KR20020056030A - Polymer complex and colloidal composition comprising it - Google Patents

Abstract

PURPOSE: Provided are a conductive polymer complex which can be easily separated, purified and redispersed, and which has improved conductivity, and water-based colloid composition comprising the conductive polymer complex. CONSTITUTION: The method comprises the steps of: (i) adsorbing an anion oligomer radical of conductive polymer produced by oxidizing high molecular monomer on surface of acryl latex particles which comprise 5-60% of acid equivalents and have molecular weight of 10,000-50,000 and particle size of 50-150 nm, in the presence of the acryl latex emulsion, and polymerizing the polymer and latex particles to form a conductive polymer-latex complex having solid content of 60-80%; (ii) swelling and filtering the latex particles of conductive polymer-latex complex with alkali compounds at 40-80 deg.C; and (iii) redispersing the filtrate in aqueous dopant and pressure filtering the aqueous solution.

Description

Polymeric complex and colloidal composition comprising it

The present invention relates to a conductive polymer composite and an aqueous colloidal composition containing the same, and more particularly, to a conductive polymer composite and an aqueous colloidal composition containing the same, which can be used as an additive for antistatic, electromagnetic wave shielding, and anticorrosion coatings. .

Polyaniline, polypyrrole and polythiopene, which are electrically conductive polymers, have been attracting much attention because they are easy to polymerize, have relatively high electrical conductivity, and have excellent properties such as oxidation stability. In addition to the electrical conductivity, these polymer compounds have anticorrosive properties and electrochromic properties, and thus may be applied to electronic materials, anticorrosive coating materials, and smart windows.

However, the polymer compound having a conjugated double bond in the main chain as described above has many restrictions in processing due to the insoluble and insoluble properties due to strong mutual attraction between the electrons included in the double bond.

Accordingly, efforts have been made to improve the processability of conductive polymers, and as a part thereof, polymers are introduced by doping conductive polymers with dopants having large molecular weights or introducing substituted monomers to reduce mutual attraction of the polymers, and polymers prepared by introducing water-soluble dopants. There have been attempts to dissolve in organic solvents or water using a method such as hydrolysis. However, this was so limited that only a very small amount of solution had limited commercialization. Therefore, recent studies have attempted to produce conductive polymers in dispersible forms rather than attempting to dissolve conductive polymers in solvents to overcome these limitations.

For example, EP 0589529A1 describes a method for preparing a conductive polymer / binder composite in which a conductive polymer is polymerized on a binder particle having a nonionic stabilizing functional group, purified by centrifugation, or the like, and then redispersed in water.

This method has the advantage that the conductive film is at least relatively high in content of the expensive conductive polymer, but since the conductive polymer is coated on a binder having a very small particle size, the separation / redispersion through centrifugation is repeated to remove the water-soluble by-products. Method or ultra fine filter should be used. Therefore, it takes a long time in the separation and purification process, there is a disadvantage that the final yield is relatively low.

In USP 5,720,903, polyaniline powder prepared by precipitation polymerization method is vigorously stirred in the presence of a polar solvent such as butyrolactone or N-methylpyrrolidone and dispersed in a solvent-based lacquer to form a coating film having a relatively high conductivity even at a low conductive polymer content. It states that it can be obtained. However, this method has the disadvantage of dispersing for a long time with a disperser such as a kneader at high temperature in order to grind / disperse the polyaniline aggregate.

USP 5,567,356 can emulsify aniline using a very hydrophobic dopant as an emulsifier, and shows that water-soluble by-products can be easily removed by separating the water layer after adding a layer of xylene to an aqueous polyaniline solution. . However, the price of the dopant is very expensive and the unreacted dopant present on the xylene cannot be removed and the conductivity of the resulting polyaniline is large compared to other inventions due to the large size of the dopant applied.

According to Synthetic matals, 55 (1993) 997, reduced polyaniline is dissolved in a solvent such as NMP, and processed into a film or fiber using dissolved polyaniline, stretched four times, and stretched to 220S / cm when doped with 1M HCl. Reported conductivity.

Accordingly, the present inventors are trying to develop an effective conductive polymer-latex composite that is easy to separate, purify and redistribute easily and improve conductivity by improving the disadvantages of the techniques described above, and the monomer of the conductive polymer includes a large amount of acid monomer. After polymerization in the presence of a latex emulsion, the acid functional group of the latex was swollen with alkali to make the particles larger. As a result, the conductive polymer coated on the surface of the latex particles was physically stretched by alkali neutralization to increase conductivity. It was found that there is an effect to make the present invention was completed.

