# US 11,993,692 B2 · High efficacy Cu-based anti-microbial films and substrates and methods of making the same

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- Number: US 11,993,692 B2
- Document ID: US11993692B2
- Status: Granted
- Kind: B2
- Application number: 18/218,790
- Filed: 2023-07-06
- Published: 2023-11-09
- Granted: 2024-05-28
- Earliest claimed: 2021-04-28
- Assignees: Corning Incorporated
- Applicants: Corning Incorporated
- Inventors: Andrew Charles Antony; Theresa Chang; Sushmit Sunil Kumar Goyal; Shrisudersan Jayaraman; Rui Qi; Vinalia Tjong; Shu Yuan
- Web page: https://patentgrep.com/patent/US11993692B2

## CPC

- C08K 13/02: Organic and inorganic ingredients
- A01N 25/08: containing solids as carriers or diluents
- A01N 59/20: Copper
- A01P 1/00: Disinfectants; Antimicrobial compounds or mixtures thereof
- C08J 5/18: Manufacture of films or sheets
- C09D 5/14: Paints containing biocides, e.g. fungicides, insecticides or pesticides (C09D5/16 takes precedence)
- C09D 7/20: Diluents or solvents
- C09D 7/48: Stabilisers against degradation by oxygen, light or heat
- C09D 7/61: inorganic
- C09D 7/63: organic
- C09D 125/06: Polystyrene
- C09D 133/12: Homopolymers or copolymers of methyl methacrylate
- C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08J 2325/06: Polystyrene
- C08J 2333/12: Homopolymers or copolymers of methyl methacrylate
- C08J 2379/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08K 3/015: Biocides (macromolecular substances as carriers for biocide material A01N25/10)
- C08K 3/16: Halogen-containing compounds
- C08K 3/40: Glass
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08K 5/098: Metal salts of carboxylic acids
- C08K 5/315: Compounds containing carbon-to-nitrogen triple bonds
- C08K 5/521: Esters of phosphoric acids, e.g. of H3PO4
- C08K 5/524: Esters of phosphorous acids, e.g. of H3PO3
- C08K 5/5313: Phosphinic compounds, e.g. R2=P(:O)OR'
- C08K 5/5333: Esters of phosphonic acids
- C08K 2003/085: {Copper}
- C08K 2003/2248: {of copper}
- C08K 2003/3045: {Sulfates}
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01P: BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

A method of forming an antimicrobial film, including providing a substrate with a polymer coating disposed thereon, the polymer coating including: an antimicrobial material, an inner surface contacting the substrate, and an outer surface opposite the inner surface; and extracting ions from the antimicrobial material toward the outer surface, such that the outer surface interacts with surface microorganisms. A composition, including a polymer; an antimicrobial material; and at least one of an organic solvent and an additive. The antimicrobial material comprises at least one of copper-containing glass particles, copper oxide particles, copper metal particles, copper salts, copper coordination complexes, cuprite crystals, and a combination thereof. Further, the additive can be selected to increase the oxidation resistance of the antimicrobial material.

## Claims

### Claim 1

A composition, comprising:
a polymer;
an antimicrobial material comprising Cu1+ ions; and
an additive configured to increase the oxidation resistance of the Cu1+ ions;
wherein the antimicrobial material comprises copper salts, and the Cu1+ ions and the additive form copper coordination complexes;
wherein the additive comprises at least one of an organo-phosphate, an organ-phosphite, and a phosphine;
wherein an antimicrobial film derived from the composition has an antimicrobial efficacy of at least 3 log kill as measured with EPA Test.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the additive comprises the organo-phosphate.

### Claim 3 (depends on 2)

The composition of claim 2, wherein the organo-phosphate is at least one of 2-ethylhexyl phosphate, dibutyl phosphate, and diphenyl phosphate.

### Claim 4 (depends on 1)

The composition of claim 1, wherein the additive comprises the phosphine.

### Claim 5 (depends on 4)

The composition of claim 4, wherein the phosphine is at least one of diphenyl phosphine, triphenyl phosphine, tripropyl phosphine, and trishydropropyl phosphine.

### Claim 6 (depends on 1)

The composition of claim 1, wherein the copper salts comprise a copper halide, a copper sulfate, copper(I) acetate, or any combination thereof.

### Claim 7 (depends on 1)

The composition of claim 1, wherein the polymer comprises at least one of nylon, melamine resin, urea-formaldehyde resins, poly(methyl methacrylate), polystyrene, poly(vinyl chloride), and polyethylene.

### Claim 8 (depends on 1)

The composition of claim 1, wherein the polymer comprises at least one of poly(etherimide), polyamide imide, polyimide, aramids, polyacrylonitrile, copolyimide, imidazole, benzoxazole, benzimidazole, benzothiazole, benzopyrrole, pyrrole-containing polymers, and indole-containing polymers.

