JP2000080482A - Ion plating method of synthetic resin and synthetic resin molding having ion plating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a synthetic resin product provided with an IP film which is applied with a film by an ion plating and has a durability and a surface state enabling to be enough evaluated as a practical product, by establishing a method applied with the ion plating for a synthetic resin member. SOLUTION: An ion plating method of a synthetic resin to be applied with a metal plating, after carrying out a degas treatment and an annealing of a synthetic resin, and then to form a metal nitride film, a metal carbide film, a metal oxide film or their mixed film on a mold surface of the synthetic resin by carrying out the ion plating is obtained. A synthetic resin molding product has the ion plating film obtained by this method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an IP method for applying an IP coating to a synthetic resin surface by ion plating (hereinafter sometimes simply referred to as IP) and a synthetic resin product coated with the IP method. It is.

[0002]

2. Description of the Related Art Conventionally, metal nitride has been applied to the surface of a metal exterior member in order to improve the surface strength of the exterior member in various products or to obtain a coloring effect for enhancing the decorativeness of the product. An ion plating method for forming a coating, a metal carbide coating, a metal oxide coating or a mixed coating thereof has been used in various fields.

As is well known, the ion plating method uses titanium (T) in a vacuum chamber 1 evacuated to a vacuum state of about 1 × 10 ⁻⁵ Torr shown in FIG.
The electron source is irradiated with an electron beam by an electron gun 4 in the presence of a gas such as nitrogen gas, acetylene gas or oxygen gas introduced from a gas supply mechanism 3 to an evaporation source 2 made of a metal component such as i). Is evaporated, and the evaporated metal element is ionized by the ionization electrode 5 and deposited on the surface of the target substrate 6 to be treated, so that a metal nitride film, a metal carbide film or a metal This is a method of forming an oxide film or a mixed film thereof.

The metal nitride film, metal carbide film, metal oxide film or mixed film obtained by the ion plating method usually has a thickness of about 0.2 to 3 μm and is a very thin film. But the hardness is about 600
It is very hard, about 3,000 HV, which makes it hard to be scratched, and is also excellent in anticorrosion properties.

[0005] In addition to the IP method, a vacuum plating method includes a vapor deposition method and a sputter link method. For example, the vapor deposition method is a method of evaporating aluminum while keeping the temperature inside the vacuum chamber low and attaching it to resin, etc., but the metal film formed by this vapor deposition method has poor hardness and adhesion, so it is used for general cargo. It is positioned and used for the production of decorative coatings for cosmetic containers.

The sputtering method is a method in which a metal is sputtered in a vacuum chamber and the metal is deposited on a substrate to be processed. However, the ionization rate is lower than the IP method and the reactivity with a gas is poor. Is made of aluminum or the like, and is used as a coating for interior parts in automobiles.

On the other hand, the IP method is characterized in that a film is coated on a substrate under the most severe conditions, but has good reactivity with gas and has a high surface hardness. I
Utilizing the characteristics of the hard surface obtained by the P method, it is used not only as a coating for products requiring abrasion resistance, such as a surface coating for cutting tools, but also for surface treatment of decorative articles because the coating has luster. It is also used as a color surface coating having a beautiful appearance that is hardly damaged.

[0008] The IP treatment of the substrate to be treated is performed in a vacuum, and is exposed to a high temperature of 200 to 300 ° C or more depending on the target film due to the energy carried by the ions and radiant heat for vaporizing a metal such as titanium. And I
The substrate to be treated is made of metal in order to apply a bias voltage to accelerate metal ions for the purpose of improving the adhesion of the P treatment film to the substrate to be treated, and the substrate to be treated is made of metal. In order to ensure the adhesion to the IP processing film, it is necessary that the material be resistant to rust.

[0009]

In the conventional IP method, as described above, the substrate to be processed is 200 to 300
The substrate to be processed is compatible with the processing environment, because it is exposed to high temperature of ℃ or bias voltage is applied to accelerate the metal ions to improve the adhesion of the film to the substrate. If they do not have the characteristics that they can perform, they may cause defects such as deformation and cannot be used as practical products. For this reason, conventionally, a metal material has been used as a workpiece for ion plating.

However, even when a metal material is used, only a uniform design and design can be obtained for each product due to restrictions on the metal material that can be used for the product and restrictions on its manufacture. There was a tendency.

