KR0149699B1 - Dispersion of slow-releasing emulsion polymer and method for preparing thereof - Google Patents

Abstract

The present invention relates to an antimicrobial emulsion dispersion and a method for preparing the same, and more particularly, to form fine pores in the interior of a particle when dried, and to contain a target material such as a bactericide in the same space of the particle. The present invention relates to a novel multistage emulsion polymerization method and a emulsion polymer dispersion prepared according to the present invention, which significantly increase the effective duration of a target substance by controlling the dissolution rate of the target substance by a polymer shell.

Description

Sustained release antibacterial emulsion dispersion and preparation method thereof

The present invention relates to a sustained-release antibacterial polymer dispersion and a method for producing the same, and more particularly, to form micropores in the interior of the particles when dried, and to provide a target material such as a bactericide in the same space of the particles. The present invention relates to a novel multi-stage emulsion polymerization method which significantly increases the effective duration of a target material by controlling the dissolution rate of the target material by the polymer shell to be contained, and an emulsion polymer dispersion prepared accordingly.

The role of the paint not only provides a beautiful appearance, but also prevents the aging of the body from the external environment. In particular, the growth of the fungus can promote the chloride of the coating and not only damage its appearance, but can also cause fatal loss in the material under the coating. In addition, the fungus parasitic in our living space has a great impact on hygiene problems such as allergies and odors, so that the conditions for growth of mold can be provided as the warm and humid indoor space increases due to the improvement of living conditions in summer or living conditions. It is becoming a more serious problem.

As a solution to this problem, a suitable antimicrobial agent is added to the paint to control the dissolution of the antimicrobial agent by the paint film, but the effect is somewhat effective. It has been used, but it has a relatively short duration of antibacterial activity. Moreover, the use of more than the required amount of fungicides in the beginning to prolong this period raises the problem of environmental pollution due to excess fungicide spills.

The microcapsule of this target material is used to restrict the diffusion of the antimicrobial agent to the particle surface by using the characteristics of the polymer forming the capsule wall so that the dissolution rate can be appropriately controlled, and the whiteness is provided by imparting opacity due to internal pores. Part of the expensive titanium dioxide, which is a pigment, can be replaced, thereby contributing to the cost reduction of a high-quality water-based antibacterial paint.

That is, in the present invention, since pores are present in the particles, they have opacity as their own, and microencapsulate the technique for preparing plastic pigments used as opaque agents in white or light aqueous paints, paper coatings, and molding compositions. By incorporating a manufacturing technique to control the elution rate of the target material is controlled to prepare a slow-release compatible polymer containing antibacterial agent having internal pores.

The method for the microencapsulation is known in various ways, the method of forming the shell can be largely divided into physical and chemical methods.

A physical method is complex-coacervation, which involves precipitation of a polymer at the interface between continuous and discontinuous phases.

That is, gelatin dissolved or dispersed in a continuous phase at a controlled temperature and pH reacts with anionic charged colloids such as gum arabic, vinyl acetate-maleic hydride copolymer, sodium alginate, polyacrylic acid, etc. ) May be coacervated or precipitated at the open surface between the organic phase and the dispersed organic phase. The shell formed at this interface can be cured by physical or chemical treatment, as disclosed in US Pat. No. 2,800,457. Coacervation processes typically require careful control of process conditions such as reaction concentration, temperature and pH and take advantage of relatively expensive gelatinous properties in forming capsule shells. This process provides a very complex and essentially microcapsule with poor water resistance.

Numerous chemical methods for forming microcapsule shells have also been proposed, for example, urea-formaldehyde pre-condensate can be dispersed in a continuous liquid phase and then encapsulated around the dispersed phase containing the target substance. Urea-formaldehyde agglomerates that form shells can be provided. It is published in US Pat. Nos. 3,016,309 and 3,796,669. The use of polymers such as gum arabic, polyacrylic acid, alkylacrylate-acrylic acid copolymers, hydrolyzed poly (ethylene-maleic anhydride) to improve the properties of urea-formaldehyde shells is also described in US Pat. No. 4,552,811. Posted.

