KR101198087B1 - Electrostatic discharge polymer filler containing graphene enclosed with thermoplatic resin layer and conductive thermoplastic resin composition and manufacturing methods therof - Google Patents

Abstract

PURPOSE: A manufacturing method of thermoconductive polymer filler is provided to prevent re-coherence of graphene which was dispersed in a polymerization step by using a water-soluble block copolymer, and to maintain the dispersed state. CONSTITUTION: A manufacturing method of thermoconductive polymer filler comprises: a step of mixing graphene, a water-soluble block copolymer, an emulsifier and water, and obtaining aqueous solution of graphene by high rate-dispersing the mixture by a homogenizer; a step of microcapsulation by emulsification polymerizing the aqueous solution and one or more monomers comprising an addition-polymerizable ethylene group to make the graphene be surrounded with a thermoplastic resin layer; and a step of forming a flock by binding the microcapsules.

Description

Electroconductive polymer filler and conductive thermoplastic resin composition comprising graphene microcapsules surrounded by a thermoplastic resin layer and a method for producing the same. {Electrostatic discharge polymer filler containing graphene enclosed with thermoplatic resin layer and conductive thermoplastic resin composition and manufacturing methods therof}

The present invention relates to a conductive polymer filler for manufacturing a conductive plastic and a method for manufacturing the same, more specifically, including a graphene (graphene), conductive including a graphene in the form of microcapsules surrounding the graphene with a thermoplastic resin layer A polymer filler and a method for producing the same.

The present invention also relates to a method for producing a conductive thermoplastic resin composition comprising the conductive polymer filler.

Polymers are easy to mold, have excellent chemical resistance, and are light, so they are applied to various fields such as automobile parts, electrical and electronic parts, building materials, and packaging materials. However, a problem may occur due to discharge, suction, repulsive force, etc. after the generation of static electricity generated by friction or the like due to the basic characteristics having insulation. There is a need for a dispersion or radiation characteristic of static electricity to remove or neutralize the static electricity generated. Electrostatic discharge (ESD) polymers are electrically conductive polymer materials having electrostatic radiation characteristics while maintaining the basic properties as polymers by various methods. ESD polymers have a surface resistance of 10 ^4-10 Ω / sq and have electrostatic dispersion characteristics that radiate static electricity generated during friction.

Regarding the method of using a conductive filler, carbon black and carbon fiber are most widely used among conductive fillers, but there is a problem in that they are not satisfactory in performance. In recent years, carbon nanotube materials have been spotlighted as fillers in terms of conductivity, but there are difficulties in dispersing technology and even though they are dispersed, the carbon nanotube particles have a strong tendency to agglomerate with each other. Very difficult to maintain and due to the lack of adhesion between the matrix resin and the carbon nanotubes there is a problem that the performance of the electrostatic properties are not sufficiently expressed.

To solve this problem, many papers and patents on chemical modification and dispersion of carbon nanotubes have been published or published. For the dispersion of carbon nanotubes, not only research papers that can increase the dispersion for physical treatment but also methods of preparing carbon nanotube dispersions using ultrasonics and surfactants have been proposed. In addition, it also exposed the limitation that dispersion stability was also poor. In particular, these methods tend to agglomerate the carbon nanotubes due to the dispersing of dispersing systems when other additives are added, and they do not exhibit uniform dispersibility when mixed with resins, thereby deteriorating electrical and physical properties. Is holding.

Recently, interest in using graphene instead of carbon nanotubes has increased. Carbon nanotubes have a specific resistance of 400Ω / □ and a body resistance of 1.0x10 ^-4 Ωcm, whereas graphene has a specific resistance of 30Ω / □ and a body resistance of 1.0x10 ^-6 Ωcm. Graphene is in the spotlight as a new conductive filler because it has 13 times less specific resistance and 100 times body resistance than carbon nanotubes.

Publication No. 10-2011-0078117 describes an antistatic resin composition containing graphene, but the method of dispersing it in the matrix polymer of graphene is not specifically presented. Like carbon nanotubes, it is very difficult to uniformly disperse graphene in a polymer resin.

Among these, the present invention is homogeneous with the thermoplastic resin which becomes a matrix after preparing the graphene in a microencapsulated form in order to impart electrostatic properties to the product by dispersing the conductive graphene alone and the graphene and the nanonized metal powder in the resin. A new type of graphene-containing conductive polymer filler and a method for preparing the same, and a method for producing a conductive thermoplastic resin composition including the graphene-containing conductive polymer filler are provided.

Republic of Korea Patent Publication 10-2011-0078117

The present invention relates to a new graphene-containing conductive polymer in which graphene is microencapsulated so as to be homogeneously mixed in a matrix thermoplastic resin in an attempt to use graphene as a conductive polymer filler in preparing a thermoplastic resin having electrostatic dispersion characteristics. It is an object to provide a filler and a resin composition containing the same.

