KR102159032B1 - A process for the preparing the antibacterial coating film of photo-curing type containing goethite and the antibacterial coating film prepared therefrom - Google Patents

Abstract

The present invention relates to a method of manufacturing a photocurable antibacterial coating film containing hightite and an antimicrobial film prepared according to the method, the steps of (1) synthesizing hightite that imparts antibacterial properties proposed in the present invention; (2) preparing a coating composition having antibacterial properties containing the hightite; And (3) the photocurable antibacterial coating film containing tight prepared according to the method for producing a photocurable antibacterial coating film composition containing hightite, characterized in that comprising the step of polymerizing the coating composition with light after light irradiation A high-tite coating composition having excellent antimicrobial properties can be polymerized through ultraviolet irradiation to provide an antibacterial coating film capable of solving not only antibacterial properties but also physical properties, mechanical properties, manufacturing processes, and productivity problems.

Description

A process for the preparing the antibacterial coating film of photo-curing type containing goethite and the antibacterial coating film prepared therefrom}

The present invention relates to a method for manufacturing a photocurable antibacterial coating film containing hightite and an antibacterial coating film prepared accordingly. More specifically, it relates to a method for producing a photo-curable antibacterial film that satisfies mechanical properties and physical properties and can exhibit an antibacterial effect by the introduction of hightite, and an antimicrobial coating film prepared accordingly.

Antimicrobial agents added to prevent the growth of bacteria can be largely divided into organic and inorganic. In the case of an organic type of antibacterial agent, it has the advantage of rapidly exerting an antibacterial effect to the surface of an object by the elution of the drug. However, characteristics such as elution have disadvantages that not only the physical properties of the product are deteriorated due to rapid movement, but also it is difficult to apply in the manufacturing process. In particular, stability problems have arisen due to the solubility of organic substances. Inorganic antibacterial agents are mainly white clay, ocher, acid clay, magnesite, perlite, montmorillonite, vermiculite, bentonite, zeolite, illite, kaolinite, haloysite, videlite, nontronite, chlorite, attapulgite, etc. It is an antibacterial composition containing clay minerals of, and has the advantage of high human stability and a long antibacterial duration. However, it has a disadvantage that the temporary antibacterial effect is lower than that of the organic antibacterial agent and its processability is lowered.

In addition to the problem of the antimicrobial agent series described above, it is a factor that deteriorates antibacterial properties and properties in the processing method. In general, coatings constitute a polymer matrix and are divided into physical crosslinking and chemical crosslinking. Physical crosslinking causes crystallinity due to the interaction of chains in the polymer matrix, and this partial crystallization plays a role of physical crosslinking, thereby maintaining its mechanical properties. In chemical crosslinking, polymer chains are crosslinked through chemical bonds. The coating method prepared by physical crosslinking has a disadvantage in that functional substances exhibiting antimicrobial properties may swell or be dissolved by heat, and the components are leaked out over time. However, the coating prepared by chemical crosslinking is thermally stable, so there is little change in structure over time. The chemical crosslinking method includes mixing an antimicrobial material in a polymer matrix and curing it with heat or light. In the crosslinking method using double heat, the use of an organic solvent is inevitable to dissolve the matrix resin, which may cause environmental problems, and a high-temperature drying process is performed, resulting in a cost. The photocuring process, which is actively being researched at present, has the advantage of fast curing speed, excellent coating performance and curing characteristics, good surface gloss, and high energy efficiency compared to ordinary heat drying, but mechanical properties are weak or regular. Process control is difficult.

Korean Patent Publication No. 2019-0040787

Accordingly, a technical problem to be solved in the present invention is to provide a method of manufacturing a photocurable antibacterial coating film capable of solving problems in physical properties, mechanical properties, manufacturing processes, and productivity.

In addition, another technical problem to be solved in the present invention is to provide a photocurable antibacterial coating film manufactured according to the above manufacturing method.

In order to solve the above technical problem, in the present invention, (1) synthesizing an iron (acid water) oxide-based compound that imparts antibacterial properties; (2) preparing a coating composition having antibacterial properties including the iron (acid water) oxide-based compound; And (3) it provides a method for producing a photo-curable antibacterial coating film composition containing high-tite, characterized in that consisting of the step of polymerizing the coating composition into a polymer after light irradiation.

In order to solve the above-described other technical problem, the present invention provides a photocurable antibacterial coating film composition containing high-tight prepared according to the above manufacturing method.

In the present invention, an antibacterial coating film capable of solving the above problem was prepared by proposing antibacterial properties of a new clay mineral through a composition containing a clay mineral containing a predetermined mineral as an active ingredient.

