JPS6037872B2 - Metal-plated polyamide resin molded product and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamide resin molded product that can be plated with metal and a method for producing the same.

The technology of applying metal plating to plastics has been researched for quite some time, and its benefits include providing electrical conductivity, reducing water absorption, improving heat resistance, and reducing costs. It is mentioned. By the way, in order for metal plating on plastic to be effectively put to practical use, the adhesion between the plastic and the metal film must be strong enough to cause no practical problems, and the cost of metal plating must also be low enough to be practical. Since the material must satisfy certain conditions, the reality is that most metal-plated plastics are currently limited to ABS resin and the like. However, it is expected that it will be applied to new fields that require various characteristics that cannot be utilized with ABS resins, etc., and many studies are being conducted on metal plating of other plastics.

Among them, metal plating of polyamide resin is also being researched, but since polyamide resin does not form the dents that are seen when ABS resin is chemically etched, it has no anchoring effect on the dents, and its adhesion. The power is quite low.

Furthermore, even if a compound that is soluble in an etching solution is mixed to form a concave mark, the polyamide resin itself will be decomposed by the etching solution, so metal plating on polyamide resin is still not practical. Ta. Therefore, the inventors of the present invention have made extensive studies and efforts to solve the above-mentioned drawbacks, and as a result, have finally completed the present invention.

That is, the present invention provides a metal-plated polyamide resin molded product, which contains 10 parts by weight of polyamide resin, 1 to 60 parts by weight of an inorganic filler, and 0 parts by weight of a triazine derivative.
．． A metal-plated polyamide resin molded article, characterized in that it is a polyamide resin composition comprising 1 to 4 parts by weight, and when plating the polyamide resin composition, the polyamide resin composition is immersed in an aqueous solution of an inorganic acid. After that, the inorganic acid is sufficiently removed, and then plating is performed. In the present invention, the polyamide resin includes a self-polycondensate of lactam, a polycondensate of diamine and dibasic acid,
A self-condensation product of w-amino acid or a copolymer thereof, specifically, -caprolactam, aminocaproic acid, phenantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, Q-pyrrolidone, Q - Polymers such as piberidone, diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid. Polymers obtained by polycondensation with dicarboxylic acids such as acids, or copolymers thereof, such as nylon 4, 6, 7
, 8, 11, 12, 6.6, 6.9, 6.10, 6.1
Examples include 1, 6・12, target, 6/6・6, 6/12, 6/target.

Next, the triazine derivative blended into the polyamide resin is a compound having a triazine ring, and specifically, melamine, cyaphenine, cyanuric acid, melamine cyanurate, methyleneaniline, methyleneaminoacetonitrile, hexamethylene Examples include tetramine,
In particular, it is preferable to incorporate melamine or melamine cyanurate from the viewpoint of improving mechanical properties.

The amount of this triazine derivative added is 100% of the polyamide resin.
The amount is 0.1 to 40 parts by weight, and if it is less than 0.1 part by weight, the adhesion strength will decrease, although it depends on the shape and purpose of the molded product. On the other hand, if the amount exceeds 4 parts by weight, it is not preferable because the moldability and physical properties of the molded product cannot withstand general use. The average particle diameter of the triazine derivative is preferably 100 F. or less, particularly preferably 1 to 30 F.

Furthermore, the inorganic filler blended in the present invention includes:
Natural silicon compounds such as quartz, asbestos, diatomaceous algae, mica, metal oxides such as titanium oxide, zinc white, baryta, alumina, metal hydroxides such as magnesium hydroxide, barium sulfate, calcium sulfate, calcium carbonate, silicon Examples include alkali metal salts such as calcium acid (wollastonite), magnesium carbonate, and magnesium silicate (talc), metal salts containing lead white, and inorganic mixtures such as clay and glass, among which talc, wollastonite, clay, etc. is preferred.

The amount of the inorganic filler added is 1 to 6 parts by weight, preferably 15 to 45 parts by weight, based on 10 parts by weight of the polyamide resin.
Parts by weight. If the amount added exceeds 6 parts by weight, moldability and physical properties will deteriorate, which is not preferable. Further, the average particle size of the inorganic filler is preferably 20 μm or less, preferably 5 μm or less in powder form.

There is no particular limitation on the method of blending the triazine derivative and inorganic filler into the polyamide resin, and they may be added during the polyamide polymerization step, at the end of the polymerization, or during molding.

In addition to the above ingredients, coloring agents, lubricants, foaming agents, elutriation agents, stabilizers, heat resistant agents, antistatic agents, ultraviolet absorbers, etc. may be added to the polyamide resin for the purpose of improving other properties. . Next, as a method for plating the polyamide resin composition having the above structure, first, the surface of the resin composition is cleaned by degreasing, etc., and then diluted with an aqueous solution of an inorganic acid. Examples of inorganic acids include hydrochloric acid and sulfuric acid, with sulfuric acid being preferred.

