JPS61247A - Olefin resin composition for electroplating - Google Patents

Abstract

PURPOSE:The titled composition which gives a molded part having a beautiful surface, and excellent plate adhesion and impact resistance, and is obtained by incorporating an oxide of a Group II metal of the periodic table, sulfur or a sulfurliberating compound, a vulcanization accelerator, and a specified carbon black into an olefin resin. CONSTITUTION:100pts.wt. olefin resin (A) (e.g. polyethylene), 0.1-10pts.wt. oxide of a Group II metal of the periodic table (B) (e.g. zinc oxide), 0.1-10pts.wt. sulfur or a sulfurliberating compound (C), 0.05-10pts.wt. vulcanization accelerator (D) (e.g. thiazole type) and 5-60pts.wt. carbon black (E) having a resistivity under a pressure of 50kg/cm<2> of 0.30OMEGA.cm or less, a hydrochloric acid absorption of 20-40ml/5g, and a specific surface of 100-400m<2>/g are compounded to give an olefin resin composition for electroplating which gives a molded part having a beautiful surface and improved impact resistance while maintaining desirable physical properties.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an olefin thread resin composition for electroplating (hereinafter referred to as
To explain in more detail, the present invention relates to a plating composition that has a beautiful surface, good plating adhesion, and high impact resistance.

[Conventional technology]

Conventionally, it has been known that plastic plating is used to reduce the weight of gold Jlli products and to improve the decorativeness, corrosion resistance, weather resistance, and durability of synthetic resin products and to increase added value.

In particular, acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) is widely used as a plating resin. Requires various and complex pre-treatments such as electrolytic plating (chemical plating),
These processes have the drawback of requiring significant labor such as washing with water or regenerating the mixed solution used for etching.

On the other hand, although olefin resin u is difficult to plate compared to ABS resin, etc., it does not require the various and complicated pre-treatments mentioned above (・), so this resin is blended with curzen black and a sulfur-containing compound to make it conductive. Compositions with improved properties and adhesion have been proposed (Japanese Unexamined Patent Publication No. 54-60349,
(Japanese Patent No. 57-168929, etc.).

However, olefin resin 1 (for electroplating,
Since the volume resistivity of the composition must be less than 103Ω・Fu, it is necessary to use Kerr, Zen black, carbon fiber, graphite powder, or acetylene black with excellent conductivity. Although it is possible to improve the conductivity by adding conductive fillers (these are called conductive fillers), when these conductive fillers are added, the processability tends to decrease and the degree of freedom in molding processing tends to be impaired. In particular, M is disadvantageous in that impact resistance, which is a characteristic of polyolefin resins, is reduced. As for external problems, when sulfur and a conductive filler coexist in a polyolefin resin, a plumping phenomenon occurs, the gloss of the surface decreases, and there are disadvantages such as poor aesthetic appearance and poor adhesion.

[Problem that the invention seeks to solve]

The present inventors have developed an olefin resin set for electroplating (...
Two. -9-1, 1,1-7.1, 9.24-states and the improvement of impact resistance was investigated.

[Means for solving problems]

The present invention includes: (a) Olefin resin 100 parts by weight (1) 1 Metal oxide of group [Group of the periodic table 0.1 to 1
0 parts by weight (0) Sulfur or sulfur-releasing compound 0.1~
10 parts by weight (d) Vulcanized Italian “General rules 0.05~
Electrical specific resistance under 10 parts by weight and (θ) 50 kg/2 pressure is 0. 'Less than 30Ω-, hydrochloric acid absorption capacity 20-4.0ml
This is an olefin resin composition for electroplating, containing 5 to 60 parts by weight of carbon black having a specific surface area of 75 g and a specific surface area of 100 to 40071 L2/1.

Examples of the olefin resin include polyethylene, polyzologylene, a copolymer of ethylene or propylene, and a copolymerized monomer, or a mixture thereof.

The metal oxide of Group 1 of the periodic table is used as a vulcanization aid, and the addition ratio thereof is preferably 0.1 to 10 parts by weight based on 100 parts of the olefin resin. 0.1
If the amount is less than 1 part by weight, the effect for complete vulcanization will be poor, and if it exceeds 10 parts by weight, precipitation will occur in the resin, making it impossible to obtain proper vulcanization, and plumes will form on the surface of the composition, so it is preferable. do not have.

