KR20190064321A - Manufacturing method for conductive composite resin, conductive composite resin and manufacturing method for the conductive composite resin - Google Patents

Abstract

The present invention relates to a method for preparing a conductive composite resin which comprises the steps of: (A) preparing a mixed solution by mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant, and phenylenediamine in an aqueous solution of alcohol or ketone; (B) preparing a polymerization product by inputting an oxidizing agent to the mixed solution and polymerizing the same; (C) obtaining a conductive nanocomposite by washing the polymerization product with a polar cleaning solvent, and filtering and drying the washed polymerization product; and (D) preparing a conductive composite resin by mixing the conductive nanocomposite with a thermoplastic resin. Accordingly, provided is the method for preparing a conductive composite resin, capable of preventing agglomeration and enhancing dispersion while improving a degree of polymerization, yield, and dispersion of the conductive nanocomposite, such that a surface resistivity of the conductive composite resin is lowered while conductivity and appearance thereof are enhanced.

Description

TECHNICAL FIELD The present invention relates to a conductive nanocomposite, a conductive composite resin, and a method for manufacturing the conductive nanocomposite, a conductive composite resin, and a method for manufacturing the conductive nanocomposite.

The present invention relates to a conductive nanocomposite manufacturing method, a conductive composite resin, and a manufacturing method thereof.

Generally, a composite resin is a resin prepared by compounding a thermoplastic resin with a mixture of different kinds of polymers, fillers, or functional additives, and means a resin having enhanced or modified physical properties as compared with a conventional thermoplastic resin.

One of such composite resins is a conductive composite resin. Recently, as the demand for electrical and electronic products has increased rapidly, there has been an increasing demand for composite resins having various electrical properties.

Conductive composite resins are manufactured in a wide variety of ways depending on the desired properties, and a method of manufacturing conductive materials by mixing them with a thermoplastic resin is well known. The conductive material may be a metallic material, a carbon-based material, a polymeric material, or the like. Depending on the characteristics of the conductive material, the manufacturing method and the use of the conductive composite resin to be implemented may be determined very differently.

As one example, a conductive hybrid resin using a polyolefin as a thermoplastic resin uses carbon black, carbon nanotubes, metal oxide particles, or the like as a conductive material in order to realize an antistatic function and an electrostatic discharge function. However, the conventional method using the conductive material has a high water dependence, and there are limitations on application due to problems such as dust and migration. Recently, attention has been paid to a technique of using a conductive nanocomposite prepared by using a polymer material capable of realizing electrical characteristics as a conductive material.

Conductive nanocomposites are made of nanoscale structures and thus can achieve excellent electrical properties that are generally difficult to implement in the state of a single monomer or in the state of high molecular weight polymer agglomerates. By dispersing such conductive nanocomposite in a non-conductive thermoplastic resin, it is possible to provide a conductive hybrid resin excellent in industrial mass production efficiency. Also, the conductive nanocomposite has advantages of being able to realize various electrical characteristics according to the intended use through doping, stable at room temperature, and excellent in economical efficiency.

However, the conductive nanocomposite has very low dispersibility with respect to ordinary thermoplastic resin and has high self-cohesion. Particularly, nanoparticles or conductive nanocomposites in the form of fibers are highly interactive with respect to particle size, and it is difficult to induce high dispersion by general mechanical processing alone. In such a case, the conductive composite resin is not easy to obtain the desired physical and electrical properties because the aggregate causes deterioration of the external appearance or low conductivity.

Therefore, there is a growing need to develop a manufacturing method that can improve the dispersibility and conductivity of the conductive nanocomposite in a thermoplastic resin while using a conductive nanocomposite as a conductive material to provide economical efficiency and various electrical characteristics.

The prior art of the present invention is disclosed in U.S. Patent 7,144,949.

It is an object of the present invention to provide a conductive nanocomposite which can prevent agglomeration of a conductive nanocomposite, improve heat resistance, conductivity and dispersibility, can improve polymerization degree, production amount and dispersibility, lower the surface resistance of a conductive composite resin, And a method for manufacturing a conductive composite resin capable of improving the appearance.

Another object of the present invention is to provide a conductive composite resin having a low surface resistance and excellent heat resistance, conductivity and appearance.

