KR102557941B1 - Antibacterial polymer coating composition and antibacterial polymer film - Google Patents

Abstract

The present invention, a urethane acrylate-based oligomer or polymer; polyfunctional acrylates containing alkylene glycol repeating units; photosensitizer; And a photoinitiator; including, an antimicrobial polymer coating composition, an antimicrobial polymer film comprising a cured product of the antimicrobial polymer coating composition, and a urethane acrylate-based oligomer or polymer; and a base layer including a polyfunctional acrylate including an alkylene glycol repeating unit; It relates to an antimicrobial polymer film comprising a; and a photosensitizer dispersed in the substrate layer.

Description

Antimicrobial polymer coating composition and antimicrobial polymer film

The present invention relates to an antimicrobial polymer coating composition and an antimicrobial polymer film.

A photosensitizer absorbs light to generate reactive oxygen species (ROS). By irradiating light of a specific wavelength from the outside, reactive oxygen species or free radicals are generated from the photosensitizer to generate various lesions or cells of cancer cells. Photodynamic therapy (PDT), which induces and destroys death, and the like are widely used.

Various attempts have been made to develop polymeric materials having antibacterial properties using this photodynamic reaction. For example, in Korean Patent Registration No. 10-1465964, silicone resin is melted, and the melted resin and light sensitive A method of mixing agents or a method of using a coating solution formed by dissolving a silicone resin and a photosensitizer in a solvent has been disclosed.

However, according to the method of melting the silicone resin and mixing it with the photosensitizer, since the dispersibility between the photosensitizer and the silicone resin is low, the photosensitizer may not be homogeneously distributed in the silicone resin and may be aggregated. In addition, when melting with silicone resin, it is impossible to adjust the thickness of silicon after melting, so it is not easy to produce products according to the applied field or use, or there is a limit that is not suitable for mass production.

In addition, when using a coating solution formed by dissolving a silicone resin and a photosensitizer in a solvent, it is known that a certain level of antibacterial activity can be achieved without being greatly restricted in the application field. It is not easy to produce active oxygen as much as possible, and since the generated active oxygen exists only for a very short time, there is a limitation in that excessive light energy must be irradiated for a relatively long period of time.

The present invention is to provide a photocurable antibacterial coating composition capable of maintaining high antibacterial properties for a long time even when using light in the visible light range and controlling antimicrobial properties within an appropriate range according to its purpose of use.

In addition, the present invention is to provide an antimicrobial coating film that maintains high antibacterial properties for a long time even when using light in the visible light range and has antimicrobial properties controlled to an appropriate range according to its purpose of use.

In the present specification, a urethane acrylate-based oligomer or polymer; polyfunctional acrylates containing alkylene glycol repeating units; photosensitizer; And a photoinitiator; containing, antimicrobial polymer coating composition is provided.

In addition, in the present specification, an antimicrobial polymer film comprising a cured product of the antimicrobial polymer coating composition is provided.

In addition, in the present specification, a urethane acrylate-based oligomer or polymer; and a base layer including a polyfunctional acrylate including an alkylene glycol repeating unit; And a photosensitizer dispersed in the base layer; containing, antimicrobial polymer is provided.

Hereinafter, an antimicrobial polymer coating composition and an antimicrobial polymer film according to specific embodiments of the present invention will be described in more detail.

In this specification, (meth)acrylate is meant to include both acrylate and methacrylate.

According to one embodiment of the invention, a urethane acrylate-based oligomer or polymer; polyfunctional acrylates containing alkylene glycol repeating units; photosensitizer; And a photoinitiator; containing, antimicrobial polymer coating composition can be provided.

The inventors of the present invention, when the urethane acrylate-based oligomer or polymer is used alone, sufficient antibacterial properties are not secured through light in the visible light region (380 nm to 780 nm wavelength range), but the urethane acrylate-based oligomer or polymer and alkylene Photocurable coatings prepared by mixing polyfunctional acrylates including glycol repeating units together with photosensitizers not only maintain high antibacterial properties for a long time even when using light in the visible light range, but also have antibacterial properties within an appropriate range depending on the purpose of use. It was confirmed through experiments that it could control and the invention was completed.