Vulcanization aids include beryllium oxide (BsO), magnesium oxide (Mg0), acid (hycalcium (OaO)
), barium oxide (Bad), cadmium oxide (aaO
), zinc oxide (ZnO), etc., but in particular, Mg
O1ZnO can improve the thermal conductivity of the resin,
It is advantageous to use thiurams as vulcanization accelerators because they form a Zn-dithiocarbamate system and are effective as anti-aging agents.

As the sulfur, sulfur flowers and vulcanizing sulfur can be used. As a sulfur releasing compound, relatively high temperature (generally 100 to 2
Compounds that release all sulfur at 00°C), such as tetramethylthiuram disulfide P, can be mentioned. In the case of sulfur-releasing compounds, they are incorporated into the composition in the form of compounds. Sulfur is a plating metal layer! -12 It is necessary to improve the adhesion to the surface of the shaped object, and it is necessary to add 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, to 100 parts by weight of the olefin resin. . If the amount of sulfur used exceeds the above range, the pluming will not be thick, the amount of pluming inhibitor added will be too large, and the physical properties of the molded product (
In particular, this is not preferable because the impact resistance deteriorates.

The vulcanization accelerator is generally a vulcanization accelerator used in the im industry, such as thiazole type, imidapurine type, dithiocarbamate type, thiourea type, thiuram type, sulfenamide type, dentate type, guanidine type, aldehyde type. etc. can be mentioned. The addition ratio of the vulcanization accelerator is preferably 0.05 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, based on 100 parts by weight of the olefin resin.

If it is less than 0.05 parts by weight, it is difficult to shorten the vulcanization time, lower the vulcanization temperature, and reduce the amount of sulfur.
If the amount exceeds 1 part by weight, the Izot impact value, tensile strength, etc. of the molded product will deteriorate, which is not preferable. 50kg/r
x2 Electrical resistivity under pressure less than 0.60 noodles, hydrochloric acid absorption amount 20-40d15g and specific surface area 100-400rIL
2/g carbon black is a high-performance acetylene black obtained by continuous pyrolysis of acetylene gas with or without the presence of unsaturated hydrocarbons by a mixed gas flow of oxygen-containing gas and water vapor. . A method for producing stiff acetylene black has already been proposed in Japanese Patent Application No. 1983-61831 by one of the present authors.The amount of acetylene black to be added is as follows:
It is preferable that the amount is 5 to 60 parts by weight based on 100 parts by weight of the resin content. If the amount is less than 5 to 2 parts, the volume resistivity of the composition will be 10 3 Ω or less, and if it exceeds 60 parts by weight, the fluidity of the composition will deteriorate and the impact resistance of the molded product will decrease, which is not preferable. Since the molded product using the material in the assembly of the present invention has a good surface σ14 condition, it is not necessary to use an anti-pluming agent, but an anti-pluming agent can be added if desired. As a pluming prevention agent, comb,
Alkylphenol resins, coumaron resins, rosin derivatives, styrene-butadiene block combinations, etc., which are known as tackifiers for plastics, can be mentioned. These can be added crushed, alone or in combination, but the addition ratio is preferably 0 to 20 parts by weight per 100 parts by weight of the olefin resin.

Even if the concentration exceeds 20, it is useless as no further suppressing effect can be expected.

The plating composition of the present invention contains all of the above-mentioned additives, but in addition, it may contain ordinary molding additives such as fluidity modifiers and heat stabilizers for improving moldability, as necessary. It may be included.

The plating composition of the present invention can be easily prepared by adding all the components to the olefin resin and mixing in a Banbury mixer, kneader, roll mill screw extruder, etc. J can be made.

〔Example〕

Next, the present invention will be explained using examples.

Examples 1 to 4, Comparative Examples 1 to 4 As the olefin resin, ethylene-zolo-1e copolymer manufactured by Mitsui Toatsu Chemical Co., Ltd. (black market name: Mitsui Noprene BJH)
H-G) 'Jk was used, and conductive fillers such as Kazen black, acetylene black, and Ketchen F were added to this as conductive fillers.
Sulfur powder manufactured by Kanto Kagaku Co., Ltd. as fO1 sulfur, quick lead leather (znO) as group II metal oxide, and vulcanization accelerator manufactured by Ohmukai Shinko Kagaku Co., Ltd. [Product name: Tsukusela M (thiazol-based) )], Denki Kagaku Kogyo (
Co., Ltd.'s styrene-detadiene block copolymer (trade name "5TR-16024"), and as an anti-aging agent, Ohmukai Shinko Kagaku Co., Ltd.'s product [trade name Tsurac 630F (mixed diallyl paraphenylene diamine)] was added in the proportions shown in the table. (all ton)
Using a Banbury mixer with an internal volume of 1.71,
The mixture was kneaded at 0°C, and then passed through a roll to obtain a rolled sheet, which was then cut with a cutter to obtain pellets of the composition.