### Claim 9 (depends on 8)

The composition of claim 8, wherein an antimicrobial film derived from the composition exhibits the antimicrobial efficacy of at least 3 log kill after at least 14 days of exposure to accelerated aging conditions of 65° C. and 75% relative humidity.

### Claim 10 (depends on 1)

The composition of claim 1, wherein the additive comprises 2-ethylhexylphosphate and the polymer comprises poly(methyl methacrylate), and further wherein an antimicrobial film derived from the composition has an antimicrobial efficacy of at least 3 log kill after 14 days at 65° C. in 75% relative humidity as measured with EPA Test.

### Claim 11 (depends on 1)

The composition of claim 1, wherein an antimicrobial film derived from the composition has an antimicrobial efficacy of at least 3 log kill with respect to at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant, E. coli, Enterobacter cloacae, Acinetobacter baumannii, Enterococcus faecalis, Klebsiella pneumoniae, Klebsiella aerogenes, Influenza H1N1, Adenovirus 5, Norovirus, and Candida auris as measured with EPA Test.

### Claim 12 (depends on 1)

The composition of claim 1, wherein the composition is in a form of a paint or coating.

### Claim 13 (depends on 1)

The composition of claim 1, wherein the composition is in a form of an article.

### Claim 14

A composition, comprising:
a polymer;
an antimicrobial material comprising Cu1+ ions; and
an additive configured to increase the oxidation resistance of the Cu1+ ions;
wherein the antimicrobial material comprises copper salts, and the Cu1 + ions and the additive form copper coordination complexes;
wherein the additive comprises an organo-phosphite; and
wherein an antimicrobial film derived from the composition has an antimicrobial efficacy of at least 3 log kill as measured with EPA Test.

### Claim 15 (depends on 14)

The composition of claim 14, wherein the polymer comprises at least one of nylon, melamine resin, urea-formaldehyde resins, poly(methyl methacrylate), polystyrene, poly(vinyl chloride), and polyethylene.

### Claim 16 (depends on 14)

The composition of claim 14, wherein the antimicrobial material comprises the copper salts, and the copper salts comprise a copper halide, a copper sulfate, copper(I) acetate, or any combination thereof.

### Claim 17 (depends on 14)

The composition of claim 14, wherein the polymer comprises poly(vinyl chloride).

### Claim 18 (depends on 14)

The composition of claim 14, wherein an antimicrobial film derived from the composition exhibits the antimicrobial efficacy of at least 3 log kill after at least 14 days of exposure to accelerated aging conditions of 65° C. and 75% relative humidity.

### Claim 19 (depends on 14)

The composition of claim 14, wherein an antimicrobial film derived from the composition has an antimicrobial efficacy of at least 3 log kill with respect to at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant, E. coli, Enterobacter cloacae, Acinetobacter baumannii, Enterococcus faecalis, Klebsiella pneumoniae, Klebsiella aerogenes, Influenza H1N1, Adenovirus 5, Norovirus, and Candida auris as measured with EPA Test.

### Claim 20 (depends on 14)

The composition of claim 14, wherein the composition is in a form of a paint.

### Claim 21 (depends on 14)

The composition of claim 14, wherein the composition is in a form of a coating.

### Claim 22 (depends on 14)

The composition of claim 14, wherein the composition is in a form of an article.

### Claim 23 (depends on 1)

The composition of claim 1, wherein the composition is in the form of a paint.

### Claim 24 (depends on 1)

The composition of claim 1, wherein the polymer comprises poly(vinyl chloride).

### Claim 25 (depends on 24)

The composition of claim 24, wherein the copper salts comprise a copper halide, a copper sulfate, copper(I) acetate, or any combination thereof.

### Claim 26 (depends on 24)

The composition of claim 24, wherein an antimicrobial article or coating derived from the composition exhibits the antimicrobial efficacy of at least 3 log kill after at least 14 days of exposure to accelerated aging conditions of 65° C. and 75% relative humidity.

### Claim 27 (depends on 24)

The composition of claim 24, wherein an antimicrobial article or coating derived from the composition has an antimicrobial efficacy of at least 3 log kill with respect to at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant, E. coli, Enterobacter cloacae, Acinetobacter baumannii, Enterococcus faecalis, Klebsiella pneumoniae, Klebsiella aerogenes, Influenza H1N1, Adenovirus 5, Norovirus, and Candida auris as measured with EPA Test.

### Claim 28 (depends on 24)

The composition of claim 24, wherein the composition is in a form of a coating.

### Claim 29 (depends on 24)

The composition of claim 24, wherein the composition is in a form of an article.