U.S. Pat. No. 4,626,471 also discloses in-situ-polymerization of certain polyfunctional epoxy resins with polyamine curing agents, and another method for encapsulating a target material is at the interface between continuous and discontinuous phases. Or an interfacial polymerization method in which the shell is polymerized near the interface is known.

Methods for preparing the opacifying agent by the continuous multistage emulsion polymerization method are U.S. Patent Nos. 4,427,836, 4,469,825, 4,594,363, 4,970,241, and Japanese Patent Laid-Open Nos. S61-66710, S62-127336, and Hyeong1-1-. 30173, etc., the same production method as the above patents can be used to prepare the polymer particles of the present invention. However, there is no example of using such a continuous multi-stage emulsion polymerization method for microencapsulation of a target substance, and particularly, the pores are contained in the particles, so that there is no antimicrobial agent and a role as an opaque agent. U.S. Patent No. 4,677,003 discloses a method for preparing microencapsulation of a target material by a continuous multistage suspension polymerization method, but is not a continuous multistage emulsion polymerization method as in the present invention, and is suitable for the presence of a suitable hydrophobic and The use of hydrophilic solvents is essential. In addition, the monomer having an acid functional group that forms pores in the particles while being swollen and dried by neutralization should be at least 10% by weight in the core-forming monomer mixture, but the above patent does not have this matter, and moreover, it is a volatile organic compound as part of environmental measures. At the present time that the use of is regulated day by day, the method by suspension polymerization method like the above patent is not useful.

The present invention includes a hydrophobic target material on the inner surface of a core or shell in a method of preparing an opaque agent for paint by the continuous multi-stage emulsion polymerization method proposed in Korean Patent No. 25024 and US Patent No. 4,427,836, that is, a target on a discontinuous phase. It relates to an emulsion polymer dispersion containing a micropore and a target material at the same time by a continuous multi-stage emulsion polymerization method containing a substance and a method for producing the same will be described in detail for each step thereof.

1) Emulsion polymerization of core particles from a mixture of acid monomers having a carboxylic acid group, a general monomer and a hydrophobic fungicide as a target material in the presence of seed particles:

2) encapsulating the core particles with a hard coating by continuously polymerizing the envelope-forming monomer in the presence of the core particles; And

3) swelling the produced core-shell polymer particles with a base at an elevated temperature to prepare a release controlled antibacterial emulsion dispersion having internal pores containing both pores and a target material therein after drying. .

The present invention also relates to a coating or impregnating composition containing less than 30% by weight of the emulsion dispersion according to the above production method.

The core particles may be prepared in a single step in the overall process, but are preferably prepared in a radiation step including the preparation of the seed polymer in terms of particle size, particle distribution, pore size and distribution of the final particles. Do.

Therefore, in the seed step, which is the first step of the polymerization process, a small amount of the acid monomer is included in the core step to provide nuclear particles so that the mixture of the acid monomer and the hydrophobic target material can be polymerized and grown on the seed particles. It doesn't matter if you include it or not. The particle size is 20-500 nanometers, preferably 30-200 nanometers.

Acid monomers used herein are commonly used in core and shell forming steps, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, aconic acid, maleic acid or anhydrides thereof, monomethyl maleate, It is selected from acid compounds having unsaturated double bonds such as monomethyl fumarate and monomethyl itaconate, and the amount used is preferably 0-10% by weight, preferably 0-5% by weight based on the monomer mixture.

In addition, the ethylenically unsaturated monomer to be copolymerized is selected from at least one of styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, bininide chloride, acrylonitrile, alkyl acrylate and alkyl methacrylate.

