Method for producing acrylic emulsion resin composition having antiviral and antibacterial effects and acrylic emulsion resin composition produced by the method

Abstract

The present invention relates to a method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects, specifically, to a method for producing an acrylic emulsion resin by polymerizing a monomer mixture containing a vinyl monomer containing a tetravalent ammonium functional group, which is widely used due to its excellent antiviral and antibacterial effects. Furthermore, the present invention relates to an acrylic emulsion resin composition having antiviral and antibacterial effects, which contains a polymer of a monomer mixture containing a vinyl monomer containing a tetravalent ammonium salt group.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects, and more specifically, to a method for producing an acrylic emulsion resin by polymerizing a monomer mixture containing a vinyl monomer containing a tetravalent ammonium functional group, which is widely used because of its excellent antiviral and antibacterial effects.

[0002] The present invention also relates to an acrylic emulsion resin composition having antiviral and antibacterial effects, which contains a polymer of a monomer mixture containing a vinyl monomer containing a tetravalent ammonium salt group. [Background technology]

[0003] Virus attacks on humans are occurring constantly, with the frequency of these attacks increasing and the severity of the damage they cause becoming more severe. Virus infections can be transmitted directly through droplets or indirectly through objects. In addition to direct infection through droplets and air, the risk of indirect infection has also been proven through various cases of infection.

[0004] Since the outbreak of the Covid-19 pandemic in 2020, endowing everyday materials with antiviral and antibacterial properties to prevent viral infections has become essential for human survival. The most common method of coating functional materials to impart antiviral and antibacterial properties is to mix metal and metal oxide particles with antiviral and antibacterial properties into commonly used coating resins.

[0005] Currently, metal and metal oxide particles having antiviral and antibacterial effects include Cu, Ag, TiO2, ZnO, CuO, CuO2, etc. Korean Patent Registration No. 10-2262892 discloses a coating composition having antiviral properties containing a functional additive that is a mixture of zinc and zeolite.

[0006] However, in this method, since metal particles are contained in the coating composition, when coating the surface of various materials, the inherent color of the metal particles can spoil the aesthetic design of the existing material, causing inconvenience in use. Furthermore, when preparing the coating composition, it is difficult to disperse heavy metal particles and metal oxide particles when blended into the coating solution, and it is difficult to distribute them outside the surface layer after coating, making it difficult to achieve antiviral and antibacterial effects.

[0007] In addition, technologies utilizing metals and metal oxides have limitations in terms of performance, either due to the principle of metal consumption oxidation or due to the photocatalytic effect, and their durability is insufficient. Furthermore, metal and metal oxide particles with antiviral and antibacterial properties are uneconomical because they are made of relatively expensive precious metals and precious metal oxides.

[0008] In addition to the technology that utilizes metals and metal oxides, there is also a method of incorporating antibacterial chemicals with antiviral and antibacterial effects into the coating layer. However, this method has limitations in its application because the chemicals may leach out during the manufacturing process or during use of the product, causing the effect to quickly fade or the leached chemicals to be absorbed by the human body, which can be harmful.

[0009] Therefore, in order to avoid such negative effects, it is necessary to develop a resin that can be used in a coating composition that has excellent inherent antiviral properties. Summary of the Invention [Problem to be solved by the invention]

[0010] The object of the present invention is to solve the problems of the prior art and to provide a method for producing an acrylic emulsion resin composition that does not contain metal, metal oxide particles, or chemical substances and has excellent antiviral and antibacterial effects, and an acrylic emulsion resin composition produced thereby. [Means for solving the problem]

[0011] One embodiment of the present invention provides a method for preparing an acrylic emulsion resin composition having antiviral and antibacterial effects, the method comprising: providing a monomer mixture containing a vinyl monomer having a tetravalent ammonium salt group; mixing a nonionic surfactant and a radical polymerization initiator to prepare an addition polymerization mixture; and mixing the monomer mixture with the prepared addition polymerization mixture to perform a polymerization reaction (emulsion polymerization reaction).