Iron (acid water) oxide is a secondary mineral having high reactivity and a large specific surface area, and has been studied in various fields. Among these iron (acid water) oxides, hightite (goethite) is widely distributed in the ground and is known as a stable mineral. Gotite has the effect of improving the adsorption capacity of anions in the form of Fe(OH) ₃ , Fe(OH) ₂ , FeO, and FeOOH, and unlike other minerals, it has a rod-shaped shape and forms a lot of space inside the aggregate. This has the effect of providing an adsorption space. Since the hightite has a positive charge, it can bind with anions, and unlike other mineral particles, it has the effect of providing an adsorption space that can contact bacteria by forming voids in the aggregate in a rod-shaped shape. Antibacterial containing high-tite that can solve physical properties, mechanical properties, manufacturing process and productivity problems by preparing a coating composition having excellent antibacterial properties by mixing an acrylate monomer and a photoinitiator with this high-tite and then polymerizing it into a polymer through ultraviolet irradiation. It is an object of the present invention to provide a coating film.

The photo-curable antibacterial coating film containing high-tite proposed in the present invention solves not only antibacterial properties, but also physical properties, mechanical properties, manufacturing process, and productivity problems by polymerizing a high-tite coating composition with excellent antimicrobial properties through ultraviolet irradiation. It can provide an antibacterial coating film that can be.

1 is a schematic diagram of a photocurable antibacterial coating composition of the present invention.
Figure 2 is a picture showing the antibacterial activity against Escherichia coli of the antibacterial coating film containing hightite according to an embodiment of the present invention.
3 is a diagram showing the antibacterial activity against Staphylococcus aureus of the antibacterial coating film containing hightite according to an embodiment of the present invention.

The present invention comprises the steps of: (1) synthesizing an iron (acid water) oxide-based compound, particularly hightite, which imparts antibacterial properties; (2) preparing a coating composition having antimicrobial properties comprising the iron (acid water) oxide-based compound; (3) It relates to a method for producing a photocurable antimicrobial coating film composition comprising the step of polymerizing the coating composition with a polymer after light irradiation.

According to a preferred feature of the present invention, the (1) step of synthesizing an iron (acid water) oxide-based compound that imparts antibacterial properties, particularly hightite, comprises a metal nitrate hydrate represented by the following formula (1) and a hydroxide represented by the formula (2). Preparing a slurry using it as a precursor; And a step of synthesizing an antimicrobial compound of a metal (acid water) oxide-based, preferably iron (acid water) oxide-based, represented by Formula 3 below.

In the above formula, M ¹ is iron; a is a positive number equal to the valence of metal M ¹ ; x is a rational number ranging from 0 to 10. Preferably, M ¹ is copper or iron and x is a rational number of 6 or 9. More preferably, M ¹ is iron and x is a rational number of 9. A preferred specific example of Formula 1 may be Fe(NO ₃ ) ₃ ·9H ₂ O or Cu(NO ₃ ) ₂ ·6H ₂ O.

In the above formula, M ² is an alkali metal such as lithium, sodium, potassium, rubidium and cesium, or an alkaline earth metal element such as calcium, barium, beryllium, and magnesium; b is a positive number equal to the valence of the alkali or alkaline earth metal ion of M ² . Preferably, M ² is sodium, potassium or calcium, more preferably M ² is sodium.

In the above formula, M ¹ is iron, c is a rational number of 0 to 2, and d is a rational number of 1 to 40. Preferably, M ¹ is iron, c is a rational number of 1, and d is a rational number of 1. A specific example of Formula 3 is FeOOH.

According to a preferred feature of the present invention, the (2) step of preparing a coating composition having antimicrobial properties includes the synthesized metal (acid water) oxide-based antimicrobial compound, trimethyol propanetricarylate (TMPTA) and 2HDDA (1,6-Hexandiol diacrylate). It consists of a step of preparing an ultraviolet curable coating composition by selecting and mixing one to two reactive acrylic monomers selected from the group consisting of.

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According to a preferred embodiment, the coating composition having antimicrobial properties may include a photoinitiator represented by the following formula (5), wherein the content of the photoinitiator is 1 to 6% by weight based on the reactive acrylic monomer.

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In the above formula, R ₄ and R ₅ are each independently an aromatic or aliphatic hydrocarbon having 2 to 12 carbon atoms, and R ₆ is an aromatic or aliphatic hydrocarbon having 2 to 12 carbon atoms that can be bonded to a non-metallic element. Examples thereof include a radical photopolymerization initiator bonded to a series such as a hydroxy group, an acetophenone group, a benzophenone group, a phosphine oxide group, a thioxanthone group, and a benzoin group. Preferably, R ₄ and R ₅ are each an aromatic phenyl group having 6 carbon atoms, and R ₆ is a 2,4,6-trimethylphenyl group having 9 carbon atoms that can be bonded to a non-metallic element.

