JPS5855172B2 - Manufacturing method of plated products - Google Patents

Description

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

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

Compared to metal plating, plastic plating, which requires many, complex, and difficult-to-manage chemical processing steps, is more likely to cause pollution due to waste liquid from each processing step, and products due to the complexity of the process. 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, but the plating method for any resin involves either neutralization-catalyst accelerator-electroless plating or neutralization-sensitizing-activation. Batting requires an electroless plating process.

In addition, in the etching process, usually - chromic anhydride 40
0? A treatment solution with a high chromium concentration, such as 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), and the molded product is made of a composition having a volume resistivity of 1039-1 or less, and then electroplated directly after etching. He has invented a 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 comprises 100 parts by weight of a single or two or more thermoplastic resins (excluding a single copolymer of vinyl cyanide, aromatic vinyl, and conjugated diene rubber) (A), and an oil absorption amount of 100 parts by weight. 2
0OrI'll/100P or more, and the surface area is 5
Carbon black (B) 3 to 10 that is 00d/7 or more
After etching a molded article made of a composition containing 0 parts by weight and having a volume resistivity of 10103 (j- or less),
This is a method of manufacturing plated products characterized by direct electroplating.

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-vinyl cyanide) resin, polyphenylene oxide resin and LVA (
(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 and 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 0d/S' or more.

With carbon black outside this range, no matter which thermoplastic resin is used, even if electroplating is performed directly after etching, an electrodeposited film may not be formed, or even if it is formed, a good plated product cannot be obtained.

The amount of carbon black (B) relative to 100 parts by weight of the thermoplastic resin (A) is 3 to 100 parts by weight, and if it is 3 parts by weight or less, the oil absorption is 200 m1/100f or more and the surface area is 500 d/f or more. Even with 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 referred to as rI.
It is expressed in units of Ll/100g.

The surface area is a value measured according to ASTM D3037-73, and is expressed in units of d/1.

Oil absorption amount of carbon black (B) is 200wLl/10
If the surface area is less than 0 g or 500 d/f, a product with a satisfactory electrodeposited film cannot be obtained.

In the present invention, the volume resistivity value of the composition is 103. p-cm
Must be below.

If it exceeds 1038 mm, a product with a satisfactory electrodeposited film cannot be obtained.

More preferably IQ2. Q-m or less.

In addition, the volume resistivity value is Br1tish 5tand
-Means the value measured according to ard 2044 (Method 2).

According to the present invention, electroplating can be performed directly after the etching process, which is not necessary in conventional methods of manufacturing plated products.

The steps of neutralization-catalyst-accelerator-electroless plating or neutralization-sensitizing-activating-electroless plating can be omitted.

Therefore, there is no need for treatment liquids required in each step, and not only can the cost of reagents be significantly reduced, but there is also no cost required for waste liquid treatment.

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

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 manufacturing plate of the plated product of the present invention were kneaded in the proportions shown in Table 1,
(Kneaded for 8 minutes at 200°C in a Banbury mixer) A composition was obtained.

After that, from the composition 70mmX 140mmX 2my
Form a flat plate of n, and the flat plate is made of chromic anhydride 30? /l
.

Etching treatment with an etching solution of concentrated sulfuric acid (500 rrtl/71°C) (75°C XIO minutes), followed by direct etching with copper sulfate 200 rrtl/71°C. /l, sulfuric acid 50? Strike plating was performed at a current density of IA/dd in an electrolytic copper plating bath of /l, and then main plating was performed at a current density of 3.5 A/dd.

Practical 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 formed.

These flat plates were subjected to etching treatment in the same manner as in Example 1, and then direct strike plating and main plating were applied.

PP: Polypropylene Sumitomo Chemical ■pv
c: Polyvinyl chloride PS
Nipolystyrene 〃PC Nibolycarbonate Teijin Chemical PMMA: Methacrylic resin Sumitomo Chemical ■Polysulfone Tomoe Kogyo (Polyester Toyobo Co., Ltd.■ PA: Polyacetal Polyplastic■
Polyamide East Shi ■ AS Nistyrene-acrylonitrile copolymer Daicel ■ PPO: Polyphenylene oxide Nijineering plastic (Open EVA: Ethylene-vinyl acetate Sumitomo Chemical ■ PE: Polyethylene
Noblen vV-501 Smilit 5X-7G Nisprite Nogun Light L-1250W Sumipex B-LG del F-560 Duracon M25-04 Amiran CM-3001G Sevian-N Noril 731 Evatate D3011 Sumirikisen G801

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. Amount 200m1/100'? or more, and the surface area is 5
00i/f or more carbon black (B) 3 to 10
0 parts by weight and a volume resistivity of 10,103 (j- or less), a method for producing a plated product characterized by electroplating directly after etching a molded product. 2. Thermoplastic resin or polypropylene. The first resin is a resin.
A method for producing a plated product as described in Section 5. 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 plated product C 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.
Manufacturing method for 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 above, which is a thermoplastic resin or a resin mixed with a polypropylene resin and a polyethylene resin. 15 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 polyphenylene 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 oxide resins. 16. The method for producing a plated product according to items 2 to 15 above, wherein the amount of 16 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 as described in Section 6.