阅读说明：本技术 抗菌塑料、其制造方法及由其制造的抗菌塑料物品 (Antibacterial plastic, method for producing same, and antibacterial plastic article produced therefrom ) 是由 孟文君 郭秀娟 陈玥颖 张明煜 于 2018-04-09 设计创作，主要内容包括：一种抗菌塑料包含抗生物淤积化合物和基础塑料。该抗生物淤积化合物任选地选自多元醇、聚醚多元醇、多元醇衍生物及其组合的组；或该抗生物淤积化合物选自由聚醚、聚(乙二醇)醚、聚山梨酯及其组合组成的组；或该抗生物淤积化合物选自聚(乙二醇)脱水山梨醇单月桂酸酯、聚(乙二醇)脱水山梨醇单油酸酯、聚(乙二醇)山梨醇六油酸酯、鲸蜡硬脂醇聚醚及其组合。该基础塑料不是低密度聚乙烯聚合物和乙基乙酸乙烯酯共聚物的共混物、聚丙烯聚合物和乙基乙酸乙烯酯共聚物的共混物、聚烯烃弹性体聚合物和聚氯乙烯聚合物的共混物。本发明还描述了制造这种抗菌塑料的方法和抗菌塑料物品。(An antimicrobial plastic comprises an anti-biofouling compound and a base plastic. The anti-biofouling compound is optionally selected from the group of polyols, polyether polyols, polyol derivatives and combinations thereof; or the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or the anti-biofouling compound is selected from the group consisting of poly (ethylene glycol) sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof. The base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a blend of a polyolefin elastomeric polymer and a polyvinyl chloride polymer. Methods of making such antimicrobial plastics and antimicrobial plastic articles are also described.)

1. An antimicrobial plastic comprising:

A) an anti-biofouling compound optionally selected from the group consisting of polyols, polyether polyols, polyol derivatives, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of poly (ethylene glycol) sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof; and

B) a base plastic, wherein the base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a blend of a polyolefin elastomeric polymer and a polyvinyl chloride polymer.

2. The antimicrobial plastic of claim 1, wherein the base plastic is a thermoplastic; or wherein the base plastic is selected from the group consisting of polyolefin polymers, thermoplastic elastomers, polyether polymers, polyvinyl polymers, polyester polymers, polyacetal polymers, polyamide polymers, polyurethane polymers, polyacrylate polymers, polycarbonate polymers, polyimide polymers, polyphthalate polymers, polysulfone polymers, polythioether polymers, polyketone polymers, and combinations thereof; or wherein the base plastic is selected from the group consisting of polypropylene polymers, polyethylene polymers, ethyl vinyl acetate copolymers, acrylonitrile butyl styrene copolymers, polyethylene terephthalate copolymers, and combinations thereof.

3. The antimicrobial plastic of any one of claims 1 or 2, wherein the anti-biofouling compound is mixed with an intermediate plastic to form a master batch, and wherein the master batch is mixed with the base plastic to form the antimicrobial plastic.

4. The antimicrobial plastic of claim 3, wherein the intermediate plastic comprises a random terpolymer; or wherein the intermediate plastic comprises a random terpolymer comprising monomers selected from the group consisting of ethylene monomers, acrylate monomers, maleic anhydride monomers, and combinations thereof; or the random terpolymer comprises an ethylene monomer, an acrylate monomer, and a maleic anhydride monomer; or a random terpolymer comprises a polymeric backbone comprising ethylene monomers, acrylate monomers, and maleic anhydride monomers.

5. The antimicrobial plastic of any one of claims 3 or 4, wherein the masterbatch comprises about 0.001% to about 50% by weight of the antimicrobial plastic; or about 0.001% to about 20%; or from about 0.01% to about 15%.

6. The antimicrobial plastic of any one of claims 2 to 5, wherein the intermediate plastic comprises at least one polymer segment that is compatible with the base plastic.

7. The antimicrobial plastic of any one of claims 3 to 6, wherein the intermediate plastic does not comprise the same polymer segments as the base plastic.

8. The antimicrobial plastic of any one of claims 4 to 7, wherein the anti-biofouling compound comprises about 0.01% to about 25% of a masterbatch by weight; or about 0.1% to about 20%; or from about 0.5% to about 15%.

9. The antimicrobial plastic of any of the preceding claims, wherein the base plastic has a temperature of greater than or equal to about 60 ℃; or a Tg of greater than or equal to about 65 deg.C, or greater than or equal to about 70 deg.C.

10. The antimicrobial plastic of any one of claims 1-3 or 5-9, wherein the base plastic has a temperature of greater than or equal to about 60 ℃; or a Tg of greater than or equal to about 65 ℃, or greater than or equal to about 70 ℃, and wherein the base plastic is selected from the group consisting of acrylonitrile butyl styrene, polyethylene terephthalate, and combinations thereof, and the anti-biofouling compound and the base plastic are mixed directly together to form the antimicrobial plastic.

11. The antimicrobial plastic of any one of the preceding claims, wherein the antimicrobial plastic is biocompatible, food contact safe, and combinations thereof.

12. The antimicrobial plastic of any one of the preceding claims, wherein the anti-biofouling compound comprises about 0.001% to about 50% by weight of the antimicrobial plastic; or about 0.001% to about 20%; or from about 0.01% to about 15%.

13. The antimicrobial plastic of any one of the preceding claims, wherein the base plastic comprises about 50% to about 99.999% by weight of the antimicrobial plastic; or about 80% to about 99.999%; or from about 85% to about 99.99%.

14. The antimicrobial plastic of any one of the preceding claims, wherein the antimicrobial plastic has one physical property, wherein the base plastic has the same physical property, and wherein the physical property of the antimicrobial plastic is less than or equal to about ± 25%; or plus or minus 20 percent; or +/-10%; or ± 5% different from the same physical property of the base plastic.