As the emulsifier, 0.1 to 2.0% by weight of the nonionic and anionic emulsifiers, alone or in combination, is used. Representative nonionic emulsifiers include octylphenoxyethylpolyethoxyethanol and nonylphenoxyethylpolyethoxyethanol, and representative anionic emulsifiers include sodium auryl sulfate, sodium dodecylbenzenesulfonate, and sodium octylphenoxyethyl. Sodium salts of polyethylsulfate and sulfosuccinate derivatives;

The water-soluble radical initiator to be added to the reaction mixture is generally used alone or pyrolysis initiators such as alkali metal persulfate, ammonium persulfate, hydrogen peroxide, tertiary butyl hydroperoxide or the like and alkali metal sulfite, hyposulfite The redox initiator may be used in the form of a mixture with a reducing agent such as sodium formaldehyde sulfoxylate. The redox initiator may be used in the range of 0.1-2.0 wt% based on the monomer and the reaction temperature is 30- Set to 300 minutes. For example, when ammonium persulfate, potassium persulfate, or sodium persulfate is used alone as a polymerization initiator, it is preferable to maintain the anticorrosive temperature at 60 ° C to 90 ° C, and sodium sulfite or sodium formaldehyde sulfoxylate and When the same reducing agent is used in combination with the oxidizing agent, it is appropriate to adjust the reaction temperature to 30 to 60 ℃.

These initiators and the criteria for setting the reaction temperature are also common to the continuous core and shell manufacturing steps as common to the general emulsion polymerization.

When the seed is polymerized in the seed step, a secondary synthesis step using a hydrophilic monomer and a hydrophobic target material, that is, a core synthesis step is performed. This core synthesis step, which contains a hydrophobic target material in the overall process, is an important feature of the present invention, and if necessary, the target material may be added to the shell synthesis step.

In the core synthesis step, 15 to 60% by weight of acid monomer, 39 to 85% by weight of general ethylenically unsaturated monomer, 0 to 2% by weight of crosslinkable monomer, and the weight ratio of the core monomer mixture to the hydrophobic target material The hydrophobic target material is included to be about 1: 0.5 to 1: 5.

This hydrophobic target material must be a liquid that is insoluble in water and miscible with the monomer used to prepare the core emulsion, or a solid that can be dissolved in the monomer and solvent, for example, 2- (methoxycarb Boninamino) benzimidazole, 2- (4-thiazolyl) -benzimidazole, 2,3,5,6, -tetrachloro-4-methylsulfonipyridine, 2-n-octyl-4-isothiazoline 3-one, 2,4,5,6-tetramoloisophthalonitrile, N, N-dimethyl-N '-(fluorodichloromethylthio) -N'-sulfamide, zinc 2-pyridinethiol- At least one or more selected from 1-oxide, diiodomethyl-p-tolyl-sulfone, 3-iodo-2-propazylbutyl carbamate, N- (fluorodichloromethylthio) -phthalimide and the like are used.

Examples of hydrophobic target materials that can be encapsulated by the method of the present invention include fungi, fungicides, insecticides, herbicides, dyes, inks, perfumes, pharmaceuticals and the like. They can be encapsulated by the present invention if they are essentially hydrophobic liquids or solids with monomer solubility so that they are essentially distributed on core particles and do not interfere with the polymerization of the core emulsion.

Typical types of acid monomers and general ethylene unsaturated monomers are as described above, and as crosslinkable monomers, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, diethylene glycol di (meth) Acrylate, trimethylpropane trimethacrylate, divinylbenbene, allal (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and the like can be used.

The core monomer and the target material may be added to the continuous water phase in the reactor in a mixed form of the monomer and the target material, but when there is no solubility in water, the target material does not exist in the core particle layer and moves to the top of the continuous water phase. Because of the phase separation, it is preferable to introduce these monomers and the target material into the reactor by using a pre-emulsification method which is uniformly dispersed in water using a suitable emulsifier. At this time, the total emulsion is prepared by stirring for about 10 minutes at about 1,000-5,000rpm using a high-speed disperser.

The amount of core monomer mixture ranges from 2 to 50% by weight based on the monomer mixture used in the overall process, whether or not there is a seed stage, and, if there is a seed stage, about 4 to 20 times that of the seed forming monomer. It is preferable to use. When adding such a monomer mixture to the reaction system, it is usually suitable for 30 minutes to 180 minutes to be added within the selected addition rate range in consideration of synthetic stability, exothermic control, particle growth behavior, and the like.

