JPS60116764A - Molded article having metallic thin film - Google Patents

Abstract

PURPOSE:To obtain a plated molded article of plastics provided with satisfactory heat resistance, mechanical strength and electric characteristics by using a 3- methylbutene-1 polymer as plastics on which a metallic thin film is formed. CONSTITUTION:A metallic thin film is formed on a molded article of a 3-methylbutene-1 homopolymer or a copolymer of 3-methylbutene-1 with 2-12C alpha-olefin and/or polyene. Unlike other polyolefin said polymer has very high adhesive strength to the metallic thin film, and the polymer is provided with high heat resistance, mechanical strength and electric characteristics, so the desired molded article can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molded article comprising a 3-methylbutene-7 polymer or copolymer coated with a metal thin film layer.

In recent years, plated plastics with excellent heat resistance, mechanical strength, and electrical properties have become increasingly important in many fields including electrical and electronic parts.

Conventionally, when it comes to plating plastics, ABS resin has been the main ingredient, and its uses have mostly been from the viewpoint of metallic decoration, and the heat resistance, electrical properties, etc. of the plated material have not been given much importance.

On the other hand, the above-mentioned plated plastics with excellent heat resistance, mechanical strength, and electrical properties are used for connectors, printed wiring boards produced by additive method,
Examples include magnetic recording systems using dry plating methods such as vapor deposition methods, and when ABS resin is used for these applications, it may be insufficient in heat resistance, mechanical strength, or electrical properties. There has been a desire for a plated plastic material that combines these three properties.

The present inventors have made extensive studies in order to obtain a plated plastic material that has the above-mentioned properties, and have focused on polyolefin resins in particular because of their good electrical properties.

Conventionally available polyolefins such as polyethylene, polypropylene, polybutene, polygmetherpentene, etc., have good electrical properties, but they all have insufficient heat resistance and poor adhesion of metal layers. It's not enough.

Therefore, the present inventors investigated poly-3-methylbutene-/, which is a crystalline polyolefin that is said to exhibit a high melting point, and surprisingly found that poly-3-methylbutene-// is similar to other polyolefins. The present invention was achieved by discovering that a molded product with very good adhesion to the metal layer Q can be obtained using a method different from the above.

That is, the present invention is a ``homopolymer of 3-methylbutene-/'', in which a metal thin film layer is applied to a copolymer of 3-methylbutene-7 and an a-olefin and/or polyene having a carbon number of λ to 7.2. "Articles".

The present invention will be explained.

Poly-3-methylbutene used in the present invention
is a homopolymer of 3-methylbutene// or a copolymer of 3-methylbutene// and an a-olefin and/or polyene having 7.2 to 7.2 carbon atoms. Number of carbon atoms copolymerized with 3-methylbutene-/! Examples of α-olefins in ~7.2 include ethylene, propylene, butene/, hexene/, comethylpentene/, octene/, styrene, vinylchlorohexane, etc., and examples of the polyene include butadiene. , hexadiene, methylhexadiene, ethyl dennorbornene, and the like. The copolymerization method may be so-called random copolymerization or block copolymerization.

Among these, preferable are homopolymers of 3-methylbutene-/, random copolymers of 3-methylbutene-/and ethylene or propylene, block copolymers, 3-methylbutene-/
It is a copolymer of methylbutene/and a small amount of diene.

The content of these copolymerized components in the polymer is preferably 0% by weight or less, and more preferably 20% by weight or less.

Regarding the molecular weight of the copolymer, there is a trade-off with moldability, but from the viewpoint of mechanical properties it is desirable that the molecular weight be as high as possible.

For example, in terms of melt viscosity, it is preferably 103 Meares or more, more preferably 104 to 107, as measured with a disc-shaped rotary rheometer at 330°C and an angular velocity of 0.122777 seconds.

Various known methods can be used for polymerization, but when polymerization is carried out using the time-controlled catalyst system described below, 3-megbutene, which has a high molecular weight and good mechanical properties, is produced compared to other methods. /Polymer is obtained.

Regarding mechanical strength, the required value varies depending on the application, so
Although not necessarily considered to be an essential condition of the present invention, if high mechanical strength is required for the pulp, the catalyst system described below may be used.
Preferably, 3-methylbutene/polymer is used.