Accordingly, the antimicrobial polymer coating composition of the embodiment can be easily applied to various fields and is suitable for mass production, and can realize high antibacterial properties even when light in the visible light range is applied when manufactured as an actual coating film or coated molded article, , In addition, the generated active oxygen can remain for a long time compared to previously known antibacterial materials, etc., so that high antibacterial efficiency can be realized.

When the polymer film or polymer molded article provided from the antimicrobial polymer coating composition of the embodiment is irradiated with light in the visible light region, active oxygen species or free radicals are generated from the photosensitizer contained in the polymer film or polymer molded article, as described above. Likewise, active oxygen can be generated more efficiently according to the synergistic action of the components included in the antimicrobial polymer coating composition, while the remaining time of active oxygen can be greatly increased.

This seems to be due to the use of the urethane acrylate-based oligomer or polymer together with a multifunctional acrylate containing an alkylene glycol repeating unit. Specifically, the multifunctional acrylate containing the alkylene glycol repeating unit is a hydrophilic group and will make the antibacterial coating surface a hydrophilic surface, thereby facilitating accessibility to bacteria present in the aqueous solution. This will improve antibacterial properties. The diffusion range of ¹ O ₂ will be within a certain distance from the surface of the antibacterial coating, and the hydrophobic surface will keep the solution containing bacteria farther than the diffusion range of ¹ O ₂ so that the antibacterial effect will not be displayed well and the hydrophilic The (Hydrophilic) surface seems to exhibit good antibacterial performance because the solution containing bacteria is located within the diffusion range of ¹ O ₂ .

The antimicrobial polymer coating composition may include 1 to 100 parts by weight of the polyfunctional acrylate including the alkylene glycol repeating unit based on 100 parts by weight of the urethane acrylate-based oligomer or polymer.

When the content of the polyfunctional acrylate including the alkylene glycol repeating unit is too small compared to the urethane acrylate-based oligomer or polymer, it may be difficult to express antibacterial properties due to lack of hydrophilic properties. When the content of the polyfunctional acrylate including the alkylene glycol repeating unit is too high compared to the urethane acrylate-based oligomer or polymer, the curing is not performed well, and when a curing agent is added to improve the curing degree, the hydrophilic balance in the matrix This collapse may reduce the antibacterial effect, and the soft coating surface may create a place where germs can live due to scratches, etc., thereby inhibiting the antibacterial effect.

Examples of the multifunctional acrylate containing the alkylene glycol repeating unit include bifunctional to 15 functional acrylate containing an alkylene glycol repeating unit having 2 to 20 repeating units and having 1 to 20 carbon atoms.

More specific examples of the multifunctional acrylate containing the alkylene glycol repeating unit include diacrylate containing polyalkylene glycol having a number average molecular weight of 100 to 1,000 or polyalkylene glycol having a number average molecular weight of 100 to 1,000 and trimethylolpropane ethoxylate triacrylate.

On the other hand, the urethane acrylate-based oligomer or polymer may have a predetermined molecular weight in consideration of specific uses or physical properties of the antimicrobial coating composition, for example, the urethane acrylate-based oligomer or polymer is 200 g / mol to 50,000 It may have a weight average molecular weight of g/mol.

In this specification, a weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method.

Specific examples of the urethane acrylate-based oligomer or polymer include various modified urethane acrylates having a weight average molecular weight of 500 g/mol to 10,000 g/mol.

Meanwhile, in the urethane acrylate-based oligomer or polymer, a molar ratio of urethane functional groups to (meth)acrylate-based functional groups may be 1 to 20 or 5 to 15. If the molar ratio of the urethane functional group to the (meth)acrylate functional group in the urethane acrylate oligomer or polymer is too small, the oxygen permeability of the polymer film or polymer molded article prepared from the polymer coating composition is significantly lowered, and visible light Active oxygen is not sufficiently generated during irradiation, and antibacterial properties are not implemented, so it may be difficult to apply to various applications.