Accordingly, an object of the present invention is to provide a conductive polymer composite that is easy to separate, purify and redisperse, and has improved conductivity.

Another object of the present invention is to provide an aqueous colloidal composition including the conductive polymer composite.

The conductive polymer composite of the present invention for achieving the above object contains a monomer of the conductive polymer in the presence of an acrylic latex emulsion containing 5 to 60% by weight of an acid equivalent, a molecular weight of 10,000 to 50,000, and a particle diameter of 50 to 150nm. The cationic oligomer radical of the conductive polymer produced by oxidation is adsorbed onto the surface of the latex particles to polymerize to prepare a conductive polymer-latex composite having a solid content of 60 to 80%, and the conductive polymer-latex with an alkali compound at 40 to 80 ° C. The latex particles of the composite are swelled and filtered, and then redispersed in an aqueous dopant solution, followed by pressure filtration.

In addition, the aqueous colloidal composition comprising 1 to 70 parts by weight of the conductive polymer composite paste, 91 parts by weight of deionized water, and 10 to 30 parts by weight of an acrylic latex containing a sulfate group is also characterized.

The present invention will be described in more detail as follows.

The present invention relates to a conductive polymer composite and an aqueous colloidal composition containing the same.

Precipitation polymerization of conventional conductive polymers is caused by oxidizing monomers of conductive polymers such as aniline, pyrrole, and thiophene under an acidic condition in an aqueous phase using an oxidizing agent. Precipitates into a powder, making aggregates. In order to disperse it in an organic solvent, re-agglomeration must be prevented. To this end, a very strong energy is applied for a long time in the presence of a low molecular or high molecular weight dispersant having a higher affinity with a conductive polymer than with a solvent capable of proper dispersing. Should.

In general, when the dispersion is optimized so that the conductive polymer has the smallest particle size, the conductive polymer contains a small amount of the conductive polymer and maximizes the physical contact of the conductive polymer in the coating film after drying, thereby showing high electrical conductivity.

Therefore, in the present invention, the reaction proceeds as the conductive polymer is adsorbed onto the latex surface in the latex emulsion containing a large amount of acid monomer, thereby minimizing the formation of the conductive polymer aggregate by controlling the reaction to have a steric stability. In addition, in the subsequent neutralization process, the acid functional group of the latex is reacted with an alkali compound to induce latex expansion, thereby facilitating the filtration process, and directly dispersing the paste of the filtered conductive polymer composite in a high speed stirrer, ball mill, bead mill, roll mill, etc. To prepare a conductive paint using a method of dispersing in the presence of an organic acid dopant and a general coating resin using. In particular, in order to increase the doping efficiency of the conductive polymer composite and stability of the finally prepared conductive polymer colloid mixture, it is preferable to use an acrylic latex having a structure similar to the core acryl latex of the conductive polymer and containing sodium sulfonate salt.

It will be described in more detail below.

(1) conductive polymer composite

In the present invention, the conductive polymer composite is produced by oxidizing monomers of a conductive polymer such as aniline, pyrrole, and thiophene under acidic conditions, preferably pH 2 to 5, in the presence of an acrylic latex emulsion. In this case, since the polymerization occurs while the cationic oligomer radicals of the conductive polymers are adsorbed onto the surface of the latex particles, the formation of the conductive polymer aggregates can be minimized. The adsorptive force of the conductive polymers to the latex of the cationic oligomer radical is due to the polar methylmethacrylate and methacrylic acid molecules.

Acrylic latexes usable in the present invention are general purpose latex emulsions and include pure acrylic latex, styrene / acrylic latex, SBR latex, and ABS latex. However, in order to induce the adsorption of the conductive polymer to the subsequent neutralization / swelling process and the latex particles, such acrylic latex should contain 5 to 60% by weight of the total latex composition, preferably 20 to 45% by weight. When the content of acid monomer in the acrylic latex is low, the stability of the acrylic latex particles is reduced by the monomer and acid catalyst of a conductive polymer such as aniline used to prepare the conductive polymer composite, and thus the conductive polymer is adsorbed evenly on the surface of the acrylic latex. It is difficult to expect the formation of a complex. In addition, when the content of the acid monomer in the acrylic latex is too high, the amount of the alkali compound required for the subsequent particle swelling process is increased, and finally, there is a risk of economic loss due to a decrease in yield and an increase in wastewater.

