JPS5855171B2 - Manufacturing method of plated products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing plated products from a composition of thermoplastic resin N and carbon black (B).

Traditionally, plastics have been used in various fields as materials for plated products, but these plastics are nonconductors and cannot be electroplated directly, requiring complex pretreatment processes as shown below. .

Compared to metal plating, plastic plating, which requires many, complex, and difficult-to-manage chemical processing steps, is more susceptible to pollution due to waste liquid from each processing step, and products due to the complexity of the steps. There are many problems such as variations in quality and rising costs.

There are some differences in the processing steps before electroless plating depending on the type of thermoplastic resin (catalyst reactor accelerator, sensitizing → activating), but the electroless plating process is required for any plating method for any resin. I need.

In addition, in the etching process, usually - chromic anhydride 40
0? A treatment solution with a high chromium concentration of about 200 ml/l of concentrated sulfuric acid is required.

Therefore, wastewater treatment is accompanied by the problem of chromium pollution.

In the current plating process, there are various problems when using a treatment solution with a low chromium concentration, and it is difficult to reduce the chromium concentration.

The present inventors have researched a method that would reduce the number of steps mentioned above and be beneficial from an economic and pollution prevention perspective, and have already developed a copolymer (ABS resin) consisting of vinyl cyanide, aromatic vinyl, and conjugated diene rubber. ) (A) and a special carbon black (B), the plated product is characterized by electroplating directly after accelerator treatment of a molded product made of a composition having a volume resistivity of 1038 or less. Invented a manufacturing method and applied for a patent.

Further, as a result of intensive research, the present inventors have arrived at the present invention.

That is, the present invention is directed to thermoplastic resins (excluding single copolymers of vinyl cyanide, aromatic vinyl, and conjugated diene rubber) (A) i
oo parts by weight and oil absorption amount 2oo7711/100? A molded article made of a composition comprising 3 to 100 parts by weight of carbon black (B) having a surface area of 500 d/7 or more and having a volume resistivity of 10332·dynamic or less,
This is a method for producing a plated product, characterized by applying electroplating directly after accelerator or activating treatment.

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 (
(ethylene-vinyl acetate) resin, etc., either alone or in a mixture of two or more.

However, ABS resin alone is excluded.

When the thermoplastic resin is a mixture of two or more resins, it is necessary to consider the compatibility of these resins.

Examples of the mixture include mixtures of polyphenylene oxide resin and polystyrene resin, polypropylene resin and polyethylene resin, and the like.

In addition, ABS resin may be mixed with other resins, and as a mixture using ABS resin, ABS resin, vinyl chloride resin,
Examples include mixtures with one or more resins selected from the group consisting of polycarbonate resins, methacrylic resins, polysulfone resins, polyacetal resins, aromatic vinyl-cyanide vinyl resins, and polyphenylene oxide resins.

Preferably, the ratio of ABS resin to other resin is 1 to 99:99 to 1.

Further, conventional auxiliary agents such as lubricants, antioxidants, plasticizers, fillers, etc. may be added.

The carbon black (B) used in the present invention has an oil absorption of 200 m1/100f or more and a surface area of 50 m1/100f or more.
It is necessary that it is 0rIf/1 or more.

With carbon black outside this range, no matter which thermoplastic resin is used, direct electroplating after accelerator or activating treatment may not produce an electrodeposited film, or even if it does, a good plated product may not be obtained. I can't do it.

The amount of carbon black (B) relative to 100 parts by weight of thermoplastic resin A) is 3 to 100 parts by weight, and if it is less than 3 parts by weight, the oil absorption is 200 m 17,100 ft or more and the surface area is 5 ooi/'? Even with the above carbon black, an electrodeposited film cannot be formed.

Moreover, if it exceeds 100 parts by weight, the physical properties of the molded product will be significantly inferior.
It cannot be put to practical use.

More preferably, it is 5 to 70 parts by weight, and most preferably 8 to 25 parts by weight.

In addition, oil absorption means a value measured according to JIS K-6221-1975, and the amount of DBP (dibutyl phthalate) measured by an abutometer is expressed as ml.
/ 100? It is expressed in units of.

The surface area is a value measured according to ASTM D 3037-73, and is expressed in units of d/1.

Oil absorption amount of carbon black (B) is 200 m1710
If the surface area is less than 01 or the surface area is less than 500 i/f, a product with a satisfactory electrodeposited film cannot be obtained.

In the present invention, the volume resistivity value of the composition must be less than 1038.

1031; If it exceeds J.Snoring, a product with a satisfactory electrodeposited film cannot be obtained.