15. A method for manufacturing an antimicrobial plastic according to any one of the preceding claims, wherein the base plastic and the anti-biofouling compound are mixed in an extruder.

16. A method for manufacturing an antimicrobial plastic comprising the steps of:

A) providing an anti-biofouling compound optionally selected from the group consisting of polyols, polyether polyols, polyol derivatives, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethylene glycol sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof;

B) providing a base plastic, wherein the base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a polyolefin elastomer polymer, or a polyvinyl chloride polymer; and

C) mixing the anti-biofouling compound with the base plastic.

17. The method of making an antimicrobial plastic according to claim 16, wherein the base plastic is a thermoplastic; or wherein the base plastic is selected from the group consisting of polyolefins, thermoplastic elastomers, polyethers, polyvinyls, polyesters, polyacetals, polyamides, polyurethanes, polyacrylates, polycarbonates, polyimides, polyphthalates, polysulfones, polythioethers, polyketones, and combinations thereof; or wherein the base plastic is selected from the group consisting of polypropylene, polyethylene, ethyl vinyl acetate copolymer, acrylonitrile butyl styrene, polyethylene terephthalate, and combinations thereof.

18. The method for manufacturing antimicrobial plastic according to any one of claims 16 to 17, further comprising the steps of:

D) providing an intermediate plastic; or wherein the intermediate plastic comprises a random terpolymer; or wherein the intermediate plastic comprises a random terpolymer comprising monomers selected from the group consisting of ethylene monomers, acrylate monomers, maleic anhydride monomers, and combinations thereof; or the random terpolymer comprises an ethylene monomer, an acrylate monomer, and a maleic anhydride monomer; or a random terpolymer comprises a polymeric backbone comprising ethylene monomers, acrylate monomers, and maleic anhydride monomers;

E) mixing the anti-biofouling compound with the intermediate plastic to form a master batch; and

F) mixing the masterbatch with the base plastic to form an antimicrobial plastic.

19. The process for manufacturing an antimicrobial plastic according to any one of claims 16 to 18, wherein the base plastic has a temperature of greater than or equal to about 60 ℃; or a Tg of greater than or equal to about 65 deg.C, or greater than or equal to about 70 deg.C.

20. The method for manufacturing an antimicrobial plastic according to any one of claims 16 to 17 or 19, wherein the base plastic is selected from the group consisting of acrylonitrile butyl styrene, polyethylene terephthalate, and combinations thereof, and wherein the anti-biofouling compound is mixed directly with the base plastic to form the antimicrobial plastic.

21. The method of any one of claims 16 to 20, wherein the mixing step occurs in an extruder, a die, and combinations thereof; or an extruder.

22. The method for making an antimicrobial plastic according to claim 21, further comprising the step of thermoforming the plastic article; or wherein the step of thermoforming comprises a process selected from the group consisting of molding, extruding, spinning, injecting, compressing, foaming, drawing, and combinations thereof; or molding, extrusion, and combinations thereof.

23. A method for manufacturing an antimicrobial plastic comprising the steps of:

A) providing an anti-biofouling compound optionally selected from the group consisting of polyols, polyether polyols, polyol derivatives, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethylene glycol sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof; or

B) Providing a base plastic having greater than or equal to about 60 ℃; or a Tg of greater than or equal to about 65 ℃, or greater than or equal to about 70 ℃, or the base plastic is or comprises ABS, PET, PS, SAN, and combinations thereof, wherein the base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a blend of a polyolefin elastomeric polymer or a polyvinyl chloride polymer; and

C) mixing the anti-bio fouling compound with the base plastic, wherein substantially no intermediate plastic is present.

24. An antimicrobial plastic article comprising the antimicrobial plastic according to any one of claims 1 to 15, or an antimicrobial plastic article manufactured according to the manufacturing method of any one of claims 16 to 23.

25. The antimicrobial plastic article of claim 24.

26. The antimicrobial plastic article of any one of claims 24 to 25, wherein the plastic article is an antimicrobial surface, an antimicrobial shell, an antimicrobial medical device, an antimicrobial handle, an antimicrobial garment, an antimicrobial building material, and combinations thereof; or an antimicrobial surface, an antimicrobial shell, an antimicrobial medical device; antibacterial kitchenware, antibacterial household articles and combinations thereof.

27. The antimicrobial plastic article of any one of claims 24 to 26, wherein the plastic article is an intermediate plastic article, and wherein the intermediate plastic article has a form selected from the group consisting of a block, a pellet, a monolith, a tube, a filter, a composite, a film, a sheet, a foam, and combinations thereof.

Technical Field

The present invention relates to plastics, a method of manufacturing plastics and a plastic article manufactured from plastics.

Background

Various articles are often made of plastic for reasons of durability, ease of manufacture, recyclability, ease of sterilization, and the like. Plastics, particularly thermoplastics, are commonly used for articles ranging from consumables to medical devices and the like. Many of these plastic articles may further require regular or regular sterilization and/or disinfection, such as chemical sterilization, radiation sterilization, heat sterilization, and the like.

The plastic articles may be manufactured by a variety of methods known in the art, such as extrusion, molding, blown film, and the like, and variations thereof, as desired.