The emulsifier, initiator and reaction temperature in the core formation step are the same as in the seed formation step, regardless of the presence or absence of the seed step, in the non-swelling state of the particle size of the synthetic polymer 70 to 300 nanometer It is good to be.

The aqueous core polymer dispersion may be stored in a semi-finished state and used in a shell forming reaction step, but it is more preferable to proceed with the subsequent shell forming step in the same reaction vessel.

It is preferable that the monomer mixture used in the shell forming step contains at least one general ethylene unsaturated monomer as mentioned above and 0 to 5% by weight of acid monomer is used. Glass transition temperature and toughness index should be considered as selection criteria for general unsaturated monomers.

The emulsifier and polymerization initiator used in the shell forming step are selected from those commonly used in the emulsion polymerization, and those exemplified in the core forming step are used, and the amount of emulsifier used has a concentration range that can satisfy both the synthetic stability and the particle growth behavior at the same time. It should be maintained, usually 0.01 to 2.0% by weight of the monomer is suitable. The shell forming step may consist of a single step or may consist of a plurality of steps. The hydrophobic target material, which is a feature of the present invention, may be added in this step. In particular, the input of the target material in the shell formation step is preferable to control the concentration of the target material that is initially eluted in order to express the initial antimicrobial properties in the composition. In the method of introduction, the preemulsification method is used as in the core forming step, and the amount of use is preferably 0 to 30% by weight based on the shell polymer's toughness in consideration of the toughness of the shell polymer.

As in the present invention, in the process consisting of core-primary shell-secondary shell, the neutralization fengyun process, which is an essential solution of pore formation, is performed after the formation of the primary shell or after the formation of the secondary shell, preferably after the formation of the primary shell. The neutralization temperature should be selected in consideration of the glass transition temperature of the primary shell to maximize the swelling of the core-shell polymer accompanying neutralization. In general, the range of 50-100 ° C. is suitable, and it is preferable to proceed continuously without changing the polymerization temperature in the whole process, so the correlation with the polymerization temperature should be considered. In this continuous multistage emulsion polymerization, the primary role of the primary shell is to control the rapid center of gravity due to the neutralization of the core particles and to prevent the degradation of the encapsulation efficiency of the secondary shell by hydrophilicity due to ionization of the core particle surface layer. In forming, the weight ratio is suitably in the range of 1: 1 to 1:50, more preferably in the range of 1: 4 to 1:10, for the core particles. On the other hand, the primary role of the secondary shell is to prevent particles from sinking in the drying process and to control the rate of diffusion of the target material into the particle surface, so that a monomer mixture having appropriate toughness must be used and the appropriate shell thickness must be maintained. . Therefore, the weight ratio is suitably in the range of 1: 1 to 1: 100, more preferably in the range of 1: 1 to 1:10 for the particles up to the primary shell. In addition, it is preferable to use 0.01 to 5% by weight, preferably 0.05 to 2.0% by weight of the crosslinkable monomer.

The base used in the neutralization process is selected from volatile bases of ammonia and tertiary amines, or from fixed bases of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and the amount of the base used is pH 7 of the emulsion dispersion after neutralization. It is good to be in 12th grade. In addition, in order to facilitate the penetration of the base into the particles, a number of organic solvents may be used during or before neutralization, which preferably has a solubility in water in which the affinity to core particles is limited to that of core polymers rather than shell polymers.

Specific examples thereof include alcohols such as ethanol, propanol, pentanol, hexanol, and texanol, alone or in combination, and the amount thereof is preferably 2 to 30% by weight based on the primary shell. The particle size of the final emulsion polymer produced by the present invention is suitable for 0.1 to 5.0 microns, preferably 0.2 to 2.0 microns and the diameter of the inner circumferential pores after drying is suitable for 0.05 to 3.0 microns, preferably 0.1 to 1.2 microns.