More preferably, it is 10102J7- or less.

In addition, the volume resistivity value is Br1tish 5tand
-ard 2044 (Met2O44).

According to the present invention, electroplating can be performed directly after accelerator (or activating) treatment, so the electroless plating step, which is unnecessary in conventional methods of manufacturing plated products, can be omitted. I can do it.

Therefore, the electroless plating solution required in the electroless plating process is not required at all, and not only the cost of reagents can be greatly reduced, but also the cost of waste liquid treatment is not required at all.

Because it is simpler than conventional treatment processes, it is easier to manage the treatment liquid and increase production power.

Furthermore, etching can be carried out satisfactorily with an etching solution with a low chromium concentration, which is advantageous in terms of pollution control.

Examples will be described below, but the present invention is not limited thereto.

Example 1 The thermoplastic resin and carbon black used in the method for manufacturing plated products of the present invention were kneaded in the proportions shown in Table 1 (kneaded at 200°C for 8 minutes in a Banbury mixer) to obtain a composition.

Thereafter, a flat plate of 7Qmm x 140mm x 2mm was formed from the composition, toluene 2QOrnl/4 trichlene 1
00rrLVt aqueous solution at 60°C for 10 minutes,
Preliminary etching was performed.

In addition, 60% turpentine and 20% surfactant
Wash with hot water (75°C x 15 minutes) in an aqueous solution containing a weight factor, and add 30% of chromic anhydride. /l, dark 57fpe 500 rn17.
Etching treatment with etching solution (75℃XI)
O minute), neutralization treatment with D-25 neutralizer manufactured by Okuno Pharmaceutical Co., Ltd.
Catalyst treatment with A-30 catalyst liquid manufactured by Okuno Pharmaceutical Co., Ltd. and accelerator treatment with D-25 accelerator liquid manufactured by Jitsukei Pharmaceutical Co., Ltd., followed by direct treatment with copper sulfate 200
? /l, sulfuric acid 50? IA in an electrolytic copper plating bath of /l
Strike plating was performed at a current density of /d-i, and then main plating was performed at a current density of 3.5 A/d-.

In addition, A-G using polypropylene and polyester
and M, sensitizing processing using TMP sensitizer manufactured by Jiken Seiyaku Co., Ltd. instead of catalyst processing, and TM manufactured by Okuno Pharmaceutical Co., Ltd. instead of accelerator processing.
Activation treatment using P activator was performed.

Example 2 As shown in Tables 2 and 3, various thermoplastic resin compositions and carbon black were kneaded in the same manner as in Example 1, and a flat plate was shaped into a bottom shape.

These flat plates were subjected to etching, neutralization, sensitizing, and activating (catalyst and accelerator in Table 3) treatments in the same manner as in Example 1, and then directly strike plating and main plating were performed.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of one or more thermoplastic resins (excluding a single copolymer consisting of vinyl cyanide, aromatic vinyl, and conjugated diene rubber) (A), and an oil-absorbing resin. The amount is 200m1/100f or more, and the surface area is 5o
o771! /P or more carbon black (B) 3~
1. A method for producing a plated product, which comprises directly applying electroplating to a molded product made of a composition containing 100 parts by weight and having a volume resistivity of 103 k·° or less after an accelerator (or activating) treatment. 2. The first above, wherein the thermoplastic resin is a polypropylene resin.
Method for manufacturing plated products described in Section 1. 3. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a vinyl chloride resin. 4. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is polystyrene resin. 5. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a polycarbonate resin. 6. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a methacrylic resin. 7. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a polysulfone resin. 8. The first above, wherein the thermoplastic resin is polyacecool resin.
Method for manufacturing plated products described in Section 1. 9. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a polyamide resin. 10. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is an aromatic vinyl-cyanide vinyl resin. 11. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a polyphenylene oxide resin. 12. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is an ethylene-vinyl acetate resin. 13. The method for producing a plated product according to item 1 above, wherein the thermoplastic resin is a mixture of polyphenylene oxide resin and polystyrene resin. 14. The method for producing a plated product according to item 1, wherein the thermoplastic resin is a mixture of polypropylene resin and polyethylene resin. 15 The thermoplastic resin is a copolymer consisting 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. 2. The method for producing a plated product according to item 1 above, wherein the resin is a mixture of one or more resins selected from the group consisting of phenylene oxide resins. 16. The method for producing a plated product according to any of the above items 2 to 15, wherein the carbon black (B) is 5 to 70 parts by weight. 17 The first volume resistivity value is 1028.
A method for producing a plated product according to item 6.