Here, examples of the acid monomer included in the acrylic latex include acrylic acid, methacrylic acid, vinylbenzene acid, isopentyl benzene acid, crotonic acid, itaconic acid, maleic acid, fmaric acid, vinylsulfonic acid, arylsulfonic acid, methylsulfonic acid, styrenesulfonic acid And acrylamido alkylsulfonic acid, and the like and selected from these can be mixed.

In addition, in order to prevent smooth dispersion and re-agglomeration of the conductive polymers, the latex used should have a greater affinity with the conductive polymer than the affinity with the solvent, and therefore, the composition of the latex should be sufficiently polar and hydrophilic. In addition, the weight average molecular weight of the latex should be adjusted to adjust the molecular weight to be between 10,000 and 50,000. This can be controlled by adding an appropriate amount of a chain transfer agent during emulsion polymerization of the latex. In principle, latex can significantly increase the electrical conductivity of the coating film by containing 0.1 to 10% by weight of the ionic monomer relative to the total weight of the insulator or latex. Examples of the ionic monomers include quaternized dimethylaminoethyl methacrylate (Japanese Industrial Chemicals Co., Ltd. LIGHT ESTER DQ-100), polystyrene sulfonate, and the like. The conductivity of the coating film depends on the physical contact of the conductive polymers and therefore depends on the dispersibility and the amount of conductive polymer introduced. Conversely, in terms of mechanical properties of the coating film, excluding price and electrical conductivity, the smaller the amount of the conductive polymer is, the better.

In addition, the smaller the particle size of the latex emulsion used in the polymerization is advantageous to the adsorption of the conductive polymer radical produced, but the particle size of 50 nm or more is preferred considering the ease of the filtration process after particle expansion in the neutralization / swelling process. It is preferable to have a particle diameter of 50-150 nm specifically ,.

On the other hand, the polymerization of the conductive polymer to the acrylic latex should proceed while maintaining the three-dimensional stability of the polymerization solution, the necessary conditions should be such that the total polymerization solution has a low solid content, preferably the total solution has a solid content of 40% by weight or less. In addition, it is advantageous if the amount of the conductive polymer to be added is small. Usually, the monomer amount of the conductive polymer in the total conductive polymer / latex composite should be polymerized at 5 to 60% by weight, and preferably 30% by weight or less. When the amount of the conductive polymer monomer is excessively added, it is difficult to expect the ease of the filtration process by the particle swelling of the subsequent process due to the conductive polymer oligomers that are polymerized separately without being adsorbed on the surface of the latex used as the core, and thus the yield is high. Will decrease.

In addition, ammonium persulfate oxidant is most preferred as a reaction catalyst for the polymerization of monomers such as aniline for the production of a conductive polymer composite, and since the amount of use is theoretically a stoichiometric reaction between the oxidizing agent and the reducing agent, However, for the purpose of molecular weight control or yield improvement, 0.5 to 1.5 moles per mole of monomer may be used.

The polymerization temperature is advantageously low temperature for suppressing side reactions, preferably -10 ~ 25 ℃. In addition, the method of injecting the oxidizing agent solution and the monomer-acid complex into the initial composition including the latex emulsion and water at the same time in a sufficiently slow time to maintain the temperature and to maintain the concentration of the monomer concentration and the initiator in the solution constant. good. If the polymerization temperature does not change, the input time does not affect the physical properties after the polymerization, and the holding time is suitable for about 2 hours to 24 hours after the completion of the injection, preferably 4 to 6 hours.

Korea polymer journal, 1999, Vol. 7, No. 4, p213-222, the swelling of the latex emulsion depends on the hydrophilicity of the monomer composition, the content of acid monomers, the amount of neutralizer used, and the like. Therefore, the neutralization / swelling process is performed at normal temperature or high temperature, preferably at a temperature of 40 to 80 ° C.

In this case, examples of the alkali compound used include inorganic and organic amines, and specific examples include inorganic bases such as ammonia, sodium hydroxide and lithium hydroxide, dimethyl ethanol amine and triethyl amine. Among them, ammonia water is preferably used so that it can be easily desorbed from the acid functional group of the latex in the subsequent drying process.