On the other hand, even if the synthetic resin material has a complicated shape as compared with the above-mentioned metal material, it can be easily formed into the shape, and has excellent workability. It is widely used because it can be selected according to the intended use. In addition, various methods, such as immersion and vapor deposition, are applied to the synthetic resin molding surface to increase its commercial value. However, the metal plating film has considerably reduced properties such as mechanical strength as compared with a metal nitride film, a metal carbide film, a metal oxide film, or a mixed film obtained by ion plating (IP).

Therefore, if the surface of the synthetic resin can be subjected to the IP treatment with such a quality that there is no practical problem, a high quality IP coated product of the synthetic resin can be obtained, and the characteristics of the synthetic resin material can be obtained. By utilizing this, it is possible to obtain a molded article of a synthetic resin having various designs and applicable to a wide range of uses.

[0013] However, conventionally, the IP treatment is easily softened by heat, such as a synthetic resin, and even if it is applied to a material that may generate gas and contaminate the inside of the vacuum chamber, a product having a commercial value is obtained. It was virtually impossible to get.

Accordingly, an object of the present invention is to establish a method of applying ion plating to a synthetic resin member, to provide a coating by ion plating, and to provide a durability and a surface which can be sufficiently evaluated as a practical product. The purpose is to obtain a synthetic resin product provided with an IP coating exhibiting a state.

[0015]

Means for Solving the Problems As a result of intensive studies, the present inventors have developed a method for stably applying a high-quality IP coating to a synthetic resin member. Problems when the IP method is applied to a synthetic resin substrate will be described below. First, since a bias voltage is applied to accelerate the metal ions for the purpose of improving the adhesion of the IP coating to the synthetic resin substrate, the synthetic resin substrate must have conductivity. For this reason, it is necessary to apply plating to the synthetic resin base material so as to have conductivity.

In the course of the research and experiments of the present inventors,
After forming a metal coating film on the synthetic resin substrate by metal plating, it was found that an IP coating was formed by performing an IP treatment, but the most problematic was that the synthetic resin substrate was used. Was the effect on the surface state due to the heat resistance characteristics, compositional components, and contained gas components.

In other words, in order to cause swelling of the formed film, which is considered to be caused by thermal deformation due to the IP treatment atmosphere and gasification of the composition contained in the synthetic resin substrate, or to enhance the heat resistance of the synthetic resin. The fact that substances such as glass fibers contained in the resin reduce the smoothness and glossiness of the surface of the coating film formed by the IP treatment,
This was an obstacle to commercialization of the P-treated synthetic resin with marketability. These problems were even more important, especially when a synthetic resin product was used as an exterior product.

When the base material is subjected to IP treatment, the temperature of the base material becomes 200 to 300 ° C. due to the energy carried by the ions during the IP treatment and the radiant heat for vaporizing a metal such as titanium. High-performance base materials can be sufficiently IP-treated at this temperature, but most synthetic resins are thermally deformed, so if synthetic resins cannot be IP-processed at lower temperatures, IP-treated products with product value will be obtained. Absent.

In addition, during the IP treatment of the synthetic resin substrate, 20
When heated to around 0 to 300 ° C., the gas inside the synthetic resin is generated as described above and tends to expand. Therefore, in order to avoid this, it is necessary to perform the IP treatment at a lower temperature. Also,
When performing IP processing on a synthetic resin substrate having high water absorbency, it is inevitable that water absorbed by the synthetic resin vaporizes and expands at a high temperature of about 200 to 300 ° C.

Therefore, the conditions under which the synthetic resin metal-plated at a temperature lower than 200 to 300 ° C. can be subjected to the IP treatment and the selection of the synthetic resin suitable for the IP treatment have to be performed by trial and error.

For example, if it is a heat-resistant resin that can be plated with metal, it is considered that IP processing can be performed. However, IP processing is actually performed using heat-resistant engineering plastic or super-engineering plastic. In some cases, the IP coating swelled or peeled off. This is considered to be due to the difference in the coefficient of thermal expansion between the resin and the metal plating layer, and by appropriately selecting the type of the resin and the metal plating, physical properties, etc., or between the metal plating and the IP coating. He predicted that finding the right relationship would be indispensable for perfecting the resin IP processing technology.

In order to perform metal plating as a surface treatment method for a synthetic resin, copper (Cu) and nickel (N
In many cases, multi-layer metal plating is performed using a metal consisting of i) and chromium (Cr). The metal plating used for the outermost layer is gold (Au) plating, palladium (Pd) plating or an alloy plating thereof instead of Cr depending on the application, and is mainly used for exterior parts and handles of automobiles. , Bumpers and so on.