The present invention provides a method for producing a new graphene-containing conductive polymer filler having the following structure and a method for producing a conductive thermoplastic resin composition using the same to solve the above object.

The present invention refers to graphene and the thermoplastic resin layer surrounding the graphene is called graphene-containing microcapsules or conductive polymer filler, and provides a method for producing the conductive polymer filler and a method for producing the conductive thermoplastic resin using the same.

In the conductive polymer filler, the thermoplastic resin layer is not particularly limited and is not limited as long as it is a thermoplastic resin that can be well mixed and dispersed in the thermoplastic resin. Thermoplastic homopolymers or copolymers produced by the present invention.

The conductive polymer filler may further include nano metal particles, wherein the nano metal particles are attached to the inside or outside of the microcapsules.

In the conductive polymer filler, graphene is stably dispersed by the water-soluble block copolymer, and the resin layer is formed by the monomers that are post-added to form graphene-containing microcapsules.

The production method of the present invention is a dispersion step of obtaining a graphene aqueous dispersion by adding a graphene and a water-soluble block copolymer in water; Microencapsulating the graphene with a thermoplastic resin layer by adding a polymerized monomer to an aqueous solution of graphene dispersed by a water-soluble block copolymer and polymerizing it; And drying the polymer through an agglomeration step of agglomerating the resulting microcapsules to form a flock.

Specifically, the present invention is a method for producing the conductive polymer filler,

1 part by weight of graphene and 0.1 to 2 parts by weight of a water-soluble block copolymer is mixed with 0.1 to 20 parts by weight of water with 50 to 1000 parts by weight of water, followed by mixing and dispersing with a homogenizer to obtain an aqueous dispersion of graphene. step;

 It provides a method for producing a graphene-containing conductive polymer filler comprising a polymerization step of microencapsulating graphene by polymerizing 10 to 1000 parts by weight of at least one monomer containing an ethylene group that can be additionally polymerized with respect to 1 part by weight of graphene. do.

In another aspect, the present invention may further comprise the step of forming a floc by agglomerating the prepared microencapsulated conductive polymer filler.

The present invention also provides a conductive thermoplastic resin composition comprising 0.1 to 30 parts by weight of the conductive polymer filler based on 100 parts by weight of the thermoplastic resin.

The graphene-containing conductive polymer filler according to the present invention is well dispersed evenly in the conductive thermoplastic resin, and also solves the problem of low adhesion between the graphene and the matrix thermoplastic resin, by using a small amount of graphene Even excellent electrostatic characteristics can be exhibited. Since graphene itself is expensive, it is clear that it is economically very advantageous if a small amount can be used to show excellent electrostatic dispersion properties.

The conductive polymer filler manufacturing method including the graphene microcapsules according to the present invention by using a water-soluble block copolymer to prevent the graphene dispersed in the polymerization step to form a resin layer to prevent agglomeration again to precipitate and maintain the dispersed state as it is This enables microencapsulation of the graphene with resin. In addition, it was possible to obtain an effect of showing a very excellent conductivity.

Hereinafter, the present invention will be described in detail.

The present invention provides a conductive polymer filler comprising graphene microcapsules including graphene and a thermoplastic resin layer surrounding the graphene.

In the present invention, the graphene-containing microcapsule is a term used in the meaning of micro-sized particles containing graphene and graphene encapsulated by a resin layer. The size of the microcapsules according to the present invention is in the range of 0.1 to 1000 μm, but on average is in the range of 1 to 500 μm. However, the size can be changed according to the conditions at the time of manufacture.

In the conductive polymer filler, the thermoplastic resin layer is not particularly limited and may be a resin that can be well mixed and dispersed in the thermoplastic resin, and preferably, by polymerization of a monomer containing an ethylene group which can be polymerized. Resulting thermoplastic homopolymers or copolymers.

The conductive polymer filler may further include nano metal particles, wherein the nano metal particles are attached to the inside or outside of the microcapsules.

In the conductive polymer filler, the graphene microcapsules may further include a water-soluble block copolymer, and if included, may be incorporated with graphene to form a graphene-water soluble block copolymer aggregate. The copolymer may be mixed in the resin layer, and some may be incorporated into graphene while the rest may be contained in the resin layer.

Hereinafter, the components of the conductive polymer filler will be described in detail.