In addition, if the molar ratio of the urethane functional group to the (meth)acrylate functional group in the urethane acrylate oligomer or polymer is too large, active oxygen may be generated at a certain level when irradiated with visible light, but the strength of the polymer film is lowered, which is supported A small amount of the photosensitizer may leak out of the film, and secondary side reactions to the leaked photosensitizer (eg, harmful effects on the human body and environmental pollution due to the photosensitizer) may be caused, and also the hardness of the polymer film It can be difficult to apply to many applications due to its low value.

On the other hand, as described above, when the antimicrobial polymer coating composition is irradiated with light in the visible light region after photocuring, the photosensitizer may reflect and generate active oxygen, etc. It may contain a photosensitizer in the amount of.

Specifically, the antimicrobial polymer coating composition may include 0.01 to 5 parts by weight of the photosensitizer based on 100 parts by weight of the urethane acrylate-based oligomer or polymer.

On the other hand, as the photosensitizer, commonly known compounds may be used, for example, porphine compounds, porphyrins compounds, chlorins compounds, bacteriochlorins compounds, phthalocyanine A phthalocyanine compound, a naphthalocyanine compound, 5-aminolevulin esters, or two or more compounds thereof may be used.

However, in order to realize higher antibacterial and antimicrobial maintenance performance in the final product prepared from the antimicrobial polymer coating composition, it is preferable to use a porphine-based compound or a porphyrin-based compound, more preferably A phenyl group into which an alkoxy having 1 to 10 carbon atoms is introduced, such as Zn(II) meso-Tetra(4-carboxyphenyl) Porphine or 5,10,15,20-tetrakis(4-methoxyphenyl)-porphine as the photosensitizer. A porphin compound or a porphyrin compound into which 1 to 8 are introduced may be used .

The antimicrobial polymer coating composition may include a photoinitiator in a predetermined amount. Specifically, 0.01 to 10 parts by weight of the photoinitiator may be included based on 100 parts by weight of the urethane acrylate-based oligomer or polymer.

Specific examples of the photoinitiator are not limited, and conventionally known photoinitiators may be used without significant limitations. Specific examples of the photoinitiator may include a benzophenone-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an oxime-based compound, or a mixture of two or more thereof.

The antimicrobial polymer coating composition may further include an organic solvent or surfactant.

The organic solvent may be added at the time of mixing each component included in the antimicrobial polymer coating composition, or may be included in the antimicrobial polymer coating composition while each component is added in a dispersed or mixed state in the organic solvent. For example, the antimicrobial polymer coating composition may include an organic solvent so that the total solid concentration of the components included is 1% to 80% by weight, or 2 to 50% by weight.

Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or a mixture of two or more thereof. Specific examples of such an organic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran or propylene glycol monomethyl ether; or a mixture of two or more thereof.

The type of the surfactant is also not significantly limited, and anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used.

The antimicrobial polymer coating composition may include 0.001 to 20 parts by weight of the surfactant based on 100 parts by weight of the urethane acrylate-based oligomer or polymer.

The antimicrobial polymer coating composition may further include inorganic fine particles. The inorganic fine particles may be included in the resin composition in a form dispersed in the polyfunctional acrylate-based monomer.

The inorganic fine particles may be inorganic fine particles having a nanoscale particle size, for example, nano fine particles having a particle size of about 100 nm or less, about 10 to about 100 nm, or about 10 to about 50 nm. In addition, the inorganic fine particles may include, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles.

By including the inorganic fine particles, the hardness of the film prepared from the composition can be further improved. When the total weight of the binder is 100 parts by weight, the inorganic fine particles may be included in about 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight.

By including the inorganic fine particles in the above range, it is possible to form an antibacterial coating film excellent in both high hardness and flexibility.

The antimicrobial polymer coating composition may further include commonly used additives such as a UV absorber, a surfactant, an anti-yellowing agent, a leveling agent, and an antifouling agent. In addition, since the content can be variously adjusted within a range that does not degrade the physical properties of the antimicrobial coating film, it is not particularly limited.

