MULTILEVEL ANTIMICROBIAL POLYMERIC COLLOIDS AS FUNCTIONAL ADDITIVES FOR LATEX COATING
20230087431 · 2023-03-23
Assignee
Inventors
Cpc classification
C09D5/14
CHEMISTRY; METALLURGY
C08K9/08
CHEMISTRY; METALLURGY
C08L79/00
CHEMISTRY; METALLURGY
C09D129/04
CHEMISTRY; METALLURGY
C09D7/70
CHEMISTRY; METALLURGY
C08L79/00
CHEMISTRY; METALLURGY
C08L29/04
CHEMISTRY; METALLURGY
C08L29/04
CHEMISTRY; METALLURGY
International classification
C09D5/14
CHEMISTRY; METALLURGY
C09D129/04
CHEMISTRY; METALLURGY
Abstract
The multilevel antimicrobial polymeric colloids as functional additives for latex coating are latex-based coatings with multilevel antimicrobial polymeric colloidal particles incorporated therein to provide antimicrobial properties. Each multilevel antimicrobial polymeric colloidal particle includes a polymer scaffold and at least one antimicrobial polymer carried on the polymer scaffold, such that the polymer scaffold and the at least one antimicrobial polymer form a hollow colloidal particle. As a non-limiting example, the polymer scaffold may be polyvinyl alcohol (PVA). As a further non-limiting example, the at least one antimicrobial polymer may be a combination of polyethyleneimine (PEI) and polyhexamethylene biguanide (PHMB). Each multilevel antimicrobial polymeric colloidal particle may also contain an antimicrobial core within the hollow colloidal particle.
Claims
1. A multilevel antimicrobial polymeric colloid as a functional additive for latex coatings, comprising a latex coating having multilevel antimicrobial polymeric colloidal particles incorporated therein, wherein the multilevel antimicrobial polymeric colloidal particles each comprise: a polymer scaffold; and at least one antimicrobial polymer carried on the polymer scaffold, wherein the polymer scaffold and the at least one antimicrobial polymer form a hollow colloidal particle.
2. The multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 1, wherein the polymer scaffold comprises polyvinyl alcohol (PVA).
3. The multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 1, wherein the at least one antimicrobial polymer comprises polyethyleneimine (PEI) and polyhexamethylene biguanide (PHMB).
4. The multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 1, wherein each of the multilevel antimicrobial polymeric colloidal particles further comprises an antimicrobial core within the hollow colloidal particle.
5. The multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 4, wherein the antimicrobial core comprises an antimicrobial agent selected from the group consisting of antimicrobial metals, antimicrobial metal ions, antimicrobial metal oxides, antimicrobial chemicals, plant-derived antimicrobial phytochemicals, silver, silver compounds, silver salts, silver oxides, copper, copper compounds, copper salts, copper oxides, disinfectants, bactericidal short chain polymers, bactericidal short chain oligomers, ionic liquid compounds, alcohols, peracetic acids, essential oils, and combinations thereof.
6. A method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings, comprising the step of mixing a multilevel antimicrobial polymeric colloid into a latex varnish paint, wherein the multilevel antimicrobial polymeric colloid comprises multilevel antimicrobial polymeric colloidal particles in water, and wherein the multilevel antimicrobial polymeric colloidal particles each comprise: a polymer scaffold; and at least one antimicrobial polymer carried on the polymer scaffold, wherein the polymer scaffold and the at least one antimicrobial polymer form a hollow colloidal particle.
7. The method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 6, wherein the latex varnish paint comprises an acrylate-urethane prepolymer emulsion in water.
8. The method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 6, wherein the polymer scaffold comprises polyvinyl alcohol (PVA).
9. The method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 6, wherein the at least one antimicrobial polymer comprises polyethyleneimine (PEI) and polyhexamethylene biguanide (PHMB).
10. The method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 6, wherein each of the multilevel antimicrobial polymeric colloidal particles further comprises an antimicrobial core within the hollow colloidal particle.
11. The method of making a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings as recited in claim 10, wherein the antimicrobial core comprises an antimicrobial agent selected from the group consisting of antimicrobial metals, antimicrobial metal ions, antimicrobial metal oxides, antimicrobial chemicals, plant-derived antimicrobial phytochemicals, silver, silver compounds, silver salts, silver oxides, copper, copper compounds, copper salts, copper oxides, disinfectants, bactericidal short chain polymers, bactericidal short chain oligomers, ionic liquid compounds, alcohols, peracetic acids, essential oils, and combinations thereof.