Therefore, when applying the IP coating to the surface of the synthetic resin molded product, first, as described above,
After applying a metal plating made of Ni and Cr, the possibility of IP treatment was examined using the synthetic resin provided with the metal plating layer.

First, as a resin having a possibility of IP processing, more than a dozen kinds were selected from engineering plastics and super-engineering plastics which are heat-resistant and capable of being plated, and subjected to IP processing. Due to the thermal environment, swelling and peeling of the metal plating film occurred.

However, two types of IP-processable resins, a polyphthalamide resin and a syndiotactic polystyrene resin, could be identified. In addition, a stable IP-treated resin product was obtained from a resin in which glass fibers or minerals were reinforced to enhance physical properties and heat resistance depending on the use of the two resins. That is, the polyphthalamide resin may be a mineral-reinforced polyphthalamide resin, and the syndiotactic polystyrene resin may be a glass fiber-reinforced syndiotactic resin, and similarly, a high-quality IP-treated product is obtained.

However, even with the above two types of resins, I
In some cases, the quality of the P-treated product was not stable, and in some cases, a small swelling of about 20% appeared on the surface of the IP-treated film.
One of the causes of the above-mentioned defective products is that the synthetic resin base material is placed in a high-temperature environment that is easily deformed by heat at about 200 to 300 ° C. during IP processing, and gas generation, expansion, and synthesis in the synthetic resin. It is considered that the difference between the coefficient of thermal expansion of the resin and the coefficient of thermal expansion of the metal plating layer causes swelling of the metal plating film. As a countermeasure, to reduce the IP processing time in order to keep the temperature near the synthetic resin low during the IP processing, the IP processing time was shortened. However, if the IP processing time was shortened, a sufficient film suitable for practical use could not be obtained.

However, the present inventor has found the following solution to such a problem. (1) In order to prevent the water absorbed in the synthetic resin from evaporating due to the high temperature during the IP processing and expanding, select a synthetic resin having low water absorption or prevent the synthetic resin from absorbing the water in advance. Place in an environment. The dehydrated synthetic resin that has absorbed water is subjected to metal plating and
P processing is performed. (2) When gas other than water is likely to be generated from the synthetic resin, degassing heat treatment is performed. Usually, before metal plating is applied to a resin molded product, a heat treatment called annealing is performed in order to remove molding distortion of the synthetic resin in order to improve adhesion of the metal plating.
This is a heat treatment at 0 ° C. for about 30 minutes. However, when IP treatment is performed on a metal-plated synthetic resin, the purpose is to remove molding distortion of the synthetic resin and to prevent gas from being generated from the synthetic resin when the resin is processed in a vacuum and at a high temperature. It is necessary to perform degassing heat treatment at a high temperature for a long time.

If the degassing treatment of the synthetic resin is not performed before the IP treatment, the metal plating layer swells and causes a poor appearance. The heat resistance changes depending on the resin and even the same resin due to glass fiber, mineral reinforcement, etc., so if the resin does not have heat resistance, it can be treated at low temperature for a long time, and if it has heat resistance, it can be treated at high temperature for a short time. It is economical. The degassing treatment of the synthetic resin is performed, for example, at 200 ° C. for 1 to 2 hours, or for 18 hours.
The heat treatment is performed at 0 ° C. for 1.5 to 3 hours or at 150 ° C. for 2 to 4 hours.

By the above heat treatment, the synthetic resin is degassed, and at the same time, the annealing treatment and the dehydration treatment are performed. If the heat treatment time at the above heat treatment temperature is short, degassing, dehydration and annealing treatments are not sufficiently performed, and if the heat treatment time at the above heat treatment temperature is too long, it is uneconomical.

[0030] Thus, in addition to the polyphthalamide resin and the syndiotactic polystyrene resin, an ABS resin, a polyamide resin, a polyphenylene sulfide resin, and a liquid crystal polymer resin are each subjected to appropriate pretreatment, whereby:
The present inventor has found that IP processing is possible.

Next, metal plating performed before the IP processing on the synthetic resin substrate will be described. As described above, Cu and Ni
In addition to plating with metal consisting of chromium and Cr, as a result of diligent studies to find metal plating suitable for IP processing of synthetic resin and its plating conditions, IP processing can be performed on a good synthetic resin substrate in the following cases It turned out that there was a case. (A) A metal plating having a thickness sufficient to suppress thermal expansion of the synthetic resin is applied to the resin. Originally, metal plating is applied to a non-conductive substrate to apply a bias voltage to the substrate during IP processing, but metal plating with a film thickness sufficient to suppress thermal expansion of the synthetic resin is applied. .

