JPS608713B2 - Resin products with partial metal plating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin and carbon black, and a resin product partially plated with metal using an ordinary thermoplastic resin.

BACKGROUND ART Conventionally, for the purpose of reducing costs and improving decorative effects, there has been a desire for products in which metal plating is applied only in partially necessary areas.

For example, a method of coating areas that are not to be plated in advance with a paint that is difficult to be oxidized by an etching solution (masking).

Or {2} Tsubaki Kosho 48-28357 and Tokuko Sho 48
As seen in No. 27917, plastic products partially plated with metal have been obtained by a method using a plateable resin and a non-plated resin (for example, plated grade and non-plated grade polypropylene). However, these methods have problems such as 1) complicated steps, difficulty in masking, and 2) product defects due to differences in molding shrinkage rates. Furthermore, when using these conventional methods, it is impossible to make an electrical contact to the surface of the plated part because it is surrounded by non-plated parts, that is, in cases such as those shown in the drawings, methods (1) and {21 above cannot be used. Therefore, partially plated resin products cannot be obtained.

At present, a major problem remains that it is necessary to apply plating to the entire surface of the product, then leave only the necessary plated parts and paint the unnecessary parts. All of these products require the following steps: etching → neutralization → sensitizing (catalyst) → activating (accelerator) → electroless finishing → electroplating.

The present inventors have arrived at the present invention as a result of intensive research into simplification of processes, reduction of costs, etc. That is, the present invention provides a thermoplastic resin having an oil absorption of 200/100 ta or more and a surface area of 500 ta or more by weight of one or more thermoplastic resins 10.
A thermoplastic resin composition (■) consisting of 3 to 10 parts by weight of carbon black with a volume resistivity of 1 pq or less and a volume resistivity of 1 pq or less is used for the metal-plated parts, and a type of Alternatively, a two-color molded product molded using two or more types of thermoplastic resin curves is partially metal-plated, which is characterized by directly electroplating the product after accelerator or activating treatment. It is a resin product.

To explain the present invention in more detail, the thermoplastic resin used in the present invention is a copolymer (ABS resin) consisting of vinyl cyanide, aromatic vinyl, and conjugated diene rubber.
, polypropylene resin, vinyl chloride resin, polystyrene resin, polycarbonate resin, methacrylic resin, polysulfone resin, polyester resin, polyacetal resin,
Polyamide resin, AS (aromatic vinyl cyanide) resin, polyphenylene oxide resin and EVA (
These include ethylene-vinyl acetate) resin, polyethylene resin, etc., and can be used alone or in combination of two or more.

In the case of two or more types, a mixture of polyphenylene oxide resin and polystyrene resin, a mixture of polypropylene resin and polyethylene resin, and a mixture of ABS resin and vinyl chloride resin, polycarbonate resin, methacrylic resin,
Examples include mixing with one or more resins selected from the group consisting of polysulfone resins, polyacetal resins, AS resins, and polyphenylene oxide resins.

Furthermore, the thermoplastic resin constituting the thermoplastic resin composition of the present invention and the thermoplastic resin used for the non-plated portion [
B} does not necessarily have to be the same type of thermoplastic resin.

For example, it may be a molded article in which the thermoplastic resin constituting the composition is ABS resin, and the thermoplastic resin portion of the non-plated portion is polypropylene resin.

In addition, these thermoplastic resin compositions ■ and thermoplastic resins'
B}' Conventional auxiliaries such as lubricants, antioxidants, plasticizers, fillers, etc. may be added.

The carbon black used in the present invention has an oil absorption of 20
It is necessary that the surface area is 0/100 ta or more and the surface area is 500 〆/ta or more.

Carbon blacks outside this range may not produce lightning deposits even when electroplated directly after accelerator or activating treatment, regardless of which thermoplastic resin they are used with, or even if they do, a good product may not be produced. I can't get it. In the thermoplastic resin composition (1), the amount of carbon black is 3 to 10 parts by weight based on 10 parts by weight of the thermoplastic resin, and 3
If the amount is less than 1 part by weight, even if the carbon black has an oil absorption of 200 w/100 ta or more and a surface area of 500 w/ta or more, a military coat cannot be formed.

Moreover, if the weight increase is 10 parts or more, the physical properties of the thermoplastic resin composition will be significantly inferior, and the composition cannot be put to practical use. More preferably 5 to 7 parts by weight, most preferably 8 to 7 parts by weight.
It is 25 parts by weight.

In addition, oil absorption means a value measured according to JISK-6221-1975, and the amount of DBP (dibutyl phthalate) measured by an absorptometer is expressed as 1/1.
It is expressed in units of 00 evenings.

The surface area is a value measured according to ASTM D3037-73, and is expressed in units of 〆/unit. If the oil absorption of carbon black is less than 200/100 ta or the surface area is less than 500/ta, a product with a satisfactory lightning deposit cannot be obtained. The volume resistivity value of the thermoplastic resin composition must be less than 1 pi* skin.

If it exceeds 1 piQ.g, a product with a satisfactory electrodeposited film cannot be obtained.

More preferably, it is less than or equal to 1.

In addition, the volume resistivity value is
It means a value measured according to d2044 (Method 2).

According to the present invention, ① there is no need for a masking process and the associated masking material; direct electroplating is possible after accelerator or activating treatment; and electroless plating, which is indispensable in conventional plating processes. Steps can be omitted and electroless lacquer is not required. (2) Moreover, since no electrolytic lacquer is required, it is also beneficial in terms of waste liquid treatment.