There are antibacterial and/or antimicrobial plastics comprising bactericidal and microbicidal materials embedded therein and/or coated thereon. These plastics attempt to kill any bacteria, microbes, etc. that come into contact with the plastic to reduce the chance of infection, transmission, etc. However, it has been found that such antibacterial and/or antimicrobial plastics may be difficult to register for use in medical devices due to the large national variation of regulations regarding antibacterial and/or antimicrobial materials. Further problems relate to how long the antibacterial and/or antimicrobial effect will last, leaching of active substances, such as nano silver particles and ions, may be harmful to the human body and cause long-term toxicity to the human body. In addition, there is an increasing concern that excessive use of antimicrobial agents will lead to increased microbial resistance and multiple microbial resistance.

There are a number of patents and publications relating to coatings or release agents for antimicrobial agents which render surfaces antimicrobial. "inhibiting Coatings: recent Developments in the Design of surface That present the underlying substrates Proteins, Bacteria, and Marine Organisms, "Banner jee et al, adv. Mater., Vol.23, 690-" 718(Wiley, 2011); US 2005/0008671 a1 by Antwerp, published on 13.1.2005; U.S. Patent No. US 2009/0155335 a1 to O' shaughessey et al, published 6, 18, 2009 and assigned to the Patent Group LLP; CN 104847971a published on 19.8.2015 and assigned to Anhui meeting Special Electric Cable Materials co., ltd.; tanahashi, published on 26.1.2000 and assigned to CN 1242781 a by Toray Industries. However, the prior art may cause problems such as forming a coating layer only on the base plastic and thus may be easily leached from the base plastic.

Other techniques graft polymers to plastics, typically on side chains, e.g., US 2011/0305898 a1 to Zhang et al, published 12/15/2011; US 2011/0124772 a1 by Wang et al, published 26/5/2011.

Another existing class of plastics is antibacterial plastics, which typically contain anti-biofouling compounds, which for example can provide a surface from which bacteria, microorganisms, etc. easily slide off. The purpose of these materials is generally to create a surface that reduces bacterial attachment thereto, thereby reducing the chances of colony growth, biofilm formation, and the like. These antibacterial plastics comprise an antibacterial material which, for example, makes it possible to mix an intermediate plastic with a masterbatch and then with a base plastic. This is the unique built-in antimicrobial function of plastics. See, for example, US 2017/0129139 a1 by Lau et al, Nano and Advanced Materials Institute, ltd, published on 11.5.2017 and assigned to hong kong. However, this technique may require the same or substantially the same backbone as the base plastic or the like.

In addition, there is a need for antimicrobial plastics that can be used with a variety of other plastics. Accordingly, there is a need for additional antimicrobial plastics, antimicrobial plastic articles made therefrom, and methods of making such antimicrobial plastic articles. There is also a need for an antimicrobial plastic wherein the antimicrobial benefit is stable and/or non-leaching, and not just a coated antimicrobial plastic on a base plastic.

Disclosure of Invention

One embodiment of the invention herein relates to an antimicrobial plastic comprising an anti-biofouling compound and a base plastic. The anti-biofouling compound is optionally selected from the group consisting of polyols, polyether polyols, polyol derivatives, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of poly (ethylene glycol) sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof. The base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a blend of a polyolefin elastomeric polymer and a polyvinyl chloride polymer.

One embodiment of the present invention relates to a method for manufacturing an antimicrobial plastic herein, wherein a base plastic and an anti-biofouling compound are mixed in an extruder.

One embodiment of the invention relates to a method for producing an antimicrobial plastic, having the following steps: providing an anti-biofouling compound, providing a base plastic, and mixing the anti-biofouling compound with the base plastic. The anti-biofouling compound is optionally selected from the group consisting of polyols, polyether polyols, polyol derivatives, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethylene glycol sorbitan monolaurate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof. The base plastic is not a blend of a low density polyethylene polymer and an ethyl vinyl acetate copolymer, a blend of a polypropylene polymer and an ethyl vinyl acetate copolymer, a polyolefin elastomer polymer, or a polyvinyl chloride polymer.

One embodiment of the present invention is directed to an antimicrobial plastic article comprising the antimicrobial plastic herein and/or made by the methods described herein.

Without being limited by theory, it is believed that the invention herein provides an antimicrobial plastic, article of antimicrobial plastic, or the like, which is permanently integrated into the plastic as opposed to being coated thereon only. Thus, the present invention can maintain antimicrobial benefits for extended periods of time without leaching or otherwise degrading, particularly if the base plastic has a temperature of greater than or equal to 60 ℃; greater than or equal to 65 ℃; or a Tg of greater than or equal to 70 ℃. It is believed that the physical mixing and thus the integration of the anti-biofouling compound with the base plastic reduces the leaching of the anti-biofouling compound from the antimicrobial plastic. It is also believed that the antimicrobial plastic herein can significantly reduce the adhesion of gram positive bacteria as well as gram negative bacteria to the antimicrobial plastic herein as compared to the base plastic itself.

It is also believed herein that the present invention allows antimicrobial benefits to be applied to a wider range of base plastics, and may also, for example, reduce manufacturing complexity, raw material storage, and the need for special processing steps. This, in turn, may provide greater flexibility to the designer and/or manufacturer.

Detailed Description

Unless specifically stated otherwise, all tests herein were performed under standard conditions, including room temperature and test temperature of 25 ℃, sea level (1atm.) pressure, pH 7, and all measurements were performed in metric units. Further, all percentages, ratios, etc. herein are based on the weight of the final product, material, plastic, etc., unless specifically indicated otherwise.

As used herein, the term "mixed" and other forms thereof, such as "mixed" and the like, means that at least two materials are physically mixed together; or physically and chemically mixed together; or physically mixed together and chemically bonded together.

As used herein, the term "bacteria" means microorganisms; or bacteria.

As used herein, the term "antimicrobial" and other grammatical forms thereof such as "antimicrobial" and the like when describing a material (or plastic article, etc.) means that the material (or plastic article, etc.) reduces the physical adhesion of microorganisms, bacteria, etc. to the material; or initial physical adhesion, and/or increase the likelihood that they will physically fall out of the plastic material.

