ANTIMICROBIAL POLYMER COATING COMPOSITION AND ANTIMICROBIAL POLYMER FILM

Abstract

The present invention relates to an antimicrobial polymer coating composition comprising: a urethane acrylate-based oligomer or polymer having a molar ratio of a urethane functional group to a (meth)acrylate-based functional group of 1 to 10; a photosensitizer; and a photoinitiator; an antimicrobial polymer film comprising a cured product of the antimicrobial polymer coating composition; and an antimicrobial polymer film comprising a predetermined urethane acrylate-based polymer resin; and a photosensitizer dispersed in the polymer resin, wherein the polymer film has oxygen permeability of 5 to 100 cc/m.sup.2 day.

Claims

1. An antimicrobial polymer coating composition comprising: a urethane acrylate-based oligomer or polymer; a photosensitizer; and a photoinitiator, wherein a molar ratio of the urethane functional group to the (meth)acrylate-based functional group in the urethane acrylate-based oligomer or polymer is 1 to 10.

2. The antimicrobial polymer coating composition of claim 1, wherein the urethane acrylate-based oligomer or polymer has a weight average molecular weight of 200 g/mol to 50,000 g/mol.

3. The antimicrobial polymer coating composition of claim 1, wherein the molar ratio of the urethane functional group to the (meth)acrylate-based functional group is in the range of 4 to 8.

4. The antimicrobial polymer coating composition of claim 1, wherein the photosensitizer is contained in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the urethane acrylate-based oligomer or polymer.

5. The antimicrobial polymer coating composition of claim 1, wherein the photosensitizer includes at least one selected from the group of porphine compounds, porphyrin compounds, chlorin compounds, bacteriochlorin compounds, phthalocyanine compounds, naphthalocyanine compounds, and 5-aminoevuline esters.

6. The antimicrobial polymer coating composition of claim 1, wherein the photosensitizer includes a porphine compound or a porphyrin compound having 1 to 8 of phenyl groups having an C.sub.1-10 alkoxy group.

7. The antimicrobial polymer coating composition of claim 1, further comprising an organic solvent or a surfactant.

8. An antimicrobial polymer film comprising a cured product of the antimicrobial polymer coating composition of claim 1.

9. An antimicrobial polymer film comprising: a substrate layer containing a urethane acrylate-based polymer resin having a molar ratio of a urethane functional group to a (meth)acrylate-based functional group of 1 to 10; and a photosensitizer dispersed in the substrate layer, wherein the polymer film has oxygen permeability of 5 to 100 cc/m.sup.2 day.

10. The antimicrobial polymer film of claim 9, wherein the antimicrobial polymer film has a thickness of 10 m to 10,000 m.

11. The antimicrobial polymer film of claim 9, wherein the antimicrobial polymer film has a singlet oxygen lifetime of 0.4 ins or more, as measured through a time-resolved phosphorescence laser spectroscopy system.

12. The antimicrobial polymer film of claim 9, wherein the antimicrobial polymer film has antimicrobial activity of 90% or more, as measured by HS R1702 (KS L ISO 27447; 2011).

13. An electronic product comprising the antimicrobial polymer film of claim 8.

14. The electronic product of claim 13, wherein the electronic product is a humidifier, a refrigerator, an air washer, or an aquarium.

15. An electronic product comprising the antimicrobial polymer film of claim 9.

16. The electronic product of claim 15, wherein the electronic product is a humidifier, a refrigerator, an air washer, or an aquarium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0066] FIG. 1 shows an IR spectrum of the urethane acrylate-based oligomer prepared in Preparation Example 1.

[0067] FIG. 2 schematically shows the method for measuring the production amount and lifetime of singlet oxygen in Experimental Example 2.

[0068] FIG. 3 schematically shows a method for measuring the antimicrobial activity of the polymer films of examples and comparative examples according to JIS R 1702 in Experimental Example 3.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0069] Embodiments of the present invention are described in more detail by way of the examples provided below.