[0012] Another embodiment of the present invention provides an acrylic emulsion resin composition having antiviral and antibacterial effects, which comprises a polymer of a monomer mixture including a vinyl monomer containing a quaternary ammonium salt group. [Effects of the Invention]

[0013] The resin composition according to the method for producing an acrylic emulsion resin composition of the present invention inherently possesses antiviral and antibacterial properties, and therefore can exhibit excellent antiviral and antibacterial effects by killing viruses or bacteria upon contact with them without the need for mixing with additional metal particles, metal oxide particles, or sterilizing chemicals. Furthermore, the acrylic emulsion resin composition can be used to produce water-based paints, and the paints can also exhibit excellent antiviral and antibacterial effects. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention may be modified in various ways and the scope of the present invention is not limited to the following embodiments.

[0015] The present invention relates to a method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects, the method including the steps of: providing a monomer mixture containing a vinyl monomer containing a tetravalent ammonium salt group; mixing a nonionic surfactant and a radical polymerization initiator to prepare an addition polymerization mixture; and mixing the monomer mixture with the prepared addition polymerization mixture to carry out an emulsion polymerization reaction.

[0016] The acrylic emulsion resin composition obtained by the above preparation method inherently has antiviral and antibacterial effects, and therefore can have excellent antiviral and antibacterial effects that can kill viruses or bacteria upon contact with them without the need for mixing with additional metal particles, metal oxide particles, or sterilizing chemicals.

[0017] The step of providing a monomer mixture containing a vinyl monomer containing a tetravalent ammonium salt group of the present invention may be carried out using a single vinyl monomer containing a tetravalent ammonium salt group or a mixture of two or more monomers containing the above-mentioned monomer and other monomers, and the above-mentioned monomers may be used by mixing with distilled water.

[0018] The vinyl monomer containing the tetravalent ammonium salt group can be used without limitation as long as it has an ammonium ion capable of undergoing an ion exchange reaction on one side and a vinyl group capable of radical polymerization on the other side. For example, [2-(methacryloyloxy)ethyl]trimethylammonium, [3-(methacryloylamino)propyl]trimethylammonium, and [2-(acryloyloxy)ethyl]trimethylammonium can be used.

[0019] As the other monomer, at least one selected from the group consisting of acrylic acid ester-based monomers, aromatic vinyl-based monomers, and organic acid-based monomers can be used.

[0020] The acrylic acid ester monomer can be at least one selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl (meth)acrylate, ethyl acrylate, butyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, benzyl (meth)acrylate, benzyl acrylate, lauryl (meth)acrylate, lauryl acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate.

[0021] The aromatic vinyl monomer can be at least one selected from the group consisting of styrene, α-methylstyrene, trans-β-methylstyrene, β-methylstyrene, and 4-methylstyrene.

[0022] The organic acid monomer may be at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid.

[0023] The monomer mixture preferably contains 0.1 to 50 wt % of the vinyl monomer containing a tetravalent ammonium salt group, and more preferably 2 to 10 wt %, based on the total weight of the entire monomer mixture. If it is less than 0.1 wt %, the effect is not achieved, but if it exceeds 50 wt %, there is a problem that the physical properties that the resin should have when used in a coating composition, such as adhesion and water resistance, are deteriorated.

[0024] In addition, since the monomer mixture is not easily dispersed in distilled water, a nonionic surfactant may be further included to adjust the viscosity of the mixture and to disperse the monomer mixture more uniformly. The distilled water is preferably mixed in an amount of 20 to 50 wt % based on the total weight of the monomer mixture, and the nonionic surfactant is preferably mixed in an amount of 1 to 3 wt % based on the total weight of the monomer mixture.

[0025] Next, the step of preparing the addition polymerization mixture of the present invention may be carried out by mixing a nonionic surfactant and a radical polymerization initiator.

[0026] The nonionic surfactant can be at least one selected from the group consisting of polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine ether, polyoxyethylene polyoxypropylene, polyethylene glycol, and sorbitan fatty acid ester.

[0027] When an anionic surfactant such as sodium dodecylbenzenesulfonate is used instead of a nonionic surfactant, there is a problem that it reacts with the tetravalent ammonium vinyl monomer, destroying the synthesis stability and making polymerization difficult.