One embodiment of the invention relates to an antimicrobial plastic comprising an anti-biofouling compound and a base plastic. The anti-biofouling compound is optionally selected from the group of polyols, polyether polyols, polyol derivatives and combinations thereof; or wherein the anti-biofouling compound is selected from the group consisting of polyethers, poly (ethylene glycol) ethers, polysorbates, and combinations thereof; or the anti-biofouling compound is selected from the group consisting of poly (ethylene glycol) sorbitan monolaurate, poly (ethylene glycol) (PEG) sorbitan monooleate, poly (ethylene glycol) sorbitol hexaoleate, ceteareth, and combinations thereof. The base plastic is not a blend of a Low Density Polyethylene (LDPE) polymer and an Ethyl Vinyl Acetate (EVA) polymer, a blend of a polypropylene (PP) polymer and an EVA polymer, a polyolefin elastomer (POE) polymer, or a blend of polyvinyl chloride (PVC) polymers.

However, the present invention is considered to be significantly different from the plastics known in the prior art, since the intermediate plastics herein do not require the exact same base polymer backbone as the base plastic, and in certain embodiments need only comprise one general polymer segment. Without being limited by theory, it is believed that in some embodiments, the intermediate is not required; or do not contain the same polymer segments as the base plastic.

The anti-biofouling compounds herein reduce the chance of bacteria (e.g., microorganisms or bacteria) adhering to the base plastic and/or components made from the base plastic. Without being limited by theory, it is believed that the anti-biofouling compound may, for example, provide a surface from which biofouling agents (e.g., bacteria, microorganisms, etc.) may easily slide off, as described herein. The anti-biofouling compound may e.g. make the plastic surface very hydrophilic, so that there is a thin layer of water on the plastic, which prevents the biofouling agent from adhering to the plastic.

The anti-bio fouling compounds herein are available from a number of suppliers at various grades around the world.

In one embodiment herein, the polyether polyol or polyol derivative is one having from about 1 to about 20C's attached_4-28A PEG molecule of an ester moiety.

Ceteareth (e.g., Ceteareth-20, CAS number 68439-49-6) is a polyglycol ether nonionic surfactant having the structure:

wherein n represents the number of ether repeating units. Ceteareth useful in the present invention has an n of from about 2 to about 100; or from about 10 to about 90; or 20, 40, 60 or 80.

Tweens are useful herein, especially tweens 20 and 80. Tween 20(CAS No. 9005-64-5) is a poly (ethylene glycol) sorbitan monooleate having the structure:

where the sum w + x + y + z is 20.

Tween 80(CAS No. 9005-65-6) is a poly (ethylene glycol) sorbitan monolaurate of the following structure: .

Where the sum w + x + y + z is 20.

Poly (ethylene glycol) sorbitol hexaoleate (e.g., CAS number 57171-56-9) has the following structure:

wherein n is a natural number from about 2 to about 100.

In one embodiment herein, the anti-biofouling compound is about 0.001% to about 50% by weight of the antimicrobial plastic; or about 0.001% to about 20%; or from about 0.01% to about 15%.

The base plastic herein is not a blend of LDPE polymer and EVA polymer, a blend of PP polymer and EVA polymer, a blend of POE polymer, or PVC polymer. In one embodiment herein, the base plastic is thermoplastic; or wherein the base plastic has a glass transition temperature (Tg) greater than or equal to about 60 ℃; greater than or equal to about 65 ℃, or greater than or equal to about 70 ℃.

In one embodiment herein, the base plastic comprises a PP polymer, a High Density Polyethylene (HDPE) polymer, an EVA polymer, and combinations thereof, but, as previously mentioned, the base plastic is not a blend of a LDPE polymer and an EVA polymer, a blend of a PP polymer and an EVA polymer, a blend of a POE polymer, or a PVC polymer. These base plastics are available in various grades and forms from suppliers around the world.

In one embodiment herein, the base plastic comprises from about 50% to about 99.999% by weight of the antimicrobial plastic; or about 80% to about 99.999%; or from about 85% to about 99.99%.

In one embodiment herein, the anti-biofouling compound and the intermediate plastic are mixed to form a master batch; or mixing the anti-biofouling compound and the intermediate plastic in an extruder to form a master batch; or the anti-biofouling compound and the intermediate plastic are polymerized together to form a master batch. Without being limited by theory, it is believed that this approach ensures that the anti-biofouling compound is permanently bound to the base plastic, which in turn may provide an improved plastic, thereby reducing the chance of leaching of the anti-biofouling compound from the base plastic and increasing the lifetime of the antimicrobial benefit.

In one embodiment herein, the anti-biofouling compound is mixed with an intermediate plastic to form a master batch. The masterbatch is then mixed with a base plastic to form the antimicrobial plastic. In one embodiment herein, the intermediate plastic is or comprises a random terpolymer; or the random terpolymer comprises monomers selected from the group of ethylene monomers, acrylate monomers, maleic anhydride monomers, and combinations thereof; or the random terpolymer comprises an ethylene monomer, an acrylate monomer, and a maleic anhydride monomer; or a random terpolymer, comprises a polymeric backbone comprising ethylene monomers, acrylate monomers, and maleic anhydride monomers. Generally, in random terpolymers, the order of the monomers is randomly determined by the actual stoichiometry and reaction kinetics of the particular monomers present at the time of polymerization.