[0070] However, the following examples are given for illustrative purposes only, and the scope of the present invention is not intended to be limited to or by these examples.

Preparation Example: Preparation of Urethane Acrylate-Based Oligomer (Polymer)

Preparation Example 1

[0071] 5 g of AOI-VM (M.W. 141.25) from Karenz and 40 g of Desmophen C1200 (equivalent weight: 1000) from Bayer which is a polyester-carbonate diol were dispersed in 20 g of acetonitrile solution, to which a small amount of DBTDL as a catalyst was added and then reacted at room temperature for 5 hours to prepare a urethane acrylate-based oligomer (polymer).

[0072] Then, as shown in FIG. 1, it was confirmed through infrared spectroscopy whether urethane acrylate was produced (the peak increased near 1630 cm.sup.1).

Preparation Example 2

[0073] 5 g of AOI-VM (M.W. 141.25) from Karenz and 40 g of Desmophen C850 (equivalent weight: 1000) from Bayer which is a polyurethane-carbonate diol were dispersed in 20 g of acetonitrile solution, to which a small amount of DBTDL as a catalyst was added and then reacted at room temperature for 5 hours to prepare a urethane acrylate-based oligomer (polymer).

Preparation Example 3

[0074] 5 g of AOI-VM (M.W. 141.25) from Karenz and 40 g of Desmophore VPLS2249/1 (Equivalent weight 100) from Bayer which is a polyester-carbonate diol were dispersed in 20 g of an acetonitrile solution, to which a small amount of DBTDL as a catalyst was added and then reacted at room temperature for 5 hours to prepare a urethane acrylate-based oligomer (polymer).

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

Example 1

[0075] Based on 100 parts by weight of the urethane acrylate-based oligomer of Preparation Example 1 (molar ratio of urethane functional group to acrylate-based functional group of about 1), 1 part by weight of 5,10,15,20-tetrakis(4-methoxyphenyl)-porphine (CAS No. 22112-78-3) as a photosensitizer, 2 parts by weight of a photoinitiator (trade name Darocure TPO), 0.1 parts by weight of a surfactant (trade name: RS90 DIC), 50 parts by weight of toluene, and 50 parts by weight of ethanol were mixed to prepare an antimicrobial polymer coating solution (solid content concentration of 50%).

[0076] Then, the antimicrobial polymer coating solution was coated using a #10 bar, and then cured at a rate of 2 m/min using a UV lamp at 0.2 J/cm.sup.2 to prepare an antimicrobial polymer film having a thickness of 10 m.

Example 2

[0077] An antimicrobial polymer coating solution (solid content concentration of 50%) and an antimicrobial polymer film (10 m thick) were prepared in the same manner as in Example 1, except that the urethane acrylate-based oligomer (the molar ratio of the urethane functional group to the acrylate-based functional group of about 4) of Preparation Example 2 was used.

Comparative Example: Preparation of Polymer Film

Comparative Example 1

[0078] Based on 100 parts by weight of methyl methacrylate (MMA), 5 parts by weight of trimethylolpropane triacrylate (TMPTA), 1 part by weight of 5,10,15,20-tetrakis(4-methoxyphenyl)-porphine (CAS No. 22112-78-3) as a photosensitizer, 2 parts by weight of a photoinitiator (trade name Darocure TPO), 0.1 parts by weight of a surfactant (trade name RS90 DIC), 50 parts by weight of toluene, and 50 parts by weight of ethanol were mixed to prepare a polymer coating solution (solid content concentration of 50%).

[0079] Then, the polymer coating solution was coated using a #10 bar, and then cured at a rate of 2 m/min using a UV lamp at 0.2 J/cm.sup.2 to prepare a polymer film having a thickness of 10 m.

Comparative Example 2

[0080] Based on 100 parts by weight of methyl methacrylate (MMA), 5 parts by weight of trimethylolpropane triacrylate (TMPTA), 1 part by weight of 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt (II) (CAS No. 28903-71-1) as a photosensitizer, 2 parts by weight of a photoinitiator (trade name Darocure TPO), 0.1 parts by weight of a surfactant (trade name: RS90 DIC), 50 parts by weight of toluene, and 50 parts by weight of ethanol were mixed to prepare a polymer coating solution (solid content concentration of 50%).

