KR20160080957A

KR20160080957A - Eco-friendly and excellent in electro-plating properties of thermoplastic resin composition

Info

Publication number: KR20160080957A
Application number: KR1020140193715A
Authority: KR
Inventors: 이섭주; 김동환; 이완성; 김형진
Original assignee: 금호석유화학 주식회사
Priority date: 2014-12-30
Filing date: 2014-12-30
Publication date: 2016-07-08
Also published as: KR101900270B1; TW201623420A; WO2016108461A1; TWI573831B

Abstract

In one embodiment of the present invention, 55 to 65 parts by weight of a diene rubber polymer and 35 to 45 parts by weight of a monomer mixture in which the aromatic vinyl monomer and the vinyl cyan monomer are mixed at a weight ratio of 60 to 80: 20 to 40, respectively, 1 to 20% by weight of a graft copolymer; 50 to 75% by weight of a first copolymer obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80: 20 to 40, respectively; And 2 to 8% by weight of a conductive filler.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition which is environmentally friendly and which has excellent plating properties. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a thermoplastic resin composition that is environmentally friendly and has excellent plating properties.

In general, a molded product (plastic) molded with a thermoplastic resin is plated and used in many cases. Of these, ABS (acrylonitrile-butadiene-styrene) resin is widely used because of its excellent moldability and plating properties.

As a method for plating a plastic surface, there has been proposed a method of depositing a metal catalyst nucleus on a plastic surface, treating the surface with a dilute acidic solution, electroless copper or electroless nickel plating to form a conductive film, and then electroplating It is commonly used.

However, formaldehyde, which is a carcinogenic substance, is contained in the plating solution used for electroless copper plating, which can adversely affect the worker. In order to dissolve copper ions in the alkaline solution during the production of the copper plating solution, a solution such as EDTA (ethylene diamine tetraacetic acid) Since a strong complexing agent is used, many processes such as filtration, activated carbon treatment, and ion exchange are required to remove copper ions in the wastewater treatment step, thereby lowering the process efficiency.

Further, since the hypophosphite included in the plating solution used for the electroless nickel plating is oxidized and converted to the phosphite, environmental regulation on the phosphorus component may be disadvantageous, and the COD of the plating process wastewater may be high, have.

Accordingly, it is necessary to develop a thermoplastic resin composition capable of appropriately responding to problems such as deterioration of health of a worker, environmental pollution, and lowering of process efficiency occurring in a plastic plating process.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide an environmentally friendly thermoplastic resin composition which is excellent in plating properties when electroplating to form a metal film or an alloy film and does not require electroless plating will be.

In order to accomplish the above object, one aspect of the present invention is to provide a rubber composition comprising 55 to 65 parts by weight of a diene-based rubbery polymer, a mixture of aromatic vinyl monomers and vinyl cyan monomers in a weight ratio of 60 to 80:20 to 40, 20 to 45% by weight of a first graft copolymer graft-polymerized in an amount of 45 parts by weight; 50 to 75% by weight of a first copolymer obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80: 20 to 40, respectively; And 2 to 8% by weight of a conductive filler.

In one embodiment, the grafting rate of the first graft copolymer may be 30-40%.

In one embodiment, the thermoplastic resin composition comprises 45 to 55 parts by weight of a diene rubber polymer, 45 to 55 parts by weight of a monomer mixture in which the aromatic vinyl monomer and the vinyl cyan monomer are mixed at a weight ratio of 60 to 80: 20 to 40, And 1 to 12% by weight of a graft-polymerized second graft copolymer.

In one embodiment, the grafting rate of the second graft copolymer may be 65-75%.

In one embodiment, the first copolymer may have a weight average molecular weight of 100,000 to 150,000.

In one embodiment, the thermoplastic resin composition comprises 1 to 25% by weight of a second copolymer having an aromatic vinyl monomer and a vinyl cyan monomer copolymerized at a weight ratio of 60 to 80:20 to 40 and having a weight average molecular weight of 80,000 to 100,000, As shown in FIG.

In one embodiment, the diene-based rubbery polymer may be polybutadiene or polyisoprene.

In one embodiment, the aromatic vinyl monomer is selected from the group consisting of styrene, alpha methyl styrene, alpha ethyl styrene, vinyl toluene, para bromostyrene, para chlorostyrene, tert-butyl styrene, dimethyl styrene, Lt; / RTI >

In one embodiment, the vinyl cyan monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures of two or more thereof.

