JPH0782426A - Resin composition for metal plating - Google Patents

Abstract

PURPOSE:To provide a resin composition capable of easily forming on the molded products therefrom a metallic deposit excellent in adhesiveness, rigidity and mechanical strength. CONSTITUTION:This resin composition comprises (A) 10-80wt.% of a polyolefin resin, (B) 90-20wt.% of a polyester resin and (C) 1-30 pts.wt., based on 100 pts.wt. of the components A and B, of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative therefrom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for metal plating which is capable of easily forming a metal plating layer having excellent adhesiveness and further has excellent rigidity and mechanical strength.

[0002]

2. Description of the Related Art Polyolefin has been widely used in various fields such as agriculture and fishery, construction, civil engineering, electricity, electronics and automobiles because it is inexpensive and excellent in moldability.

However, polyolefin resins have not been used for parts that require a metal plating process. The reason is that there are problems such as poor adhesion strength and appearance of metal plating, use of a large amount of solvent in the step of performing metal plating, or increase of the number of steps accordingly.

For this reason, in general, in parts requiring metal plating, resins other than polyolefin resins, especially AB
S resin was used.

There are some attempts to improve the etching effect by adding a filler or the like as a metal plating improver in order to improve the adhesion of the above-mentioned polyolefin to the metal plating, but the etching time becomes longer and, as a result, the appearance of the metal plating surface is increased. Becomes poor.

However, there are many applications of metal-plated parts in the fields of automobiles and home appliances, and there has been a demand for a resin composition for metal plating which is excellent in adhesion strength and appearance of metal plating in a relatively simple process similar to ABS resin. .

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin composition for metal plating, which can easily form a metal plating layer having excellent adhesiveness and which is excellent in rigidity and mechanical strength. To do.

[0008]

[Means for Solving the Problems] As a result of intensive investigations by the present inventors in view of the above situation, a polyester resin and an unsaturated carboxylic acid or a derivative thereof are modified with a polyolefin resin in order to increase the adhesion strength of metal plating. The inventors have found that a resin composition obtained by adding a specified amount of the above polyolefin-based resin can solve the above problems, and completed the present invention.

That is, the present invention relates to a polyolefin resin modified by (A) 10 to 80% by weight of a polyolefin resin, (B) 90 to 20% by weight of a polyester resin, and (C) an unsaturated carboxylic acid or a derivative thereof. A resin composition for metal plating, which contains 1 to 30 parts by weight of resin with respect to (A) + (B) = 100 parts by weight.

As the polyolefin resin (A) used in the resin composition for metal plating of the present invention, ethylene,
Propylene, 1-butene, 1-hexene, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
Homopolymers of α-olefins such as 1-pentene, copolymers of these α-olefins with one or more other α-olefins, or these α-olefins and other copolymerizable unsaturated monomers And a blend of two or more of them is used. Of the above (A) polyolefin resins, polypropylene is particularly preferably used because of its rigidity and mechanical strength.

Taking polypropylene as an example, it is a homopolymer of propylene or a copolymer of propylene and a small amount of one or more α-olefins, and its MFR is
(JIS K6758, 230 ° C., 2.16 kgf) 0.1 to 80 g / 10 min, further 0.5 to 50
Those of g / min are preferably used. If the MFR is outside the above range, the moldability may be poor. The propylene homopolymer has an isotactic index of 80% or more, preferably 9 or more, as determined from its room temperature xylene-soluble content.
It is 5% or more. Furthermore, α which is a comonomer
Examples of the olefin include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. A preferred example of the propylene copolymer is specifically shown. Propylene / ethylene copolymer containing 0.1 to 20 mol% of ethylene Propylene / 1-butene containing 0.1 to 20 mol% of 1-butene Copolymer, 0.1-20 mol% ethylene and 0.1-20
Propylene-Ethylene-containing mol% 1-butene
Examples thereof include 1-butene copolymer.

The (B) polyester resin used in the present invention is a thermoplastic resin generally composed of a saturated dicarboxylic acid and a saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly Examples thereof include cyclohexane-1,4-dimethylol terephthalate and polyneopentyl terephthalate, and one or a blend of two or more of these is used. Of these, polyethylene terephthalate or polybutylene terephthalate is preferable.

In addition to the above polyester resin, one or more kinds of other polymer compounds such as polyvinyl chloride, polymethylmethacrylate, polyvinyl acetate, polyacrylonitrile, ethylene-vinyl acetate copolymer, polycarbonate, polysulfone, polystyrene, polyphenylene. Ether, polyphenylene sulfide, polyamide, polyacetal, epoxy resin, unsaturated polyester and the like may be blended.