When neutralizing with alkaline compounds, the salts form while binding to the acid functional groups of the latex, and the particles expand as the latex composition swells with water.At this time, the conductivity of the conductive polymer film coated on the surface of the particles is expected to improve conductivity. Larger particle diameters greatly facilitate the subsequent filtration process.

When the particles are swelled with an alkali compound, the particle size of the final conductive polymer composite aggregates is increased to 3 ~ 5um due to the increase of the particle size.In this case, when using a paper filter or a glass filter with a pore size of 1 ~ 2um, the separation and purification It becomes easy.

In addition, when dispersed in a subsequent process it is possible to produce a stable colloidal mixture of the conductive polymer composite is dispersed in primary particles of 150 ~ 500nm. In the case of the neutralizing agent, the pH of the solution is generally added in the range of 8.0 to 13, and the dopant of the conductive polymer doped with an acid during polymerization after the particle swelling according to the neutralization process is desorbed by binding to the base, thereby losing electrical conductivity. do. At this time, the filtration process washes with water several times until the pH of the filtrate is neutral to remove water-soluble by-products such as unreacted aniline monomer and oxidizing agent. If the filtration to complete the manufacturing of the conductive polymer paste consisting of 60 to 80% solids and the remaining water.

In this case, the prepared conductive polymer / latex powder may be dried in a vacuum dryer at room temperature to use a powder state, but it is inconvenient to vary the vacuum drying conditions according to the glass transition temperature of the acrylic latex used as the core of the composite. Therefore, in the present invention, the paste is prepared by pressurization during the filtration process. Solid content of the paste manufactured by such a method is 60 to 80 weight%.

In order to disperse the paste of the prepared conductive polymer composite in an organic solvent and water, conventional dispersers such as a high speed stirrer, a ball mill, a bead mill, a roll mill, etc. are used, and in addition to the conductive polymer / latex powder paste prepared above, a dopant Is used. At this time, if excess dopant other than the dopant participating in the doping remains in the film of the application step, there is a disadvantage in reducing the water resistance of the coating film, so that the previously prepared paste and excess dopant are dispersed in water in advance and then doped. Filtered doped paste is used.

The dopant oxidizes the molecular structure reduced by alkali during particle swelling of the conductive polymer composite of the present invention to facilitate delocalization of electrons by conjugated double bonds, thereby increasing conductivity. The type of dopant may be varied according to its application and conductivity. Examples of the dopant used herein may include an organic acid, particularly an organic acid having a high molecular weight in order to prevent desorption at high temperatures and maintain conductivity. Usually alkylbenzene sulfonic acids having 0-20 carbon atoms can be used, with p-toluene sulfonic acid and dodecylbenzene sulfonic acid being preferred. 0.5 mole per 1 mole of the monomer of the conductive polymer is introduced, but 0.5 to 1 mole may be used for the purpose of improving conductivity.

The dopant aqueous solution is prepared by mixing 1 to 99% by weight of the above alkylbenzene sulfonic acid and 1 to 99% by weight of deionized water.

The doped paste finally has 50 to 80% solids.

(2) aqueous colloid composition

The coating composition may be prepared using the paste obtained above, and specifically, 1 to 70 parts by weight of the conductive polymer composite paste, 91 parts by weight of deionized water, and 10 to 30 parts by weight of an acrylic latex containing a sulfate group. .

Here, when the content of the conductive polymer composite paste exceeds 70 parts by weight, there is a disadvantage in that the stability of the colloidal composition due to aggregation of the conductive polymer composite is inferior.

The acrylic latex containing a sulfate group is a paste having a structure similar to core acryl latex, which increases the doping efficiency of the conductive polymer composite and is due to the stability of the conductive polymer colloid mixture. Specific examples include 5 to 30% by weight of at least one selected from 2-acrylamido-2-methylpropanesulfonic acid sodium, acrylamido thibutylsulfonic acid, styrene sodium sulfate, isoprene sulfate sodium salt and aryl sodium sulfate salt. And at least one selected from the group consisting of pure acrylic latex, styrene / acryl latex, styrene-butadiene rubber latex and acrylonitrile-butadiene-styrene latex.