In one embodiment, the conductive filler may be one selected from the group consisting of carbon nanotubes, fullerene, graphene, graphite, carbon fiber, and a mixture of two or more thereof.

According to one aspect of the present invention, the conductive filler is added to the thermoplastic resin composition to impart conductivity, thereby omitting the electroless plating process at the time of plating, thereby improving the environment friendliness and plating characteristics.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an SEM image of a thermoplastic resin composition of Example 3 and a plated layer of copper-plated plastic prepared therefrom.
2 is an SEM image of a thermoplastic resin composition of Comparative Example 2 and a plated layer of a copper-plated plastic produced therefrom.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

One aspect of the present invention relates to a rubber composition comprising 55 to 65 parts by weight of a diene rubber polymer and 35 to 45 parts by weight of a monomer mixture in which the aromatic vinyl monomer and the vinyl cyan monomer are mixed at a weight ratio of 60 to 80:20 to 40, 20 to 45% by weight of a graft copolymer; 50 to 75% by weight of a first copolymer obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80: 20 to 40, respectively; And 2 to 8% by weight of a conductive filler.

(One) Graft Copolymer

(1-1) First Graft Copolymer

The graft copolymer is obtained by graft-polymerizing 55 to 65 parts by weight of a diene-based rubbery polymer and 35 to 45 parts by weight of a monomer mixture in which the aromatic vinyl monomer and the vinyl cyan monomer are mixed at a weight ratio of 60 to 80:20 to 40, respectively And the content thereof may be in the range of 20 to 45% by weight based on the total weight of the thermoplastic resin composition.

Examples of the diene-based rubbery polymer include butadiene-aromatic vinyl compound copolymers such as polybutadiene, butadiene-styrene copolymer and butadiene-vinyl toluene copolymer; Or a butadiene-vinyl cyanide copolymer such as a butadiene-acrylonitrile copolymer or a butadiene-methacrylonitrile copolymer may be used, but two or more of these may be used in combination if necessary.

If the content of the diene rubber polymer is less than 55 parts by weight, the content of the rubber latex in the thermoplastic resin composition may be decreased and the mechanical properties such as impact strength may be deteriorated. When the amount is more than 65 parts by weight, So that moldability and plating adhesion may be deteriorated.

The diene-based rubbery polymer is preferably prepared by emulsion polymerization in consideration of ease of particle diameter control, but not limited thereto, and catalysts and emulsifiers used in emulsion polymerization may be used.

The graft copolymer is obtained by graft-polymerizing the monomer mixture to the diene rubber-like polymer, and the polymerization method for producing the graft copolymer is a known method such as emulsion polymerization, suspension polymerization, solution polymerization, May be used alternatively or in combination of two or more.

In the graft polymerization, the monomer mixture may be administered together with known emulsifiers, polymerization initiators, catalysts, etc., and may be continuously administered for a predetermined time, if necessary. The graft copolymer first obtained by the above graft polymerization may be in the form of a latex, which may be treated with an acid or a salt, followed by coagulation and drying to finally obtain a powdery solid.

The monomer mixture may be a mixture of an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80:20 to 40, respectively, and if necessary, a monovinyl monomer copolymerizable with the aromatic vinyl monomer and the vinyl cyan monomer may be added in a range of 0 to 20% It may be mixed.

If the content of the vinyl cyan monomer is less than 20% by weight based on the total weight of the monomer mixture, it is hard to be kneaded with the SAN resin produced by the bulk or solution polymerization method, and the impact strength of the final molded product, Even if the weight% is exceeded, it is difficult to be kneaded with the SAN resin produced by the bulk or solution polymerization method, and the surface properties may be deteriorated due to yellowing at high temperature molding.

Wherein the aromatic vinyl monomer is one selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, vinyltoluene, para-bromostyrene, para-chlorostyrene, tert-butylstyrene, dimethylstyrene, And preferably styrene, but is not limited thereto.

The vinyl cyan monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and a mixture of two or more thereof, preferably acrylonitrile, It is not.

Also, the monovinyl monomer may be at least one selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methylmethacrylate, methyl acrylate, butyl acrylate, Acid anhydrides, and mixtures of two or more thereof.

The graft ratio of the graft copolymer may be 30 to 40%, and when the graft ratio of the graft copolymer is out of the range, the degree of dispersion of the thermoplastic resin composition may be lowered and the formability and the plating adhesion may be lowered .