There is no particular limitation on the above polyester resin, but the intrinsic viscosity [η] of 0.3 to 1.2 dl / g (the intrinsic viscosity [η] is 25 ° C. in an o-chlorophenol solvent.
It is obtained from the solution viscosity measured in step. Those having) are preferably used. The polyester resin (B) may have a terephthalic acid moiety substituted with an alkyl group, a halogen group, or the like, and a glycol moiety may contain up to about 50% by weight of other glycol.

The polyolefin serving as the main chain of the polyolefin resin modified with the unsaturated carboxylic acid or its derivative used in the present invention is ethylene, propylene, 1-butene and A homopolymer of 1-hexene or the like or a copolymer thereof can be exemplified, and it is a blend of one kind or two or more kinds thereof. As the unsaturated carboxylic acid or its derivative which is an acid group, acrylic acid, maleic acid,
Unsaturated carboxylic acids such as fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, and derivatives thereof such as acid halides, amides, imides, anhydrides and esters, and particularly maleic anhydride. Modified ones are preferred.

The amount of the unsaturated carboxylic acid or its derivative added is not particularly limited, but a modified polyolefin resin added by 0.1 to 10% by weight to the polyolefin resin forming the main chain is preferable.

The method for producing the (C) polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof is not particularly limited, and various conventionally known methods can be adopted. In particular, for polyolefin powders, the above-mentioned unsaturated carboxylic acids or their derivatives are added to usual radical generators such as di-t-butyl peroxide, dicumyl peroxide, benzoperoxide, 2,5-dimethyl-2,
A method in which an organic compound such as 5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene is added and melt-kneaded using an extruder is simple and suitable for use. .

The resin composition for metal plating of the present invention comprises 10 to 80% by weight, preferably 20 to 70% by weight of the above (A) polyolefin resin, and 90 to 20% by weight of (B) polyester resin. Preferably 80 to 30% by weight,
(C) The above-mentioned (A) + (B) = 100, which is a polyolefin resin modified with an unsaturated carboxylic acid or its derivative.
1 to 30 parts by weight is included with respect to parts by weight.

(A) 10% by weight of polyolefin resin
If it is less than 80% by weight, the polyester resin does not appear on the surface of the resin molded product, and if it exceeds 80% by weight, the adhesion strength of metal plating cannot be sufficiently obtained.

(C) A polyolefin resin modified with an unsaturated carboxylic acid or its derivative is (A) +
If less than 1 part by weight with respect to (B) = 100 parts by weight, the compatibility of the (A) polyolefin resin and the (B) polyester resin becomes poor, and defects such as poor appearance appear, and 30 parts by weight are used. If it exceeds the limit, mechanical properties such as impact resistance are poor.

To obtain the polyolefin-based resin composition of the present invention, the above-mentioned (A) polyolefin-based resin, (B) polyester-based resin and (C) unsaturated carboxylic acid or its derivative-modified polyolefin-based resin are used. Various methods known in the above range, such as Henschel mixer, V
A method may be adopted in which after mixing with a blender, a ribbon blender, a tumbler blender, etc., the mixture is melt-kneaded with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc., and granulated or pulverized.

The resin composition for metal plating of the present invention contains a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a lubricant, a slip agent,
Nucleating agents, flame retardants, plasticizers, pigments, additives generally added to polyolefins such as dyes, or glass fibers, carbon fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay,
Inorganic or organic reinforcing materials and fillers such as kaolin, fine powder silica, mica, calcium silicate, aluminum oxide, magnesium oxide, and wood powder may be added within a range that does not impair the object of the present invention.

As an impact resistance improver, an ethylene / α-olefin copolymer (modified with an unsaturated carboxylic acid or a derivative thereof) having a maximum peak temperature (Tm) of less than 100 ° C., which is shown by differential scanning calorimetry, is used. Ethylene ・ α-
(Although it may be an olefin copolymer) may be added within a range not impairing the object of the present invention. Specific examples of α-olefins include propylene, 1-butene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-hexene and the like can be mentioned. Of these, a copolymer obtained from propylene or 1-butene is preferably used in terms of physical properties and copolymerizability.

The method of measuring Tm by the differential scanning calorimeter is as follows.

A sample of about 5 mg was weighed from a film having a thickness of about 100 μm formed by hot press, and the sample was measured at 80 ° C. to 80 ° C.
The temperature is raised to 230 ° C. at a heating rate of / min and held for 5 minutes. The temperature is lowered to -10 ° C at a rate of 10 ° C / min. −
The temperature is maintained at 10 ° C. for 5 minutes, then again raised to 230 ° C. at a rate of 10 ° C./min, and the temperature at the apex of the maximum peak among the peaks appearing during the temperature rise is defined as Tm.