As such a catalyst system, for example, JP-A-57-/Otsu, 2
Examples include catalyst systems described in 9g, 76/ri6, 5t-ifsλOX, and the like. For example, four jiCa
titanium chloride in the presence of ether with the general formula AIRnXa-n
(In the formula, R is a hydrocarbon group with carbon number/~20, n is/
The number of ~3, X represents a].rogen atom. ) at 130°C.
Finely divided solid titanium trichloride obtained by contacting with a liberating agent such as a Lewis acid at the following temperature is preferably used.

These catalysts are used in combination with organoaluminum. Polymerization conditions are not particularly limited.

Metals used in the present invention include copper, solder,
Examples include silver, tin, nickel, gold, and ronram.

The method of applying the metal layer in the present invention can be either a wet method or a dry method using conventionally known techniques. Dry methods include vapor deposition, spackling, etc. Although there are no particular restrictions on the process, for example, the most commonly used wet plastic plating process, which involves degreasing, etching, catalyticization, activation, chemical locking, and electroplating, is sufficient to achieve sufficient plating. It is possible. Although a plated film with good adhesion can be obtained by this known method, a plated product with even better adhesion can be obtained by using a hydrocarbon compound in the degreasing or pretreatment step. Hydrocarbon compounds include aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as tetralin, or these 7.
Among them, aromatic compounds and hydrocarbons are preferable.

The metal film thickness is preferably 0.0/~100μ.

The polyolefin in the present invention may contain known additives that are added to polyolefin in order to improve the processability or physical properties of polyolefin, such as stabilizers, dispersants,
Pigments, flame retardants, inorganic or organic fillers, polymers, etc. may be added.

Applications of the metal plating obtained by the present invention include automobile parts, electrical and electronic parts, miscellaneous goods, etc. as mentioned above, but among them, injection moldable printed circuit boards that take advantage of the heat resistance of polyolefin are promising. It is.

Examples will be shown below, but the present invention is not limited to the examples.

In the examples, the adhesion of the metal thin film was tested as follows. That is, by peeling off the cellophane tape attached to the surface of the metal-plated pressed piece, we observed how the plated metal peeled off, and as follows: A, 13. It was evaluated by Hiro rank of O and D.

8-No peeling at all D-Completely peeling Production example/(Production of solid titanium trichloride catalyst complex) (A) Production of homogeneous titanium trichloride solution Dry argon-substituted four with a capacity of 300 me Purified toluene itOme and titanium tetrachloride in a flask.
ol and further add di-n-butyl ether 9 Q f
flmol was added. Titanium tetrachloride and di-n-butyl ether reacted with some heat and were uniformly dissolved in toluene to obtain an orange-yellow homogeneous solution. The solution was stirred 2
While maintaining the temperature at j℃, add diethylaluminum monochloride to this≠! When a solution dissolved in λ0 mg of toluene was gradually added, a dark orange homogeneous liquid of titanium trichloride was obtained.

(B) Precipitation formation of titanium trichloride and production of catalyst (A+
When the homogeneous solution of titanium trichloride obtained in the step was heated to S° C., a purple precipitate of titanium trichloride was observed during the temperature rise. The precipitate was separated and washed five times with too ml of r]-heptane to obtain a fine particulate purple titanium trichloride catalyst complex. Elemental analysis reveals that this catalyst complex has the formula Ti0J! 3 (Aj2cA3)0.00
It had a composition of 4C(nc4Ho)20: ] 0.05.

Example/ 3-Methylbutene-
The polymerization of / is carried out as follows. In an autoclave thoroughly dried under vacuum and purged with nitrogen, the solid trichloride technocatalyst complex obtained in Production Example 8/7.679 and di-yne-butylaluminum monochloride were added to λ at 1 mH.
I prepared lo:l. Then, liquefied 3-methylbutene/213Y was charged and polymerization was carried out at 1.20° C. for 7 parts and hours. Next, normal haegisan 5ooal for 4 people and 30
After stirring at ℃ for 30 minutes, the supernatant liquid was extracted and the catalyst component 6 in the polymer was removed. After repeating this operation three times, the resulting poly-3-methylbutene/slurry was taken out and dried, resulting in a white powdery poly-3-methylbutene//.
</, 3g was obtained.