(1-2) Second Graft Copolymer

On the other hand, when 45 to 55 parts by weight of the diene rubber polymer, and 45 to 55 parts by weight of the monomer mixture in which the aromatic vinyl monomer and the vinyl cyan monomer are mixed at a weight ratio of 60 to 80: 20 to 40, respectively, 1 to 12% by weight of a graft copolymer. That is, the same graft copolymer may be used singly, and if necessary, a different kind of diene rubber polymer may be mixed and used. Specifically, by using the graft copolymer having a relatively small content of the diene-based rubbery polymer in combination, the adhesion of the plating can be further improved.

If the content of the graft copolymer exceeds 12% by weight based on the total weight of the thermoplastic resin composition, the plating adhesion and plating appearance of the final molded product may be deteriorated.

When the graft ratio of the second graft copolymer is out of the above range, the degree of dispersion of the thermoplastic resin composition is lowered and the moldability and the plating adhesion are lowered .

In addition, the types and contents of the aromatic vinyl monomer and the vinyl cyan monomer are as described above.

(2) Copolymer

(2-1) First copolymer

The copolymer may be an aromatic vinyl monomer and a vinyl cyan monomer copolymerized in a weight ratio of 60 to 80:20 to 40, respectively, and the content thereof may be 50 to 75% by weight based on the total weight of the thermoplastic resin composition . The kind and content of the aromatic vinyl monomer and the vinyl cyan monomer are as described above.

When the content of the copolymer is in the range of 50 to 75% by weight, the impact strength and the plating adhesion of the plastic molded body as the final product can be improved, and the expansion of the plated film can be prevented by suppressing the increase of the linear expansion coefficient.

On the other hand, the weight average molecular weight of the copolymer may be from 100,000 to 150,000. If the weight average molecular weight of the copolymer is less than 100,000, the impact strength of the final molded product may be deteriorated. If the weight average molecular weight is more than 150,000, Resulting in deterioration of moldability and plating adhesion.

(2-2) Second copolymer

On the other hand, the thermoplastic resin composition further comprises 1 to 25% by weight of a second copolymer having an aromatic vinyl monomer and a vinyl cyan monomer copolymerized in a weight ratio of 60 to 80:20 to 40, respectively, and having a weight average molecular weight of 80,000 to 100,000 . That is, the same type of copolymer may be used singly, and if necessary, different kinds of polymers having different weight average molecular weights may be mixed and used. Specifically, by using a copolymer having a relatively small weight average molecular weight, a moldability, a plating appearance, and a plating adhesion can be further improved.

If the content of the copolymer is more than 25% by weight based on the total weight of the thermoplastic resin composition, the impact strength of the plastic molded article as a final product may be lowered.

(3) Conductivity filler

The thermoplastic resin composition may include an electrically conductive filler, and the content thereof may be 2 to 8% by weight based on the total weight of the thermoplastic resin composition. Since the conductive filler can impart conductivity to the thermoplastic resin composition and the plastic molded article itself produced from the thermoplastic resin composition, the electroless plating process can be omitted at the time of plastic plating, thereby enhancing the eco-friendliness of both the product and the process And, in particular, the process efficiency can be greatly improved.

However, the content of the conductive filler in the thermoplastic resin composition can be controlled to a certain range, for example, 2 to 8 wt%. If the content of the conductive filler is less than 2 wt%, the effect of imparting conductivity is weak, If the content of the graft copolymer is less than 8% by weight, the relative content of the graft copolymer and the copolymer may be decreased, so that the impact strength of the final molded product may be deteriorated. The dispersion degree may be lowered.

The conductive filler may be one selected from the group consisting of carbon nanotubes, fullerene, graphene, graphite, carbon fiber, and a mixture of two or more thereof. Preferably, Nanotubes, and more preferably, multi-walled carbon nanotubes in consideration of commercial availability and economical efficiency. However, the present invention is not limited thereto.

(4) Other additives

In addition to the graft copolymer, the copolymer and the conductive filler, the thermoplastic resin composition may further contain a certain amount of additive, if necessary.

As the additive, commonly used stabilizers; slush; Metal soap; Ultraviolet absorber; Plasticizers; Colorants (pigments, dyes); Carbon fiber or glass fiber; Talc, wollastonite, calcium carbonate, silica, wood powder and the like; Flame retardant; Drip inhibitor; Antimicrobial agents; Antifungal agents; Coupling agents; And mixtures of two or more thereof, but is not limited thereto.

