ANTIBACTERIAL POLYMER COATING COMPOSITION AND ANTIBACTERIAL POLYMER FILM

Abstract

The present disclosure relates to: an antibacterial polymer coating composition comprising a (meth)acrylic polyol resin, which has a number average molecular weight of 3,000-20,000, a (co)polymer containing an ethylene glycol repeating unit, and a photosensitizer; an antibacterial polymer film comprising a cured product of the antibacterial polymer coating composition; and an antibacterial polymer film which comprises a substrate layer and a photosensitizer, the substrate layer comprising a (meth)acrylic polyol resin having a number average molecular weight of 3,000-20,000 and a (co)polymer containing an ethylene glycol repeating unit, and the photosensitizer being dispersed in the substrate layer.

Claims

1. An antibacterial polymer coating composition comprising: a (meth)acrylic polyol resin having a number average molecular weight of 3,000 to 20,000; a (co)polymer containing an ethylene glycol repeating unit; and a photosensitizer.

2. The antibacterial polymer coating composition according to claim 1, wherein the (meth)acrylic polyol resin having a number average molecular weight of 3,000 to 20,000 includes a copolymer of a monomer mixture including an alkyl (meth)acrylate having 1 to 10 carbon atoms; a hydroxyalkyl(meth)acrylate having 1 to 10 carbon atoms; and a vinyl-based monomer.

3. The antibacterial polymer coating composition according to claim 1, wherein the (co)polymer containing an ethylene glycol repeating unit has a weight average molecular weight of 1,000 to 5,000.

4. The antibacterial polymer coating composition according to claim 1, wherein the (co)polymer containing the ethylene glycol repeating unit includes poly(oxyalkylene (Oxy-A1) having 1 to 5 carbon atoms)-poly(oxyalkylene (Oxy-A2) having 1 to 5 carbon atoms) glycol random copolymer, and the number of carbon atoms of the A1 and A2 are different, and at least one of A1 and A2 has 2 carbon atoms.

5. The antibacterial polymer coating composition according to claim 1, wherein the (co)polymer containing the ethylene glycol repeating unit is a polyoxytetramethylene-polyoxyethylene glycol copolymer having a weight average molecular weight of 1,000 to 5,000.

6. The antibacterial polymer coating composition according to claim 1, comprising: 10 to 100 parts by weight of the (co)polymer containing the ethylene glycol repeating unit; and 0.01 to 5 parts by weight of the photosensitizer, based on 100 parts by weight of the (meth)acrylic polyol resin having a number average molecular weight of 3,000 to 20,000.

7. The antibacterial polymer coating composition according to claim 1, wherein the photosensitizer includes at least one selected from the group consisting of a porphine compound, a porphyrin compound, a chlorin compound, a bacteriochlorin compound, a phthalocyanine compound, a naphthalocyanine compound, and a 5-aminolevulinate ester compounds.

8. The antibacterial polymer coating composition according to claim 1, wherein the photosensitizer includes a porphine compound or a porphyrin compound and wherein the porphine or porphyrin compound contains 1 to 8 phenyl groups to which an alkoxy having 1 to 10 carbon atoms is introduced.

9. The antibacterial polymer coating composition according to claim 1, further comprising a thermal initiator or a crosslinking agent.

10. The antibacterial polymer coating composition according to claim 9, wherein the crosslinking agent includes a multifunctional isocyanate.

11. An antibacterial polymer film comprising a cured product of the antibacterial polymer coating composition of claim 1.

12. An antibacterial polymer film comprising: a substrate layer, wherein the substrate layer comprises a photosensitizer, a (meth)acrylic polyol resin having a number average molecular weight of 3,000 to 20,000 and a (co)polymer containing an ethylene glycol repeating unit, and the photosensitizer is dispersed in the substrate layer.

13. The antibacterial polymer film according to claim 12, wherein the antibacterial polymer film has a thickness of 10 μm to 10,000 μm.

14. The antibacterial polymer film according to claim 12, wherein the antibacterial polymer has an antibacterial activity of at least 90% as measured according by KS L ISO 274474.