The graphene in the present invention is not limited to the form it is possible to use all known types of graphene. The particle size of the graphene used in the present invention is not particularly limited, but in order to maintain a dispersed state, it is preferable to have an average particle diameter of 0.1 to 500 μm. Preferably it is 0.1-20 micrometers, More preferably, 0.5-4 micrometers is good. The graphene used in the present invention can be used all known, for example, the graphite (graphite) in sulfuric acid / nitric acid (7: 3) solution and oxidized at 80 ^o C for 48 hours and then used hydrazine monohydrate And reduced ones can be used.

The thermoplastic resin forming the thermoplastic resin layer of the present invention microencapsulates the graphene by surrounding the graphene. The resin layer according to the present invention can be used as long as the resin layer is made of the same kind of thermoplastic resin that can be dispersed well in the thermoplastic resin that is a matrix in producing the conductive thermoplastic resin. Examples include thermoplastic homopolymers or copolymers produced by addition polymerization of monomers comprising vinyl groups that can be addition polymerized. As a specific example according to the present invention, the resin layer may include a homopolymer or a copolymer formed by a polymerization reaction from one or more types of monomers selected from ethylene, vinyl, acrylic and methacryl, but is not limited thereto. no. The copolymer includes all types of copolymers such as alternating, irregular, block, graft copolymers, and the like. The ethylene monomers include ethylene, propylene, 1,3-butadiene, isobutylene, isoprene, styrene, alphamethyl styrene, and the like. System monomers include vinyl chloride, vinylidene chloride, vinyl halides such as tetrafluoroethylene, and vinyl C ₁ to C ₁₀ alkylates containing vinyl acetate (CH ₂ CH— OC (O) R, R are C ₁ ~ C ₁₀ Alkyl), or vinyl C ₁ to C ₁₀ Alkyl ethers (CH ₂ CH-OR, R is C ₁ ~ C ₁₀ alkyl), vinylpyrrolidone, vinyl carbazole and the like can be exemplified, but is not limited thereto.

Examples of the acrylic monomers are exemplified by acrylic acid (acrylic acid), acrylonitrile (acrylonitrile), acrylic amide (acryl amide), or C ₁ ~ C ₁₀ alkyl acrylate, _{(C 1 ~ C 10 alkyl acrylate} ) , etc. But it is not limited to this.

Specific examples of the methacrylic monomers are methacrylic acid (methacrylic acid), methacrylonitrile (methacrylonitrile), methacrylamide (methacryl amide) or C ₁ ~ C ₁₀ alkyl methacrylate (C ₁ ~ C ₁₀ alkyl) methacrylate) and the like, but is not limited thereto. The C ₁ -C ₁₀ alkyl includes methyl, ethyl, n-butyl, iso-butyl or 2-ethylhexyl.

In the conductive polymer filler, the thermoplastic resin layer occupies a weight ratio that surrounds graphene to form microcapsules, but according to a specific embodiment of the present invention, 1 part by weight of graphene is averaged in the microcapsule aggregate. It may be included in the ratio of 10 to 1000 parts by weight.

When the amount is less than 10 parts by weight, the resin layer surrounding the graphene is insufficient, resulting in an incomplete microcapsule state, resulting in poor homogeneous dispersion during the production of the conductive thermoplastic resin. In the graphene content is too small, too many fillers are required in the production of the conductive thermoplastic resin, there is a problem that it is difficult to mix as well as to match the physical properties of the desired thermoplastic resin. In addition, when the resin layer is manufactured through a process such as a polymerization reaction, it is difficult to form a resin layer in excess of 1000 parts by weight in the manufacturing process.

In addition, in the present invention, the conductive polymer filler of the present invention may include 0.01 to 10 parts by weight of nano metal particles, preferably 0.05 to 1 part by weight, based on 100 parts by weight of graphene. The size of the nano metal particles may be in the range of nano size, and specific examples include the range of 10 to 150 nm. The nano metal particles may be located anywhere in the graphene microcapsules, specifically, for example, mainly located on the inside of the resin layer or the outer surface of the resin layer. In the case of using the nano-metal particles of the present invention, it was found that the electrostatic dispersing characteristics were remarkably improved and exerted a very good effect. The metal nanoparticles of the present invention can be used as powder or paste. The metal nanoparticles are not limited as long as they are conventional ones having electrical conductivity. For example, any one or two or more excellent electrical conductivity such as silver, nickel or tungsten may be used. In the manufacturing process, the nano metal particles may be attached to a combination of graphene and a water-soluble block copolymer in the resin layer of the microcapsules or may be attached to the outer surface of the resin layer, depending on the time of addition. That is, when added before the polymerization step of the resin layer may be attached to the inside of the resin layer, and to the outer surface of the resin layer when added after the polymerization step.