In one embodiment herein, the intermediate plastic comprises at least one polymer segment that is compatible with the base plastic. However, the present invention is considered to be significantly different from the plastics known in the prior art, since the intermediate plastic herein does not require the exact same basic polymer backbone as the base plastic, and in some embodiments need only comprise one general polymer segment. Without being limited by theory, it is believed that in some embodiments, the intermediate need not comprise the same polymer segment as the base plastic.

In one embodiment herein, the masterbatch may be about 0.001% to about 50% by weight of the antimicrobial plastic; or about 0.001% to about 20%; or from about 0.01% to about 15%.

In one embodiment herein, the base plastic may be about 50% to about 99.999% by weight of the antimicrobial plastic; or about 80% to about 99.999%; or from about 85% to about 99.99%.

In one embodiment herein, when a masterbatch is present, then the anti-biofouling compound may be about 0.01% to about 25% by weight of the masterbatch; or about 0.1% to about 20%; or from about 0.5% to about 15%.

Alternatively, in one embodiment herein, when the base plastic is a thermoplastic; or selected from the group consisting of polyolefin polymers, thermoplastic elastomers, polyether polymers, polyvinyl polymers, polyester polymers, polyacetal polymers, polyamide polymers, polyurethane polymers, polyacrylate polymers, Polycarbonate (PC) polymers, polyimide polymers, polyphthalate polymers, polysulfone polymers, polythioether polymers, polyketone polymers, Polystyrene (PS) polymers, poly (styrene-acrylonitrile) (SAN) polymers, and combinations thereof; or wherein the base plastic is selected from the group consisting of polypropylene (PP) polymers, Polyethylene (PE) polymers, Ethyl Vinyl Acetate (EVA) copolymers, Acrylonitrile Butyl Styrene (ABS) copolymers, polyethylene terephthalate (PET) copolymers, and combinations thereof; or PP polymers, High Density Polyethylene (HDPE) polymers, EVA copolymers, PC polymers, ABS copolymers, PET copolymers, and combinations thereof. In one embodiment herein, particularly when the base plastic is selected from PP polymers, HDPE polymers, EVA copolymers, and combinations thereof, the base plastic and masterbatch are present in an amount of about 100: 1 to about 1: 1; or about 75: 1 to about 25: 1; or from about 60: 1 to about 30: 1; or about 55: 1 to about 35: 1 by weight. In this case, the intermediate plastic is compatible with the base plastic, which means that the intermediate plastic and the base plastic are homogeneously mixed together without causing any visible discoloration or physical defects.

In one embodiment herein, the base plastic has a glass transition temperature (Tg) of greater than or equal to about 60 ℃; or greater than or equal to about 65 ℃, or greater than or equal to about 70 ℃; or the base plastic is or comprises ABS, PET, PS, SAN, and combinations thereof, and the base plastic is not a blend of LDPE polymer and EVA copolymer, a blend of PP polymer and EVA copolymer, a blend of POE polymer, or PVC polymer. Substantially free of; or without an intermediate plastic. In this case, the base plastic and the anti-bio fouling compound may be mixed to form (directly) the antimicrobial plastic. Surprisingly, when the anti-biofouling compound according to the present invention is mixed with ABS, PET, PS, SAN and combinations thereof, it has surprisingly been found that no intermediate plastic is needed to help bind the anti-biofouling compound to the polymer having a molecular weight of greater than or equal to about 60 ℃ prior to forming the antimicrobial plastic; a Tg of greater than or equal to about 65 ℃, or greater than or equal to about 70 ℃; or a base plastic comprising ABS, PET, PS and/or SAN. This in turn avoids the need for a pre-formed masterbatch, which may improve efficiency and/or production speed. Without being limited by theory, it is believed that this is due to the filamentous nature of the base plastic, which readily entangles with the anti-biofouling compound and facilitates its uniform distribution therein.

In one embodiment herein, a base plastic; or the antibacterial plastic has a temperature of greater than or equal to 60 ℃; a Tg of greater than or equal to about 65 deg.C, or greater than or equal to about 70 deg.C. Without being limited by theory, it is believed that in any unreacted chemical, including but not limited to anti-bio fouling compounds, may leach out of the base plastic or antimicrobial plastic unless the plastic is near its glass transition temperature (Tg) or higher. Below Tg, it is believed that the anti-biofouling compound is well encapsulated and/or otherwise immobilized within the base plastic or antimicrobial plastic. However, when the temperature of the molecular chain reaches Tg, the anti-biofouling compound may start to migrate in the base plastic or antibacterial plastic matrix. In short, when the temperature is below Tg, the polymer chains freeze. Upon reaching Tg, the polymer structure may begin to relax at least partially, thereby increasing the mobility of low molecular weight molecules (e.g., anti-biofouling compounds) through the substrate, which may lead to leaching of the anti-biofouling compounds from the base plastic or the antimicrobial plastic. Thus, it is believed that if the Tg of the base plastic or antimicrobial plastic is greater than or equal to about 60 ℃; greater than or equal to about 65 ℃; or greater than or equal to about 70 c, the chance of leakage of the anti-bio fouling compound is significantly reduced during normal use and/or storage.

In one embodiment herein, ABS, PET, and combinations thereof are mixed with an anti-biofouling compound at a ratio of about 100: 1 to about 5: 1; or from about 75: 1 to about 10: 1; or about 50: 1 to about 15: 1 by weight.

Additives may be present in the antimicrobial plastic, the base plastic, the anti-biofouling compound, the intermediate plastic and/or the master batch. Additives may include, for example, ultraviolet light protectants (e.g., ultraviolet absorbers, ultraviolet blockers, ultraviolet reflectors, etc.), pigments, plasticizers, fillers, extenders, coatings, stabilizers, blowing agents, antiblocking agents, clarifying agents, antistatic agents, impact modifiers, fillers, lubricants, and combinations thereof. The additive may be about 0.0001% to about 10% by weight of the antimicrobial plastic.

