JPS59182829A - Olefinic based resin composition for electroplating - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a mixtue of an oxide of a metal of Group II in the periodic table with sulfur, a vulcanization accelerator, a carbon source material and carbon black with an olefin based resin in a specific proportion, and having improved fluidity with slight blooming, and suitable for metallic products, etc. CONSTITUTION:An olefin based resin composition obtained by incorporating (A) 100pts.wt. olefin based resin with (B) 0.5-20pts.wt. oxide of a metal of Group IIin the periodic table, (C) 0.1-10pts.wt. sulfur or a compound releasing the sulfur, e.g. tetramethylthiuram disulfide, (D) 0.05-10pts.wt. vulcanization accelerator, e.g. thiuram, (E) 5-60pts.wt. carbon powder obtained by thermal decomposition of a mixture of (i) an organic high polymer having carbon bonded to the molecule and/or a bituminous material with (ii) carbon black and (F) 0.5- 20pts.wt. blooming inhibitor.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an olefin resin composition for electroplating (hereinafter referred to as
To explain in more detail about the plating composition (referred to as a plating composition), it is beautiful with little pluming on the surface of the composition (plating phenomenon), has good plating adhesion, and has particularly good fluidity.
This invention relates to a plating composition with high impact resistance.

[Prior art]

Traditionally, we have focused on reducing the weight of metal products, the decorativeness of synthetic resin products,
It is known that plastic plating is used to improve corrosion resistance, weather resistance, durability, and 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 electroless 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, olefin resins are easier to plate than ABS resins (although they do not require the various and complicated pretreatments mentioned above, so carbon black and sulfur-containing compounds are blended with this resin to improve conductivity and adhesion). Compositions have been proposed that aim to improve the
-168929 etc.).

However, in order to electroplating olefin resin, the volume resistivity of the composition must be less than 103Ω・Fu, so carbon black, carbon fiber, graphite powder, or highly conductive acetylene black, Although raw black and the like (hereinafter referred to as conductive fillers) are blended to improve conductivity, when these conductive fillers are blended, workability tends to decrease and the degree of freedom in molding processing tends to be impaired. Particularly important is the drawback that 1Iiii-1 impact strength, which is the VF 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.

[Purpose of the invention]

The present inventors have completed the present invention as a result of intensive research to solve the above-mentioned drawbacks, and the purpose is to maintain the conventional favorable physical properties of olefin resin compositions for electroplating. At the same time, the objective is to particularly improve fluidity and impact resistance.

[Structure of the invention]

The present invention provides an olefin resin composition for electroplating that has excellent electroplating properties, (fb for 100! - fffi parts of the al olefin resin) 0.5 to 20 parts by weight of oxide of (c)
0.1 to 10 parts by volume of sulfur or sulfur-releasing compound, (cl+
0.05 to 10 parts by weight of vulcanization accelerator, (5 to 60 parts by weight of carbon powder obtained by thermally decomposing a mixture of carbon black and/or an organic polymer substance with carbon bonded in each molecule)
It is characterized by containing 0.5 to 20 parts by weight of (f+blooming inhibitor).

The present invention will be explained in detail below.

(Al As the olefin resin, polyethylene,
Examples include polyzolopylene, a copolymer of ethylene or propylene with a copolymerizable monomer, or a mixture thereof.

(bl) Metal oxides from group Ⅰ of the periodic table are used as vulcanization aids, but the addition ratio is 1 oz of olefin resin.
It is preferably 0.5 to 20 parts by weight. If it is less than 0.5 parts by weight, the effect of achieving complete vulcanization is poor, and if it exceeds 20 parts by weight, precipitation will occur in the resin, making it impossible to obtain proper vulcanization, and plumes may appear on the surface of the composition. Therefore, it is not desirable. As a vulcanization aid, benzyl oxide
J IJum (Be()), Magnenium oxide (MgO
), calcium oxide (CaO), barium oxide (Bad
), cadmium oxide (CaO), zinc oxide (ZnO)
In particular, MgO-ZnO can improve the thermal conductivity of the resin, and when thiurams are used as vulcanization accelerators, they are effective in creating the Zn-dithiocarbamate system and as anti-aging agents. Therefore, it is advantageous.