12. An antimicrobial plastic overlay, comprising: a plastic substrate sheet; a primer layer coated on the plastic substrate sheet; and a topcoat layer coated on the primer layer, wherein each of the primer layer and the topcoat layer comprises a multilevel antimicrobial polymeric colloid as a functional additive for latex coatings comprising a latex coating having multilevel antimicrobial polymeric colloidal particles incorporated therein, wherein the multilevel antimicrobial polymeric colloidal particles each comprise: a polymer scaffold; and at least one antimicrobial polymer carried on the polymer scaffold, wherein the polymer scaffold and the at least one antimicrobial polymer form a hollow colloidal particle.
13. The antimicrobial plastic overlay as recited in claim 12, wherein the polymer scaffold comprises polyvinyl alcohol (PVA).
14. The antimicrobial plastic overlay as recited in claim 12, wherein the at least one antimicrobial polymer comprises polyethyleneimine (PEI) and polyhexamethylene biguanide (PHMB).
15. The antimicrobial plastic overlay as recited in claim 12, wherein each of the multilevel antimicrobial polymeric colloidal particles further comprises an antimicrobial core within the hollow colloidal particle.
16. The antimicrobial plastic overlay as recited in claim 15, wherein the antimicrobial core comprises an antimicrobial agent selected from the group consisting of antimicrobial metals, antimicrobial metal ions, antimicrobial metal oxides, antimicrobial chemicals, plant-derived antimicrobial phytochemicals, silver, silver compounds, silver salts, silver oxides, copper, copper compounds, copper salts, copper oxides, disinfectants, bactericidal short chain polymers, bactericidal short chain oligomers, ionic liquid compounds, alcohols, peracetic acids, essential oils, and combinations thereof.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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[0022] Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] The multilevel antimicrobial polymeric colloids as functional additives for latex coating are latex-based coatings with multilevel antimicrobial polymeric colloidal particles incorporated therein to provide antimicrobial properties. Each multilevel antimicrobial polymeric (MAP) colloidal particle includes a polymer scaffold and at least one antimicrobial polymer carried on the polymer scaffold, such that the polymer scaffold and the at least one antimicrobial polymer form a hollow colloidal particle. As a non-limiting example, the polymer scaffold may be polyvinyl alcohol (PVA). As a further non-limiting example, the at least one antimicrobial polymer may be a combination of polyethyleneimine (PEI) and polyhexamethylene biguanide (PHMB). Each multilevel antimicrobial polymeric (MAP) colloidal particle may also contain an antimicrobial core within the hollow colloidal particle. The core may be made of any suitable type of antimicrobial agent or agents, such as, but not limited to, antimicrobial metals, antimicrobial metal ions, antimicrobial metal oxides, antimicrobial chemicals, plant-derived antimicrobial phytochemicals, silver, silver compounds, silver salts, silver oxides, copper, copper compounds, copper salts, copper oxides, disinfectants, bactericidal short chain polymers, bactericidal short chain oligomers, ionic liquid compounds, alcohols, peracetic acids, essential oils, and combinations thereof. As a non-limiting example, the MAP colloidal particles may have diameters on the order of 600 nm.
[0024] Latex is a stable emulsion of polymer microparticles in water and includes natural and synthetic latexes that find broad uses, such as in paints and coatings. In order to make the multilevel antimicrobial polymeric colloids as functional additives for latex coating, MAP colloids in water were added to a latex varnish paint. The latex varnish paint contained an acrylate-urethane prepolymer emulsion in water. Rapid stirring was used to mix the MAP colloid with the latex varnish paint. The mixture of the liquid multilevel antimicrobial polymeric colloids as functional additives for latex coating was used as both a primer coating and a topcoat paint during testing. The MAP colloid in this experimental example included 4.17 w/w % PVA (Mw 30,000˜70,000), 1.33 w/w % PEI (Mn 10,000), 0.33 w/w % PHMB (Mw 2,300), and 94.17 w/w % distilled deionized (DDI) water. The latex varnish paint in this experimental example included an acrylate-urethane prepolymer emulsion in water with a 50 w/w % content, and which was transparent with a low gloss.