One embodiment of the present invention relates to a method for producing a conductive polymer, comprising the steps of (A) adding a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine to an aqueous solution of an alcohol or a ketone to prepare a mixed solution; (B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; And (C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite; And a method for producing the conductive nanocomposite.

Another embodiment of the present invention is a method for producing a conductive polymer, comprising the steps of: (A) preparing a mixed solution by mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine in an aqueous solution of an alcohol or a ketone; (B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; (C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite; And (D) melt-kneading the conductive nanocomposite and the thermoplastic resin to prepare a conductive composite resin; The present invention also relates to a method for producing a conductive composite resin.

Another embodiment of the present invention relates to a conductive composite resin formed by the above-described method for producing a conductive composite resin, and a conductive composite resin having a structure in which a conductive nanocomposite is dispersed in a thermoplastic resin.

The present invention relates to a conductive composite which can improve the polymerization degree, production amount and dispersibility of a conductive nanocomposite, prevent agglomeration and increase dispersibility, lower the surface resistance of the conductive composite resin, and improve the heat resistance, conductivity and appearance A resin manufacturing method is provided.

One embodiment of the present invention relates to a method for producing a conductive polymer, comprising the steps of (A) adding a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine to an aqueous solution of an alcohol or a ketone to prepare a mixed solution; (B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; And (C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite; And a method for producing the conductive nanocomposite.

Accordingly, it is an object of the present invention to provide a conductive nanocomposite which can improve both polymerization degree, production amount and dispersibility of a conductive nanocomposite, prevent agglomeration, increase dispersibility, lower surface resistivity of conductive hybrid resin, improve heat resistance, conductivity and appearance And a method for manufacturing the conductive composite.

In particular, the method for producing a conductive composite resin of the present invention includes a step of polymerizing a conductive nanocomposite to prevent the conductive nanocomposite from self-aggregating, and to balance the polymerization degree, the production amount and the dispersibility of the conductive nanocomposite The effect of improving is very good.

Specifically, the method for producing a conductive composite of the present invention comprises the steps of (A) preparing a pre-polymerization pre-mix by mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and a phenylenediamine in an aqueous solution of an alcohol or a ketone, do. When the conductive nanocomposite is pre-mixed, the degree of polymerization and production of the conductive nanocomposite can be further improved and the uniformity of the particle size and shape can be improved.

In the step of preparing the mixed solution, the order of mixing the monomer for preparing the conductive polymer, the water-soluble dispersant, the phenylenediamine and the dopant in the aqueous solution of the alcohol or the ketone is not particularly limited. For example, Dopants can be added in the order of preference than diamines. In this case, the aqueous solution of alcohol or ketone forms a microemulsion by the addition of a dopant, and micelles can be formed by the phenylenediamine introduced at a subordinate position. The micelle acts on the polymerization reaction to further improve the degree of polymerization and production of the conductive nanocomposite and improve the uniformity of particle size and shape.

The aqueous solution of the alcohol or ketone is a mixture of water and a mixture of water and a ketone of 1 to 10 carbon atoms or a mixture of water and an alcohol of 1 to 10 carbon atoms and a ketone of 1 to 10 carbon atoms . In this case, the degree of formation of micelle by the action of the aqueous solution of alcohol or ketone and the dopant and the phenylenediamine is increased, the solubility of the monomer and the oxidizing agent (initiator) is increased, and the degree of polymerization and production of the conductive nanocomposite can be further improved , The uniformity of particle size and shape can be improved. When the reaction solvent is a single solvent of water, alcohol, or ketone, which is not an aqueous solution of the alcohol or the ketone, it is difficult to realize an effect of increasing the formation of micelles and increasing the solubility of monomers and oxidants at the same time. it's difficult.

The alcohols having 1 to 10 carbon atoms may include, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and isomers thereof.

The ketone having 1 to 10 carbon atoms may include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, and isomers thereof.

In an embodiment, the aqueous solution of the alcohol or ketone may include 10 to 50% by weight of an alcohol having 1 to 10 carbon atoms or a ketone having 1 to 10 carbon atoms. Within the above range, the degree of formation of micelles by the action of an aqueous solution of alcohol or ketone and the action of dopant and phenylenediamine is increased, the solubility of the monomer and the initiator is increased, the polymerization degree and yield of the conductive nanocomposite can be further improved, The uniformity of particle size and shape can be improved.