If the content is less than 5 parts by weight of water dispersion stability is poor, the stability of the colloid composition is lowered, if more than 30 parts by weight of the adsorption of the conductive polymer oligomer to the core emulsion is difficult to form a complex.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Preparation Example 1 Preparation of Acrylic Latex Emulsion (AE1)

First, acrylonitrile, acrylamide, methyl methacrylate, butyl acrylate, methacrylic acid, and light ester DQ-100 (Japanese public chemical) were 86.2g, 43.1g, 120.5g, 151.5g, 30.0g and 12.9, respectively. g A preemulsion is prepared by adding 6.4 g of CO-436 (from Rhodia, anionic emulsifier) and 12.1 g of nonylphenol ethoxylate (Triton X-405) to the mixed monomer solution mixture solution. In addition, 2.6 g of ammonium persulfate was dissolved in 58.3 g of deionized water to prepare an oxidant solution, and 1.7 g of sodium bisulfite was dissolved in 58.3 g of deionized water to form an oxidant solution. A reflux tube, a thermocouple thermometer, and a dropping tank are installed in a four-necked 2L round flask equipped with a heating mantle and a stirrer, and 259.1 g of deionized water and 3.8 g of CO-436 are heated up to 65 degrees. 5% of the total emulsion containing the monomer mixture was added dropwise, followed by 5% of the oxidizing agent and the reducing agent solution for 10 minutes. The mixture was heated up to 72 degrees by exotherm, and 12.9 g of 3-mercaptopropionic acid was mixed with the remaining amount of the monomer mixture, followed by dropwise addition for 180 minutes, and the oxidizing agent and the reducing agent solution were simultaneously dropped at 72 degrees for 195 minutes each. After dropping, hold for 60 minutes at 80 degrees. This is cooled to room temperature and filtered through a 400 mesh nylon filter to remove the coagulum. The particle size produced was about 120 nm as measured by laser light scattering. The solid content was 45% and the weight average molecular weight was about 25,000 when measured by the universal assay using GPC.

Preparation Example 2 Preparation of Acrylic Latex Emulsion (AE2)

Prepared in the same manner as in Preparation Example 1, but acrylonitrile, acrylamide, methyl methacrylate, butyl acrylate, methacrylic acid, Light ester DQ-100 (Japanese public company chemistry) 86.2g, 43.1g, 86.2 g, 129.4 g, 86.2 g, and 12.9 g are prepared using mixed monomer solution mixture. The prepared particles had a size of 100 nm, a home content of 45% and a molecular weight of 20,000.

Preparation Example 3 Preparation of Acrylic Latex Emulsion (AE3)

Manufactured in the same manner as in Preparation Example 1, but acrylonitrile, acrylamide, methyl methacrylate, butyl acrylate, methacrylic acid, Light ester DQ-100 (Japanese public company chemistry) 86.2g, 43.1g, 86.0 g, 96.0g, 120.2g, 12.9g prepared by using a mixed monomer solution mixture. The prepared particles had a size of 130 nm, a solid content of 45% and a molecular weight of 23,000.

Example 1 Preparation of Polyaniline / AE1 Paste

116.1 g of the acrylic latex emulsion AE1 obtained in Preparation Example 1 and 285.1 g of deionized water were added to a 1 L four-necked open flask equipped with a stirrer, a dropping tank, a thermometer, and a cooling jacket, and the temperature was decreased to 0 degrees. An oxidant solution in which 28.2 g of ammonium persulfate was dissolved in 176.5 g of deionized water and a monomer solution of 10.5 g of distilled aniline, 124.7 g of 1M hydrochloric acid and 58.8 g of deionized water were added dropwise at the same time for 1 hour. At this time, the temperature of the polymerization solution is located at 5 ~ 7 degrees. The color of the solution turns from milky white to green and after 6 hours of maintenance. The solution is placed in a four-necked 2L round flask equipped with a heating mantle, agitator and reflux tube, and heated to 50 degrees. Here, a neutralizer solution obtained by dissolving 40 g of ammonia water (25%) in 120 g of deionized water was added dropwise for 30 minutes and maintained for 30 minutes. At this time the color of the solution turns dark blue. After cooling to room temperature, the resultant is filtered with a glass filter having a pore size of 1um at a pressure of 5bar, and all the solutions are not filtered. The powder forms a cake and the filtration of water soluble by-products is very easy. If the pH of the filtrate is washed with water until the pH of 6-7 and filtered until no more filtrate, the solid content of the prepared paste is 65%. The polyaniline yield was 45% as a result of calculating the content of the elements by vacuum drying at room temperature and preparing the powder by elemental analysis. Then, 50 g of the polyaniline composite paste prepared therein was redispersed in 200 g of 10% aqueous dodecylbenzenesulfonic acid solution for doping, and then, the filtrate was washed with deionized water until the pH was 6-7, and filtered under pressure. Solid content is 72%. At this time, the prepared paste was vacuum dried at room temperature for 3 days, and when the dried powder was analyzed by elemental analysis, it was confirmed that 90% of aniline was doped in the composite.