The concentration of the aqueous solution of the inorganic acid is preferably 5 to 15%. In addition, in the case of the composition of the present invention, plating can be performed without performing the bonding treatment with the aqueous solution of the inorganic acid.
Although the reason for this is not clear, it is thought that the additive of the present invention sublimes to produce an anchoring effect. When the inorganic acid aqueous solution immersion treatment is performed, it is necessary to neutralize with an aqueous solution such as sodium hydroxide or potassium hydroxide to sufficiently remove the inorganic acid.

Thereafter, the molded article of the present invention is obtained by performing sensitizing treatment, activation treatment, chemical plating, and electroplating according to conventional methods, but in the case of competitive painting, etc., the treatment up to chemical plating is sufficient. The molded product of the present invention obtained by the above method can be plated with strong adhesion by a simple method, and the physical properties of the molded product itself maintain the physical properties inherent to the polyamide resin.

Its uses include heat-resistant accessories, lamp mirror surfaces, foam housings, door handles, rearview mirror holders, window handles, foil caps, etc. It can replace conventional metal materials, is easier to mold than metal, and is more heat-resistant than ABS resin. It's expensive. EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, in the following description, all parts mean parts by weight, and the measurement method to show each characteristic was in accordance with the method shown below.・Adhesion strength: Based on cross-cut Sellotape test method.

- Izod impact strength: Measured with a notch according to ASTM D256. - Appearance: visual judgment Example Relative viscosity (96% sulfuric acid, 1% solution measured at 25°C) 3.
A predetermined amount of the additives shown in Table 1 was blended with No. 0 nylon 6, and then melted at 250 oo and pelletized.

Using an injection molding machine, each pellet is made into 150 pieces vertically and 7 pieces horizontally.
It was molded into three ribs in thickness.

However, the molding conditions are mold temperature 8000, injection pressure 500
It is sand with k9/uniformity, injection time of 1, and cooling time of 2. Next, the obtained molded product was plated according to the steps shown below.

However, it was washed with water after each step. '11 Pretreatment: Soak in a 10% aqueous solution of sulfuric acid for about 7 minutes.

Then neutralize with 5% aqueous sodium hydroxide solution and wash with water. ■
Sensitizing: Immerse in palladium chloride 0.3 t/t, stannous chloride 20 t/t, and hydrochloric acid 200 cc for about 3 minutes at a liquid temperature of 25°C.

'3} Activation: Sulfuric acid 200 t/soni liquid temperature 4
Soak for about 1 to 2 minutes at 0 to 50 o'clock.

[4] Chemical nickel plating: pH 7 with a composition consisting of nickel sulfate 30 cc/ml, sodium hypophosphite 20 ml, sodium citrate 40 cc/ml, and ammonia water 25 cc/ml.
．． Immerse the bond in the solution No. 5 at 30-40°C for about 5-10 minutes.

(51 Electrolytic copper sulfate coating: In an aqueous solution consisting of sulfuric acid steel 220 g, copper sulfate 50 g/g, brightener 5 g/g, 20 g
~3 pin 0, electric density 2~4A/d, current 15~4
It was run for 0 minutes. '6} Electro-bright nickel plating: In an aqueous solution consisting of nickel sulfate 270 g/s, nickel chloride 50 g/s, shelf acid 40 g/s and a nickel brightener, 4
At 5-55℃, the electric density is 2-5A'd and the current is 10-55℃.
It was run for 30 minutes.

'7} Electrochrome plating: K.

250% of sulfuric acid, 2.5% of sulfuric acid, 2% of trivalent chromium
Electrical density 1 at 15 to 50 qo in an aqueous solution consisting of
A current was applied for 1.5 to 4 minutes at a rate of 5 to 2 p/d. The adhesion strength and impact strength of the molded product sealed through the above steps were measured according to the test method described above, and the results are also listed in Table 1.

Table 1

Claims (1)

[Scope of Claims] 1. A metal-plated polyamide resin molding, the resin molding comprising 100 parts by weight of polyamide resin, 1 part by weight of an inorganic filler.
A metal-plated polyamide resin molded article, characterized in that it is a polyamide resin composition consisting of ~60 parts by weight and 0.1 to 40 parts by weight of a triazine derivative. 2 100 parts by weight of polyamide resin, 1 to 60 parts by weight of inorganic filler
When plating a polyamide resin composition consisting of parts by weight and 0.1 to 40 parts by weight of a triazine derivative, the polyamide resin composition is immersed in an aqueous solution of an inorganic acid, the inorganic acid is sufficiently removed, and then plating is performed. A method for manufacturing a metal-plated polyamide resin molded article.