 In embodiments, the weight ratio of water to alcohol or ketone in the aqueous solution of the alcohol or ketone may be from 1: 0.1 to 1: 0.5. Within the above range, the degree of formation of micelles by the action of an aqueous solution of alcohol or ketone and the action of dopant and phenylenediamine is increased, the solubility of the monomer and the initiator is increased, the polymerization degree and yield of the conductive nanocomposite can be further improved, The uniformity of particle size and shape can be improved.

The water-soluble dispersant may be a polyalkylene glycol-based dispersant. In this case, it is easily dissolved in the aqueous solution of alcohol or ketone, and the degree of dispersion of the components injected into the mixed solution is increased without hindering the formation of micelles, thereby improving the uniformity of particle size and shape of the conductive nanocomposite . In addition, when a dispersant such as polyvinyl alcohol or the like is used instead of the polyalkylene glycol dispersant, it is difficult to lower the surface resistance of the conductive hybrid resin.

Wherein the polyalkylene glycol-based dispersant includes at least one of polyethylene glycol, polypropylene glycol, polydiethylene glycol, polydipropylene glycol, polytetriethylene glycol, polytripropylene glycol, polytetraethylene glycol, and polytetrapropylene glycol can do. In this case, the uniformity of the particle size and shape of the conductive nanocomposite can be improved, the dispersibility can be further increased, and the surface resistance of the conductive hybrid resin obtained by using the conductive nanocomposite can be further reduced.

In one embodiment, the polyalkylene glycol-based dispersant may be polyethylene glycol, polypropylene glycol, or the like. In this case, the uniformity of the particle size and shape of the conductive nanocomposite can be improved and the dispersibility can be further increased.

The monomer for producing a conductive polymer may include at least one of substituted or unsubstituted aniline, substituted or unsubstituted pyrrole, and substituted or unsubstituted thiophene. In this case, the surface resistance of the conductive nanocomposite is low, and more various electrical characteristics can be realized.

As used herein, "substituted" means that at least one of hydrogen directly bonded to the corresponding compound is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, A sulfonyl group, a nitro group, a halogen group and the like. The functional group is not particularly limited as long as it can be generally used as a substituent. In addition, when substituted aniline is used, phenylenediamine used as a reaction promoter described later is excluded.

Examples of the monomer for producing a conductive polymer include aniline, an alkyl substituted aniline having 1 to 5 carbon atoms, an alkoxy substituted aniline having 1 to 5 carbon atoms, a dialkoxy substituted aniline having 1 to 5 carbon atoms, a sulfonyl aniline, a nitroaniline, Pyrrole, ethylenedioxythiophene (EDOT), and thiophene. In this case, the surface resistivity of the conductive hybrid resin obtained by using the conductive nanocomposite is further lowered, and the conductivity can be further excellent.

More specifically, the monomer for producing a conductive polymer may include at least one of unsubstituted aniline, unsubstituted pyrrole, and unsubstituted thiophene. In this case, the unsubstituted aniline, unsubstituted pyrrole, and unsubstituted thiophene are excellent in interactivity with phenylenediamine used as a reaction promoter, so that they act in combination during polymerization to increase the reaction rate, Can be further improved. In addition, when the monomer for preparing a conductive polymer as described above is used, a conductive nanocomposite which is more uniform, has excellent durability and has a low surface resistance can be realized.

In one embodiment, when aniline unsubstituted as the monomer for preparing a conductive polymer is used, a polyaniline conductive nanocomposite having a structure represented by the following formula (1) may be obtained. The polyaniline conductive nanocomposite of this structure may have even higher particle size uniformity.

[Chemical Formula 1]

In another embodiment, when the unsubstituted pyrrole is used as the monomer for preparing a conductive polymer, a polypyrrole conductive nanocomposite having a structure represented by the following general formula (2) can be obtained. The polypyrrole conductive nanocomposite having such a structure may have higher uniformity of particle size and higher heat resistance.

(2)

In another embodiment, when a thiophene unsubstituted as the monomer for preparing a conductive polymer is used, a polythiophene conductive nanocomposite having a structure represented by the following formula (3) may be obtained. The polythiophene conductive nanocomposite of this structure can have even higher particle size uniformity and higher conductivity.

(3)

(In the above formulas 1 to 3, n is an integer of 1 to 10,000,000.) The value of n is not particularly limited.