The manufacturing method comprises the following steps:

in one embodiment herein, a method for manufacturing an antimicrobial plastic comprises the steps of: providing an anti-biofouling compound, providing a base plastic, and mixing the anti-biofouling compound with the base plastic.

Typically, the mixing step is a physical mixing of at least two different materials (e.g., base plastic and anti-biofouling compound; anti-biofouling compound and intermediate plastic; master batch and base plastic; etc.); or physical and chemical mixing; or physical mixing and chemical mixing are carried out simultaneously; or physical mixing and/or chemical bonding: . The mixing step may be performed when the base plastic, the anti-biofouling compound, the intermediate plastic, the masterbatch and/or any additives are molten and/or in liquid state.

In one embodiment of the invention, when the base plastic is a thermoplastic; or PP polymers, HDPE polymers, EVA polymers, and/or combinations thereof, the manufacturing process herein may further comprise the steps of: providing an intermediate plastic, mixing the anti-biofouling compound with the intermediate plastic to form a master batch, and then mixing the master batch with the base plastic to form the antimicrobial plastic.

In one embodiment of the invention, the anti-bio fouling compound and the base plastic are mixed; or anti-biofouling compounds, intermediate plastics and base plastics; or mixing the master batch and the base plastic together to form the antibacterial plastic. The mixing step herein can be carried out by methods such as melting, casting, molding, injection molding, vacuum forming, blow molding, extrusion, coextrusion, mixing, and combinations thereof; or extrusion, melting, injection molding, and combinations thereof; or extrusion, injection molding, and combinations thereof. The extrusion may be performed in a die, an extruder, or a combination thereof. The extruder may be, for example, a single screw extruder, a twin screw extruder, a non-screw extruder, and other extruders known in the art of plastic manufacturing. Without being limited by theory, it is believed that extrusion may ensure adequate mixing of the anti-biofouling compound, the intermediate plastic, and/or the master batch with the base plastic to form a consistent and relatively uniform antimicrobial plastic. It is also believed that mixing the anti-biofouling compound and the base plastic into the extruder may achieve a sufficiently durable and uniform mixing such that the anti-biofouling compound does not significantly leach out of the base plastic during use, storage, etc.

In one embodiment herein, when the base plastic comprises ABS, PET, SAN, PS, and combinations thereof, then the anti-biofouling compound can be mixed directly with the base plastic to form the antimicrobial plastic.

An antimicrobial plastic article:

the antimicrobial plastic herein may be formed into an antimicrobial plastic article. The antimicrobial plastic article may be generally made of plastic; or any article made of thermoplastic. In one embodiment herein, the antimicrobial plastic article is selected from the group consisting of an antimicrobial surface, an antimicrobial shell, an antimicrobial medical device, an antimicrobial cookware, an antimicrobial household item, an antimicrobial handle, an antimicrobial garment, an antimicrobial building material, and combinations thereof; or an antimicrobial surface, an antimicrobial shell, an antimicrobial medical device; or an antimicrobial cookware, an antimicrobial household item, and combinations thereof. The antimicrobial surface herein can be, for example, a table, a wall, a tile, a floor, a film, an elevator button, a handrail, a toilet, a chopping board, a sink, a computer screen, a keyboard, a computer mouse, a board, a cup, a touch screen, and combinations thereof. The antimicrobial enclosure herein may be, for example, a package, an equipment enclosure, a light enclosure, a telephone enclosure, a mobile telephone enclosure, and combinations thereof. The antimicrobial medical device herein may be, for example, an implantable medical device, a protective medical device (e.g., bedding, etc.), a catheter, a blood bag, a laboratory equipment, a pipette tip, a medical tube, a sample plate, a sample container, a sample bottle cap, a test tube, a medical/biohazard waste container, a microscope, a laboratory sink, a laboratory bench, a microplate reader, a centrifuge, a rocker, a stir bar, a tube lid, a syringe, a thermometer, a magnetic stir bar, a funnel, a beaker, an incubator, a cooler, a humidity cabinet, a pipette, a dropper, a measuring cylinder, a flask, and combinations thereof. Antimicrobial cookware useful herein can include, for example, cutting boards, sinks, eating utensils, cookware, blades, kitchen utensils, kitchen films, sponges, trash cans (e.g., trash cans), refrigerators, freezers, and combinations thereof. Antimicrobial household items useful in the present invention may include, for example, railings, doors, door frames, countertops, desks, walls, tiles, floors, elevator buttons, arm rests, toilets, computer screens, keyboards, computer mice, shelves, wallpaper, furniture, chairs, tables, window films, flower pots, bathroom mirror films, trash cans (e.g., trash cans), and combinations thereof.

Antimicrobial handles useful herein include, for example, knife handles, door handles, refrigerator handles, sink handles, toilet flush handles, bathroom faucets, window handles, and combinations thereof. The antimicrobial apparel herein may include, for example, footwear (e.g., socks, shoes, etc.), slacks, skirts, dresses, shirts, undergarments, scarves, gloves, dresses, bibs, aprons. A hat, glasses, a mask, and combinations thereof. The antimicrobial building materials herein can include, for example, door handles, industrial films, plastic covers, plastic sheets, plastic barrier films, plastic building films, window films, and combinations thereof.

In one embodiment herein, the plastic article may be an intermediate plastic article having a shape; or an intermediate form, which is then converted and/or processed into the final plastic article. Thus, the plastic article herein may be in a form selected from, for example: blocks, particles, monoliths, tubes, filters, composites, membranes, sheets, foams, and combinations thereof. Such intermediate plastic articles may then be formed, for example by thermoforming, into the plastic articles herein.