Particularly, the flame retardant plays a role of imparting flame retardancy to the thermoplastic resin composition having poor thermal and flame resistance. The halogen flame retardant, the inorganic flame retardant, the phosphorus flame retardant, and the melanin flame retardant may be used depending on the components.

The halogen-based flame retardant may be classified into a bromine-based flame retardant and a chlorine-based flame retardant. The bromine-based flame retardant can achieve excellent flame retardant effect even in a small amount, but it is impossible to recycle the plastic, and toxic environmental pollutants such as dioxin are discharged during combustion.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc stannate, molybdate, guanidine, and zirconium. Of these, aluminum hydroxide has advantages of low toxicity, low ductility, excellent electrical insulation and low cost, but it can be applied only to plastics having a decomposition temperature of 180 to 220 캜 and a low processing temperature, and must be applied in a large amount in order to impart flame retardancy Therefore, the mechanical properties and processability of the plastic material may be deteriorated.

The phosphorus flame retardant includes, for example, ammonium phosphate, ammonium polyphosphate, and haloalkyl phosphate. The phosphorus flame retardant exhibits an excellent flame retardant effect in the solid phase reaction, and is particularly effective for plastics containing a large amount of oxygen.

Examples of the melanin-based flame retardant include melanin phosphate, melanin cyanurate, and melanin phosphate. The melanin-based flame retardant is free from the generation of toxic gases, and the amount of soot generated during combustion is small, so there is little risk to the environment.

Hereinafter, embodiments of the present invention will be described in detail.

Example One

34 parts by weight of a first ABS resin having a polybutadiene rubber content of 59% by weight, a grafting ratio of 35% and a weight average molecular weight of 150,000, 68% by weight of styrene and 32% by weight of acrylonitrile, 63 weight parts of a first SAN resin having an index of 12 (230 占 폚, based on 3.8 kg), and powder-type multi-walled carbon nano-powder having an average diameter of 8 to 15 nm, an average length of 26 占 퐉 and an apparent specific gravity of 0.020 to 0.026 g / 3 parts by weight of the tube was added to a Henschel mixer and blended for 3 minutes, followed by melt-kneading using a 32 mm? Extruder (cylinder set temperature 250 占 폚) and cutting to prepare a thermoplastic resin composition for direct plating in the form of pellets.

Example 2

24 parts by weight of a first ABS resin and 10 parts by weight of a second ABS resin having a polybutadiene rubber content of 50% by weight, a graft ratio of 70% and a weight average molecular weight of 80,000 were used as the ABS resin. 1, a thermoplastic resin composition was prepared.

Example 3

50 parts by weight of the first SAN resin, 50 parts by weight of styrene, and 32 parts by weight of acrylonitrile, and having a weight average molecular weight of 95,000 and a melt index of 27 (230 DEG C, based on 3.8 Kg) Except that 13 parts by weight of SAN resin was used in combination.

Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the amounts of the first SAN resin and the powder type multi-walled carbon nanotubes were changed to 62 parts by weight and 4 parts by weight, respectively.

Example 5

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the amounts of the first SAN resin and the powder-like multi-walled carbon nanotubes were changed to 61 parts by weight and 5 parts by weight, respectively.

Comparative Example One

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the dose of the first ABS resin was changed to 37 parts by weight and the powdery multi-walled carbon nanotubes were not administered.

Comparative Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the dosage amounts of the first ABS resin and the powder type multi-walled carbon nanotubes were changed to 36 parts by weight and 1 part by weight, respectively.

Comparative Example 3

The thermoplastic resin composition was prepared in the same manner as in Example 2 except that the amounts of the first and second ABS resins were changed to 20 parts by weight and 14 parts by weight, respectively.

Comparative Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the amounts of the first ABS resin and the powder type multi-walled carbon nanotubes were changed to 27 parts by weight and 10 parts by weight, respectively.

The dose of each component in Examples 1 to 5 and Comparative Examples 1 to 4 is shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The first ABS 34 24 24 24 24 37 36 20 27 The second ABS - 10 10 10 10 - - 14 - First SAN 63 63 50 62 61 63 63 63 63 Second SAN - - 13 - - - - - - CNT 3 3 3 4 5 - One 3 10

(Unit: parts by weight)

Experimental Example

The thermoplastic resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were introduced into an injection molding machine (electromotive type 250 tons, LSIS) and subjected to molding at a cylinder set temperature of 200 占 폚 and a mold temperature of 60 占 폚, 100x100x3 mm) was prepared. The specimens were immersed in a cleaner at 40 DEG C for 3 minutes and then degreased. Thereafter, the substrate was washed with water at 20 占 폚 and immersed in an etching solution (chromic acid 400 g / l, sulfuric acid 400 g / l) at 69 占 폚 for 10 minutes and etched. The specimen was then rinsed with water at 20 DEG C, pre-dipped in 35% aqueous hydrochloric acid at 35 DEG C for 1 minute, and the specimen was rinsed with 20 DEG C water.