The above-mentioned polyolefin resin composition is molded into various parts, sheets, films, plates, containers, etc., by any conventional molding means such as extrusion molding, injection molding and rolls. And known vapor deposition in the case of any molded product,
It is possible to perform metal plating having excellent adhesion on the surface of the resin molded product by using a vacuum plating method such as sputtering or ion plating, or an electroplating method.

For example, regarding the above metal plating method,
There is no particular limitation, and conventionally known techniques can be applied.

[0028]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

The measuring method used in the present invention is as follows.

Metal plating adhesion strength: After electroplating, bright copper sulfate plating was performed to form a plating layer having a thickness of about 70 μm. After drying at 80 ° C. for 2 hours, it was left at room temperature.
Then, a notch having a width of 1 cm is made in the metal-plated product, and a tensile tester (made by Tsushima Seisakusho, Autograph SD-100-
The 180 degree peel strength between the metal plating layer and the resin was measured using C).

Appearance of metal plating: A metal-plated test piece was visually observed, and a metal plating having a smooth and even gloss was evaluated as ◯, and a metal plating having unevenness and being glossy was evaluated as x.

Example 1 Polypropylene (MFR, 20 g / 10 min (230
C.), hereinafter referred to as PP-1), 65% by weight, polybutylene terephthalate (PBT720, manufactured by Kanebo Co., Ltd., hereinafter referred to as PBT-1) 35% by weight, maleic anhydride modified polypropylene (maleic anhydride addition amount: 0. 5% by weight)
20 parts by weight to 100 parts by weight of the total amount of polypropylene and polybutylene terephthalate were mixed with a tumbler blender for 15 minutes, and then L / D = 36 mm, 57 mmφ
Resin temperature of 250 ° C with a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.)
It was melt-kneaded and granulated. Resin temperature of these pellets was 2 using an injection molding machine (150MSII type manufactured by Mitsubishi Heavy Industries, Ltd.).
Injection-molded at 60 ° C for test pieces (150 mm x 110 mm
X 2 mm thickness) was produced. The produced test piece was metal-plated by the following method.

(1) Degreasing Aesculin A-220 (Okuno Pharmaceutical Co., Ltd., 50 g / l, 50 ° C., 5 minutes) (2) Etching hychromic acid type (Okuno Pharmaceutical Co., Ltd., 65 ° C., 8 minutes) (3) Neutralization HCl (50 ml / l, 25 ° C., 2 minutes) (4) Catalyst addition Catalyst C (Okuno Pharmaceutical Co., Ltd.,
40 ml / l, HCl 150 ml / l, 25 ° C., 4 minutes) (5) Activated H ₂ SO ₄ (100 ml / l, 40
(° C, 4 minutes) (6) Chemical nickel plating TMP chemical nickel (Okuno Pharmaceutical Co., Ltd., 40 ° C, 7 minutes) (7) Electroplating Table 1 shows the measurement results of physical properties.

Example 2 Polypropylene (MFR, 5 g / 10 min (230
C), hereinafter referred to as PP-2), 35% by weight, polybutylene terephthalate (manufactured by Kanebo Co., Ltd., PBT719, hereinafter referred to as PBT-2) 65% by weight, maleic anhydride-modified polypropylene is a total of polypropylene and polybutylene terephthalate. Example 1 was repeated except that the amount was 15 parts by weight based on 100 parts by weight. Table 1 shows the measurement results of physical properties.

Example 3 The procedure of Example 1 was repeated, except that PP-2 was 35% by weight, PBT-1 was 65% by weight, and maleic anhydride-modified polypropylene was 15 parts by weight. Table 1 shows the measurement results of physical properties.

Comparative Example 1 The procedure of Example 1 was repeated except that PP-1 was used alone. The results of measurement of physical properties are shown in Table 1.

Comparative Example 2 Example 1 was repeated except that 85% by weight of PP-1 and 15% by weight of PBT-1 and 20 parts by weight of maleic anhydride-modified polypropylene were used. Table 1 shows the measurement results of physical properties.

[0038]

[Table 1]

[0039]

INDUSTRIAL APPLICABILITY The polyolefin resin composition of the present invention retains mechanical properties and is excellent in adhesion strength and appearance in metal plating, as compared with conventionally known polyolefin resins, and is comparatively similar to the ABS resin process. Since metal plating can be performed in a simple process, it can be used for automobile parts, electrical equipment parts,
It is suitable for applications requiring a metal plating process as well as general physical properties such as rigidity of mechanical parts, industrial parts, and miscellaneous goods parts.

Claims (2)

[Claims] 1. A polyolefin resin of (A) 10-80.
% By weight, 90 to 20% by weight of (B) polyester resin
And (C) a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, wherein (A) + (B) = 10.
A resin composition for metal plating, which comprises 1 to 30 parts by weight with respect to 0 parts by weight. 2. The resin composition for metal plating according to claim 1, wherein the polyolefin resin (A) is polypropylene.