(c) As the sulfur, sulfur for vulcanization and sulfur for vulcanization can be used. Sulfur releasing compounds include compounds that release sulfur at relatively high temperatures (generally 100-200'C!), such as tetramethylthiuram disulfide. In the case of sulfur-releasing compounds, they are incorporated into the composition in the form of compounds. Sulfur is necessary to improve the adhesion between the plated metal layer and the surface of the molded product, and is added in an amount of 0.1 to 10 Mt per 100 parts by weight of the olefin resin.
fr parts, preferably 0.5 to 2 parts by weight, are added. If the amount of sulfur used exceeds the above range, the pluming will become thicker, the amount of the pluming inhibitor added will become too large, and the physical properties (particularly impact resistance) of the molded product will deteriorate, which is not preferable.

(dl Vulcanization accelerators are vulcanization accelerators generally used in the rubber industry, such as thiazole series, imidacillin series, dithiocarbamate series, thiourite series, thiuram series, sulfenamide series, zuntate series, and guanidine series). vulcanization accelerator, aldehyde type, etc. The addition ratio of the vulcanization accelerator is approximately 0.05 to 10 parts by weight per 100 parts by weight of olefin resin.
It is preferably parts by weight, and more preferably 2 to 71 parts by weight.

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 it exceeds the heavy lid part, it is not preferable because the Izo impact value, tensile strength, etc. of the molded product will deteriorate.

(θ) The conductive filler may be carbon powder obtained by thermally decomposing a mixture of carbon black and an organic polymer material with carbon bonded in its molecules and/or bituminous material (hereinafter referred to as carbon source material). Good pressure.

That is, the conductive filler used in the present invention is
This carbon black is obtained by heat-treating a mixture of the above-mentioned carbon source material and carbon black at a temperature not lower than the thermal decomposition temperature of the carbonaceous liquid crystal constituting the carbonaceous liquid crystal but not higher than the thermal decomposition temperature of the constituent carbonaceous liquid crystal but not by heating the carbon source material.

The carbon source material may be any substance that can essentially become carbon when heat treated, such as polyvinyl chloride, polyacrylonitrile, polystyrene-polyethylene, ethylene-
Vinyl acetate copolymer, styrene-butadiene copolymer,
Polybutadiene, organic molecular substances such as natural rubber, tar,
Bituminous materials such as pitch and asphalt can be drilled. Next, as carbon black, any carbon black is 1
Particularly preferred are tyrene black, which can be used as is, but which has a certain degree of conductivity as it is, and carbon black, such as "Ketjen Black EC" manufactured by Nihon Een Co., Ltd.

The blending ratio of the carbon source material and carbon black described above is
10-40% by weight of carbon source material in carbon black
It would be better if the ratio was as good as the amount of money that was said to be. If the weight ratio is less than 10, the isoelectric performance is not sufficient, and if it exceeds 40M, the coarse particles tend to be large, which is not preferable.

The addition ratio of the conductive filler used in the present invention is preferably 5 to 60 parts by weight per 100 parts by weight of the olefin resin. If the amount is less than 5 M parts, the volume resistivity of the composition will not be less than 103 Ω·cIn, and the volume resistivity of the composition will not be less than 60
If the amount exceeds 1 part by weight, the fluidity of the composition becomes poor and the impact resistance of the molded product decreases, which is not preferable.

(fl) Examples of anti-blooming agents include alkylphenol resins known as tackifiers for rubber and plastics, coumaron resins, rosin visiters, styrene-butadiene block copolymers, etc.
It can be added alone or in combination, but the addition ratio is approximately [],
Preferably, the weight is 55 to 20% by weight.

If it is less than 0.5 parts by weight, the blooming suppressing effect of sulfur will be poor, and if it exceeds 20 parts by weight, no more than a stiffening effect can be expected.

The plating composition of the present invention contains each of the above-mentioned additives, but in addition, it also contains ordinary molding additives such as a fluidity modifier and a heat stabilizer for improving moldability, as necessary. You may let them.

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

[Embodiments of the invention]

Next, embodiments of the present invention will be explained.