The water-soluble block copolymer of the present invention is not limited as long as it is water-soluble as a component that can be included in the graphene microcapsules. The weight ratio of the water-soluble block copolymer in the conductive polymer filler composed of the graphene microcapsules is not particularly limited, but may be included in a ratio of 0.01 to 2 parts by weight based on 1 part by weight of graphene. The water-soluble block copolymer of the present invention refers to a polymer that can be dissolved in water, and the water-soluble block copolymer may be a homopolymer or a copolymer of hydrophilic chains, and may be an amphiphilic copolymer including a hydrophilic chain and a hydrophobic chain together. Can be. The water-soluble block copolymer is typically a repeating unit of the hydrophilic chain is carboxyl, carboxyl salt, amine, amine salt, phosphoric acid, phosphate, sulfuric acid, sulfate, alcohol, thiol, ester, amide. Functional groups of ethers, ketones, and aldehydes.

The water-soluble block copolymer according to the present invention preferably contains a functional group in which the repeating unit of the hydrophilic chain is selected from carboxyl, metal salt of carboxylic acid, and ether group. The water-soluble block copolymer according to the present invention may include a hydrophobic chain portion in the copolymer having the functional group. That is, it may be a copolymer having both a hydrophilic chain and a hydrophobic chain of the repeating unit including the functional group. The copolymer includes all of alternating, irregular, block, and graft copolymers but preferably includes block copolymers. The hydrophobic chain portion according to the present invention may be relatively hydrophobic with respect to the hydrophilic chain portion of the copolymer. Therefore, not only completely hydrophobic polymers such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), poly acrylate (PA), and poly methacrylate (PMA), but also polypropylene oxide (PPO) and polyacryl Late or derivatives thereof, polymethacrylate or derivatives thereof, polyvinyl acetate and the like.

Specifically, for example, a copolymer of a repeating unit including a hydrophilic functional group may include poly (ethylene oxide-b-propylene oxide) (PEO-b-PPO). In poly (ethylene oxide-b-propylene oxide) (PEO-b-PPO), PPO is relatively hydrophobic to PEO and acts as a hydrophobic chain. On the other hand, examples of the copolymer of the hydrophilic chain and hydrophobic chain of the repeating unit including a hydrophilic functional group include polystyrene-b-poly acrylic acid (PS-b-PAA) and the like. In the case of poly (ethylene oxide-b-propylene oxide), a copolymer prepared in a ratio of EO and PO of 0.05: 1 to 1: 0.05 mole ratio may be used, and more specifically, 0.15: 1, 0.33: 1, 0.8: 1 Copolymers prepared in such a molar ratio may be used, and commercially commercialized ones may be used. The water-soluble block copolymer is an amphiphilic copolymer, and the ratio of the hydrophilic chain and the hydrophobic chain is not particularly limited, but specific molar ratios of hydrophilic: hydrophobic ratio of 0.05: 1 to 1: 0.05 may be used.

In the case of using a water-soluble block copolymer made of an amphiphilic block copolymer including both a hydrophilic chain and a hydrophobic chain in a polymer molecule, dispersion stability may be further improved. That is, the hydrophobic chain can be formed into graphene, and a hydrophilic chain can form a kind of micelle-like structure in which it is exposed toward water. It is suitable that the said water-soluble block copolymer has a molecular weight (weight average molecular weight) of 1000-100000, Preferably it is 1000-50000.

Hereinafter, a method for preparing a graphene-containing conductive polymer filler according to the present invention will be described in detail.

Graphene-containing conductive polymer filler according to the present invention,

a) 1 part by weight of graphene and 0.01-2 parts by weight of a water-soluble block copolymer are mixed with 0.1-20 parts by weight of emulsifier, preferably 1-10 parts by weight of water, preferably 50-1000 parts by weight of purified water or pure water. Dispersing with a stirrer to obtain a dispersion solution of the graphene-water soluble block copolymer conjugate in which graphene and the water-soluble block copolymer are combined;

b) a polymerization step of polymerizing 10 to 1000 parts by weight of a thermoplastic resin monomer with respect to 1 part by weight of graphene to encapsulate the graphene with a thermoplastic resin layer formed from the monomers and microencapsulate it;

c) coagulating the resulting microcapsules to form a floc.

Furthermore, the manufacturing method may further include a pulverizing step of heating and cooling the floc to a glass transition temperature (Tg) or higher of the resin produced by the polymerization reaction, followed by the flocculation step. .

The role of the water-soluble block copolymer used in the dispersion step of graphene in the step of the production method is as follows.

The present invention proposes a method for producing graphene microcapsules by enclosing the graphene in a resin layer by a polymerization reaction in a state in which graphene is dispersed, but dispersion by ultrasonic wave as a method of dispersing graphene oxide It was found that it is difficult to expect the improvement of conductivity by losing the conductivity of graphene. Therefore, in the present invention, it is possible to surround the graphene with a thermoplastic resin layer through an emulsion polymerization reaction. To this end, in the case of dispersing using a water-soluble block copolymer together with graphene, the dispersion of graphene is stabilized in the long term to stabilize the dispersion. It was found that the improvement of the conductivity can be obtained.