[0028] The radical polymerization initiator can be at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0029] The addition polymerization mixture can be produced by mixing 1 to 20 parts by weight of a nonionic surfactant and 0.1 to 3 parts by weight of a radical polymerization initiator based on 100 parts by weight of the monomer mixture.

[0030] If the amount of nonionic surfactant is less than 1 part by weight, the particles may become unstable and precipitation may occur, and if it exceeds 20 parts by weight, the viscosity may increase, which may cause problems such as reduced workability when used in a coating composition.

[0031] If the amount of the radical polymerization initiator is less than 0.1 parts by weight or exceeds 3 parts by weight, there is a problem that the reactivity decreases when the molecular weight is taken into consideration.

[0032] Furthermore, the step of preparing the addition polymerization mixture may be carried out by further mixing at least a portion of the monomer mixture, preferably about 5 wt % based on the total weight of the monomer mixture.

[0033] The addition polymerization mixture can also be used by mixing it with a buffer solution so that it has a pH similar to that of the monomer mixture.

[0034] The emulsion polymerization step of the present invention involves mixing the prepared addition polymerization mixture with the monomer mixture to carry out a polymerization reaction. For example, the emulsion polymerization step may be carried out by adding the monomer mixture dropwise to the addition polymerization mixture.

[0035] Meanwhile, the method for preparing an acrylic emulsion resin composition of the present invention may further include a pH adjusting step of adding a pH adjuster to the resultant of the emulsion polymerization step. The pH adjuster may be at least one selected from the group consisting of aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-methylpropane, 2-amino-2-methylpropane, and triethylamine, and more preferably 2-amino-2-methylpropane.

[0036] The pH adjustment step may be to adjust the pH of the resultant of the emulsion polymerization step to 6 to 9. If the pH is adjusted to less than 6, there are problems in that the viscosity increases and compatibility with thickeners decreases during storage after the preparation of the acrylic emulsion resin composition, while if the pH is adjusted to more than 9, there are problems in that compatibility with cationic antibacterial agents decreases during storage.

[0037] The pH adjuster can be added in an amount of 0.5 to 4 parts by weight per 100 parts by weight of the addition polymerization mixture. When the pH adjuster is added in the above range of parts by weight, it can be easy to adjust the pH to 6 to 9.

[0038] On the other hand, the present invention relates to an acrylic emulsion resin composition having antiviral and antibacterial effects, which contains a polymer of a monomer mixture containing a vinyl monomer containing a tetravalent ammonium salt group.

[0039] The acrylic emulsion resin composition can be produced by the production method described above.

[0040] The monomer mixture containing the vinyl monomer containing the tetravalent ammonium salt group and the polymer thereof may be the same as those mentioned in the above production method.

[0041] The acrylic emulsion resin composition obtained by the production method of the present invention can be used as a binder for various materials, and when used in a paint composition in particular, it can impart properties having antiviral and antibacterial effects. The acrylic emulsion resin composition of the present invention can be used to produce a paint composition having antiviral and antibacterial effects, and the paint can be an aqueous paint.

[0042] The present invention will be described in more detail below with reference to specific examples. The following examples are merely illustrative examples to aid in understanding the present invention, and are not intended to limit the scope of the present invention. [Example]

[0043] 1. Preparation of acrylic emulsion resin composition Manufacturing Example 1 A nonionic surfactant (raw material A), a monomer mixture (raw material B), a radical polymerization initiator (raw material C), and a pH adjuster (raw material D) were prepared in the amounts shown in Table 1 below.

[0044] [Table 1]

[0045] Raw material A in Table 1 above was placed in a 2L four-neck round-bottom flask, which was then connected to a nitrogen inlet tube, condenser, thermocouple, and dropping funnel and heated to 80°C under a nitrogen atmosphere. After heating, approximately 5 wt% (based on the weight) of raw material B was added dropwise while maintaining the temperature. Then, raw material C was added and the remainder of raw material B was added dropwise over 2 hours. After the addition was completed, the mixture was maintained for 1 hour. Raw material D was then added and maintained for 30 minutes, and then cooled to 35°C to obtain an acrylic emulsion resin composition.

[0046] Manufacturing Example 2 An acrylic emulsion resin composition was obtained in the same manner as in Production Example 1, except that a monomer mixture (raw material B) formulated in the amounts shown in Table 2 below was used.