The dopant may be selected from, for example, benzene sulfonic acid (BSA), benzenedisulfonic acid (BDSA), benzethysulfonic acid, benzene tetrasulfonic acid (BTSA), benzene peptasulfonic acid (BPSA), hydroxybenzenesulfonic acid ), Hydroxydisulfonic acid, hydroxytrisulfonic acid, hydroxytetrasulfonic acid, hydroxypeptosulfonic acid, dodecylbenzenesulfonic acid (DBSA), dodecylbenzenedisulfonic acid, dodecylbenzenetrisulfonic acid, alkyl At least one of benzene sulfonic acid (ABSA), camphorsulfonic acid (CSA), p-toluenesulfonic acid (TSA), naphthalene sulfonic acid (NSA) and naphthalene disulfonic acid (NDSA). In this case, the heat resistance and conductivity of the conductive hybrid resin obtained by using the conductive nanocomposite can be further improved. In addition, the dopant in the above example is more advantageous to be polymerized in a solution state in the production of the conductive nanocomposite, and can impart high heat resistance.

The phenylenediamine can be used as a reaction promoter using its structural characteristics. Such phenylenediamine acts in combination with a water-soluble dispersant, a monomer for preparing a conductive polymer, and a dopant in an initial polymerization reaction, which starts with the introduction of an oxidizing agent (initiator) in a step to be described later, to further promote the polymerization reaction. In the case where phenylenediamine is not added, it is difficult to realize the reaction promoting effect in the initial polymerization reaction, and it is difficult to control the completion of the polymerization reaction together with the introduction of the initiator, so that it is difficult to obtain a uniform type of conductive nanocomposite. In addition, the phenylenediamine may act to promote the formation of micelles by reacting with the microemulsion formed by the addition of the dopant in the aqueous solution of alcohol or ketone.

The mixed solution is prepared by mixing 30 to 50% by weight of a water-soluble dispersant, 5 to 15% by weight of a monomer for preparing a conductive polymer, 40 to 60% by weight of a dopant, and 0.001 to 1% And 800 parts by weight to 1500 parts by weight of an aqueous solution of an alcohol or a ketone. Within this range, the degree of formation of micelles by the action of the aqueous solution of alcohol or ketone and the dopant and the phenylenediamine is increased, and the solubility of the monomer and the oxidizing agent (initiator) is increased to further improve the polymerization degree and yield of the conductive nanocomposite And the uniformity of particle size and shape can be improved.

In an embodiment, the weight ratio of the aqueous solution of the alcohol or ketone to the monomer for preparing the conductive polymer may be from 1: 0.01 to 1: 1.5. Within this range, the solubility of the monomer relative to the aqueous solution of alcohol or ketone can be further increased, the polymerization degree and yield of the conductive nanocomposite can be further improved, and the uniformity of particle size and shape can be improved.

In embodiments, the weight ratio of the aqueous solution of the alcohol or ketone to the water soluble dispersant may be from 1: 0.01 to 1: 0.1. Within this range, the dispersibility of the polymerized units due to the action of the aqueous solution of alcohol or ketone and the water-soluble dispersant is increased, so that the degree of polymerization and production of the conductive nanocomposite can be further improved and the uniformity of the particle size and shape can be improved have.

In an embodiment, the weight ratio of the monomer for preparing a conductive polymer to the phenylenediamine may be 1: 0.01 to 1: 0.1. Within the above range, the polymerization degree and the production amount of the conductive nanocomposite due to the complex action of micelle formation and polymerization initiation in the action of phenylenediamine can be further improved, and the uniformity of particle size and shape can be improved.

In an embodiment, the weight ratio of the monomer for preparing a conductive polymer to the water-soluble dispersant may be 1: 4 to 1: 6. Within the above range, the water-soluble dispersant and the monomer for preparing a conductive polymer can be dispersed at an appropriate ratio, the polymerization degree and the production amount of the conductive nanocomposite can be further improved, and the uniformity of particle size and shape can be improved.

In an embodiment, the molar ratio of the monomer for preparing a conductive polymer to the dopant may be 1: 0.3 to 1: 3.5. Within the above range, the degree of formation of micelles due to the action of an aqueous solution of alcohol or ketone and the action of dopant and phenylenediamine is increased to further improve the polymerization degree and yield of the conductive nanocomposite, and to improve the uniformity of particle size and shape .