In particular, in the present invention, when using an amphiphilic water-soluble block copolymer containing a hydrophobic chain portion as the water-soluble block copolymer, the hydrophobic portion is located in graphene, the hydrophilic portion is placed in the water phase to form a kind of micelle, and thus the dispersion state is further improved. It has been found that there is an effect that can be maintained well and further improve the conductivity.

In addition, by using the water-soluble block copolymer of the present invention with graphene, it was found that even when the graphene particles and the nano metal particles are added together to disperse, the dispersion stability is excellent. In the present invention, an emulsifier may be used together with the water-soluble block copolymer.

The polymerization method of the present invention may be carried out according to a known polymerization method such as suspension polymerizarion or emulsion polymerization. Preferably it can be carried out under emulsion polymerization conditions and the polymerization reaction can be appropriately designed and carried out by those skilled in the art under known reaction conditions.

Examples of the manufacturing method according to the present invention can be carried out under the following conditions, but are not limited thereto.

When the polymerization reaction is emulsion polymerization, the polymerization temperature is preferably 0 ° C to 280 ° C, more preferably 40 to 120 ° C. The emulsifiers that can be used for the polymerization thereof to perform the emulsion polymerization are not particularly limited, and various emulsifiers known in the art can be used. Examples include anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl phosphate ester salts and dialkyl sulfoco salts; Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitol fatty acid ester, and glycerin fatty acid ester; Cationic surfactants such as alkylamine salts; Amphiphilic surfactants can be used. However, the emulsifier is used as it is emulsifier used in the water dispersion step, and may be added to the reaction by including in a dispersion for supplying a monomer.

Specific examples of emulsifiers include sodium dodecyl sulfate, sodium dodecyl benzene sulfate, polyoxyethylene alkyl ethers (alkyl alcohol ethoxylates), sodium dioctyl sulfosuccinate, polyoxyethylene alkylether sulfate salts, emulsifiers such as polysorbate 20 or 80 Tween series emulsifiers, and triton X-100. have. Of course, this is only an example of a commercial emulsifier and all known emulsifiers can be used without particular limitation.

Prior to the polymerization step, the dispersed graphene aqueous dispersion is transferred to the reactor after further water is added as necessary. The solution in the reactor is continuously stirred. The supply of monomers for the polymerization reaction is distributed homogeneously with the emulsifier in water and fed to the reactor. The emulsifier for monomer dispersion is preferably the same emulsifier used in the dispersing step by the homogenizer.

100 parts by weight of the monomer is mixed with 50 to 300 parts by weight of water and 1 to 20 parts by weight of the emulsifier, then the monomer dispersion is stirred and slowly added to the reactor. For the polymerization reaction, after the addition of the monomer, a polymerization initiator is added to initiate the polymerization reaction. The polymerization initiator may be used either alone or redox of the water-soluble initiator or the oil-soluble initiator. Specific examples of the water-soluble initiator include inorganic initiators such as persulfate, and specific examples of oil-soluble initiators include benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxy peroxide, lauroyl peroxide, octanoyl peroxide and methyl. Organic peroxides such as ethyl ketoperoxide, diisopropylperoxydicarbonate, cyclohexanone peroxide, t-butylhydroperoxide or diisopropylbenzenehydroperoxide; An azo nitrile compound, an azo acyclic amide compound, an azo cyclic amide compound, an azo amide compound, an azo alkyl compound or an azo ester compound, and the like. Any one or more of these may be used. It is preferable to use the said polymerization initiator in the ratio of 0.001-10 weight part with respect to 100 weight part of monomers, and it is more preferable to use it in the ratio of 0.001-1 weight part.

Hereinafter, a coagulation step of coagulating the microcapsules formed in the polymerization step will be described in detail. In the coagulation step, the formed microcapsules can be coagulated using a known filtration, dialysis, or salting method, and preferably, a salting method is used. In the salting method, a flocculant is added to form a floc. The flocculant is a monovalent to trivalent metal salt or an acid such as sulfuric acid or acetic acid. Specifically, the metal salt is mainly used CaCl ₂ , MgSO ₄ or Al ₂ (SO ₄ ) ₃ . Microcapsules in which aggregation occurs are obtained by centrifugation. On the other hand, the flocculant of the microcapsules obtained through the flocculation step is preferably to remove the moisture through drying.

In addition, when the flocculant is added, the nano metal particles may be added together. By doing so, nano metal particles may be attached to the outer surface of the resin layer of the microcapsules.