At this time, the catalytic efficiency (fI・poly3-methylbutene-
//7・catalyst) was 29. Irganox TO10 was added as an additive to the obtained poly-3-methylbutene-/
o, x parts, Irgafos) p-E-pcr, o, 2 parts (all manufactured by Ciba Geigy, Japan) were added, and then 3g press-molded test pieces were prepared at 0°C and copper plated. I did it. The copper plating process is shown below.

After treating the test piece in Tetralin at 700°C for 3 minutes,
It was washed with ethanol for 7 minutes at room temperature and then with hot water for 1 minute at ≠θ°C. Next, crotic acid mixture (ty-00V C!
r02. + tt00f/H2SO4/l) in 7
After processing for 10 minutes at 0°C, wash with water and then add 3 inches of HO.
12 aqueous solution. Further, each sample was treated with Okuno Seiyaku 2 I = Gyosha's neutralizing agent "B-noOO Neutralizer" and "rTMP Neutralizer" at room temperature for 2 minutes. A water washing step was added between each step.Next, the mixture was treated with "Catalyst C" manufactured by Okuno Pharmaceutical Co., Ltd. for 3 minutes at room temperature, and then washed with water. ~ 3 minutes treatment J4i!, L rlr water 6 ~, then g at room temperature
Electroless copper plating was performed for minutes. The plating solution used was manufactured by Okuno Pharmaceutical Co., Ltd. [chemical copper @10OB J/00ral
, and [chemical copper #10OA j /θOrne with pure water 41. o Added to Orne (2 marks 11!! Notice).

The film thickness was θ0gμ.

Water 61': After evaluation of the adhesion of the plating film, it was found to be palatable.

In addition, poly-3-methylbutene-
Melting point of / manufactured by Seiko Electronics Co., Ltd. DSC-! Melting point (TM) was 307° C. when measured using θ type I7.

In addition, when the dielectric voltage was measured using a horizontal Heulet Percad Automatenku Capacitance IJ Tsujigno 70A model, it was 20℃, / K, Hz.
-/θOKH2 range tanδ=0.000/~o,
It showed a very small value of oooa.

Further, this plated product was kept at 750° C. for 30 minutes, but there was no change in appearance and the heat resistance was good.

Example - Example -/, except that in Example -/, a small amount of ethylene was introduced every 5 minutes at the same time as the polymerization was started, and 3-80% by weight of ethylene was introduced relative to the total amount of polymer produced for copolymerization. I did exactly the same thing. The obtained copolymer was Haru Otsu 7.

The TM of this copolymer was 300° C., and the adhesion of the plating film was Parank.

Example-3 In implementation flJ-/, 34t of vinylchlorohexane
, except that Yo2 was introduced at the initial stage of polymerization and copolymerized.
I did exactly the same thing. The obtained copolymer was 37. Jf/
Met.

The TM of this copolymer was 30/°C, and the adhesion of the plating film was Parank.

Example - Example 1 was conducted in exactly the same manner as Example -/, except that electroless nickel plating was applied to the electroless copper plating 9 in Example -/.

The plating solution used was ``TMP New Kagaku Nickel'' manufactured by Okuno Pharmaceutical Co., Ltd.

The thickness of this nickel plating film is 0.7μ, and the adhesion is L.
It was fiA rank.

Comparative Example-/Example-/Instead of poly-3-methylbutene-/, polypropylene manufactured by Mitsubishi Kasei Co., Ltd., Tsuvatenku P1 was used.
Electroless copper plating was performed in exactly the same manner as in Example 7, except that ≠θoE was used and press molding was performed at 230°C.

The adhesion of the Menki film was ranked D.

Comparative Example 2 Electroless copper plating was carried out in exactly the same manner as in Comparative Example 1, except that in Comparative Example 1) K Mitsubishi Rayon ABS (Diapent ABs3oo1M) made of polypropylene was used.

The adhesion of the plating was excellent.

On the other hand, the Vicat softening point of Diapet ABS300/M (
ISOR-31,0, J Engineering 5K6f7o) The temperature was 6°C.

In addition, this plated product was heated at 760°C for 30 minutes as in the example.
When held for a minute, the profiteering melted and deformed.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase = (7 others)

Claims (1)

[Claims] (1) Molded product with a metal thin film layer applied to a homopolymer of 3-methylbutene or a copolymer of 3-methylbutene and an α-olefin and/or polyene having 7.2 to 7.2 carbon atoms