Example 2: Preparation of Polyaniline / AE2 Paste

Example 1 and all the manufacturing process is the same and the latex emulsion AE2 of Preparation Example 2 was used. Solid content of the prepared paste is 71%. This was vacuum dried at room temperature to prepare a powder, and the yield of the polyaniline obtained as a result of calculating the content of elements by elemental analysis of the dried powder was 87%. Then, 50 g of the polyaniline composite paste prepared therein was redispersed in 200 g of 10% aqueous solution of dodecylbenzenesulfonic acid for doping, and then, the same was prepared by filtration while washing with deionized water until the filtrate reached pH 6-7. 75%. At this time, the paste was vacuum dried at room temperature for 3 days and when the dried powder was analyzed by elemental analysis, it was confirmed that 93% of the aniline in the composite was doped.

Example 3: Preparation of Polyaniline / AE3 Paste

Example 1 and all the manufacturing process was the same and the latex emulsion AE3 of Preparation Example 3 was used. Solid content of the prepared paste is 70%. The polyaniline yield was 93% as a result of calculating the content of the elements by vacuum drying at room temperature and preparing the powder by elemental analysis. Then, 50 g of the polyaniline composite paste prepared therein was redispersed in 200 g of 10% aqueous dodecylbenzenesulfonic acid solution for doping, and then, the same was applied under the same method as the filtrate was washed with deionized water until pH 6-7. Is 68%. At this time, the prepared paste was vacuum dried at room temperature for 3 days and when the dried powder was analyzed by elemental analysis, it was confirmed that 87% of the aniline in the composite was doped.

Comparative Example 1 Preparation of Polyaniline Paste by Precipitation Polymerization

Synthetic Metals, 1988, Vol. 26, 383-389 prepared by oxidizing the aniline-hydrochloride complex in aqueous solution with ammonium persulfate and then de-doped with ammonia water, filtered and filtered under the same pressure as in Example 1 to obtain 80% of the solid content of the paste. The yield of obtained polyaniline was 35%. Then, 50 g of the polyaniline paste prepared therein was redispersed in 200 g of 10% aqueous dodecylbenzenesulfonic acid solution for doping, and then the solid content of the paste prepared by pressure filtration was washed with deionized water until the filtrate reached pH 6-7 in the same manner. 65%. At this time, the paste was vacuum dried at room temperature for 3 days and when the dried powder was analyzed by elemental analysis, it was confirmed that 95% of the aniline in the composite was doped.

Preparation Example 4 Preparation of Acrylic Latex Containing Sodium Sulfonate Salt

First, 440g of deionized water and 4.3g of RHEODACAL DS-10 are pre-injected into the reaction vessel with an emulsifier, and then 213.4g of deionized water, 15.8g of RHEODACAL DS-10, 333g of butyl acrylate, and 324g of methyl methacrylate are prepared as a double emulsion. 22.6 g and 12.0 g deionized water are charged into the reactor. Thereafter, 10.06 g of methacrylic acid was added, and an initiator solution of 3.3 g of ammonium persulfate and 126.0 g of deionized water was prepared, and then the initiator solution and the remainder of the pre-emulsified solution prepared above were injected at a rate of 2.5 ml / min at 80 to 82 degrees. . At this time, the time required for injection takes about 3 ~ 4 hours. After completion of the injection, the reaction was carried out at the same temperature for 1 hour to remove the coagulum with a 400 mesh nylon filter to prepare a core emulsion. Then, 220 g of deionized water was introduced into a new reactor, and an initiator solution using a preemulsified solution using 176.4 g, 1.21 g of RHEODACAL DS-10, 399.9 g of butyl acrylate, and 452.1 g of styrene, an ammonium persulfate, 2.51 g of deionized water, and 18.0 g was used. Buy it. Into the reactor, 54.1 g of the prepared core emulsion, 18.0 g of deionized water was added, and 34.8 g of 2-acrylamido-2-methylpropanesulfonate sodium salt, 216 g of deionized water, 72 g of deionized water, and 1.8 g of ammonium persulfate were 78 to 80 It is dripped at the rate of 2.0 ml / min in the figure. After completion of the dropwise addition, the reaction was maintained at the same temperature for 1 hour and cooled again to 54-56 degrees. At the same temperature, 0.9 g of t-butylhydroperoxide, 28.8 g of deionized water, 0.44 g of sodium formaldehyde sulfonate and 9.0 g of FeSO4 · 7H2O were added. Insert the mixed solution over 1 hour, and after 20 minutes reaction, prepare a mixed solution of 0.9 g t-butylhydroperoxide, 28.8 g deionized water, 0.44 g formaldehyde sulfonate sodium and 9.0 g FeSO ₄ · 7H ₂ O again. The reaction is continued for 20 minutes and the reaction is terminated. After cooling to room temperature and then filtered through a 400 mesh nylon filter to obtain an acrylic latex containing 51 ~ 53% solids, 280um of sulfone groups.