The hiding power of the antimicrobial agent and pore-containing emulsion polymer and the pore-containing emulsion polymer used as the target material prepared according to the present invention were blended to 30% by weight in an acrylic latex forming a continuous coating film at room temperature. When comparing the aqueous antimicrobial paint containing titanium dioxide pigment and antimicrobial agent with the initial antibacterial property and the antibacterial property after accelerated aging, the hiding power and initial antibacterial property were almost similar, whereas the antibacterial property after accelerated aging was produced according to the present invention. It was found that the use of the emulsified polymer was superior to paints containing the same amount of the same antibacterial agent. This fact indicates that the emulsion polymer according to the present invention not only has opacity due to pore content, but also has a great effect on controlling the dissolution rate by encapsulation of the antiseptic agent.

The present invention will be described in more detail with reference to the following Examples, which do not limit the scope of the present invention and unless otherwise indicated, percentages and parts refer to weight values.

Example 1

In a 1 liter four-necked flask equipped with a thermometer, a nitrogen inlet tube, a dropping channel, a stirrer, and a reflux condenser, 300 g of ion-exchanged water, 0.5 g of sodium bicarbonate, and 0.5 g of sodium dodecylbenbensulfonate were weighed, followed by 80 injections of nitrogen. The solution was heated to 占 폚 and dissolved in 15 g of ion-exchanged water with sodium persulfate 0.5.

While maintaining the reaction temperature at 80 ° C., a monomer mixture consisting of 10 g of butyl acrylate, 10.5 g of methyl methacrylate, and 0.5 g of methacrylic acid was slowly added dropwise to the flask over 30 minutes, and then maintained at the temperature for 30 minutes. To prepare. At this time, the particle diameter of the seed was 71 nanometer and the solid content was 6.5 by the light scattering measuring device. Subsequently, a solution obtained by dissolving 0.49 g of sodium persulfate in 20 g of ion-exchanged water was added thereto, and 150 g of ion-exchanged water, 1.0 g of sodium dodecylbenzenesulfonate, 15 g of butyl acrylate, 60 g of methyl methacrylate, and methyl while maintaining 80 ° C. A mixture of 23 g of methacrylic acid, 0.5 g of ethylene glycol dimethacrylate, and 98 g of 2-n-octyl-4-isothiazolin-3-one was slowly added dropwise into the reactor over 120 minutes in an emulsion. After aging for 60 minutes, cooled and prepared core emulsion.

The average particle diameter of the core emulsion particles measured by the light scattering measuring device was about 140 nanometers and the solid content was 31.2%.

In another 1 liter four-neck flask, 200 g of ion-exchanged water and 60 g of co-emulsion were added, heated to 80 ° C, and an aqueous solution of 1.0 g of sodium persulfate dissolved in 30 g of ion-exchanged water was added. While maintaining the reaction temperature at 80 ° C, a monomer mixture of 15 g of butyl methacrylate, 50 g of methyl methacrylate, 20 g of styrene, and 2 g of methyl methacrylate was slowly added dropwise over 120 minutes, aged for 60 minutes, and the pH was adjusted to 11.0 with ammonia water. Adjust to a degree and hold for 60 minutes at the same temperature. Subsequently, an aqueous solution of 0.5 g of sodium persulfate and 0.2 g of sodium dodecylbenzenesulfonate was added to 50 g of ion-exchanged water, followed by 55 g of styrene, 30 g of methyl methacrylate, 12 g of butyl acrylate, and 1.0 g of ethylene glycol dimethacrylate. The secondary shell monomer mixture is slowly added dropwise for 120 minutes, held for 60 minutes and then cooled. At 55 ° C., 0.15 g of sodium formaldehyde sulfoxylate and 0.1 g of tertiary butylhydroperoxide at 70% concentration are added, and then the reaction is slowly cooled and packaged below 40 ° C.

The average particle diameter of the finally obtained emulsion polymer was measured by transmission electron microscopy, and the average diameter of the pores was 300 nanometers.