[0047] [Table 2]

[0048] Manufacturing Example 3 An acrylic emulsion resin composition was obtained in the same manner as in Production Example 1, except that a monomer mixture (raw material B) formulated in the amounts shown in Table 3 below was used.

[0049] [Table 3]

[0050] Comparative Manufacturing Example 1 An acrylic emulsion resin composition was obtained in the same manner as in Production Example 1, except that a monomer mixture (raw material B) formulated in the amounts shown in Table 4 below was used.

[0051] [Table 4]

[0052] Comparative Manufacturing Example 2 An acrylic emulsion resin composition was obtained in the same manner as in Production Example 1, except that a monomer mixture (raw material B) formulated in the amounts shown in Table 5 below was used.

[0053] [Table 5]

[0054] 2. Production of a coating composition using an acrylic emulsion resin composition The acrylic emulsion resin compositions obtained in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 and 2 were mixed with a dispersant (TEGO Dispers 750W, Evonik, Germany), an antifoaming agent (TEGO Antifoam 793, Evonik, Germany), a film-forming agent (Texanol, Eastman Chemical Company), a thickener (Bermocal EHM300, Akzo Nobel) and distilled water to prepare coating compositions according to the formulations shown in Table 6 below.

[0055] [Table 6]

[0056] 3. Characterization of coating compositions The coating compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for antiviral properties, antibacterial properties, water resistance, adhesion, rust prevention, and heat resistance.

[0057] (1) Antiviral properties (coronavirus inactivation effect) The coating compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were coated on steel plates to a thickness of approximately 2 μm using a bar coater, and then the test pieces were heated to 100°C in an induction heater to reach the peak metal temperature (PMT) to cure the coating layer.

[0058] The experiment was conducted using feline coronavirus (FCoV) in the CRFK cell line according to the modified ISO 21702 method. The reaction was carried out at a temperature of 25±1°C for 2 hours.

[0059] Antiviral efficacy was confirmed in coronavirus inactivation tests using the tissue culture infectious dose (TCID) method. Because the 50% tissue culture infectious dose (TCID50) is a measure of infectious virus titer, this endpoint dilution assay quantifies the amount of virus required to kill 50% of infected hosts or produce a cytopathic effect (CPE) in 50% of inoculated culture cells. TCID50 assays are commonly used to determine the lethal dose of viruses and in clinical research for non-plaque-forming viruses. Cell monolayers inoculated with the virus at 10-fold dilutions were observed for the presence or absence of CPE, and the percentage of wells confirmed to be infected was calculated. The 50% endpoint was calculated using the Reed-Muench method. It took up to 7 days to establish infection in cell cultures by TCID50 analysis. Evaluation: ◎: Very good (reduction rate of 95% or more), ○: Good (reduction rate of 90% or more and less than 95%), △: Slightly deteriorated (reduction rate of 80% or more and less than 90%), X: Very deteriorated (reduction rate of less than 80%)

[0060] (2) Antibacterial properties (kills E. coli) The above coating composition was spray-painted twice onto an iron test piece, and after drying for one day, an experiment was carried out on Escherichia coli according to the JIS Z 2801 method.

[0061] After inoculating 0.4cc of liquid bacteria onto a 5mm x 5mm test piece, a sterilization film (4mm x 4mm) was attached and the piece was left in a thermo-hygrostat at about 36°C for 24 hours, after which the degree of bacterial death was measured. Evaluation: ◎: Very good (reduction rate of 95% or more), ○: Good (reduction rate of 90% or more and less than 95%), △: Slightly deteriorated (reduction rate of 80% or more and less than 90%), X: Very deteriorated (reduction rate of less than 80%)

[0062] (3) Water resistance The above coating composition was spray-painted twice onto an iron test piece, and after drying for one day, the test piece was immersed in fresh water and the change in the coating film was observed. Evaluation: ◎: Very good (no paint loss), ○: Good (paint loss area: over 0% but less than 10%), △: Slight deterioration (paint loss area: 10% or more but less than 20%), X: Very deterioration (paint loss area: 20% or more)