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[0026] To make the plastic card overlay, the surface of plastic sheet 14 was cleaned of dirt and dust, and the primer coating layer 12 was applied using a paint roller on the PVC-PVAc plastic sheet 14. The roller traced an “S” track on the sheet 14 and the paint was carefully spread over the surface with the roller before lightly spreading the paint uniformly over the entire surface. When the primer coating 12 was dry to the touch, the topcoat paint 10 was applied using the roller in a similar manner. Paint defects were removed by smoothing out the surface using a wet paint roller. Primer was coated on the plastic sheet 14 at 16 m.sup.2/L, and allowed to dry for approximately 30 minutes. The topcoat was applied at 30 m.sup.2/L and, after approximately 7 minutes, the topcoat layer 10 was smoothed using a wet clean paint roller, which was repeated three times to ensure that any defects were removed.
[0027] The card plastic overlays were tested for adhesion following the scratch-tear assay of the ISO2409 and ASTM D3359 standards. The coated card plastic overlay was cut with a 2 mm hatch cutter in a lattice pattern before using tape to remove the cut coating. The adhesion resistance against tape tearing was assessed according to the standards and the results are shown below in Table 1 for 7 samples. The results indicate that the MAP colloid latex primer coating and topcoat paint have excellent adhesion strength with all 5B grades out of 7 tests. ASTM D3359 class 5B represents no film pull-off, which is the highest level of coating adhesion.
TABLE-US-00001 TABLE 1 Adhesion (scratch-tear) test results Sample No. ASTM D3359 Grade 1 5B 2 5B 3 5B 4 5B 5 5B 6 5B 7 5B
[0028] Table 2 below summarizes the bactericidal activity against E. coli and S. aureus, and antimicrobial activity against the Phi-6 bacteriophage viral particle for different formulated topcoat paints in the MAP colloid and latex coating.
TABLE-US-00002 TABLE 2 Topcoat formulation, aesthetic, and antimicrobial activities Antimicrobial reduction 2.sup.nd layer formula (log.sub.10) Example (vol %) Aesthetics/ E. S. No. Map-1 Latex homogeneity coli aureus Phi-6 1 100% 0% A 3.77 3.46 2.56 2 97% 3% A 3.62 3.38 2.56 3 95% 5% A 3.53 3.30 2.56 4 90% 10% B 1.83 1.08 1.00 5 80% 20% C 0.05 0.61 0.57
[0029] In Table 2, the following aesthetics evaluation grades are used: “A” represents a uniformly clear and transparent coating, “B” represents one defect per 10 cm.sup.2, and “C” represents more than one defect per 10 cm.sup.2, where each grade represents assessment of two samples. Antimicrobial reduction is based on a contact killing test of 10 minutes, averaged over three samples. With regard to aesthetics, testing was performed on samples smoothed three times, every 7 minutes, which was performed to improve coating coverage and remove spots. This was performed for both blank overlay sheets and overlay sheets including magnetic strips (similar to credit cards).
[0030] Table 3 below represents the measured thickness of each layer in the experimental samples. The total thickness of the coating (the primer coating and the topcoat paint together) was 14.96±1.48 μm based on 80 measurements on eight coated overlays, with the standard deviation below the suggested roughness range of 1.4˜2.2 μm in the card overlay industries. The primer coating accounts for 10.70 μm and the topcoat paint is 4.26 μm.
TABLE-US-00003 TABLE 3 Thickness measurements Layer Thickness in micron (n = 10) Primer coating 10.70 Topcoat paint 4.26 Primer coating + topcoat paint 14.96 ± 1.48 Overall thickness including 74.96 ± 1.48 overlay plastic sheet
[0031] Flatness was determined by placing the coated overlays on a flat bench and the gap between the highest point of the edge and the table was measured. All sheets had no measurable warpage on their edges. With a precision of 0.5 mm, three magnetic strip overlayed sheets had a measured gap of less than 0.1 mm, and eight blank overlayed sheets also had a measured gap of less than 0.1 mm.