The emulsion particles were dried, washed with methyl alcohol, and the encapsulation rate of the antiseptics measured by liquid chromatography was 76%, and the antiseptics content in the final emulsion was 1.7%.

Example 2

A seed polymer was prepared in the same manner as in Example 1, except that sodium dodecylbenzenesulfonate was 0.1 g in the preparation of the seed emulsion.

At this time, the particle size of the seed was 160 nanometer and the solid content was 6.5% as measured by the light scattering measuring device.

A core emulsion was then prepared in the same manner as in Example 1. The average particle diameter of the core particles was 310 nanometers and the solid content was 31.2%.

Hereinafter, primary shell formation, neutralization, and secondary shell formation steps were performed in the same manner as in Example 1.

The average particle diameter of the final emulsion polymer was 1,000 nanometers and the diameter of the process was 800 nanometers. The encapsulation rate of the fungicide was 76% and the fungicide content in the final emulsion was 1.7%.

Example 3

A seed was prepared in the same manner as in Example 1, except that the same amount was replaced with monomers in the same proportion without using a 2-n-octyl-4-isothiazolin-3-one, which is a fungicide, in preparing the core emulsion. To prepare a core emulsion. Subsequently, 9.5 g of copper antimicrobial agent was added to the monomer mixture in the first shell forming step, followed by preemulsification, and the neutralization and the secondary shell were performed in the same manner as in Example 1.

The average particle size of the final emulsion polymer was 450 nanometers and the pore diameter was 320 nanometers. The encapsulation rate of the fungicide was about 50% and the fungicide content in the final emulsion was 1.7%.

Example 4

Seed and core emulsion are prepared in the same manner as in Example 3, and the first shell and the neutralization process are performed in the same manner as in Example 1, except that the second shell is introduced with a fungicide in the secondary shell forming step. 9.5 g of the same fungicide was added to the monomer mixture to preemulsify to obtain a final emulsion.

The average particle diameter of the final emulsion polymer was 450 nanometers and the pore diameter was 320 nanometers. The encapsulation rate of the fungicide was about 35% and the fungicide content in the final emulsion was 1.7%.

Example 5

Seed, core, the primary shell and the neutralization process in the same manner as in Example 1 and the secondary shell was prepared in the same manner as in Example 4 to obtain a final emulsion polymer.

The average particle diameter of the final emulsion polymer was 430 nanometers and the pore diameter was 300 nanometers. The encapsulation rate of the fungicide was about 58% and the fungicide content in the final emulsion was 3.4%.

Comparative Example 1

In order to compare the difference with the present invention was prepared in the same manner as in Example 1, there is a difference only in the core step, that is, the final emulsion polymer was prepared in the same manner as in Example 3 without using a fungicide.

The average particle diameter of the final emulsion polymer was 450 nanometers and the average diameter of pores was 330 nanometers.

Comparative Example 2

In order to compare the difference with the present invention was prepared in the same manner as in Example 1 except that the final emulsion polymer was prepared without undergoing a neutralization process.

The average particle diameter of the final emulsion polymer was 320 nanometers and no pores were observed. The encapsulation rate of the fungicide was about 80% and the fungicide content in the final emulsion was 1,7%.

[Application Example 1]

In order to compare the concealment efficiency of the emulsion polymers prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the composition prepared by mixing each of them with a film-forming latex binder (H5250 Koryo Chemical Co., Ltd.) by 30% by weight of solids Was applied on a black and white hiding test paper using a bird applicator with a wet film thickness of 8MIL, and then dried at 25 ° C. and 55% RH for at least 24 hours to prepare a test piece for measuring the hiding power, and then the hiding rate was measured according to KSM5435. It was. The test results are shown in Table 1 below.

[Application Example 2-9]

Using the paint prepared by the aqueous internal paint formulation shown in Table 2 below, the hiding power comparison test and antibacterial test were performed. The viscosity of the paint was adjusted to 90-95 KU and the solid content was prepared to 54 ± 1.