Various physical properties were measured using this pellet, and the results are shown in the table.

As is clear from the table, the plating composition of the present invention is particularly improved in surface smoothness and impact resistance, as shown in the Examples.

The methods for measuring the physical properties of the substances and plating compositions used in Examples and Comparative Examples are shown below.

Acetylene black produced by material methods. Physical properties 50kg/6rrL2 Electrical specific resistance under pressure 0.18 Ωa1 Hydrochloric acid absorption amount 5'bm11 5&, Specific surface area 250 rrL''/g.

Acetylene black produced by method PE' 50 to 9/crt? Electrical specific resistance under pressure (1,21 Qcm, tM acid absorption protein 26rn11 59, specific surface area 6U 0m2/9 (4) Acetylene black...manufactured by Denki Kagaku Kogyo Co., Ltd., grain AB015) Ketjen EC... Made by Japan EC, by-product Kargun.

Measurement method (1) Volume resistivity...composition pellets) e250°C
A sheet with a thickness of 1.2 g was obtained by pressing for 10 minutes, and a test piece with a length of 70 mm and a width of 20 mm was prepared. Dotite (manufactured by Fujikura Kasei) was applied to both ends of the specimen to a thickness of 5 mm, and this was placed in a constant humidity room at 20°C and 60% temperature for 24 hours. After 24 hours, a multimeter (TR-6856, manufactured by Takeda Riken) was used. The resistance was measured. The volume resistivity was calculated using the following formula.

l′ However, Rv: Volume specific resistance Ωα R: resistance value Ω l': distance between electrodes Ta.

After alkaline degreasing using a 5% by weight aqueous sodium phosphate solution, the sample was heated at 50°C in a -4 bath containing 2501/l of nickel sulfate, 50 g/l of nickel chloride, and 601/l of boric acid. Electroplating was carried out to create a nickel layer of several microns, and the thickness of the copper plating layer was approximately 20 μm in a copper plating bath with a pH of 1.7 using copper sulfate 2001/l and sulfuric acid 50 g/It as main components. Plating is carried out so that it becomes micron. The sample thus obtained was cooled at -20°C for 1 hour, left at room temperature for 1 hour, heated to 80°C and left for 1 hour, left at room temperature for 1 hour, and this cycle was repeated four times. Changes in appearance (abnormalities such as blistering) were visually observed.

(6) Surface condition: A photograph of the surface of the object to be plated was taken with a stereomicroscope SMZ-10 manufactured by Nippon Kogaku Co., Ltd. and magnified 57 times, and one particle in an area of 5.0 V x 2 was measured. The ranks of the debris are as follows: debris with a cross-sectional area of 0.05 m1 or more is large debris, and debris with a cross-sectional area of 0.05 m1 or more is large debris; The ranks of the decks were classified as follows, with decks below 2 in Ot order being classified as small decks.

For example, 0 large decks, 10 small decks. In this case, it is displayed as A-1.

〔Effect of the invention〕

The olefin resin composition for electroplating of the present invention has a beautiful surface state and impact resistance while maintaining the conventional favorable physical properties by incorporating a specific conductive filler into the olefin resin together with other constituent components. It is excellent in that it has improved performance.

Claims (1)

Scope of Claims: (a) 100 parts by weight of olefinic resin (b) 0.1 to 10 parts by weight of metal oxide of Group II of the periodic table (c) 0.1 to 10 parts by weight of sulfur or sulfur-releasing compound (d
) 0.05 to 10 parts by weight of vulcanization accelerator and (e) 50 kg
/cm^2 Electrical resistivity under pressure less than 0.3Ωcm, hydrochloric acid absorption amount 20-40ml/5g, and specific surface area 100-4
An olefin resin composition for electroplating containing 5 to 60 parts by weight of carbon black of 00m^2/g.