According to a preferred feature of the present invention, in the step of (3) irradiating the coating composition with light and then polymerizing a polymer, a polyolefin, polyester, or polyacrylic film is selected as the coating substrate, or in some cases, corona treatment or primer Treated substrates can be used; It is characterized in that a UV-curable coating composition containing a metal (acid water) oxide is applied to a predetermined thickness on the selected coating substrate.

According to a preferred feature of the present invention, the (3) coating composition having antibacterial properties is composed of 3 to 40% by weight of a metal (acid water) oxide, 1 to 6% by weight of a radical photopolymerization initiator, and 54 to 96% by weight of a reactive acrylic monomer. It is characterized.

In order to effectively perform the curing, an inert gas atmosphere such as nitrogen or argon is formed to increase curing efficiency. A curing device capable of emitting ultraviolet rays is not limited as a method for polymerizing the ultraviolet curable coating composition; An antibacterial film is formed by using an ultraviolet irradiation device using commonly used metal halide, gallium, mercury, and the like as light emitting materials. The wavelength range of the light source for polymerizing the UV-curable coating composition is characterized in that the range of 180nm to 420nm, it can be polymerized by selecting a single or multiple light sources. More preferably, it features a manufacturing method of forming an antibacterial coating film using an ultraviolet irradiation device, characterized in that 220nm to 380nm.

The antimicrobial coating film containing the metal (acid water) oxide prepared by the above method is formed through the following reaction formulas 1 to 3.

[Scheme 1]

[Scheme 2]

(In Reaction Scheme 2, M is a compound represented by Chemical Formula 4.)

[Scheme 3]

로 표기한다,The reaction formula (1) represents the initiation reaction of the photoinitiator, for convenience

Denoted as,

Reaction Scheme (2) shows that the reactant starts to polymerize the reactive acrylic monomer by the disclosed photoinitiator;

The reaction formula (3) represents the process of curing by mixing the added metal (acid water) oxide together with the reactive monomer that has started to be polymerized.

In the present invention, there is provided a photocurable antibacterial coating film composition comprising cotite prepared according to the above manufacturing method.

In the method for producing an antibacterial film using hightite proposed in the present invention, a uniform coating film can be formed by uniformly dispersing the acrylate-based monomer and the synthesized hightite. Therefore, it hardens within a few minutes. The combination of functional monomers, ease of polymerization, and the ability to produce an antibacterial coating film in a short time with only light irradiation without a separate polymerization process is useful in that it satisfies high productivity and the exclusion of volatile organic compounds along with energy saving It's worth it.

Hereinafter, the present invention will be described in more detail through examples. These examples are merely presented by way of example so that the present invention may be more understood, and thus the scope of the present invention is not limited to these examples.

<Production Example 1> Synthesis of iron hydroxide

In order to prepare an additive for the antibacterial activity function, hightite, an iron hydroxide, was synthesized. After dissolving 25 g of iron nitrate (Fe(NO ₃ ) ₃ , Iron(III) nitrate) in 400 g of distilled water in a 1 L three-necked flask, 150 mL of 2.5 M sodium hydroxide solution was added to reach pH 12 at a rate of 1 mL/min under a nitrogen atmosphere. It was dripped until. When dropping, the stirring speed was set to 250 rpm, and the reaction was stabilized for 2 hours after the dropping was completed. The reaction product was aged at 60° C. for 24 hours to obtain a solid, and then dried to be used as an antibacterial active additive.

<Production Example 2> Preparation of film composition and film curing

The film composition was prepared by physically mixing an aliphatic polyfunctional urethane acrylate oligomer, a trifunctional acrylate monomer, a bifunctional acrylate monomer, and a photoinitiator, and the prepared film composition was applied to a substrate and then irradiated with ultraviolet rays to produce a photocurable polymer film. Was prepared. More detailed content is shown through the examples below.

<Comparative Example 1>

Aliphatic polyfunctional urethane acrylate oligomer EB264 18.9 wt%, trifunctional acrylate monomer TMPTA (trimethyol propanetriarylate) 37.7 wt% and bifunctional acrylate monomer HDDA (1,6-Hexandiol diacrylate) 37.7 wt%, photoinitiator 5.7 wt. % Was mixed to prepare a film composition solution, and then applied to a substrate and irradiated with ultraviolet rays for 5 minutes to prepare a photocurable polymer film.