Concealment test was applied to the wet film thickness of 6 MIL to measure the concealment in accordance with KSM5435. In addition, the antibacterial test was carried out in the same manner as the hiding power test, and the target strains were repeated with FED TEST METHOD STD NO 141,6271-2 using blue mold (Penicillium citrinum) and black mold (Cladosporium cucumerium). The results were evaluated through. The evaluation criteria were the size of the inhibiting zone. In other words, if the size of the support is 5mm or more, it is excellent, if it is 5-2mm, and if it is 2mm or less, it is generally evaluated as bad if the support is not formed. In addition, the initial antibacterial property is within 24 hours after specimen preparation, and the accelerated aging antibacterial property is to be tested for 120 hours after immersion in fresh water for 24 hours after specimen preparation.

The test results are shown in Table 3 below.

1) Dispersant, antifoaming agent, thickener, pH adjusting agent, fusing agent, freeze thawing stabilizer, pigment wetting agent, etc.

2) talc, calcium carbonate, china clay, etc.

3) 2-n-octyl-4-isothiazolin-3-one

4) Application Examples 2-6 correspond to Examples 1-4 and Comparative Examples 2 and 7, and 8 correspond to Comparative Examples 1 and 5, respectively.

5) Acrylic emulsion as product of Koryo Chemical Co., Ltd.

As can be seen from Table 3, according to the manufacturing method of the present invention, hiding power and initial antibacterial properties are almost similar to the conventional one, while the antibacterial property after accelerated aging is the same as that using the emulsified polymer prepared by the present invention. It was shown to be superior to the conventional paint compounded in the same amount. This fact proves that the dissolution rate of the target material is controlled by microencapsulating the hydrogen-based antiseptic target material because the pores are present in the emulsion polymer particles according to the present invention.

Claims (10)

Method for producing a sustained-release antibacterial emulsion dispersion comprising the following steps. 1) emulsion polymerizing core particles from a mixture of an acid monomer having a carboxylic acid group and a monomer and a monomer containing a hydrophobic fungicide as a target material; 2) encapsulating the core particles with a hard coat by continuously emulsion polymerizing the envelope forming monomer containing 1-30% by weight of the target material in the presence of the core particles; And 3) swelling the resulting core-shell polymer particles with a base at an elevated temperature to prepare a release controlled anti-bacterial emulsion dispersion having internal pores containing both pores and a target material therein after drying. step. The method of claim 1, wherein the core forming step comprises a single step or a plurality of steps including a seed preparation step. The method of claim 1, wherein the target material is a liquid which is insoluble in water and miscible with a monomer or a solid which can be dissolved in a monomer and a solvent, and includes 2- (methoxycarbonylamino) benzimidazole, 2- ( 4-thiazolyl) -benzimidazole, 2,3,5,6-tetrachloro-4-methylsulfonipyridin, 2-n-octyl-4-isothiazolin-3-one, 2.4.5.6-tetrachloroi Sophthalonitrile, N, N-dimethyl-N '-(fluorodichloromethylthio) -N'-sulfamide, zinc-2-pyridinethiol-1-oxide, diiodomethyl-p-tolyl-sulfone, 3- A method for producing a sustained-release antibacterial emulsion dispersion comprising at least one selected from iodo-2-propazyl butyl carbamate and N- (fluorodichloromethylthio) -phthalimide. The method of claim 1 or 3, wherein the target material is used in the core forming step so that the weight ratio of the core monomer and the target material is 1: 0.5 to 1: 5. . 5. The method of claim 4, wherein the target material is used by pre-emulsification with each monomer mixture. The method of claim 1, wherein the envelope forming step comprises a single or a plurality of steps. The method of claim 1, wherein the step of neutralizing and swelling with the base is carried out after the final envelope forming step or in the middle of the plurality of envelope forming steps. The method of claim 1, wherein the weight ratio of the shell component to the core component is 1: 1 to 1:50. The method of claim 1, wherein the size of the final emulsion particles is 0.1-5.0 microns. A composition for coating or impregnation containing less than 30% by weight of an emulsion polymer dispersion prepared by the method according to claim 1.