Specifically, the method for producing a conductive composite resin of the present invention comprises the steps of (B) adding an oxidizing agent to the mixed solution prepared above, and then polymerizing to prepare a polymerization reaction product. The oxidizing agent acts as an initiator of the polymerization reaction and initiates polymerization of the monomer for preparing a conductive polymer to form a conductive nanocomposite in the reaction solution.

The oxidizing agent is not particularly limited as long as it is capable of initiating the polymerization reaction. For example, persulfate, iodate, chlorate, dichromate, metal chloride or a mixture thereof may be used.

For example, ammonium persulfate, potassium persulfate or sodium persulfate may be used as the persulfate.

For example, potassium iodate and the like can be used as the iodic acid salt.

For example, potassium chlorate or the like can be used as the chlorate.

For example, potassium bicarbonate may be used as the heavy calcium salt.

For example, the metal chloride may be iron chloride, ferric chloride, cupric chloride, copper chloride or the like.

In one embodiment, the oxidizing agent may include at least one of ammonium persulfate, iron chloride, copper chloride, and potassium persulfate. In this case, the polymerization efficiency is further improved and the production amount of the conductive nanocomposite can be further improved.

The molar ratio of the monomer for preparing a conductive polymer and the oxidizing agent may be 1: 0.1 to 1: 1. Within the above range, the amount of the oxidizing agent and the amount of the conductive polymer suitably correspond to each other, so that the polymerization efficiency is further improved, the production amount of the conductive nanocomposite is further improved, and the degree of polymerization is lowered to improve the uniformity of particle size and shape .

The polymerization reaction is not particularly limited, but may be carried out at, for example, -20 캜 to 100 캜, or 0 캜 to 30 캜. Within this range, the degree of polymerization and production of the conductive nanocomposite can be further improved, and the uniformity of particle size and shape can be improved.

Specifically, in the step of (C) obtaining the conductive nanocomposite, the polymerization reaction product prepared as described above is washed with a polar cleaning solvent, followed by filtration and drying to obtain a conductive nanocomposite. In this case, in the conductive composite resin, aggregation of the conductive nanocomposite can be prevented, dispersibility can be improved, surface resistivity of the conductive hybrid resin can be lowered, and conductivity and appearance can be improved.

The washing solvent is not particularly limited, and examples thereof include water, alcohols having 1 to 10 carbon atoms and ketones having 1 to 10 carbon atoms, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone ), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF). In this case, the compatibility of the conductive nanocomposite with a thermoplastic resin described later can be further improved.

The conductive nanocomposite prepared by washing, filtering and drying as described above may have a surface resistance of 10 ¹ Ω / sq to 10 ³ Ω / sq. In this case, it is possible to realize an excellent antistatic function and an electrostatic discharge function because of its high conductivity, and it is more advantageous to be applied to various kinds of housings and exterior materials for electrical and electronic products.

Another embodiment of the present invention is a method for producing a conductive polymer, comprising the steps of: (A) preparing a mixed solution by mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine in an aqueous solution of an alcohol or a ketone; (B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; (C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite; And (D) melt-kneading the conductive nanocomposite and the thermoplastic resin to prepare a conductive composite resin; The present invention also relates to a method for producing a conductive composite resin.

(A) mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine in an aqueous solution of an alcohol or a ketone to prepare a mixed solution; (B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; And (C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite.

The conductive nanocomposite and the thermoplastic resin obtained in the above-mentioned method for producing a conductive nanocomposite are kneaded to prepare a conductive composite resin.

Specifically, in the step (D) of producing a conductive composite resin, the conductive nanocomposite and the thermoplastic resin are mixed and melt-kneaded to produce a conductive composite resin. At this time, the melt kneading method is not particularly limited, and a method known in the art can be used. For example, the thermoplastic resin is put into an apparatus such as a uniaxial compressor, a twin-screw extruder, a multi-screw extruder, a kneader, a planetary mixer, a roll mill, Lt; / RTI >

Wherein the thermoplastic resin is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene copolymer, polypropylene copolymer, polystyrene copolymer, polybutene copolymer, polybutadiene, polybutadiene copolymer, polyethylene wax, polypropylene wax, polyethylene copolymer wax, poly Propylene copolymer wax, and paraffin wax. In this case, the processability, flowability, melting property, moldability, and the like of the conductive hybrid resin can be further improved.