15. The antibacterial polymer film according to claim 12, wherein the substrate layer includes 10 to 100 parts by weight of the (co)polymer containing the ethylene glycol repeating unit relative to 100 parts by weight of the (meth)acrylic polyol resin having a number average molecular weight of 3,000 to 20,000.

16. The antibacterial polymer film according to claim 12, wherein the (co)polymer containing the ethylene glycol repeating unit has a weight average molecular weight of 1,000 to 5,000.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0082] FIG. 1 schematically shows the results of measuring the antibacterial activity of the polymer films of Example 1 and Comparative Example 1.

[0083] Below, the present disclosure will be described in more detail by way of examples.

[0084] However, these examples are provided for illustrative purposes only, and should not be construed as limiting the scope of the present disclosure to these examples.

Preparation Example: Preparation of (Meth)Acrylic Polyol Resin

[0085] In a synthesis four-necked flask equipped with a thermometer and a stirrer, 20 g of n-butyl acetate, 35 g of methyl methacrylate and 0.25 g of azoisobutyronitrile were inserted, and then the temperature was raised to the reflux temperature, and after the reflux was stabilized, the reflux was maintained for 60 minutes.

[0086] Then, 15 g of hydroxyethyl methacrylate, 10 g of styrene, and 10 g of butyl methacrylate were uniformly separated and added dropwise for 180 minutes, and the reaction product was diluted with butyl acetate. Then, the reaction product was cooled to 60° C. to obtain an acrylic polyol resin A having a solid content of 50% (the number average molecular weight using polystyrene calibration measured by GPC method was about 10,000, and the glass transition temperature was 50° C.).

Example: Preparation of Antibacterial Polymer Coating Composition and Antibacterial Polymer Film

Example 1

[0087] 10 g of the (meth)acrylic polyol resin synthesized in Preparation Example, 2 g of Polycerin DC-1800E (polyoxytetramethylene-polyoxyethylene glycol random copolymer having a weight average molecular weight of 1,800 g/mol, manufactured by NOF Corporation), and a photosensitizer [Zn(II) meso-tetra(4-carboxyphenyl) Porphine] were dissolved in toluene at a concentration of 3 mM, and added at a weight ratio of 0.3 relative to 100 weight ratio of the (meth)acrylic polyol resin synthesized in the Preparation Example, and 0.3 g of a curing agent (product name TKA-100) and toluene were further added to prepare an antibacterial polymer coating solution (solid content concentration of 45%).

[0088] Then, the coating solution was coated with #20 bar, and then thermally cured in an oven at 120° C. for 2 minutes and aged in an oven at 40° C. for 24 hours to prepare an antibacterial polymer film having a thickness of 10 μm.

Example 2

[0089] An antibacterial polymer coating solution (solid content concentration of 50%) and an antibacterial polymer film (thickness of 10 μm) were prepared, except that 2 g of Polycerin DCB-2000 (polyoxytetramethylene-polyoxypropylene glycol random copolymer having a weight average molecular weight of 2000 g/mol, manufactured by NOF Corporation) was used instead of 2 g of Polycerin DC-1800E.

Example 3

[0090] An antibacterial polymer coating solution (solid content concentration of 50%) and an antibacterial polymer film (thickness of 10 μm) were prepared in the same manner as in Example 1, except that 4 g of Polycerin DC-1800E was used instead of 2 g of Polycerin DC-1800E.

Example 4

[0091] An antibacterial polymer coating solution (solid content concentration of 50%) and an antibacterial polymer film (thickness of 10 μm) were prepared in the same manner as in Example 1, except that 4 g of Polycerin DC-1800E was used instead of 2 g of Polycerin DC-1800E, and 0.6 g of curing agent (trade name TKA-100) was used instead of 0.3 g of curing agent (product name TKA-100).

Comparative Example 1

[0092] A polymer film having a thickness of 10 μm was prepared in the same manner as in Example 1, except that the Polycerin DC-1800E was not used.