Example 4 Preparation of Colloidal Mixture of Conductive Polymer Composites

20 g of the paste of Example 1, 10 g of acrylic latex containing sodium sulfonate salt of Preparation Example 4, and 15 g of deionized water were stirred with a high speed stirrer for 20 minutes to disperse, and then the prepared colloidal mixture was stirred at room temperature using a bar coater. When the film was prepared with a thickness of 10 μm and the surface resistance was measured by the four-terminal method, the volume conductivity was 0.2 S / cm and showed stable colloidal dispersion stability after 3 months without precipitation. The content of aniline in this colloidal mixture is 13%.

Example 5: Preparation of Colloidal Mixture of Conductive Polymer Composites

20 g of the paste of Example 2, 10 g of acrylic latex containing sodium sulfonate salt of Preparation Example 4, and 15 g of deionized water were dispersed by stirring with a high speed stirrer for 20 minutes, and then the colloidal mixture was prepared using a bar coater at 10 um at room temperature. The film was prepared with a thickness of and the surface resistance was measured by the four-terminal method. As a result, the volume conductivity was 0.5 S / cm and showed a stable colloidal dispersed phase with no precipitate occurring until 3 months. The content of aniline in this colloidal mixture is 17%.

Example 6: Preparation of Colloidal Mixture of Conductive Polymer Composites

20 g of the paste of Example 3, 10 g of acrylic latex containing sodium sulfonate salt of Preparation Example 4, and 15 g of deionized water were dispersed by stirring with a high speed stirrer for 20 minutes, and then the colloidal mixture was prepared at room temperature using a bar coater. The film was prepared with a thickness of 10 μm, and the surface resistance was measured by the four-terminal method. As a result, the volume conductivity was 0.4 S / cm, and the stable colloidal dispersed phase was shown in the form of no precipitate until three months. The content of aniline in this colloidal mixture is 17%.

Comparative Example 2: Preparation of Colloidal Mixture of Conductive Polymer Composite

20 g of the paste of Comparative Example 1, 10 g of acrylic latex containing sodium sulfonate salt of Preparation Example 4, and 15 g of deionized water were dispersed by stirring with a high speed stirrer for 20 minutes, and then the colloid mixture was prepared using a bar coater at 10 um at room temperature. The film was prepared with a thickness of and the surface resistance was measured by the four-terminal method. As a result, the volume conductivity was 2.1 S / cm, and after one day, a precipitate occurred and no redispersion occurred. The content of aniline in this colloidal mixture is 60%.

Comparative Example 3: Preparation of Colloidal Mixture of Conductive Polymer Composite

The paste of 6.7 g of Comparative Example 1, 15 g of acrylic latex containing sodium sulfonate salt of Preparation Example 4, and 23.3 g of deionized water were stirred with a high speed stirrer for 20 minutes and dispersed, and then the prepared colloid mixture was heated at room temperature using a bar coater. The film was prepared with a thickness of 10 μm at and the surface resistance was measured by the four-terminal method. As a result, the volume conductivity was 0.21 S / cm, and after one week, a precipitate was generated and no redispersion occurred. The content of aniline in this colloidal mixture is 20%.