The weight ratio of the conductive nanocomposite to the thermoplastic resin may be 1: 0.05 to 1: 0.5. Within the above range, the effect of reducing the deterioration occurring in the melt-kneading process of the conductive nanocomposite and the thermoplastic resin is excellent, thereby further improving the heat resistance and conductivity of the composite resin.

The conductive composite resin may have a surface resistance of 10 ¹ ? / Sq to 10 ¹¹ ? / Sq. In this case, it is possible to realize an excellent antistatic function and an electrostatic discharge function because of its high conductivity, and it is more advantageous to be applied to various kinds of housings and exterior materials for electrical and electronic products.

Another embodiment of the present invention relates to a conductive composite resin produced by the above-described method for producing a conductive composite resin. Such a conductive hybrid resin has a low surface resistance of 10 ¹ Ω / sq to 10 ¹⁰ Ω / sq, high conductivity and dispersibility, and can realize excellent electrical characteristics and uniform physical properties.

The conductive hybrid resin is excellent in antistatic function and electrostatic discharge function when it is applied to products such as a film or a sheet for electrostatic dispersion, a tray for packaging an electronic product, The advantage can be increased.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example 1

405 g of ethanol was mixed with distilled water to prepare a reaction solvent. 40 g of a water-soluble dispersant (compound name: polyethylene glycol, manufacturer: Lotte Chemical, product name: PEG-4000) and 40 g of a monomer for producing a conductive polymer , 61 g of a dopant (compound name: linear alkyl benzene sulphonic acid, linear alkyl benzene sulfonic acid, manufactured by jintung petrochemical), and 0.1 g of a reactive promoter (compound name: paraphenylenediamine, manufactured by Sigma Aldrich) And the mixture was stirred at 30 ° C for 10 minutes.

To the stirred solution was added 25 g of an oxidizing agent (compound name: ammonium persulfate, manufactured by Sampei Co., Ltd.) as a polymerization initiator, and it was confirmed that the polymerization started after changing the color after about 5 minutes. The polymerization was carried out with stirring at a temperature of 25 ° C and a pressure of 200 rpm for 60 minutes at normal pressure. Thereafter, 405 g of ethanol was added as a washing solvent to terminate the polymerization reaction, and the polymerization reaction product was precipitated by stirring and filtered. The filtered material was dried in an oven to prepare a conductive nanocomposite.

Subsequently, 8 g of the conductive nanocomposite thus prepared was added to 32 g of a linear (linear) low density polyethylene resin (compound name: polyethylene, weight average molecular weight: 200,000 g / mol, MI: 2 g / 10 min) mixer under the conditions of 180 캜, 100 rpm, 3 min 30 sec to prepare a conductive composite resin.

Example 2

A conductive composite resin was prepared in the same manner except that the content of the water-soluble dispersant used in Example 1 was changed to 60 g.

Example 3

A conductive composite resin was prepared in the same manner as in Example 1 except that the content of the conductive nanocomposite was changed to 6 g and the content of the thermoplastic resin was changed to 34 g.

Example 4

A conductive composite resin was prepared in the same manner as in Example 2, except that the content of the conductive nanocomposite was changed to 6 g and the content of the thermoplastic resin was changed to 34 g.

Example 5

A conductive composite resin was prepared in the same manner except that the content of phenylenediamine used in Example 1 was changed to 0.5 g.

Example 6

A conductive composite resin was prepared in the same manner except that the content of phenylenediamine used in Example 2 was changed to 0.5 g.

Example 7

A conductive hybrid resin was prepared in the same manner except that the thermoplastic resin used in Example 1 was changed to a low density polyethylene (molecular weight: weight average molecular weight: 200,000 g / mol, MI: 2 g / 10 min).

Example 8

A conductive hybrid resin was prepared in the same manner except that the thermoplastic resin used in Example 1 was changed to ethylene vinyl alcohol (molecular weight: weight average molecular weight: 115,000 g / mol, MI: 2.5 g / 10 min) .

Example 9

A conductive hybrid resin was prepared in the same manner as in Example 1, except that the thermoplastic resin used was changed to polypropylene (molecular weight: weight average molecular weight: 240,000 g / mol, MI: 4 g / 10 min).

Example 10

A conductive composite resin was prepared in the same manner as in Example 1 except that 648 g of ethanol was used as a reaction solvent in 200 g of distilled water.