<Example 1>

Compositions participating in photocuring include 18.9% by weight of EB264, an aliphatic polyfunctional urethane acrylate oligomer, 37.7% by weight of trimethyol propanetriarylate (TMPTA), a trifunctional acrylate monomer, and 1,6-Hexandiol diacrylate (HDDA), a bifunctional acrylate monomer. 37.7% by weight and 5.7% by weight of the photoinitiator were mixed, and 5% by weight of the synthesized iron hydroxide of Preparation Example 1 was added based on 100% by weight of the composition participating in the photocuring to prepare an antibacterial film composition solution. After the antibacterial film composition was applied to the substrate, ultraviolet rays were irradiated for 5 minutes to prepare a photocurable polymer film.

<Example 2>

Compositions participating in photocuring include 18.9% by weight of EB264, an aliphatic polyfunctional urethane acrylate oligomer, 37.7% by weight of trimethyol propanetriarylate (TMPTA), a trifunctional acrylate monomer, and 1,6-Hexandiol diacrylate (HDDA), a bifunctional acrylate monomer. 37.7% by weight and 5.7% by weight of the photoinitiator were mixed, and 10% by weight of the synthesized iron hydroxide of Preparation Example 1 was added based on 100% by weight of the composition participating in the photocuring to prepare an antibacterial film composition solution. After the antibacterial film composition was applied to the substrate, ultraviolet rays were irradiated for 5 minutes to prepare a photocurable polymer film.

<Example 3>

Compositions participating in photocuring include 18.9% by weight of EB264, an aliphatic polyfunctional urethane acrylate oligomer, 37.7% by weight of trimethyol propanetriarylate (TMPTA), a trifunctional acrylate monomer, and 1,6-Hexandiol diacrylate (HDDA), a bifunctional acrylate monomer. 37.7% by weight and 5.7% by weight of the photoinitiator were mixed, and 20% by weight of the synthesized iron hydroxide of Preparation Example 1 was added based on 100% by weight of the composition participating in the photocuring to prepare an antibacterial film composition solution. After the antibacterial film composition was applied to the substrate, ultraviolet rays were irradiated for 5 minutes to prepare a photocurable polymer film.

<Experimental Example 1> Evaluation of photocuring conversion efficiency through infrared spectroscopy

The FT-IR spectra was used to evaluate the curing efficiency of the photocurable films prepared by Examples and Comparative Examples. Infrared spectroscopy was used by Nicolet's iS50 FT-IR product, and light absorption was measured at a wavelength in the range of 4,000 to 400 cm-1 by using attenuated total reflectance (ATR). The photocuring behavior was measured by changing the area ratio of the twisting vibration peak of the C=C double bond in the 810cm-1 wavelength band and the C=O stretching vibration peak in the 1730cm-1 wavelength band. In addition, the area under the wavelength of 790 to 830 cm-1 including 810 cm-1 was integrated, and the area under the wavelength of 1670 to 1800 cm-1 including 1730 cm-1 was integrated to evaluate the value. The photocuring conversion efficiency (α) was calculated according to Equation 1 below after evaluating the peak area before and after UV curing.

In the above equation, A is the absorbance area under the vibration peak in each wavelength band, and ( A ₈₁₀ / A ₁₇₃₀ ) ₀ and ( A ₈₁₀ / A ₁₇₃₀ ) _t are the relative absorption ratios of C=C bonds before and after curing.

Table 1 below shows the photocuring conversion rate of the antibacterial film prepared through the Examples and Comparative Examples.

According to the results of Table 1, the composition of the photocurable coating film showed a significant decrease in the peak area of the 810cm-1 wavelength band by C=C bonding before and after photocuring, and accordingly, it was confirmed that the photocuring conversion rate was high. . According to the results of Examples 1 to 3, which are coating films containing antimicrobial active additives, a photocuring conversion rate of 60% or more is shown, and in particular, Examples 1 and 2 are photocurable compared to Comparative Example 1, which is a general photocurable film. The conversion rate was excellent. From this, it was confirmed that the photocuring process of the antibacterial film containing hightite according to the present invention was effectively performed, and the curing conversion rate for forming the film was sufficiently achieved even when the antibacterial active additive that did not participate in the curing was included.