Experimental Example: Measurement of Antibacterial Activities of Polymer Films of Examples and Comparative Example

Experimental Example 1: Evaluation of Antibacterial Activity

[0093] 1) Preparation of Bacterial Suspension

[0094] As test bacteria, E. coli ATCC 8739, 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, cultured at 37° C. for 16 to 24 hours, and then stored in a refrigerator at 5° C. Within 1 month, the above process was replicated and the secondary culture was repeated. During the secondary culture, the maximum number of colony-forming units (CFU) should be 10. The LB nutrient medium was prepared by a process in which 25 g/L of Luria Broth powder and 15 g/L of agar powder (available from Sigma-Aldrich) were mixed with distilled water and sterilized in an autoclave, and when the temperature was lowered to ˜40° C., an appropriate amount was quantified in a petri dish.

[0095] The bacterial culture was centrifuged to separate the bacteria and the LB liquid medium, and then the bacteria were transferred to a saline solution. 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 bacterial suspension was used for the experiment.

[0096] In a specific dilution method, each plate was diluted by 1/10, and the number of CFU was also reduced by 1/10. The amount of suspension used for plating was 0.1 ml. Since the number of CFU of C.sub.4 was 299 and the amount of liquid used was 0.1 ml, 299 CFU/0.1 ml=2,990 CFU/ml. The number of CFU of C.sub.1 was ˜3.0×10.sup.6 CFU/ml multiplied by 1,000, and C.sub.1 is one in which a bacterial stock solution (C0) was diluted by 1/10, so the number of CFU of the bacterial suspension was 3.0×10.sup.7 CFU/ml.

[0097] 2) Inoculation of Bacteria on the Test Specimen

[0098] 0.2 mL of bacterial suspensions (C1, C2, C3, C4) were each quantified on the previously prepared test specimen, and then a polypropylene adhesive film having a transmittance of 80% or more was disposed thereon, whereby it was prepared in a sandwich structure including a bacterial suspension located between a polymer film carrying a photocatalyst sample and an adhesive film.

[0099] 2) Antibacterial Test (Light Condition; Light)

[0100] For each of the above test specimens, (1) the condition of irradiating 1,000 Lux of White LED for 6 hours and (2) the condition of irradiating 1,000 Lux of Green LED for 6 hours were applied, and (3) the conditions of 405 nm and 0.35 mW/cm.sup.2 were compared with (4) the case leaving for 6 hours in each dark condition.

[0101] 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.

R=log.sub.10[(V1×T1)/(V2×T2)]  [General Formula 1]

[0102] R: virus reduced concentration expressed as log

[0103] V1: volume of sample before light treatment

[0104] T1: virus concentration of sample before light treatment

[0105] V2: volume of sample after light treatment

[0106] T2: virus concentration of sample after light treatment

TABLE-US-00001 TABLE 1 Antibacterial activity White LED Green LED 405 nm 1,000 Lux 1,000 Lux 0.35 mW/cm.sup.2 6 hrs 6 hrs 6 hrs Comparative <log.sub.10 <0.5 log.sub.10  <0.5 log.sub.10 Example 1 Example 1 3.6 log.sub.10 2.8 log.sub.10 4.0 g Example 2 3.0 log.sub.10 2.6 log.sub.10 4.0 g Example 3   4 log.sub.10 2.8 log.sub.10 4.0 g Example 4 2.5 log.sub.10 1.9 log.sub.10 3.0 g

[0107] As shown in FIG. 1, it was confirmed that the polymer film prepared from the antibacterial polymer coating composition of Example 1 exhibits higher antibacterial activity compared to the polymer film prepared from the antibacterial polymer coating composition of Comparative Example 1.

[0108] More specifically, as shown in the results in Table 1, it was confirmed that the polymer films prepared from the antibacterial polymer coating compositions of Examples 1 to 4 each exhibit a virus reduction factor of about 1.9 log.sub.10 or 2.0 log.sub.10 or more, and have an antibacterial activity of about 99% or more. On the contrary, it was confirmed that the polymer film prepared from the antibacterial polymer coating composition of Comparative Example exhibits a virus reduction factor of less than 1 log.sub.10, and exhibits a lower level of antibacterial activity than Examples.