Experimental Example: Preparation of Antistatic Paint

214g of acrylic resin R5541 (Korea Chemical, 45% solids content), 1.16g of dispersant (Soya stick), 132.7g of methyl isobutyl ketone, and disperse strongly with a high-speed disperser in a 1.5L cup, 77.3g of rutile titanium dioxide, magnesium Add 27.0 g of silicate and 27.0 g of mica, and optimize the dispersion by checking the dispersion with a Hegman particle size meter. While stirring, 300 g of the colloidal dispersion prepared in Example 6 and 19.32 g of a thickener (thixogel) were added as a rheology control agent. Stir for 30 minutes. The coating was applied to the glass plate with an applicator and dried at 60 ° C. for 20 minutes. The thickness of the coating was 30 μm, and the surface resistance was ⁸ × 10 ⁸ ohm / cm.

As described above in detail, according to the present invention, a conductive polymer composite is formed by adsorbing cationic oligomer radicals of a conductive polymer produced by oxidizing a conductive polymer monomer in an acrylic latex composition containing a large amount of acid monomer on the surface of latex particles. In the case of the conductive polymer composite prepared by swelling the latex particles using an alkali compound, filtering the filtrate and filtering the pressure, the chain structure of the conductive polymer adsorbed and polymerized onto the acrylic latex particles through a swelling process using the alkali compound of the acrylic latex particles. When doping with an organic acid by giving physical stretching action, the conductivity is increased by facilitating delocalization of electrons by conjugated double bond, and water and by-products can be easily removed in the filtration process by particle swelling of the conductive polymer composite. bar It can be prepared as a colloidal mixture of conductive polymer composites with excellent storage properties by mixing with acrylic latex containing sulphate and organic acid.Furthermore, conductive polymer colloids can be used for antistatic, electromagnetic shielding, It can be used as an additive for anti-corrosion paints.

Claims (7)

In the presence of an acrylic latex emulsion containing 5 to 60% by weight of acid equivalents, a molecular weight of 10,000 to 50,000, and a particle diameter of 50 to 150 nm, cationic oligomer radicals of the conductive polymer produced by oxidizing the monomer of the conductive polymer are converted into the latex particles. The polymer was adsorbed on the surface to polymerize to prepare a conductive polymer-latex composite having a solid content of 60 to 80%, and swelled and filtered the latex particles of the conductive polymer-latex composite with an alkali compound at 40 to 80 ° C. A conductive polymer composite obtained by redispersion followed by pressure filtration. The conductive polymer composite according to claim 1, wherein the monomer of the conductive polymer is at least one selected from the group consisting of aniline, pyrrole, thiophene and derivatives thereof, and the content thereof is 5 to 60% by weight of the total composite. . The acrylic latex composition according to claim 1, wherein the acrylic latex composition is acrylic acid, methacrylic acid, vinylbenzene acid, isopentyl benzene acid, crotonic acid, itaconic acid, maleic acid, fmaric acid, vinylsulfonic acid, arylsulfonic acid, metharylsulfonic acid, styrenesulfonic acid and acrylics. It comprises a single or two or more acid monomers selected from the group consisting of amido alkylsulfonic acid, characterized in that selected from the pure acrylic latex, styrene / acrylic latex, styrene-butadiene rubber latex and acrylonitrile-butadiene-styrene latex Conductive polymer composite. The conductive polymer composite according to claim 1, wherein the alkali compound is at least one selected from the group consisting of inorganic bases such as ammonia, sodium hydroxide and lithium hydroxide, and dimethyl ethanol amine and triethylamine. The conductive polymer composite according to claim 1, wherein the aqueous dopant solution is an aqueous solution obtained by dissolving an alkylbenzene sulfonic acid having 0 to 20 carbon atoms in 1 to 99% by weight of deionized water. An aqueous colloidal composition comprising 1 to 70 parts by weight of the conductive polymer composite paste of claim 1, within 91 parts by weight of deionized water and 10 to 30 parts by weight of an acrylic latex containing a sulfate group. Acrylates according to claim 1, wherein the acrylate containing sulfate group is one selected from 2-acrylamido-2-methylpropanesulfone sodium, acrylamido thibutylsulfonic acid, styrene sodium sulfate, isoprene sulfate sodium salt, and aryl sodium sulfate salt. An aqueous colloidal composition comprising at least one selected from the group consisting of pure acrylic latex, styrene / acryl latex, styrene-butadiene rubber latex and acrylonitrile-butadiene-styrene latex containing 5-30% by weight or more.