Examples 1 to 5, Comparative Examples 1 to 4 As the olefin resin, ethylene-propylene copolymer manufactured by Mitsui Toatsu Chemical Co., Ltd. (Dutch product name: Mitsui Norprene BJHH)
-G) ti was used, pyrolytic carbon powder (A), CB) was used as the conductive filler, M sulfur powder from Kanto Kagaku Co., Ltd. was used as the m yellow, zinc leather (ZnO) was used as the group metal oxide, and Kasho As a promoting Mlj, Iruuchi Shinko Kagaku (8K) [trade name Tsukusela M (thiazole thread)] was used, and as a plumping inhibitor, a styrene-detadiene block copolymer manufactured by Denki Kagaku Kogyo Co., Ltd. (trade name 1sTR-16D2J) was used. As an anti-aging agent, manufactured by Iriuchi Shinko Kagaku Co., Ltd. [Product name: Tsucrak 630F (mixed diallyl paraphenylene diamine)]
Pamba IJ with an internal volume of 1.71 in the proportions shown in the table (parts by weight)
The mixture was kneaded at 200° C. using a No. 5 mixer, and then passed through a roll to obtain a roll sheet, which was 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 has particularly improved fluidity 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.

Substance (2) Pyrolytic carbon (Al...Acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. and vinyl chloride resin (manufactured by Sumitomo Chemical Co., Ltd., trade name [Sumilit GX-A]) in weight proportions. Granulated product mixed at a ratio of 100:25 and baked at 1300°C for 1 hour.

Surface area: 50 m", 7 g (BET method), acetone absorption: 18 CC, 15 g (3) Pyrolytic carbon (B+..."Ketjenblack E (J) manufactured by Japan EC Co., Ltd. and vinyl chloride resin (Sumitomo Chemical) A granulated product prepared by mixing 10D to 25% by weight of [Sumilit EX-Aj] manufactured by Co., Ltd., was baked at 800°C for 1 hour.

Surface area 760 m2/& (BET method), acetone absorption amount 17eC15,9 7Q m2//! 9゛ (BET method), acetone absorption amount 2
3CC15g (5) Ketjen EC... By-product carbon black manufactured by Japan GC (closed) Surface area 910 m''/9 (BET method) ・Press for 10 minutes to obtain a 1-2w thick sheet and determine the length A specimen with a width of 70 nm and a width of 20 mm was prepared.

Dotite (wisteria) was placed on both ends of the specimen. (manufactured by Kura Kasei) to a thickness of 5 mrrr. cloth and heat it at 20°C560% Place in a constant temperature and humidity room for 24'HR. After the elapsed time multimeter (bamboo) Da Riken TR-6856) Resistance was measured. Volume specific The resistance was calculated using the following formula.

However, Ry: Volume resistivity r') cm R: resistance 1iMΩ l': distance between electrodes It was set to 5 kg.

Measured according to JISK-7110 did.

(4) Tensile strength, elongation: Test specimens were prepared using an injection molding machine and evaluated in accordance with JISK-7113.

(5) Pluming property... Volume resistivity 11
Place a standard test piece in the bottom of an enamel container, leave it in a blow dryer at 50℃, and visually observe the surface of the test piece on the bottom side of the enamel container over time. First, blooming of sulfur fish meal is confirmed. The light was indicated by the number of days it was left unused.

(6) Metsky's secret... 1o by press Seichin
oxio.

A flat plate with an adhesion strength of 2 mm was prepared, and the surface of this plate was degreased with alkaline water using a 5x lid of an aqueous solution of phosphoric acid, and then nickel sulfate was added at 2509/l and nickel chloride was added at 509/l-boric acid. Electroplating was performed at a temperature of 50°C in a bath containing 30 &/l of pH 4 to form a nickel layer of several microns, and further containing copper sulfate of 200 μ/l and sulfuric acid of 50 g/l as main components, with a pH of 1. Plating is carried out in a copper plating bath of No. 7 so that the thickness in the copper plating bath is about 20 microns. The specimen cake 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. The appearance of the mask (whether there were any abnormalities such as puffiness) was observed in children with eyes.

〔Effect of the invention〕

As mentioned above, the olefin resin composition for electroplating of the present invention has conventional favorable physical properties by containing a specific electroplating filler in the olefin subside together with other constituent components. It is excellent in that it significantly improves fluidity and impact resistance while maintaining the same properties.

Patent applicant: Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] (k+1 for 100 parts by weight of at olefin resin)
Metal oxides of group Ⅰ of the periodic table 0.5 to 20 parts, (C
) 0.1 to 10 parts by weight of shinhuang or shinhuang releasing compound, (di
0.05 to 10 parts by weight of a vulcanization accelerator, (θ) an organic polymeric substance with carbon bonded in its molecule, and/or carbon powder obtained by thermally decomposing a mixture of bituminous material and carbon black.
An olefin resin composition for electroplating, characterized in that it contains 60 parts by weight and 5 to 20 parts by weight of an f+ bloom inhibitor.