<Experimental Example 2> Evaluation of antibacterial activity of a photocurable antibacterial coating film containing hightite

In order to prove the antibacterial effect according to the present invention, the antibacterial activity was evaluated using a film adhesion test. The antimicrobial activity of the photocurable antimicrobial coating film prepared in Example 1 was commissioned by Korea Institute of Construction and Life Testing and was conducted according to the test method of KCL-FIR-1003:2018. Specifically, in this experiment, a 5cm×5cm test piece (Example 1, antibacterial coating film) and a 5cm×5cm control piece (Stomacher film) were used, and the bacteria present in the test sample 24 hours after inoculating the strain on the test piece By checking the concentration of the bacteria reduction rate was tested. Escherichia coli ATCC 8739 for Escherichia coli and Staphylococcus aureus ATCC 6538P for Staphylococcus aureus were used as strains. Each inoculum was injected at a concentration of 1.3×10 ⁵ CFU/mL of Escherichia coli and 2.1×10 ⁵ CFU/mL of Staphylococcus aureus.

Table 2 shows the results of testing the antibacterial activity on Escherichia coli (Escherichia coli) and Staphylococcus aureus (Staphylococcus aureus) in the antimicrobial coating film containing a high-tight according to the first embodiment of the present invention.

From Table 2, it was confirmed that the photocurable antibacterial coating film had an antibacterial effect of 99.9% or more against E. coli and staphylococcus, from which it was confirmed that the antibacterial action of the antibacterial film containing the hightite according to the present invention was very excellent. .

Claims (8)

(1) synthesizing an iron (acid water) oxide-based compound represented by the following formula (3) imparting antibacterial properties; (2) preparing a coating composition having antibacterial properties including the iron (acid water) oxide-based compound; And (3) polymerizing the coating composition with a polymer after light irradiation,
The coating composition having antimicrobial properties in step (2) includes 3 to 40% by weight of an iron (acid water) oxide-based compound synthesized in step (1), 1 to 6% by weight of a radical photopolymerization initiator, and trimethyol propanetriarylate (TMPTA) and 2HDDA (1,6-Hexandiol diacrylate) A method for producing a photocurable antibacterial coating film composition, characterized in that consisting of 54 to 96% by weight of one to two reactive acrylic monomers selected from the group consisting of.
[Formula 3]

In the above formula, M ¹ is iron, c is a rational number of 0 to 2, and d is a rational number of 1 to 40.
According to claim 1
The (1) synthesizing an iron (acid water) oxide-based compound imparting antimicrobial properties may include preparing a slurry using a metal nitrate hydrate represented by Formula 1 and a hydroxide represented by Formula 2 as precursors; And synthesizing a metal (acid water) oxide-based antimicrobial compound represented by Chemical Formula 3, wherein the method for producing a photocurable antibacterial coating film composition containing hightite comprises:
[Formula 1]

In Formula 1, M ¹ is iron; a is a positive number equal to the valence of metal M ¹ ; x is a rational number ranging from 0 to 10.

[Formula 2]

In the above formula, M ² is an alkali metal such as lithium, sodium, potassium, rubidium and cesium and an alkaline earth metal element such as calcium, barium, beryllium, and magnesium; b is a positive number equal to the valence of the alkali or alkaline earth metal ion of X.

[Formula 3]

In the above formula, M ¹ is iron, c is a rational number of 0 to 2, and d is a rational number of 1 to 40.
According to claim 1
The (2) step of preparing a coating composition having antibacterial properties is one selected from the group consisting of the synthesized metal (acid water) oxide-based antimicrobial compound, trimethyol propanetricarylate (TMPTA), and 2HDDA (1,6-Hexandiol diacrylate). A method for producing a photocurable antibacterial coating film composition comprising the step of preparing an ultraviolet curable coating composition by selecting and mixing two kinds of reactive acrylic monomers:
The method of claim 3, wherein the reactive acrylic monomer of Formula 4 is one or a mixture of three or more.
The method of claim 3, wherein the radical photoinitiator is a photoinitiator represented by the following formula (5):
[Formula 5]

In the above formula, R ₄ and R ₅ are each independently an aromatic or aliphatic hydrocarbon having 2 to 12 carbon atoms, and R ₆ is an aromatic or aliphatic hydrocarbon having 2 to 12 carbon atoms that may be bonded to a non-metallic element.
delete The method of claim 1,
(3) In the step of polymerizing the coating composition with light after light irradiation, a polyolefin, polyester, or polyacrylic-based film may be selected as the curing substrate of the blended antibacterial coating composition, or a corona-treated or primer-treated substrate may be selected as the curing substrate Can be used; A method for producing a photocurable antibacterial coating film composition, characterized in that applying an ultraviolet curable coating composition containing a metal (acid water) oxide to a uniform thickness on the selected coating substrate.
A photocurable antibacterial coating film composition prepared according to the manufacturing method of any one of claims 1 to 5 or 7.

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