In addition, an anti-yellowing agent may be included as the additive, and the anti-yellowing agent may include a benzophenone-based compound or a benzotriazole-based compound.

On the other hand, the antimicrobial polymer coating composition may optionally further include a monomer or oligomer having a monofunctional or multifunctional functional group in addition to the urethane acrylate-based oligomer or polymer.

Specifically, the antimicrobial polymer coating composition may include (meth)acrylate or a monomer or oligomer containing a vinyl group.

Specifically, the photopolymerizable compound may include a monomer or oligomer including one or more, two or more, or three or more (meth)acrylate or vinyl groups. Specific examples of the monomer or oligomer including the (meth)acrylate include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, )Acrylate, tripentaerythritol hepta(meth)acrylate, torylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acryl rate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, epoxide acrylate oligomer, ether acryl rate oligomers, dendritic acrylate oligomers, or mixtures of two or more thereof. At this time, it is preferable that the molecular weight of the oligomer is 1,000 to 10,000. Specific examples of the monomer or oligomer containing the vinyl group include divinylbenzene, styrene, or paramethylstyrene.

Meanwhile, according to another embodiment of the invention, an antimicrobial polymer film including a cured product of the antimicrobial polymer coating composition may be provided.

As described above, the antimicrobial polymer film prepared by curing the antimicrobial polymer coating composition can be easily applied to various fields, is suitable for mass production, and can achieve high antibacterial properties even when light in the visible light range is applied, In particular, since the generated active oxygen remains longer than previously known antimicrobial materials, high antibacterial efficiency can be realized.

The antimicrobial polymer film may be obtained by applying the antimicrobial polymer coating composition on a predetermined substrate and photocuring the resultant coating. The specific type or thickness of the substrate is not particularly limited, and a substrate known to be used in the manufacture of a conventional polymer film may be used without significant limitations.

Methods and devices commonly used for applying the antimicrobial polymer coating composition may be used without particular limitations, for example, bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot die coating method, 2 roll coating method, etc. can be used.

The coating thickness of the antimicrobial polymer coating composition may be determined according to the purpose of the finally manufactured antimicrobial polymer film, and the like. For example, the antimicrobial polymer coating composition may be coated (applied) to a thickness of 0.1 μm to 1,000 μm.

In the step of photocuring the antimicrobial polymer coating composition, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm may be irradiated, and an exposure amount during irradiation is preferably 50 to 2,000 mJ/cm 2 . The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of irradiation light, or the amount of exposure.

In addition, in the step of photocuring the antimicrobial polymer coating composition, nitrogen purging may be performed in order to apply nitrogen atmospheric conditions.

On the other hand, according to another embodiment of the invention, a urethane acrylate-based oligomer or polymer; and a base layer including a polyfunctional acrylate including an alkylene glycol repeating unit; And a photosensitizer dispersed in the substrate layer; containing, antimicrobial polymer film may be provided.

As the substrate layer includes the urethane acrylate-based oligomer or polymer and the multifunctional acrylate including an alkylene glycol repeating unit, a predetermined polymer structure may be formed therein, thereby emitting light in the visible light range. Even when used, high antibacterial properties can be maintained for a long time, and antimicrobial properties can be controlled within an appropriate range according to the purpose of use.

When such an antimicrobial polymer film is irradiated with light in the visible light region, active oxygen species or free radicals are generated from the photosensitizer contained in the base layer. As described above, active oxygen can be generated more efficiently, while active oxygen The remaining time can be greatly increased.

In addition, the antibacterial property of the antimicrobial polymer film measured according to JIS R1702 (KS L ISO 27447: 2011 fine ceramics - antibacterial test method for semiconductor photocatalyst materials) may be 90% or more, or 90% to 99.99%.

The antimicrobial polymer film may have a thickness of 0.1 μm to 100 μm.

Meanwhile, according to another embodiment of the present invention, an electronic product including the antimicrobial polymer film described above may be provided.

Examples of the electronic product are not particularly limited, and for example, it can be applied to products in which harmful bacteria (mold, etc.) easily grow, such as humidifiers, water tanks, refrigerators, air washers, aquariums, and air purifiers.