The metal plated with the synthetic resin expands under a high temperature (about 200 ° C. to 300 ° C.) environment during the IP processing. However, the synthetic resin and the plated metal film have different coefficients of expansion, and generally the synthetic resin has a higher coefficient of thermal expansion than the plated metal film. Accordingly, a force is generated that pushes the synthetic resin plated metal film. When the plated metal film is spread out by the synthetic resin to a temperature equal to or higher than the coefficient of thermal expansion of the metal, the metal film is stretched and may be broken in some cases.

The metal film that has grown at a high temperature contracts when the temperature returns to normal temperature, but the plating metal film and the synthetic resin separate from each other or swell due to the difference in shrinkage between the synthetic resin and the metal film. I do. In order to prevent this, it may be effective to adopt a method in which a plating metal film having a large thickness is applied to the synthetic resin, and expansion of the synthetic resin is suppressed by the plating metal film.

For example, Cu (20 μm) + Ni (10 μm)
20 to 30 μm) + (Pd—Ni) (1 μm)
It is desirable to apply a metal plating film having a thickness of about 50 μm on the synthetic resin.

It is uneconomical to provide a plating metal film having a thickness of 50 μm or more because the plating processing cost increases. Further, a plated metal film having a thickness of 20 μm or less cannot suppress the thermal expansion of the synthetic resin.

Next, a film having the following composition is used as a film obtained by the IP treatment. Examples include titanium nitride, titanium carbide, titanium oxide, and a mixed film thereof.

The products obtained by the resin IP treatment of the present invention include, for example, peripheral parts for watches (cases,
Watch bands, decoration rings), fishing gear peripheral parts (reels bobbin, handle, body, guides for fishing rods, etc.), camera-related parts (camera body), peripheral parts of home appliances (body, knobs, switches, mobile phones) MD
Exterior parts such as players and CD players), daily necessities, daily necessities (tableware, eyeglass frames), ornaments (pendants, key chains), automobiles (emblems, interior parts), housing-related articles (exterior and interior decorations), office work It is used for other resin parts such as supplies (stationery, writing utensils), fasteners for bags, buttons for clothes, and the like.

[0038]

Embodiments of the present invention will be described below. Syndiotactic polystyrene resin (trade name: Zarek (Idemitsu Petrochemical Co., Ltd.)), polyphthalamide resin (trade name: Amodel (trade name) as a material of a resin molded product subjected to ion plating (IP) treatment in the embodiment of the present invention. Teijin Amoko), ABS resin (trade name: Diapet ABS (Mitsubishi Rayon Co., Ltd.), polyamide resin (PA): MXD6 (trade name: Reny (Mitsubishi Gas Chemical Co., Ltd.), polyamide resin (PA): Nylon-6
(Trade name Toyobo Nylon (Toyobo Co., Ltd.), polyphenylene sulfide resin (PPS) (trade name Sastile (Tosoh Corporation), liquid crystal polymer resin (LCP) (trade name Vectra (Polyplastics Co., Ltd.)) Polyether sulfone resin (PES) (trade name: Sumika Excel (Sumitomo Chemical Co., Ltd.)), polyarylate resin (PA
R) (trade name: U-Polymer (Unitika), polyetherimide resin (PEI) (trade name: Ultem (Nippon GE Plastics)), polyethylene terephthalate resin (PET) (trade name: G-PET (Unitika) )) Was used.

The thermal properties of the main resins among the above-mentioned resins are listed. (A) Syndiotactic polystyrene resin (trade name: Zarek (Idemitsu Petrochemical Co., Ltd.) (a-1) Standard product Deflection temperature under load (tested by ASTM D648) 1.80 MPa: 95 ° C. 0.45 MPa: 110 ° C. Linear expansion coefficient (MD) (Tested with ASTM D696) 9.2 × 10 ⁻⁵ / ° C. (a-2) Glass fiber reinforced non-flame retardant product (glass fiber 15
Deflection temperature under load (tested by ASTM D648) 1.80 MPa: 170 ° C. 0.45 MPa: 260 ° C. Linear expansion coefficient (MD) (tested by ASTM D696) 3.9 × 10 ⁻⁵ / ° C.

(A-3) Glass fiber reinforced flame-retardant product (containing 40% by weight of glass fiber) Deflection temperature under load (tested by ASTM D648) 1.80 MPa: 245 ° C. 0.45 MPa: 268 ° C. Linear expansion coefficient (MD) ( 2.3 × 10 ⁻⁵ / ° C. (a-4) Calcium carbonate reinforced product (calcium carbonate 20)
Deflection temperature under load (tested with ASTM D648) 1.80 MPa: 97 ° C. Linear expansion coefficient (MD) (tested with ASTM D696) 11 × 10 ⁻⁵ / ° C.