In addition to molded products where it is impossible to make electrical contacts on the surface to be plated, even molded products whose periphery is surrounded by non-plated parts as shown in the drawing, we can make electrical contacts on the back side.
There are advantages such as the ability to obtain products that are partially plated with metal. Examples will be described below, but the present invention is not limited thereto.

Thermoplastic resin and carbon black were mixed in the proportions shown in Tables 1 to 3, and mixed in a Banbury mixer at 200 oo
The mixture was kneaded for 8 minutes to obtain pellets of thermoplastic resin composition. A two-color molded product as shown in the drawing was obtained using the composition and a commercially available thermoplastic resin molding machine using a 5-ounce injection molding machine. Next, for the molded product, add 6,000 ml of toluene 200 to the aqueous solution of
Preliminary etching was performed by immersing it in water for 10 minutes. moreover,
Washing with hot water (7500 x 15 minutes) in an aqueous solution containing 6% by weight of turbentin 6 and % by weight of surfactant 2, chromic anhydride 30 minutes/so, concentrated sulfuric acid 500 minutes/etching treatment with the etching solution (7500 x 10 minutes) ), neutralization treatment with D-25 neutralizer manufactured by Okuno Pharmaceutical Co., Ltd., A-30 manufactured by Okuno Pharmaceutical Co., Ltd.
Catalyst treatment with catalyst liquid and accelerator treatment with D-25 accelerator liquid manufactured by Okuno Pharmaceutical Co., Ltd. were performed, and electrical contacts were made at the locations shown in Figure 3. After that, strike plating was performed directly at a current density of IA/d with sulfuric acid steel 200 m/d and sulfuric acid 50 m/d/thick copper plating, and then the current density was increased to 3.5 A/d for main plating. (
Copper) was carried out. Furthermore, at 4 A/d, nickel and 3
Each was plated with 0A/d Mechrome.

In addition, for A to C, F to days and 0 using polypropylene and polyester in the thermoplastic resin composition (1), TMP manufactured by Okuno Pharmaceutical Co., Ltd.
Instead of sensitizing treatment using a sensitizer and accelerator treatment, activation treatment was performed using a TM circular activator manufactured by Okuno Pharmaceutical Co., Ltd.

Example 1 Table-1 Table-2 Table-3 ABS: Acrylonitrile Ruthtyrene Rubber Naugatac ■ Clarastic MH Tagene Copolymer PP
：Polypropylene Sumitomo Chemical ■
Noblen W-501PVO: Polyvinyl chloride
〃Dumirit SX-
70PS: Polystyrene
S-Bright PO: Polycarbonate
Teijin Kasei Panlight L
-1250WPMMA: methacrylic resin
Sumitomo Chemical Sumibex B-LG Polysulfone Tomoe Kogyo Udel Bolster Toyobo RF-
560PA: Polyacetal Polyplastic ■ Duracon M25-04 Polyamide
Toray ■ Amiran OM-3001
GAS: Styrene-acrylonitrile Tycel■
Sepian-N copolymer PPO: Polyphenylene oxide engineering bra Noryl 73
1 stick ■EVA: Ethylene-pinyl acetate
Sumitomo Chemical Evatate D3011P
E: Polyethylene
Sumikasen G801

[Brief explanation of drawings]

FIG. 1 is a front view of a partially metal-plated resin product showing one embodiment of the present invention, and FIG. 2 is a sectional view thereof. 1 is a thermoplastic resin curve, 2 is a thermoplastic resin composition ■, 3 is an electrical contact, and 4 is a metal plating film. Figure 1 Figure 2

Claims (1)

[Claims] 1. 100 parts by weight of one or more thermoplastic resins, an oil absorption of 200 ml/100 g or more, and a surface area of 500 m
A thermoplastic resin composition (A) consisting of 3 to 100 parts by weight of carbon black with a resistivity of ^2/g or more and a volume resistivity of 10^3 Ωcm or less is used for the part to be metal plated, and the non-plated part is A two-color molded product molded using one or more thermoplastic resins (B) is subjected to an accelerator or activation treatment, and then electroplated directly. Applied resin products. 2. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a copolymer consisting of vinyl cyanide, aromatic vinyl, and conjugated diene rubber. 3. The first above, wherein the thermoplastic resin is a polypropylene resin.
Resin products partially plated with metal as described in Section 1. 4. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a vinyl chloride resin. 5. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is polystyrene resin. 6. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a polycarbonate resin. 7. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a methacrylic resin. 8. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a polysulfone resin. 9. The first above, wherein the thermoplastic resin is a polyacetal resin.
Resin products partially plated with metal as described in Section 1. 10. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a polyamide resin. 11. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is an aromatic vinyl-cyanide vinyl resin. 12. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a polyphenylene oxide resin. 13. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is an ethylene-vinyl acetate resin. 14 The first above, wherein the thermoplastic resin is a polyethylene resin.
Resin products partially plated with metal as described in Section 1. 15. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a mixture of polyphenylene oxide resin and polystyrene resin. 16. The partially metal-plated resin product according to item 1 above, wherein the thermoplastic resin is a mixture of polypropylene resin and polyethylene resin. 17 A copolymer in which the thermoplastic resin is composed of vinyl cyanide, vinyl aromatic and conjugated diene rubber, vinyl chloride resin, polycarbonate resin, methacrylic resin, polysulfone resin, polyacetal resin, aromatic vinyl-vinyl cyanide resin and polyester resin. The partially metal-plated resin product according to item 1 above, which is a resin mixed with one or more resins selected from the group consisting of phenylene oxide resins. 18. The partially metal-plated resin product according to items 2 to 17 above, wherein the carbon black (B) is 5 to 70 parts by weight. 19. The partially metal-plated resin product according to item 18 above, which has a volume resistivity of 10^2 Ω·cm or less.