Example 11

A conductive composite resin was prepared in the same manner as in Example 1, except that the reaction solvent was a mixture of 800 g of distilled water and 162 g of ethanol.

Comparative Example 1

A conductive composite resin was prepared in the same manner as in Production Example 6, except that 810 g of a 99% alcohol solution was used instead of the aqueous alcohol solution prepared as the reaction solution.

Comparative Example 2

A conductive composite resin was prepared in the same manner as in Preparation Example 6, except that the introduction of phenylenediamine was omitted.

Comparative Example 3

A conductive composite resin was prepared in the same manner as in Preparation Example 6 except that the water-soluble dispersant was omitted.

Unit (g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Reaction solvent 905 905 905 905 905 905 Solvent type mix mix mix mix mix mix Water-soluble dispersant 40 60 40 60 40 60 Conductive monomer 10 10 10 10 10 10 Dopant 61 61 61 61 61 61 Phenylenediamine 0.1 0.1 0.1 0.1 0.5 0.5 Oxidant 25 25 25 25 25 25 Conductive nanopolymer 8 8 6 6 8 8 Thermoplastic resin 32 32 34 34 32 32 Thermoplastic resin type LLDPE LLDPE LLDPE LLDPE LLDPE LLDPE

Unit (g) Example 7 Example 8 Example 9 Example 10 Example 11 Reaction solvent 905 905 905 848 962 Solvent type mix mix mix mix mix Water-soluble dispersant 60 60 60 40 40 Conductive monomer 10 10 10 10 10 Dopant 61 61 61 61 61 Phenylenediamine 0.5 0.5 0.5 0.1 0.1 Oxidant 25 25 25 25 25 Conductive nanopolymer 8 8 8 8 8 Thermoplastic resin 32 32 32 32 32 Thermoplastic resin type LDPE EVA PP LLDPE LLDPE

Unit (g) Comparative Example 1 Comparative Example 2 Comparative Example 3 Reaction solvent 810 905 905 Solvent type Alcohol single mix mix Water-soluble dispersant 60 60 0 Conductive monomer 10 10 10 Dopant 61 61 61 Phenylenediamine 0.5 0 0.5 Oxidant 25 25 25 Conductive nanopolymer 8 8 6 Thermoplastic resin 32 32 34 Thermoplastic resin type LLDPE LLDPE LLDPE

Property evaluation method

1) Conductivity: The conductive composite resin prepared in the above Examples and Comparative Examples was pelletized and measured by a 4-probe probe method under a pressure of 20 kg using a surface resistance meter (manufactured by BEGA: FPP-RS-8) Respectively. "Compliant" when the surface resistance is 10 ¹¹ Ω / sq or less, and "Not suitable" when it exceeds 10 ¹¹ Ω / sq. The results are shown in Tables 4 to 6 below.

2) Dispersibility: The conductive composite resin prepared in the above Examples and Comparative Examples was prepared into pellets having a size of 10 mm in diameter, and the degree of dispersion of the conductive nanocomposite was visually evaluated. "Poor" when an aggregate or weld line occurred, and "Excellent" when no aggregate and weld line occurred. The results are shown in Tables 4 to 6 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Surface resistance (Ω / sq) 10 ^ 10 10 ^ 9 10 ^ 11 10 ^ 10 10 ^ 10 10 ^ 9 conductivity fitness fitness fitness fitness fitness fitness Dispersibility Great Great Great Great Great Great

Example 7 Example 8 Example 9 Example 10 Example 11 Surface resistance (Ω / sq) 10 ^ 9 10 ^ 9 10 ^ 9 10 ^ 11 10 ^ 11 conductivity fitness fitness fitness fitness fitness Dispersibility Great Great Great Great Great

Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface resistance (Ω / sq) 10 ^ 12 10 ^ 13 10 ^ 13 conductivity incongruity incongruity incongruity Dispersibility Bad Bad Bad

As can be seen from Tables 3 and 4, the conductive hybrid resin of the examples of the present invention has low surface resistance, and is excellent in conductivity and dispersibility.

On the other hand, as can be seen from Table 6, in Comparative Example 1 using a single alcoholic solvent instead of a mixed solvent, Comparative Example 2 containing no phenylenediamine and Comparative Example 3 containing no water-soluble dispersant, It was confirmed that the resin had low conductivity and dispersibility and it was difficult to achieve a surface resistance of 10 ¹¹ Ω / sq or less.