[0081] Then, the polymer coating solution was coated using a #10 bar, and then cured at a rate of 2 m/min using a UV lamp at 0.2 J/cm.sup.2 to prepare a polymer film having a thickness of 10 m.

Comparative Example 3

[0082] A polymer coating solution (solid content concentration of 50%) and a polymer film (10 m thick) were prepared in the same manner as in Example 1, except that the urethane acrylate-based oligomer (the molar ratio of the urethane functional group to the acrylate-based functional group of about 11) of Preparation Example 3 was used.

Experimental Example

Experimental Example 1: Measurement of Oxygen Permeability of Polymer Films of Examples and Comparative Examples

[0083] The oxygen permeability of the polymer films of the examples and comparative examples was measured at 25 C. under a 60 RH % atmosphere using an Oxygen Permeation Analyzer (Model 8000, Illinois instruments product) according to ASTM D 3895.

Experimental Example 2: Measurement of the Production Amount and Lifetime of Singlet Oxygen of the Polymer Films of Examples and Comparative Examples

[0084] The production amount and lifetime of singlet oxygen of the polymer films of the examples and comparative examples were measured using a time-resolved phosphorescent laser spectroscopy system shown schematically in FIG. 2.

[0085] Specifically, .sup.1O.sub.2 (singlet oxygen) exhibits photoluminescence at 1275 nm. Accordingly, the presence/absence of production of .sup.1O.sub.2 and the relative amount were measured by using a near infrared photomultiplier tube (NIR-PMT) in a wavelength range of 900 nm to 1400 nm, and the movement of .sup.1O.sub.2 was observed through a time-resolved spectrum.

[0086] In the case of NIR-PMT, a photoluminescence value in the wavelength region of 900 to 1400 nm could be obtained. Since singlet oxygen exhibited light emission at 1275 nm, in order to optionally detect light emission at 1275 nm, only the light emission (PL) value detected at 1275 nm was obtained by mounting an M/C (monochromator) in front of the PMT.

Experimental Example 3: Measurement of Antimicrobial Activity of Polymer Films of Examples and Comparative Examples

[0087] The antimicrobial activities of the polymer films of the examples and comparative examples were measured by the method shown schematically in FIG. 3 according to JIS R 1702.

TABLE-US-00001 TABLE 1 Molar ratio of urethane functional Oxygen Singlet oxygen (.sup.1O.sub.2) group to (meth)acrylate- permeability Production amount Lifetime Antimicrobial based functional group (cc/m.sup.2 day) (relative value) (us) activity Example 1 1 30 3.5 400 91.2 Example 2 4 70 12.0 440 99.99 Comparative 0 2 1 (reference 20 81 Example 1 value) Comparative 0 3 0.1 Example 2 Comparative 11 120 9.4 360 Example 3

[0088] As can be seen in Table 1 above, it was confirmed that the polymer films of Examples 1 and 2 prepared using a urethane acrylate-based oligomer having a molar ratio of urethane functional groups to acrylate-based functional groups in the range of 4 to 10 showed a 3.5-times higher production amount of singlet oxygen as compared with the polymer film of Comparative Example 1, and particularly, the singlet oxygen lifetime was increased by about 20 times, and that the antimicrobial activity was shown as 99% or more.

[0089] On the other hand, it was confirmed that in the case of the polymer films prepared in Comparative Examples 1 and 2, not only was the amount of singlet oxygen produced small, but also the singlet oxygen lifetime was extremely short.

[0090] In addition, it was confirmed that in the case of the polymer film prepared in Comparative Example 3, the singlet oxygen production amount was large and the singlet oxygen lifetime was long, whereas the polymer film strength was weak and a trace amount of the photosensitizer was melted out by the bacteria-inoculated strains. Therefore, the antimicrobial activity based on the above criteria has not been confirmed.