The test method comprises the following steps:

swab testing

Preparation of bacterial test inoculum: escherichia coli (8739^TM) And Staphylococcus aureus (6538P^TM)。

Test inocula of bacteria were prepared and counted at the time of incubation according to Japanese Industrial Standard (JIS Z2801: 2000). With a slight modification, the JIS can be used to test the antibacterial activity and the efficacy against bacteria on the surface of the sample. Referring to the flow chart of FIG. 1, the process is illustrated in graphical format and described as follows:

1) single bacterial colonies were picked from agar plates (kept in a refrigerator at 4 ℃) and transferred to 3mL nutrient broth for overnight incubation;

2) transferring 300. mu.L of the cultured bacteria to 3mL of fresh nutrient broth and culturing for about 3-4 hours;

3) bacteria were harvested by centrifugation at 8000rpm for 1-2 minutes (for E.coli, the OD600 had to be adjusted to 0.6-0.7; it must be adjusted to 1.5-1.7 for staphylococcus aureus);

4) the bacteria were washed 3 times with 0.9% NaCl aqueous solution and centrifuged;

5) the obtained bacteria were resuspended in 1/500 solution of nutrient broth (1/500NB refers to 500 fold dilution of nutrient broth adjusted to pH 6.8-7.2) to prepare bacterial solution as test inoculum. Multiple dilutions are dependent on the test sample. Typically, the E.coli suspension is diluted 10-fold and the S.aureus suspension is diluted 500-fold.

Sample incubation and swab testing

After inoculation of the samples with the test inoculum (E.coli or S.aureus), the samples were incubated at 37 ℃ for 24 hours. A swab test is used to check for bacteria adhering to the surface of the sample. The experimental procedure was as follows (see scheme 2):

1) samples (e.g., tubes) are cut into small pieces and then placed into sterilized 6-well plates.

2) 8mL of the prepared bacterial suspension was transferred to each well and incubated at 37 ℃ for 24 hours.

3) The bacterial suspension was carefully removed.

4) Rinse with 0.9% NaCl aqueous solution and rinse each sample with the same volume.

5) Wiping the sample surface and plate using sterile cotton cloth or a 3M quick swab head applicator can be done manually using a cell distributor, or more consistently using an automated spiral plate spreader (e.g., EddV Jet 2. iul.s.a.).

6) After incubation overnight or up to 24 hours, colonies formed on the agar plates were counted.

Without being limited by theory, it is believed that the use of E.coli in the above tests may represent adherence of other gram negative bacteria and the use of S.aureus in the above tests may represent other gram positive bacteria. Thus, it is believed that the results of this test may be representative of other bacteria in general.

Based on the above tests, and as used herein, the percent reduction in bacteria was calculated as follows:

[ average # cfu on control plastics-average # cfu on test plastics]*100

[ average # cfu on control plastics [ ]]

As used herein, the term "cfu" denotes a bacterial colony forming unit.

In one embodiment herein, the antimicrobial plastic has an elongation of at least about 50%; or at least about 75%; or at least about 85%; or at least about 90%; or an antimicrobial efficiency of at least about 95%. In one embodiment herein, the antimicrobial plastic has an antimicrobial efficiency against e.coli of at least about 80%; or at least about 85%; or at least about 90%; or at least about 95%. In one embodiment herein, the antimicrobial plastic has an antimicrobial efficiency against staphylococcus aureus of at least about 60%; or at least about 70%; or at least about 80%; or at least about 85%.

In one embodiment herein, the antimicrobial plastic is biocompatible according to ISO 10993 testing, ISO 18562 testing, and combinations thereof; or biocompatible according to ISO 10993-5, ISO 10993-10 and ISO 18562 tests.

Other tests known in the art may be relevant, such as tensile tests, melt flow index tests, thermal property tests, and the like. In particular ASTM D1238-10, which measures the melt flow index of samples at 190 ℃ and a weight of 2.16kg, may be used herein. While certain embodiments herein may be tested under other conditions (e.g., 230 ℃, 5.0kg in weight) or other conditions to indicate infringement and/or are within the scope of the present disclosure and/or claims, ASTM D1238-10 test conditions are specified as 190 ℃ and weigh 2.16 kg.

In one embodiment herein, the antimicrobial plastic is food contact safe and/or food compatible. Industry standard food contact safety tests include, for example, european union regulation 10/2011 and U.S. food and drug administration 21 c.f.r.177. However, one advantage of the antimicrobial plastic herein is that the antimicrobial plastic differs little from the base plastic for such physical properties as measured by such tests. Thus, in one embodiment herein, the antimicrobial plastic has one physical property, while the base plastic has the same physical property. Examples of physical properties useful herein include, for example, melt flow index, hardness, mechanical strength, compressive strength, elongation, thermal properties, and combinations thereof. When the physical properties of the antimicrobial plastic are measured according to an industry standard test, and the same physical properties of the base plastic are measured by the same industry standard test, the physical properties of the antimicrobial plastic are less than or equal to about ± 25%; plus or minus 20 percent; or +/-10%; or + -5% different from the same physical properties of the base plastic.

Example 1

100 grams of ethylene/acrylic acid/maleic acid terpolymer intermediate plastic was formed into a master batch in the presence of 10 grams of ceteareth anti-biofouling compound. The base plastic is a commercially available PP polymer. The weight ratio of the master batch to the base plastic is 1: 45. the masterbatch and base plastic were fed into a single screw extruder at a temperature ranging from 110 ℃ at the front to 200 ℃ at the back to form the antibacterial plastic (a). The antibacterial plastic (A) is extruded in a sheet form by a single screw extruder.