Claims (15)

(A) preparing a mixed solution by adding a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine to an aqueous solution of an alcohol or a ketone;
(B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product; And
(C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite;
≪ / RTI >
The method according to claim 1,
Wherein the aqueous solution of the alcohol or ketone comprises 10 to 50% by weight of an alcohol having 1 to 10 carbon atoms or a ketone having 1 to 10 carbon atoms.
The method according to claim 1,
Wherein the water-soluble dispersant is a polyalkylene glycol-based dispersant, and the polyalkylene glycol-based dispersant is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polydiethylene glycol, polydipropylene glycol, polytriethylene glycol, polytripropylene glycol, Glycol, and polytetrapropylene glycol. ≪ Desc / Clms Page number 24 >
The method according to claim 1,
Wherein the monomer for producing a conductive polymer comprises at least one of substituted or unsubstituted aniline, substituted or unsubstituted pyrrole, and substituted or unsubstituted thiophene.
The method according to claim 1,
The dopant may be selected from the group consisting of benzene sulfonic acid (BSA), benzenedisulfonic acid (BDSA), benzenetric sulfonic acid, benzene tetrasulfonic acid (BTSA), benzene peptadosulfonic acid (BPSA), hydroxybenzenesulfonic acid (HBSA) But are not limited to, disulfonic acid, disulfonic acid, hydroxytrisulfonic acid, hydroxytetrasulfonic acid, hydroxypeptosulfonic acid, dodecylbenzenesulfonic acid (DBSA), dodecylbenzene disulfonic acid, dodecylbenzenesulfonic acid, Wherein the nanocomposite comprises at least one of ABSA, camphorsulfonic acid (CSA), p-toluenesulfonic acid (TSA), naphthalenesulfonic acid (NSA) and naphthalenedisulfonic acid (NDSA).
The method according to claim 1,
Wherein the molar ratio of the monomer for preparing a conductive polymer to the dopant is 1: 0.3 to 1: 3.5.
The method according to claim 1,
Wherein the weight ratio of the monomer for preparing a conductive polymer to the phenylenediamine is 1: 0.01 to 1: 0.1.
The method according to claim 1,
Wherein the mixed solution comprises 100 parts by weight of a solid component consisting of 30 to 50% by weight of a water-soluble dispersant, 5 to 15% by weight of a conductive polymer producing monomer, 40 to 60% by weight of a dopant, and 0.001 to 1% by weight of phenylenediamine By division,
And from 800 to 1500 parts by weight of an aqueous solution of an alcohol or a ketone.
The method according to claim 1,
Wherein the oxidizing agent comprises at least one of a persulfate, an iodate, a chlorate, a dichromate, and a metal chloride.
The method according to claim 1,
Wherein the molar ratio of the monomer for preparing a conductive polymer to the oxidizing agent is 1: 0.1 to 1: 1.
(A) mixing a water-soluble dispersant, a monomer for preparing a conductive polymer, a dopant and phenylenediamine in an aqueous solution of an alcohol or a ketone to prepare a mixed solution;
(B) introducing an oxidizing agent into the mixed solution and then polymerizing to prepare a polymerization reaction product;
(C) washing, filtering and drying the polymerization reaction product to obtain a conductive nanocomposite; And
(D) melt-kneading the conductive nanocomposite and the thermoplastic resin to prepare a conductive composite resin;
Wherein the conductive composite resin is a polyimide resin.
The method of claim 11, wherein
Wherein the thermoplastic resin is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene copolymer, polypropylene copolymer, polystyrene copolymer, polybutene copolymer, polybutadiene, polybutadiene copolymer, polyethylene wax, polypropylene wax, polyethylene copolymer wax, poly A propylene copolymer wax, and a paraffin wax.
12. The method of claim 11,
Wherein the conductive composite resin comprises 10 to 30% by weight of the conductive nanocomposite and 30 to 90% by weight of the thermoplastic resin.
A conductive hybrid resin formed by the method according to claim 11, wherein the conductive hybrid resin has a structure in which a conductive nanocomposite is dispersed in a thermoplastic resin.
15. The method of claim 14,
Wherein the conductive composite resin has a surface resistance of 10 ¹ / sq to 10 ¹⁰ sq / sq.