(B) Polyphthalamide resin (trade name: Amodel (Amoco)) (b-1) Standard product Deflection temperature under load (tested with ASTM D648) 18.6 kg / cm ² : 120 ° C. (b-2) Mineral reinforcement Product (containing 20% by weight of a mineral composed of calcium carbonate) Deflection temperature under load (tested by ASTM D648) 18.6 kg / cm ² : 179 ° C Linear expansion coefficient (MD / TD) (tested by ASTM E831) 3.4 / 4.0 × 10 ⁻⁵ cm / cm · ° C. Here, MD represents a flow direction, and TD represents a direction perpendicular to the flow.

(C) Polyamide resin MXD6 (trade name: Lenny (Mitsubishi Gas Chemical Co., Ltd.)) Load deflection temperature (tested by ASTM D648) 18.5 kg / cm ² : 160 ° C. Coefficient of thermal expansion (tested by ASTM D696) 2.7 × 10 ⁻⁵ cm / cm · ° C. Mold shrinkage (tested with ASTM D955) 0.92%

(D) Polyamide resin nylon-6 (trade name: Toyobo Nylon (Toyobo Co., Ltd.) (d-1) Standard product Deflection temperature under load (tested by ASTM D648) 18.6 kg / cm ² : 143 ° C. 4.6 kg / Cm ² : 204 ° C. Linear expansion coefficient (MD / TD) (tested with ASTM D696) 7.0 × 10 ⁻⁵ cm / cm · ° C. (d-2) 15 wt% of glass fiber and 20 wt% of mineral
Deflection temperature under load (tested by ASTM D648) 18.6 kg / cm ² : 155 ° C 4.6 kg / cm ² : 205 ° C. Linear expansion coefficient (tested by ASTM D696) 4.3 × 10 ⁻⁵ cm / cm · ° C.

(E) ABS resin (trade name: Diapet A)
BS (Mitsubishi Rayon Co., Ltd.) Deflection temperature under load (tested by ASTM D648) 18.56 kg / cm ² : 92 ° C 4.64 kg / cm ² : 99 ° C. Coefficient of thermal expansion (tested by ASTM D696) 8.5 × 10 ⁻⁵ cm / Cm ・ ℃ Molding shrinkage (tested with ASTM D955) 0.5%

(F) Liquid crystal polymer resin (trade name: Vectra (Polyplastics Co., Ltd.)) Load deflection temperature (tested by ASTM D648) 18.56 kg / cm ² : 200 ° C. (g) Polyphenylene sulfide resin (trade name: SUSTYL ( Deflection temperature under load (tested with ASTM D648) 18.56 kg / cm ² : 260 ° C or higher Thermal expansion coefficient (tested with ASTM D696) 2.2 × 10 ⁻⁵ cm / cm · ° C.

(1) An outline of the steps up to IP processing will be described below by taking the above-mentioned syndiotactic polystyrene resin (trade name Zarek (Idemitsu Petrochemical Co., Ltd.)) as an example. Process: Injection molding or the like using the resin material
Form a resin molded product as a product. Second step: A degassing treatment, an annealing treatment or a dehydration treatment of the obtained resin molded product is performed to prevent the coating film from peeling off from the base material during the metal plating treatment and the IP treatment in the next and subsequent steps.

In this embodiment, heat treatment was performed at 200 ° C. for 1 to 2 hours as a degassing treatment, an annealing treatment or a dehydration treatment. For example, a method was used in which the temperature of the drying furnace was raised to 200 ° C., and the resin molded product was left therein for 1 to 2 hours.

Third step: A large number of fine holes are formed on the surface of the resin molded product by etching, and a part of the base metal film generated by metal plating in a later step enters the fine holes so as not to peel off. deep.

Fourth step: After the etching, I
Cu, Ni, P as a conductivity imparting process for performing the P process
Metal plating with d-Ni or the like is performed. Fifth step: The resin molded product after metal plating is put in a vacuum chamber for IP,
Perform ion plating. This ion plating is performed by a known method.