The nano metal particles may be added in advance in the dispersing step using a water-soluble block copolymer or a water-soluble block copolymer and an emulsifier together with graphene, or may be added in the flocculating step by adding a flocculant to further include nano metal particles. Conductive polymer fillers containing fins can be prepared.

In the present invention, the flocculated floc of the microcapsules from which the coagulant is removed from the water can be commercialized into a desired size through a step of heating and pulverizing. The grinding step may use a known grinding process, and may be a method such as knife cutting or milling. The average particle diameter of the product obtained in the grinding step is preferably adjusted to be 0.05 ~ 2.00 mm, more preferably 0.10 ~ 1.00 mm.

The conductive polymer filler obtained according to such a manufacturing method may be used in the production of a conductive thermoplastic resin by varying the amount of the conductive polymer filler as necessary and including it in the thermoplastic resin. It is obvious that the present invention can be used in addition to additives for obtaining other properties such as flame retardant additives other than the conductive polymer filler according to the present invention.

After mixing an additive for another extrusion process with a conductive thermoplastic resin composition in which 0.1 to 30 parts by weight of the conductive polymer filler according to the present invention is mixed with 100 parts by weight of the thermoplastic resin, a conductive thermoplastic resin may be manufactured through a known extrusion process. When the conductive polymer filler according to the present invention is used in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of a thermoplastic resin, sufficient surface resistance can be obtained, and in the case of using 10 to 30 parts by weight, it may be used as a master batch concept. .

The thermoplastic resin is polyacetal resin, acrylic resin, polycarbonate resin, styrene resin, polyester resin, vinyl resin, polyphenylene ether resin, polyolefin resin, acrylonitrile-butadiene-styrene copolymer resin, polyarylate Resin, polyamide resin, polyamideimide resin, polyarylsulfone resin, polyetherimide resin, polyethersulfone resin, polyphenylene sulfide resin, fluorine-based resin, polyimide resin, polyetherketone resin, polybenzoxazole resin, Polyoxadiazole resin, polybenzothiazole resin, polybenzimidazole resin, polypyridine resin, polytriazole resin, polypyrrolidine resin, polydibenzofuran resin, polysulfone resin, polyurea resin, polyphosphazene resin and One or more resins or resin mixtures selected from the group consisting of liquid crystalline polymer resins, or It includes the copolymer obtained through the copolymerization of the monomer.

The present invention provides a conductive plastic additive composition prepared by the method for producing a conductive plastic additive composition.

Hereinafter, the present invention will be described by way of examples. This embodiment is presented for the understanding of the present invention, and the scope of the present invention should not be construed by the present embodiment.

Example 1

0.5 g of poly (ethylene oxide-b-propylene oxide) [hydrophilic: hydrophobic molar ratio = 0.8: 1, weight average molecular weight 2900] copolymerized from ethylene oxide and propylene oxide as a water-soluble block copolymer in 100 g of pure water After stirring for about 10 minutes with a homogenizer, 1 g of 3 μm of graphene synthesized by itself and 4 g of an emulsifier (sodium dodecyl benzene sulfate) are added to the solution, followed by stirring for about 2 hours. Graphene used in the present invention was used in the graphite (graphite) in sulfuric acid / nitric acid (7: 3) solution and oxidized at 80 ^° C for 24 hours and then reduced using hydrazine monohydrate.

The homogenizer is used to disperse the dispersed solution in the reactor for polymerization, and then add 400 g of pure water and stir. At this time, the temperature was 55 ℃, the stirring speed was fixed to 300rpm. Then, a mixed solution of 80 g and 20 g of styrene and acrylonitrile monomers, 8 g of sodium dodecyl benzene sulfate, and 100 g of pure water was stirred for about 10 minutes with a homogenizer, and then into a reactor containing a dispersion solution containing graphene. Slowly add dropping. After stirring for about 30 to 60 minutes, 1 g of benzoyl peroxide, a polymerization initiator, is diluted and added to 40 g of pure water to initiate the polymerization reaction. At this time, the reaction temperature is set to 70 ° C and the polymerization reaction is started. Styrene and acrylonitrile monomers surround the graphene particles dispersed by the water-soluble block copolymer and a polymerization reaction occurs to form microcapsules. 1N sulfuric acid (H ₂ SO ₄ ) is added to the emulsion solution in which the microcapsules are formed, and then the aggregated particles are formed to maintain the strength to a certain extent while the reaction temperature is raised to 100 ° C. at a high speed. After cooling, washed with pure water several times and dried to obtain a floc of the conductive polymer filler formed by agglomeration of the conductive polymer filler in the form of microcapsules. 100 g (containing 1 g of graphene) obtained as a floc was compounded with 1000 g of polycarbonate resin to prepare a conductive thermoplastic resin using an extruder.

