, the molding step S
11. Perform a physical roughening S12, a chemical roughening S13 and an electroless nickel plating step S14. Instead of the electrolytic nickel plating step S15, a copper sulfate plating bath for decoration (U-Bac EP standard composition; manufactured by Ebara Uzilite) At a temperature of 25 ° C., a current density of 4 A / dm ² for 12 minutes to deposit copper to a thickness of about 10 μm, and after washing with water, a bright nickel plating bath (# 66 standard composition; Ebara Eiji Light) at a temperature of 50 ° C., a current density of 4 A / dm ² ,
Under conditions of 5 minutes, nickel was laminated to a thickness of about 10 μm.

Result: Each physical property of the manufactured metal / plastic composite article As in Example 1, the adhesiveness is high, but the elastic modulus of copper is slightly low (about 100 GPa), so the laminated plating layers Had a low bending stiffness of 3.1 Nm.

As a result of the same thermal decomposition treatment as described above, the metal residue was 1.9 g, and the result of elemental analysis was that copper and nickel were about 50% each. When the temperature was further increased by the thermal decomposition and melting was performed, only a low-strength metal composed of a copper-rich phase and a nickel-rich phase was obtained. This is because copper and nickel do not alloy with each other and were not useful.

[0058]

As described above, according to the metal / plastic composite article and the method of manufacturing the same according to the present invention, the metal component used for achieving conductivity, mechanical strength and high rigidity is only nickel. Therefore, when the composite article is subjected to recycling after disposal, there is an advantage that nickel having high added value can be easily collected.

[Brief description of the drawings]

FIG. 1 is a partially cutaway perspective view of a metal / plastic composite product according to the present invention.

FIG. 2 is an enlarged sectional view taken along line II-II in FIG.

FIG. 3 is a process chart showing a method for manufacturing a metal / plastic composite article according to a preferred embodiment of the present invention.

FIG. 4 is a partially cutaway perspective view of a metal / plastic composite product according to another invention of the present application.

FIG. 5 is an enlarged sectional view taken along line II-II in FIG.

FIG. 6 is a process chart showing a method for producing a metal / plastic composite article according to another embodiment.

[Explanation of symbols]

 12 Plastic molding 15 Electroless nickel plating layer 16 Electrolytic nickel plating layer 20 Polymer layer

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AB16B AB16C AB16D AB16H AK01A AK01D BA03 BA04 BA07 BA10A BA10C BA13 BA26 CA23D EG002 EH112 EH612 EH71B EH71C EH712 EJ152 EJ68D EJ862 JG01 JG04 AB12 AB01B02A BB21 CB21 GA02

Claims (9)

[Claims] 1. A plastic molded product (12) molded from an electrically non-conductive plastic raw material; an electroless nickel plating layer (15) applied to a required surface of the plastic molded product (12); An electrolytic nickel plating layer (16) deposited on the nickel plating layer (15), wherein the thickness of the electrolytic nickel plating layer (16) is 10 to 50 μm.
A metal / plastic composite product characterized by the following. 2. A plastic molded article (12) molded from an electrically non-conductive plastic raw material, and a polymer layer (20) applied to a required surface of the plastic molded article (12) and containing a nickel filler. Electrolytic nickel plating layer deposited on the polymer layer (20)
(16), wherein the thickness of the electrolytic nickel plating layer (16) is 10 to 50 μm
A metal / plastic composite product characterized by the following. 3. A plastic molded product (12) having a required shape is formed from an electrically nonconductive plastic raw material, and a required surface of the plastic molded product (12) to be plated is chemically roughened. The plastic molded product (12) is subjected to electroless plating to form an electroless nickel plating layer (15), and then the plastic molded product (12) is made of the same nickel as nickel used for the electroless plating. Producing a metal / plastic composite article, wherein electrolytic plating is performed to deposit an electrolytic nickel plating layer (16) in a range of 10 to 50 μm on the electroless nickel plating layer (15). Method. 4. The method for producing a metal / plastic composite article according to claim 3, wherein said electrolytic nickel plating layer (16) is applied to at least 80% of the total area of said plastic molded article (12). 5. The metal / plastic composite article according to claim 3, wherein the difference in thickness between the electrolytic nickel plating layers (16) applied to the front and back surfaces of the plastic molded article (12) is within 20%. Manufacturing method. 6. A polymer compound containing a nickel filler on a required surface of a plastic molded product (12) to be plated by molding a plastic molded product (12) of a required shape from an electrically non-conductive plastic raw material. The polymer compound is dried to form a polymer layer (20), and then the polymer layer (20) is subjected to nickel electroplating, whereby an electrolytic nickel plating layer (16 ) Is deposited in the range of 10 to 50 μm in thickness. 7. The method according to claim 6, wherein the polymer layer (20) is applied by spray coating. 8. The method for producing a metal / plastic composite article according to claim 6, wherein the electrolytic nickel plating layer (16) is applied to at least 80% of the entire area of the plastic molded article (12). 9. The metal according to claim 6, wherein the difference between the thicknesses of the electrolytic nickel plating layers (16) applied to the front and back surfaces of the plastic molded product (12) is within 20%.・ Method of manufacturing plastic composite products.