In order to generate active oxygen or radicals in the antimicrobial polymer film, the electronic product may include a light irradiation device. In addition, the electronic product may further include a device for distributing generated active oxygen or radicals, such as an air circulation device.

According to the present invention, even when light in the visible light region is used, high antibacterial properties are maintained for a long time, antibacterial properties can be controlled within an appropriate range according to the purpose of use, and an antibacterial material suitable for mass production can be provided. A fire-type antibacterial coating composition and an antimicrobial coating film capable of maintaining high antibacterial properties for a long time even using light in the visible light range may be provided.

Embodiments of the invention are described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

(Production Example: Production of Urethane Acrylate Oligomer (Polymer))

[Production Example 1]

1,6-Hexanedioldiacrylate (20% by weight of total solids), a reactive diluent, was added to a 5-liter round-bottom flask equipped with a stirrer to suppress the rapid exothermic reaction at the beginning, and a polyamide having a weight average molecular weight of 2,000 1.2 equivalents of caprolactonediol, 0.8 equivalents of hexamethylene diisocyanate (HMDI), and about 200 ppmw of dibutyltin dilaurylate were slowly added dropwise.

After the reaction was carried out while maintaining the reaction temperature at about 75°C, the reaction temperature was decreased to about 50°C. In addition, 500 ppm of hydroquinone and 500 ppm of phenoxyanine were added as polymerization inhibitors, and 1.8 equivalents of 2-hydroxyethyl acrylate were added to proceed with the reaction.

After the addition, while maintaining the reaction temperature of about 75 ℃ for about 9 hours, check until the NCO peak completely disappears with an infrared spectrometer, complete the reaction, cool it, and add methyl ethyl ketone, a diluent solvent, to urethane (meta) An acrylate oligomer (weight average molecular weight in terms of polystyrene measured by GPC method: about 5,500, viscosity at 25°C: 6540 cps) was prepared.

[Example: Preparation of antimicrobial polymer coating composition and antimicrobial polymer film]

Example 1

10 g of the urethane acrylate oligomer (molar ratio of urethane functional groups to acrylate functional groups: about 1) of Preparation Example 1, 5 g of polyethylene glycol 600 dimethacrylate (PEG600DMA, Miramer M286), 0.3 g of photoinitiator (trade name: Irgaqure 127) Together, the photosensitizer [Zn (II) meso-Tetra (4-carboxyphenyl) Porphine] was dissolved in toluende at a concentration of 3 mM, and added at a weight ratio of 0.3 to 100 weight ratio of the urethane acrylate-based oligomer of Preparation Example 1, and toluene was added. was added to prepare an antibacterial polymer coating solution (45% solid content).

In addition, the antimicrobial polymer coating solution was coated using #10 bar, dried at 120 ° C for 2 minutes, cured at a rate of 2 m / min using a 0.2 J / ㎠ UV lamp, and an antimicrobial polymer film with a thickness of 10 μm. was manufactured.

Example 2

Antimicrobial polymer coating solution (solid concentration 45%) and antimicrobial polymer film (10 μm thick ) was prepared.

Example 3

Except for the fact that 10 g of the polyethylene glycol 600 dimethacrylate (PEG600DMA, Miramer M286) was used, An antimicrobial polymer coating solution (solid concentration: 50%) and an antimicrobial polymer film (10 μm thick) were prepared in the same manner as in Example 1.

Example 4

Except for the fact that 7.5 g of trimethylolpropane (EO)15 Triacrylate [Trimethylolpropane (EO)15 Triacrylate] was used instead of 5 g of the polyethylene glycol 600 dimethacrylate (PEG600DMA, Miramer M286), An antimicrobial polymer coating solution (solid concentration: 50%) and an antimicrobial polymer film (10 μm thick) were prepared in the same manner as in Example 1.