(A) Metal plating was performed on the surface of the resin molded article etched in the third step as follows. In addition, the capacity | capacitance or weight of the chemical | medical agent used in the following processing is performed to 1 L (liter) of water. First, the resin surface is degreased with a solution containing 20 g / L of sodium borate, 20 g / L of sodium phosphate, and 2 g / L of a higher fatty acid surfactant at 50 ° C. for 3 to 5 minutes. % Sulfuric acid 400g / L and CrO ₃ 400g
/ L at 65 ° C. for 15 to 20 minutes to form fine irregularities on the resin surface to enhance the adhesion of plating and make it hydrophilic.

Then, after washing with water, 10 ml / L of 36 wt.
% Of hydrochloric acid and 10 ml / L of 30 wt% hydrogen peroxide at 25 ° C. for 0.5 to 2 minutes to remove and neutralize the etching solvent.

After washing with water, a polarity is applied to the resin surface in order to improve the adsorbability of the catalyst described later.
The mixture is treated with a 1 / L aqueous solution of polyethyleneimine at 50 ° C. for 5 minutes. After washing with water, Pd and Sn complex compounds are adsorbed to form catalyst nuclei necessary for the first deposition of electroless plating. 0.2 g of palladium chloride as Pd compound
5 to 20 g / L of stannous chloride as an L and Sn complex compound was mixed with 100 to 200 ml / L of concentrated hydrochloric acid, and subjected to a catalyst application treatment at 25 ° C for 4 minutes.

Next, after washing with water, 30 ml with 100 ml of concentrated sulfuric acid.
処理 50 ° C. for 3-4 minutes to remove the tin component, metallize the palladium component, and wash with water.

After the above operations, the following metal plating layers are sequentially formed. (B-1) Electroless nickel plating 240 g / L of nickel sulfate, 20 g / sodium hypophosphite
L, ammonium citrate 50 g / L was added, and the pH was adjusted to 8 to 9.5 with NH ₃ (ammonia).
Electroless nickel plating is performed at a temperature of 5 ° C. for 5 to 10 minutes to form a nickel conductive layer of 0.2 to 0.8 μm. (B-2) Strike plating Next, after washing with water, concentrated sulfuric acid 100 ml / L at 25 ° C.
The oxide is removed from the nickel layer by treating for 0.5 to 1 minute to activate the nickel layer. After washing with water, nickel sulfate 240 g / L, nickel chloride 45 g / L and boric acid 30
g / L at 30-45 ° C. for 3-6 minutes,
A treatment is performed at 0.5 to 1 A / dm ² , and strike plating for electrodepositing 2 to 3 μ of nickel to reinforce the nickel layer is performed.

(B-3) Electro-copper plating After washing with water, a current consisting of 200 g / L of copper sulfate, 50 g / L of sulfuric acid and an appropriate amount of brightener is applied at 20-30 ° C. for 20-60 minutes at a current of ^2-4 A / dm ² . 20μ electrolytic copper plating by value
m electrodeposited. (B-4) Electric semi-bright nickel plating After washing with water, nickel sulfate 300 g / L, nickel chloride 50
g / L, boric acid 45 g / L and an appropriate amount of an additive at 50 ° C.,
Electrodeposit 5 μ of semi-bright nickel plating at a current value of ^{2 to} 4 A / dm ² for 0 to 30 minutes.

(B-5) Electro-bright nickel plating Next, nickel sulfate 300 g / L, nickel chloride 50
g / L, boric acid 45 g / L and appropriate amount of brightener at 50 ° C.,
5 μm of bright nickel plating is electrodeposited at a current value of ^{2 to} 4 A / dm ² for 0 to 30 minutes. (B-6-1) after electrical Pd-Ni plating was washed with water, a palladium salt _{(Pd (NH 3) 4Cl 2} · H 2
O) 25 g / L and nickel salt (Ni (CH ₃ COO)
₂ Cl ₂ .4H ₂ O) 10 g / L at 30 ° C. for 1 minute
A / dm ² is adjusted to pH 8 with NaOH, and Pd-Ni is electrodeposited at 1 μm. After that, it is washed with water, dried, and removed from the jig.

By the above operation, a resin-plated product having a Pd-Ni plating layer as the outermost layer can be obtained. In addition, ABS
The resin does not need to have the polarity.

Further, the outermost plating layer can be replaced with the following plating layer. The procedure for forming the plating layer will be described with reference to the plating layer to be formed. (B-6-2) Gold (Au) plating 1.23 g / L potassium gold cyanide, 7.5 g / L free potassium cyanide, and 15 g / L potassium phosphate
0 ° C. The Au plating is flash-0.5 μm electrodeposited at a current density of 1.0 A / dm ² for 1-2 minutes. (B-6-3) Au-Cu plating 12 g / L of potassium gold (I) cyanide, 7 g / L of potassium potassium cyanide, 10 g / L of potassium rhodan, and 8 g / L of 2-pyridinecarboxylic acid were adjusted to pH 8 with KOH. , 70
Au-C at a current density of 0.4 A / dm ² for 1 to 2 minutes.
Electrodeposit u-flash ~ 0.5 [mu] m.