[0032] The topcoat paint on the card plastic overlay observed under a Hitachi® TM3030 scanning electron microscope (SEM), as shown in
[0033] The optical transmittance or transparency was measured by a Varioscan spectrophotometer according to chapter “5.10 Opacity” of the ISO/IEC 10373-1:2006(E) standard. Measurement indicated that card plastic overlays with two layers of primer coating and topcoat paint have a light transmittance above 95% for visible light (i.e., 400-800 nm), as shown in
[0034] The primer coating and topcoat paint on the card plastic overlay were characterized using attenuated total reflection-Fourier transformed infrared spectroscopy (FTIR-ATR).
[0035] The water contact angles were measured using a Attension® Theta Auto 4 optical tensiometer, manufactured by Biolin Scientific®. 2 μL of deionized distilled water was placed on the surface and imaged for 10 seconds in 14 FPS and processed by onboard software. The results are shown in
[0036] A washability test was conducted according to ASTM D4828 and D3450. The coated card plastic overlay was quick-wiped with a slightly wet Scotch-Brite® sponge with a 500 g weight for 100 cycles over a 10 cm×10 cm area. After the test, inspection showed that the general appearance remained unchanged, with slight scratches along one of the edges. The thickness measured using a Digimatic® Micrometer, manufactured by Mitutoyo®, at 10 testing points for each sample. As shown in
[0037] With regard to thermal stability, the coated card plastic overlay was tested according to ISO10373-1 at 50° C., 95% RH for 72 hours. No visual changes in appearance were detected nor was coating delamination observed after the test. Some samples showed slight warpage within the tolerance range of the ISO standard. The results confirmed that the primer coating and topcoat paint are stable for the intended use. Table 4 below shows the results of the ISO10373-1 testing. In Table 4, the average deflection is calculated from four edges of triple repeats. Maximum deflection is the average of the largest warpages. “ND” indicates “not detectable”.
TABLE-US-00004 TABLE 4 ISO10373-1 test of coated card plastic overlays ISO10373 requirement Antimicrobial overlay Avg. deflection Δh ≤ 10 mm Δh avg. = 3.2 ± 2.4 mm Max. deflection Δh ≤ 10 mm Δh max. = 8.2 ± 1.0 mm Delamination ND ND Visual variation ND ND
[0038] The antimicrobial properties of the coated card plastic overlay were tested against Gram-positive S. aureus and Gram-negative E. coli bacteria, an MS2 bacteriophage as a surrogate for nonenveloped viruses, and phi-6 representing enveloped viruses. Briefly, 25.4 mm×25.4 mm square coupons of the coated card plastic overlay were deliberately challenged with 10.sup.6 CFU of bacteria and PFU of bacteriophages. After 10 minutes of contact at room temperature (20° C.) and humidity (ca. 60% R.H.), the samples were vortexed in D/E neutralizing broth containing 3% Tween® 80, 3% saponin and 3% lecithin at pH 7.0. It can be seen from
[0039] Plastic overlays are widely used for interior and exterior decorations in product items, such as credit cards. Hot-press lamination is a common method to fix and strengthen the overlay on plastic, wood, and metal surfaces. The coated card plastic overlays were heat laminated on wood-pulp paper samples, as detailed in Table 5 below. The laminated samples were tested against the panel of microbes listed in Table 6 below for 10 minutes of contact. The blank card plastic overlay served as a negative control. The results in Table 7 below show that the MAP colloid and latex coating remains active against bacteria and viruses. Table 7 shows data from triplicate measurements with the results normalized against negative control (blank card plastic overlay), with 10 minutes of contact at room temperature and 60% R.H. The E. coli and P. aeruginosa were purchased from the Carolina Biological Supply Co.®, and the S. aureus was provided from the Department of Biology of the Hong Kong University of Science and Technology.