Example 5

Except for the fact that 10 g of trimethylolpropane ethoxylate triacrylate [Trimethylolpropane (EO)15 Triacrylate] was used instead of 5 g of the polyethylene glycol 600 dimethacrylate (PEG600DMA, Miramer M286), An antimicrobial polymer coating solution (solid concentration: 50%) and an antimicrobial polymer film (10 μm thick) were prepared in the same manner as in Example 1.

Example 6

Antimicrobial polymer coating solution ( The solid concentration was 50%) and an antimicrobial polymer film (10 μm thick) was prepared.

[Comparative Example: Manufacture of polymer film]

Comparative Example 1

Antimicrobial polymer coating solution (solid content concentration 50% ) and an antimicrobial polymer film (10 μm thick) were prepared.

<Experimental Example: Measurement of antibacterial properties of polymer films of Examples and Comparative Examples>

Experimental Example 1: Antimicrobial evaluation

1) Preparation of bacterial suspension

As the test bacteria, E.coli ATCC 8739, which is a standard E. coli specified in the KS L ISO 27447 standard, was used. The E.coli ATCC 8739 strain was inoculated into LB nutrient medium using a platinum loop, incubated at 37°C for 16 to 24 hours, and then stored in a refrigerator at 5°C. The secondary culture was repeated by mimicking the above process within 1 month. The maximum number of CFU (colony forming units) in the secondary culture should be 10. LB nutrient medium is prepared by mixing 25 g/L Luria Broth powder and 15 g/L agar powder (available from Sigma-Aldrich) in distilled water, sterilizing in an autoclave, and then placing an appropriate amount on a petri dish when the temperature drops to ~40°C. did

The bacteria culture medium was centrifuged to separate the bacteria from the LB liquid medium, and then the bacteria were transferred to saline. The suspension was diluted so that the absorption value of the bacteria-saline solution at 600 nm was 0.5 using a spectrophotometer, and the bacteria suspension was used for the test.

As for the specific dilution method, since each plate is diluted 1/10, the number of CFU is also reduced by 1/10. The amount of suspension used for plating is 0.1 ml. Since the number of CFU in C ₄ is 299 and the amount of liquid used is 0.1 ml, 299 CFU / 0.1ml = 2,990 CFU/ml The number of CFU in C ₁ is ~3.0 x 10 ⁶ CFU/ml multiplied by 1,000, and C ₁ is Since the bacterial stock solution (C0) was diluted 1/10, the number of CFUs in the bacterial suspension was 3.0 x 10 ⁷ CFU/ml.

2) Bacterial inoculation on the specimen

On the previously prepared test piece, 0.2 mL of each bacterial suspension (C ₁ , C ₂ , C ₃ , C ₄ ) was quantified, and then a polypropylene adhesive film having a transmittance of 80% or more was placed thereon to support the photocatalyst sample. It was prepared as a sandwich structure containing a microbial suspension placed between a polymer film and an adhesive film.

3) Antibacterial test (light condition; light)

For each of the specimens, (1) conditions of irradiating 1,000 Lux of White LED for 6 hours and (2) conditions of irradiating 1,000 Lux of Green LED for 6 hours were applied, and (3) conditions of 405 nm and 0.35 mW/cm ² ( 4) Each case was compared with the case where it was left for 6 hours in the dark condition.

Then, the concentration of bacteria in each sample was confirmed and the virus reduction factor (R) was calculated according to the following general formula 1.

[Formula 1]

R = log ₁₀ [(V1 X T1) / (V2 X T2)]

R: virus reduction concentration expressed as log

V1: Capacity of sample before light treatment

T1: virus concentration of sample before light treatment

V2: Capacity of sample after light treatment

T2: Virus concentration of the sample after light treatment

antibacterial White LEDs
1,000 Lux
6 hours Green LEDs
1,000 Lux
6 hours 405 nm
0.35 mW/cm ²
6 hours Comparative Example 1 0.76 log ₁₀ 0.8 log ₁₀ 0.7 log Example 1 4 log ₁₀ 1.2 log ₁₀ 4 log ₁₀ Example 2 4 log ₁₀ 2.6 log ₁₀ 4 log ₁₀ Example 3 4 log ₁₀ 3.6 log ₁₀ 4 log ₁₀ Example 4 2 log ₁₀ 1 log ₁₀ 4 log ₁₀ Example 5 2.5 log ₁₀ 1.5 log ₁₀ 4 log ₁₀ Example 6 4.0 log ₁₀ 3 log ₁₀ 4 log ₁₀