(B-6-4) Au-silver (Ag) plating: 15 g / L potassium potassium cyanide, 3 g / L potassium potassium cyanide, 20 g / L nickel potassium cyanide, 10 g / L potassium potassium cyanide Then, 80 g / L of potassium cyanide and 20 g / L of ammonia are flash-deposited with 0.5 μm of Au-Ag plating at a current density of 0.6 A / dm ² at 15 ° C. for 1 to 2 minutes. (B-6-5) Au-Sn plating, 30 g / L of potassium gold (I) cyanide, 7 g / L of stannous sulfate, and 100 g / L of potassium pyrophosphate at room temperature for 1 to 2 minutes at a current density of 1 A
/ Dm ² to flash Au-Sn plating to 0.5 μm
Electrodeposit.

(B-6-6) Au-Cu-Cd plating
15 g / L potassium potassium cyanide, 5 g / L potassium cadmium cyanide, 200 g / potassium potassium cyanide
L-L-glutamic acid 50 g / L is subjected to flash-0.5 μm electrodeposition of Au—Cu—Cd plating at 70 ° C. for 1-2 minutes at a current density of 1 A / dm ² . (B-6-7) Au-Co plating, potassium gold (I) cyanide 8g / L, sodium citrate 80g / L, cobalt sulfate 3g / L at 21 ° C for 1-2 minutes, current density 1A
/ Dm ² flashes Au-Co plating to 0.5 μm
Electrodeposit.

(B-6-8) Au-Ni-Co plating,
Potassium gold cyanide 8 g / L, citric acid 150 g /
L, potassium citrate 100 g / L, nickel citrate 25 g / L, cobalt sulfate 1 g / L, potassium cyanide 1 g / L at 40 ° C. for 1-2 minutes, current density 1 A / dm ²
To deposit Au-Ni-Co plating by flashing to 0.5 [mu] m. (B-6-9) Au-Ni-In plating, 12 g / L potassium gold cyanide, 85 g / L citric acid, 140 g / L potassium citrate, 5 g / L nickel citrate, 5 g / L indium sulfate Flash Au-Ni-In plating at a current density of 1 A / dm ² at 40 ° C. for 1-2 minutes.
Electrodeposit 0.5 μm.

(B-6-10) Platinum (Pt) plating, dinitrodiamine platinum 10 g / L, ammonium nitrate 100 g / L, sodium nitrite 10 g / L, ammonium hydroxide 55 ml / L at 90 ° C. for 1-2 minutes. Flash Pt plating at current density of 1 A / dm ² to 0.5 μm
m electrodeposited. (B-6-11) Pd plating, diamine palladium nitrite 100 g / L, ammonium nitrate 90 g / L, sodium nitrite 10 g / L at 70 ° C. for 1 to 2 minutes, Pd plating at a current density of 1.0 A / dm ^2. Flash ~ 0.5
μm electrodeposited.

(B-6-12) Rhodium (Rh) plating, rhodium sulfate 2 g / L, sulfuric acid 30 ml / L, 50
The Rh plating is flash-0.5 μm electrodeposited at a current density of 2 A / dm ² at 1 ° C. for 1-2 minutes. (B-6-13) Ruthenium (Ru) plating Ruthenium sulfate 5 g / L and sulfamic acid 15 g / L are flash-deposited with 0.5 μm of Ru plating at a current density of 1 A / dm ² at 50 ° C. for 1 to 2 minutes. .

(B-6-14) Ni-P plating, nickel sulfate 150 g / L, orthophosphoric acid 50 g / L, sodium chloride 20 g / L, boric acid 20 g / L, sodium hypophosphite 20 g / L 5 ° C, current density 5A
/ Dm ² of Ni-P plating is 1μm electrodeposition in. (B-6-15) Sn-Ni plating 28 g / L of tin chloride, 30 g / L of nickel chloride, 200 g / L of potassium pyrophosphate, 20 g / L of glycine, and 5 ml / L of aqueous ammonia at 50 ° C. for 5 to 10 minutes. Electrodeposit Ni-P plating at a density of 1 A / dm ² at 1 μm.