[0063] (4)Adhesion The coating composition was spray-coated twice onto an iron test piece and allowed to dry for one day, after which a cross-cut (100x100) tape test was carried out to measure the area ratio remaining in the coating film. Evaluation: ◎: Very good (no paint loss), ○: Good (paint loss area: over 0% and less than 5%), △: Slight deterioration (paint loss area: 5% to less than 10%), X: Very deterioration (paint loss area: 10% or more)

[0064] (5) Rust prevention The above coating composition was spray-coated twice onto an iron test piece, and after drying for one day, a salt spray test was carried out. Evaluation: ◎: Very good (corrosion area less than 5%), ○: Good (corrosion area over 0% and less than 10%), △: Slightly deteriorated (corrosion area between 10% and less than 20%), X: Very deteriorated (corrosion area over 20%)

[0065] (6) Heat resistance The above coating composition was spray-coated twice onto an iron test piece, dried for one day, and then left to stand at 80°C for 24 hours, after which the change in whiteness of the coated surface was measured. Evaluation: Color difference ΔE: ◎: Very good (ΔE<0.5), ○: Good (0.5≦ΔE<1), △: Slightly deteriorated (1≦ΔE<2), X: Very deteriorated (2≦ΔE)

[0066] As a result, as shown in Table 7 below, Examples 1 to 3 were shown to be excellent in all of water resistance, adhesion, rust prevention, and heat resistance, while also having significantly better antiviral and antibacterial properties than Comparative Examples 1 and 2.

[0067] [Table 7]

[0068] Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and it will be obvious to those skilled in the art that various modifications and variations are possible within the scope that does not deviate from the technical idea of ​​the present invention described in the claims.

Claims

1. providing a monomer mixture comprising a vinyl monomer containing a quaternary ammonium salt group; mixing a nonionic surfactant and a radical polymerization initiator to prepare an addition polymerization mixture; an emulsion polymerization step of mixing the monomer mixture with the prepared addition polymerization mixture to carry out a polymerization reaction; and a pH adjusting step of adding a pH adjusting agent to the result of the emulsion polymerization reaction step; the nonionic surfactant is at least one selected from the group consisting of polyoxyethylene alkyl esters, polyoxyethylene alkylamine ethers, and sorbitan fatty acid esters; The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects, wherein the pH adjuster is 2-amino-2-methylpropane.

2. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the vinyl monomer containing a tetravalent ammonium base is at least one selected from the group consisting of [2-(methacryloyloxy)ethyl]trimethylammonium, [3-(methacryloylamino)propyl]trimethylammonium, and [2-(acryloyloxy)ethyl]trimethylammonium.

3. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the radical polymerization initiator is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.

4. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the monomer mixture contains 0.1 to 50% by weight of a vinyl monomer containing a tetravalent ammonium salt group, based on the total weight of the monomer mixture.

5. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the monomer mixture further contains at least one selected from the group consisting of an acrylic acid ester-based monomer, an aromatic vinyl-based monomer, and an organic acid-based monomer.

6. 6. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 5, wherein the acrylic acid ester monomer is at least one selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl (meth)acrylate, ethyl acrylate, butyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, benzyl (meth)acrylate, benzyl acrylate, lauryl (meth)acrylate, lauryl acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate.

7. 6. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 5, wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene, α-methylstyrene, trans-β-methylstyrene, β-methylstyrene, and 4-methylstyrene.

8. 6. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 5, wherein the organic acid monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid.

9. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the step of preparing the addition polymerization mixture is performed by further mixing at least a portion of the monomer mixture.

10. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the addition polymerization mixture is produced by mixing 1 to 20 parts by weight of a nonionic surfactant and 0.1 to 3 parts by weight of a radical polymerization initiator based on 100 parts by weight of the monomer mixture.

11. 2. The method for preparing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the emulsion polymerization reaction is carried out by adding a monomer mixture dropwise to an addition polymerization mixture.

12. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the pH adjusting step adjusts the pH of the resultant of the emulsion polymerization step to 6 to 9.

13. 2. The method for producing an acrylic emulsion resin composition having antiviral and antibacterial effects according to claim 1, wherein the pH adjuster is added in an amount of 0.5 to 4 parts by weight per 100 parts by weight of the addition polymerization mixture.

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