After the injection molding the prepared conductive thermoplastic resin composition 100 mm in diameter, 3 mm thick disk plate was measured surface resistance, the results are shown in Table 1.

[Example 2]

In Example 1, a conductive thermoplastic resin was prepared in the same manner as in Example 1, except that 0.05 g of silver (Ag) powder having an average particle size of 20 nm was added to 1 g of graphene during dispersion. It was. SDS (sodium dodecyl sulfate) was used as an emulsifier.

[Example 3]

In Example 1, a conductive thermoplastic resin was prepared in the same manner as in Example 1, except that 100 g of methyl methacrylate and 50 g of butyl methacrylate were mixed instead of the styrene and acrylonitrile monomers. Triton X-100 was used as an emulsifier.

Example 4

In Example 1, except that 0.01g of silver (Ag) powder having an average particle size of 20 nm was included in the coagulant 1N sulfuric acid (H ₂ SO ₄ ) in the emulsion solution in which the microcapsules were formed after the polymerization was completed, and then coagulated. A conductive thermoplastic resin was prepared in the same manner as in Example 1, except that only in the same manner as in Example 1. M-LE1050 (lauryl alcohol ethoxylate; product of trithermal acid) was used as an emulsifier.

[Example 5]

In Example 1, a conductive thermoplastic resin was prepared in the same manner as in Example 1 except that 40 g and 10 g of styrene and acrylonitrile were used, respectively. EU-D0113 (sodium dioctyl sulfosuccinate) was used as an emulsifier.

Comparative Example 1

In Example 1, all processes were performed in the same manner, but the conductive thermoplastic resin was prepared without using the water-soluble block copolymer. However, in the polymerization step, the dispersion of the graphene was not maintained, but the graphenes aggregated together to form precipitates, thereby failing to obtain microcapsules including graphene. As a result, a conductive thermoplastic resin could not be produced.

Comparative Example 2

A conductive thermoplastic resin was prepared by extruding a composition in which 10 g of graphene was mixed with 1000 g of polycarbonate resin.

Composition ratio and surface resistance measurement when manufacturing conductive thermoplastic Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Grapina 1 g 1 g 1 g 1 g 1 g 1 g 10g PEO-b-PPO 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g - - Styrene 80g 80g - 80g 40g 80g - Acrylonitrile 20g 20g - 20g 10g 20g - Methyl methacrylate - - 100g - - - - Butyl methacrylate - - 50 g - - - - Nano silver - 0.05g - - - - - Ag when agglomerated - - - 0.01 g - - - Graphene-containing microcapsules (dry basis) 100g 100g 100g 100g 50 g - - PC 1000 g 1000 g 1000 g 1000 g 1000 g - 1000 g
Surface resistance
(Ω / sq) 1.8 x 10 ⁶ 3.2 x 10 ⁴ 3.5 x 10 ⁶ 4.2 x 10 ⁵ 2.1 x 10 ⁶ -
2.6 x ^{10 12}

Remarks - Nano silver particles added during dispersion - Nano silver particles added during aggregation - Microcapsules fail due to broken dispersion -

In the case of Examples 1 to 4, the graphene-containing microcapsules were used in 1000 parts by weight of the thermoplastic resin at 0.1 parts by weight (based on graphene content).

In the case of Examples 1 to 4 it can be seen that the graphene contained in the conductive thermoplastic resin 1000g shows very good conductivity even when using a very small amount of less than 1g has a very good antistatic function. As in Comparative Example 2, it can be seen that the remarkably superior surface resistance compared to the case where a large amount of graphene is added, the effect of the configuration of the present invention is very excellent, and the water-soluble block copolymer of the present invention is not mixed with graphene. In the case of Comparative Example 1 that does not become a dispersion itself shows a poor performance. That is, in the case of Comparative Example 1 was attempted to encapsulate the graphene with a resin without using a water-soluble block copolymer, but did not obtain the desired microcapsules containing graphene. As a result, a uniformly dispersed conductive thermoplastic resin specimen could not be produced, and thus a measurement of surface resistance could not be obtained. From these results, the resin composition containing the graphene according to the present invention should be applied to add at least 5 to 10 parts by weight to show the antistatic function of most existing antistatic agents, but according to the present invention 0.1 It can be seen that even a small amount added by weight part shows a significantly improved surface resistance value. In Example 5, the resin content encapsulating the outside of the graphene was reduced, but the surface resistance did not change much.

Therefore, in Examples 1, 3, and 5, although the graphene is used less than 1/10 compared to Comparative Example 2 in which the amount of graphene is increased by 10 times without using a water-soluble block copolymer, the surface resistance is about 1/10. 10 ⁵ times (100,000 times) improvement was obtained.