(2) Next, the IP processing step will be described. A procedure for forming an IP coating of a composite film of titanium carbide and titanium nitride on a resin whose surface has been subjected to the metal plating treatment will be described.

First, the substrate to be processed is attached to the IP jig, and the pre-processing and the IP processing are performed as follows. (2-1) Pretreatment step For example, a nonionic chemical detergent (trade name: sonic-cean20)
5. Degreasing treatment for removing fingerprints, oils, dusts and the like adhering to the substrate to be treated is performed in an ultrasonic bath at 40 ° C. for 3 minutes using Ultrasonic Industry Co., Ltd.

Next, neutralization treatment is performed at room temperature for 3 minutes with a 0.2 wt% nitric acid solution so that no alkali component remains on the workpiece. Next, at room temperature for 3 minutes x 3 times, the washing liquid was washed away with tap water in an ultrasonic triple tank, and the washing liquid was washed away.
Further, pure water cleaning is performed to prevent generation of cleaning stains. Next, moisture is removed by drying with hot air at 70 ° C. for 3 minutes × 3 times.

(2-2) IP Processing Step A jig to which a substrate of a substrate to be processed is attached is set in a vacuum chamber 1 (FIG. 1) of an IP device, and titanium is used as an evaporation material in an evaporation source 2 of the IP device. Set the block. Next, the chamber 1 is closed and a vacuum is drawn for several tens minutes.
At this time, the final pressure value varies depending on the type of the IP film, but is set to about 1 to 9 × 10 ⁻⁵ torr.

Next, titanium is applied to the processed surface of the substrate 6 to be processed.
20 V, plus 20-40 V, 20 for the ionization electrode 5
~ 60A, electron gun 4 has minus 6 ~ 9kV, 400 ~
A voltage and a current value of 800 mA are set for each coating, and titanium is applied for 3 to 4 minutes. The reason why titanium is applied here is that even if a gas is introduced from the beginning, a sufficient reaction cannot be obtained at room temperature, so that the temperature is raised to some extent while titanium is applied to improve the reactivity.

Next, in order to color the IP coating,
An appropriate amount of nitrogen gas, acetylene gas, oxygen or the like is injected into the chamber 1, and the pressure is set to 1 × 10 ^{−4 to} 5 × 10 ⁻³ torr.
r, and the substrate of the substrate 6 to be processed is minus 120
V, plus 20 to 60 V, 40 to 8 for the ionization electrode 5
0A, minus 6-9 kV, 500-10 for electron gun 4
About 15 to 2 by setting the voltage and current of 00 mA, respectively.
Perform for about 0 minutes.

Thereafter, after cooling for a certain period of time, the atmosphere is injected into the chamber 1 to make it atmospheric pressure, the jig is taken out of the chamber, the jig is attached to the jig, and the substrate 6 to be processed is removed from the jig.

The following Table 1 shows that the various resins were treated with Cu plating (20 μm), Ni plating (C5 μm + 5 μm) and Pd-Ni plating (1 μm), and further, an IP film made of a mixed film of titanium carbide and titanium nitride. Shows the degree of finish by visual observation of the appearance of the IP film when the coating process of Example 1 was performed.

[0073]

[Table 1]

According to the present invention, a synthetic resin product is subjected to an ion plating process, thereby making use of a variety of designs and light weight which are characteristics of the synthetic resin material, and having high wear resistance and decorativeness. Can be provided at a low cost.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an IP processing device of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum chamber 2 Evaporation source 3 Gas supply mechanism 4 Electron gun 5 Ionization electrode 6 Substrate to be processed

Claims (5)

[Claims] The present invention is characterized in that after performing a degassing process and an annealing process of a synthetic resin, a metal plating is performed, and thereafter, an ion plating is performed to form an ion plating film on a molding surface of the synthetic resin. Ion plating method for synthetic resin. 2. The ion plating method for a synthetic resin according to claim 1, wherein a dehydration treatment is performed before or after the degassing treatment and the annealing treatment of the synthetic resin. 3. The synthesis according to claim 1, wherein the synthetic resin is heat-treated at 200 ° C. for 1-2 hours, at 180 ° C. for 1.5-3 hours, or at 150 ° C. for 2-4 hours. Ion plating method for resin. 4. A synthetic resin molded article having an ion plating film in which a metal plating film and an ion plating film are sequentially formed on a molding surface of a synthetic resin subjected to a degassing treatment and an annealing treatment. 5. The metal plating of the synthetic resin is 50 to 20 μm.
The synthetic resin molded article having the ion plating film according to claim 4, wherein