The washed specimens were electroplated at room temperature for 60 minutes to form a copper plating film having a thickness of 30 to 50 μm, washed with water at 20 ° C. and dried at 80 ° C. for 2 hours to prepare copper plating specimens. The impact resistance, plating adhesion, and plating appearance of each of the prepared samples were evaluated according to the following methods, and the results are shown in Table 2 below.

- Impact resistance: Izod impact strength according to ASTM D256 was evaluated.

Plating adhesion: The copper plated specimen was cut to a width of 10 mm, and the copper plated film was peeled from the test piece at an angle of 90 degrees to evaluate its strength (filling strength).

- Plating Appearance: The surface of the copper plating specimen was visually evaluated.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Impact strength
(J / m) 20 18 15 14 10 30 25 22 Less than 4 Plated
Adhesiveness △ ○ ○ ○ △ X X △ X Plated
Appearance ○ ○ ○ ○ ○ X △ △ X
1. Evaluation criteria of coating adhesion
-?: Not less than 7 N / cm; DELTA: 4 N / cm or more and less than 7 N / cm; X: less than 4 N / cm

2. Evaluation criteria for plating appearance
- & cir &: plating unevenness observation, plating film uniformity; ?: No plating observation or plated film unevenness; X: no plating observation, plated film unevenness

Referring to Tables 1 and 2 and FIGS. 1 and 2, when a carbon nanotube as a conductive filler is added to a thermoplastic resin composition, the impact strength is somewhat reduced, but the plating adhesion and plating appearance are improved (Example 1 , Comparative Example 1). When the dose of the carbon nanotubes was less than 2 parts by weight or more than 8 parts by weight, the plating adhesion and the plating appearance were greatly reduced (Comparative Examples 2 and 4).

Further, when the first and second ABS resins or the first and second SAN resins having different properties were used in combination, the adhesion of the plating was further improved (Examples 2 to 5), the dose of the second ABS resin was 12 It was confirmed that the plating adhesion and the plating appearance were deteriorated (Example 2, Comparative Example 3).

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims

55 to 65 parts by weight of a diene rubber polymer and 20 to 40 parts by weight of an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80:20 to 40, 45% by weight;
50 to 75% by weight of a first copolymer obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80: 20 to 40, respectively; And
And 2 to 8% by weight of a conductive filler.

The method according to claim 1,
Wherein the graft ratio of the first graft copolymer is 30 to 40%.

The method according to claim 1,
45 to 55 parts by weight of a monomer mixture obtained by mixing 45 to 55 parts by weight of a diene rubber polymer and 60 to 80: 20 to 40 parts by weight of an aromatic vinyl monomer and a vinyl cyan monomer, And 1 to 12% by weight of a graft copolymer.

The method of claim 3,
And the graft ratio of the second graft copolymer is 65 to 75%.

The method according to claim 1,
Wherein the first copolymer has a weight average molecular weight of 100,000 to 150,000.

6. The method of claim 5,
The thermoplastic resin composition further comprises 1 to 25% by weight of a second copolymer having an aromatic vinyl monomer and a vinyl cyan monomer copolymerized in a weight ratio of 60 to 80:20 to 40 and having a weight average molecular weight of 80,000 to 100,000 By weight of the thermoplastic resin composition.

The method according to claim 1,
Wherein the diene-based rubbery polymer is polybutadiene or polyisoprene.

The method according to claim 1,
Wherein the aromatic vinyl monomer is one selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, vinyltoluene, para-bromostyrene, para-chlorostyrene, tert-butylstyrene, dimethylstyrene, Wherein the thermoplastic resin composition is a thermoplastic resin composition.

The method according to claim 1,
Wherein the vinyl cyan monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures of two or more thereof.

The method according to claim 1,
Wherein the electrically conductive filler is one selected from the group consisting of carbon nanotubes, fullerene, graphene, graphite, carbon fibers, and a mixture of two or more thereof.