In addition, when the nano metal particles are used together in the dispersion, the surface resistance could be improved by about 8 × 10 ⁷ times, and when the nano metal particles were added during the aggregation of the graphene-containing microcapsules, the surface resistance could be improved by 5 × 10 ⁶ times.

Claims (11)

a) 1 part by weight of graphene having an average particle diameter of 0.1 ~ 500㎛, 0.1 to 2 parts by weight of water-soluble block copolymer, 0.1 to 20 parts by weight of emulsifier and 50 to 1000 parts by weight of water are mixed and rapidly dispersed with a homogenizer A dispersion step of obtaining an aqueous dispersion solution of the pin;
b) a thermoplastic resin layer prepared by emulsion polymerization of an aqueous dispersion solution of graphene with 10 to 1000 parts by weight of at least one monomer containing an ethylene group which can be additionally polymerized with respect to 1 part by weight of graphene. Polymerization step of encapsulation by encapsulation:
c) flocculation step of flocculating the resulting microcapsules to form a flock. delete The method of claim 1,
And a pulverizing step of heating the floc to a glass transition temperature (Tg) or higher of the resin produced by a polymerization reaction and then cooling and pulverizing the floc. The method of claim 1,
The water-soluble block copolymer includes poly (ethylene oxide-b-propylene oxide) or polystyrene-b-polyacrylic acid,
The poly (ethylene oxide-b-propylene oxide) is a ethylene oxide (EO) and propylene oxide (PO) ratio is produced in a molar ratio of 0.05: 1 to 1: 0.05 Method for producing a conductive polymer filler, characterized in that. delete The method of claim 1,
During the polymerization step or after the polymerization step, a method for producing a conductive polymer filler further comprising the step of introducing metal nanoparticles. The method according to claim 6,
The conductive polymer filler is a method for producing a conductive polymer filler further comprises a metal nanoparticles in a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of graphene. The method of claim 1,
In step b), the at least one monomer including the ethylene group includes at least one monomer selected from the group consisting of an ethylene monomer, a vinyl monomer, an acrylic monomer, and a methacryl monomer, wherein the ethylene monomer is At least one selected from the group consisting of ethylene, propylene, 1,3-butadiene, isobutylene, isoprene, styrene, and alpha-methyl styrene; The vinyl monomer is vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinyl C ₁ ~ C ₁₀ alkylate (CH ₂ CH-OC (O) R, R is C ₁ ~ C ₁₀ Alkyl), vinyl C ₁ to C ₁₀ Alkyl ethers (CH ₂ CH-OR, R is C ₁ ~ C ₁₀ Alkyl), vinyl pyrrolidone, vinyl carbazole, and at least one selected from the group consisting of acrylic acid (acrylic acid), acrylonitrile (acrylonitrile), acrylamide (acryl amide) and C ₁ ~ C ₁₀ alkyl acrylate, _{(C 1 ~ C 10 alkyl acrylate} ) including at least one selected from the group, the methacrylate-based monomer consisting of the methacrylic acid (methacrylic acid), nitrile (methacrylonitrile), methacrylonitrile, methacrylic Method for producing a conductive polymer filler comprising at least one selected from the group consisting of methamide (methacryl amide) and C ₁ ~ C ₁₀ alkyl methacrylate (C ₁ ~ C ₁₀ alkyl methacrylate). Claim 1, 3, 4 and 6 to 8 of the conductive polymer filler comprising a graphene prepared by the method of any one selected from the method comprising a thermoplastic resin surrounding the graphene.  A conductive material comprising 0.01 to 30 parts by weight of a conductive polymer filler prepared by any one of claims 1, 3, 4, and 6 to 8 with respect to 100 parts by weight of the thermoplastic resin. Thermoplastic resin composition. The method of claim 10,
The thermoplastic resin may be polyacetal resin, acrylic resin, polycarbonate resin, styrene resin, polyester resin, vinyl resin, polyphenylene ether resin, polyolefin resin, acrylonitrile-butadiene-styrene copolymer resin, polyarylate Resin, polyamide resin, polyamideimide resin, polyarylsulfone resin, polyetherimide resin, polyethersulfone resin, polyphenylene sulfide resin, fluorine-based resin, polyimide resin, polyetherketone resin, polybenzoxazole resin, Polyoxadiazole resin, polybenzothiazole resin, polybenzimidazole resin, polypyridine resin, polytriazole resin, polypyrrolidine resin, polydibenzofuran resin, polysulfone resin, polyurea resin, polyphosphazene resin and One or two or more resin mixtures selected from the group consisting of liquid crystalline polymer resins, or The conductive thermoplastic resin composition is selected from the polymer.