TABLE-US-00005 TABLE 5 Lamination process industry treatment lamination Superficial film plastic overlays coated card plastic overlay Laminated cores Wood, metal, or Wood-pulp plastic substrates paper card Experiment 120~170° C., ~10 140° C., 10 details MPa, 20~60 min MPa, 20 min
TABLE-US-00006 TABLE 6 Microbial panel Species Source Category E. coli K12 Carolina 15-5065A Gram (−) bacteria P. aeruginosa Carolina 15-5250A Gram (−) bacteria S. aureus HKUST stock Gram (+) bacteria E. faecelis ATCC 700802 Gram (+) bacteria MS2 DSMZ 13767 Non enveloped virus Phi6 DSMZ 21518 Enveloped virus
TABLE-US-00007 TABLE 7 Bactericidal and virucidal results for laminated overlay compared to coated card plastic overlay Gram (−) Gram (+) Log.sub.10 reduction E. P. S. E. Phage virus (Av12. ± SD) coli aeruginosa aureus faecelis MS2 Phi6 Laminated 99.98 99.99 98.33 99.98 98.88 99.22 overlay Overlay 99.99 99.99 99.61 99.99 99.11 96.91
[0040] The coated card plastic overlays were laminated on plastic card cores by an industrial lamination process and their antimicrobial properties were tested against the microbial panel listed in Table 6 above. Tests were done on 25.4 mm×25.4 mm square coupons of the test card samples at room conditions with a contact time of 10 minutes. The test conditions comply with the European standard EN 13727 and Table 8 below shows that the bactericidal properties met the requirements of EN 13727, ISO 22196, ASTM E3031, HS L-1902, 2002, and GB-21551.2-2020. The virucidal activity against MS2 and phi-6 bacteriophages is 99.7%. Triplicate measurements with results normalized against negative control (pure latex-coated card plastic), 10 min contact at room temperature and 60% R.H. Note: (a): ISO 22196 stipulates ‘active bactericidal’ as ‘no less than 2 log 10 reductions compared with control’. (b): ASTM E3031 stipulates ‘bactericidal’ as ‘Log reduction no less than natural reduction’. (+)/(−): gram positive or negative.
TABLE-US-00008 TABLE 8 Bactericidal and virucidal results for laminated test cards Antimicrobial ISO ASTM Unit: in log.sub.10 results (n = 3) 22196 (a) E3031 (b) E. coli K12 (−) 3.62 ± 0.48 ✓ ✓ P. aeruginosa (−) 5.08 ± 0.21 ✓ ✓ S. aureus (+) 3.38 ± 0.14 ✓ ✓ E. faecelis (+) 3.88 ± 0.21 ✓ ✓ MS2 2.56 ± 0.21 ✓ ✓ Phi6 2.56 ± 0.21 ✓ ✓
[0041] Additionally, test cards prepared by industrial lamination of the coated card plastic overlay on plastic cores were subjected to accelerated aging at 55° C. and 75% R.H. for 38 days, which is equivalent of aging for 2.7 years at room temperature according to the “Chinese Technical Standard for disinfection 2002” and one year according to the “US ASTM F1980 standard”. ASTM F1980 is widely recommended for sterile surfaces and systems. The aging factor Q.sub.10 is generally pre-assumed to be 2.0 (which is related to the activation energy Ea during aging). Therefore, the accelerated aging factor (AAF) is 9.84 at 55° C. and 38 days at this condition is equivalent to a year at room temperature (see Table 9 below). The test cards maintained better than 2.2 log reduction (99.4%) against viral particles and higher than 99.0% against bacteria.
TABLE-US-00009 TABLE 9 Accelerated aging standards ASTMF1980 - 16: Technical Standard Guide for Accelerated Referring Standard For Aging of Sterile Barrier standard disinfection (2002) Systems for Medical Devices Region/ China US organization Accelerated (1) 54~56° C., Temperature at or condition RH % ≥ 75%, below 60° C. (*), 14 days; RH % not specified. (2) 37~40° C., RH % ≥ 75%, 90 days; Accelerated aging (1) RT 1 year, AAF = Q.sub.10.sup.[(T.sup.
TABLE-US-00010 TABLE 10 Antimicrobial properties of test cards following accelerated aging (1 year) Day 0 Day 7 Day 14 Day 26 Day 38 Unit: in Log10 (n = 3) (n = 3) (n = 3) (n = 3) (n = 3) E. coli 3.62 ± 0.48 2.14 ± 0.15 2.14 ± 0.60 2.85 ± 0.23 2.01 ± 0.53 S. aureus 3.38 ± 0.14 2.67 ± 0.42 3.67 ± 0.35 2.99 ± 0.42 3.19 ± 0.48 Phi-6 2.56 ± 0.21 2.76 ± 0.03 2.60 ± 0.25 2.60 ± 0.11 2.26 ± 0.20
[0042] For Table 10 above, ISO 22196 stipulates “active bactericidal” as “no less than 2 log 10 reductions compared with control”. All results have been normalized with negative controls.
[0043] It is to be understood that the multilevel antimicrobial polymeric colloids as functional additives for latex coating are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.