As shown in the results in Table 1, the polymer films prepared from the antimicrobial polymer coating compositions of Examples exhibited a virus reduction factor of 2.0 log ₁₀ or more under the conditions of White LED, 1,000 Lux and 6 hours, and had antibacterial activity of about 99% or more. It was confirmed that high antimicrobial activity was realized under the conditions of Green LED, 1,000 Lux and 6 hours.

In contrast, it was confirmed that the polymer film prepared from the antimicrobial polymer coating composition of Comparative Example 1 exhibited a virus reduction factor of less than 1 log ₁₀ , indicating a lower level of antibacterial activity than that of Example.

Claims (13)

urethane acrylate-based oligomers or polymers;
polyfunctional acrylates containing alkylene glycol repeating units;
photosensitizer; and
Including; photoinitiator,
In the urethane acrylate-based oligomer or polymer, the molar ratio of the urethane functional group to the (meth) acrylate-based functional group is 1 to 20,
The multifunctional acrylate containing alkylene glycol repeating units is a bifunctional to 15 functional acrylate containing alkylene glycol repeating units having 1 to 20 carbon atoms and having 2 to 20 repeating units,
The photosensitizer is a porphine-based compound, a porphyrin-based compound, a chlorin-based compound, a bacteriochlorins compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, and An antimicrobial polymer coating composition comprising at least one selected from the group consisting of 5-aminolevulin esters.
delete According to claim 1,
The multifunctional acrylate containing the alkylene glycol repeating unit is diacrylate containing polyalkylene glycol having a number average molecular weight of 100 to 1,000 or trimethylolpropane containing polyalkylene glycol having a number average molecular weight of 100 to 1,000 An ethoxylate triacrylate, an antimicrobial polymer coating composition.
According to claim 1,
The urethane acrylate-based oligomer or polymer has a weight average molecular weight of 200 g / mol to 50,000 g / mol, antimicrobial polymer coating composition.
delete According to claim 1,
The urethane acrylate-based oligomer or polymer is a caprolactone-modified urethane acrylate-based oligomer having a weight average molecular weight of 500 g / mol to 10,000 g / mol, antimicrobial polymer coating composition.
According to claim 1,
Compared to 100 parts by weight of the urethane acrylate oligomer or polymer
1 to 100 parts by weight of the multifunctional acrylate containing the alkylene glycol repeating unit;
0.01 to 5 parts by weight of the photosensitizer; and
0.01 to 10 parts by weight of the photoinitiator;
Containing, antimicrobial polymer coating composition.
delete According to claim 1,
Further comprising an organic solvent or surfactant, the antimicrobial polymer coating composition.
An antimicrobial polymer film comprising a cured product of the antimicrobial polymer coating composition of claim 1.
urethane acrylate-based oligomers or polymers; and a base layer including a polyfunctional acrylate including an alkylene glycol repeating unit; and a photosensitizer dispersed in the substrate layer.
In the urethane acrylate-based oligomer or polymer, the molar ratio of the urethane functional group to the (meth) acrylate-based functional group is 1 to 20,
The multifunctional acrylate containing alkylene glycol repeating units is a bifunctional to 15 functional acrylate containing alkylene glycol repeating units having 1 to 20 carbon atoms and having 2 to 20 repeating units,
The photosensitizer is a porphine-based compound, a porphyrin-based compound, a chlorin-based compound, a bacteriochlorins compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, and Containing at least one selected from the group consisting of 5-aminoevuline esters,
Antimicrobial polymer film.
According to claim 11,
The antimicrobial polymer film has a thickness of 0.1㎛ to 100㎛. Antimicrobial polymer film.
According to claim 11,
JIS R1702 (KS L ISO 27447; 2011) as measured by 90% or more antibacterial, antimicrobial polymer film.