Thus, the weight percentages in the final plastic sheet are: 2% of an ethylene/acrylic acid/maleic acid terpolymer intermediate plastic, 0.2% of ceteareth anti-biofouling compound and 97.8% of a PP polymer.

A comparative plastic (control 1) comprising the same PP polymer was also prepared in the same manner, except that the comparative sample did not comprise any master batch, intermediate plastic or anti-biofouling compound.

The swab test (described above) was performed to compare the antibacterial properties of the antibacterial plastic (a) and the comparative plastic (control 1).

Example 1, table 1:

as can be seen from Table 1, the antibacterial plastic (A) of the invention reduced E.coli in the swab test by more than 99.9% compared to the comparative plastic (control 1).

Example 1, table 2:

as can be seen from Table 2, the antibacterial plastic (A) of the present invention reduced Staphylococcus aureus by 97% in the swab test compared to the comparative plastic (control 1). In other words, the adhesion of the antimicrobial plastic (A) was only 3% of that of the comparative plastic (control 1).

Melt Flow Index (MFI) testing was performed at 230 ℃ and 2.16kg according to ASTM D1238-10. The MFI of the PP antibacterial plastic (A) is + 15.4% compared with unmodified PP (control 1).

Example 2

An antimicrobial plastic (B) and a comparative plastic (control 2) were prepared as in example 1, except that the base plastic was HDPE and the temperature of the single screw extruder in the preparation of the antimicrobial plastic ranged from 110 ℃ in the front to 190 ℃ in the rear.

A swab test (described above) was performed to compare the antimicrobial properties of the antimicrobial plastic (B) and the comparative plastic (control 2).

Example 2, table 1:

as can be seen from Table 1, the antibacterial plastic (B) of the present invention reduced > 99% E.coli in the swab test compared to the comparative plastic (control 2).

Example 2, table 2:

as can be seen from Table 2, the antibacterial plastic (B) of the present invention reduced Staphylococcus aureus by 92% in the swab test compared to the comparative plastic (control 2). In other words, the adhesion of the antimicrobial plastic (B) was only 8% of that of the comparative plastic (control 2).

Melt Flow Index (MFI) testing was performed at 190 ℃ and 2.16kg according to ASTM D1238-10. The MFI of the HDPE antimicrobial plastic (B) is + 1.4% compared with the unmodified HDPE (control 2).

Example 3

A masterbatch was prepared according to example 1 except that the base plastic was EVA to form the antimicrobial plastic (C). The temperature at the front of the single screw extruder was 110 ℃ and the temperature at the back was 190 ℃.

A comparative plastic sample (control 3) comprising only the base plastic (EVA) was also prepared in the same manner except that the master batch, intermediate plastic or anti-biofouling compound was not included.

A swab test (described above) was performed to compare the antibacterial properties of the antibacterial plastic sample (C) and the comparative plastic sample (control 3).

Example 3, table 1:

as can be seen from Table 1, the antibacterial plastic (B) of the invention reduced > 99% E.coli in the swab test compared to the comparative plastic (control 3).

Example 3, table 2:

as shown in table 2, the antibacterial plastic (C) of the present invention reduced staphylococcus aureus by 98% in the swab test when formed into a sheet shape compared to the comparative plastic (control 3).

Melt Flow Index (MFI) testing was performed at 190 ℃ and 2.16kg according to ASTM D1238-10. The EVA antimicrobial plastic (C) had an MFI of + 11.7% compared to unmodified EVA (control 3).

Example 4

In a twin-screw extruder, 100 parts of commercially available ABS and 5 parts of PEG sorbitol hexaoleate were mixed together to form antibacterial plastic (D). The temperature range of the twin-screw extruder was 150 ℃ at the front to 210 ℃ at the back.

Then the antibacterial plastic is made into a sheet shape at the temperature of 200 ℃ by hot press molding.

A comparative plastic sample containing only ABS was also prepared in the same manner except that no master batch, intermediate plastic or anti-biofouling compound was included (control 4).

A swab test (described above) was performed to compare the antibacterial properties of the antibacterial plastic sample (D) and the comparative plastic sample (control 4).

Example 4, table 1:

as can be seen from Table 1, the antibacterial plastic (C) of the invention reduced > 96% E.coli in the swab test compared to the comparative plastic (control 4).

Example 4, table 2:

as shown in table 2, the antimicrobial plastic of the invention (D) when formed into a sheet reduced staphylococcus aureus by 90% in the swab test compared to the comparative plastic (control 4).

Melt Flow Index (MFI) testing was performed at 200 ℃ and 2.16kg according to ASTM D1238-10. The MFI of the ABS antibacterial plastic (D) compared with unmodified ABS (control 4) was + 24.1%.

Example 5

In a twin screw extruder, 100 parts of commercially available PET and 5 parts of PEG sorbitol hexaoleate were mixed together to form the antibacterial plastic (E). The temperature of the twin-screw extruder ranged from 180 ℃ at the front to 240 ℃ at the back.

Then the antibacterial plastic is formed into a sheet shape at the temperature of 240 ℃ by hot press forming.

A comparative plastic sample containing only PET was also prepared in the same manner except that the master batch, intermediate plastic or anti-biofouling compound was not included (control 5).

A swab test (described above) was performed to compare the antibacterial properties of the antibacterial plastic sample (E) and the comparative plastic sample (control 5).

Example 5, table 1:

as can be seen from Table 1, the antibacterial plastic (D) of the invention reduced in swab tests > 93% E.coli compared to the comparative plastic (control 5).

Example 5, table 2:

as can be seen from table 2, the antibacterial plastic (E) of the present invention reduced staphylococcus aureus by 68% in the swab test compared to the comparative plastic (5) when formed into a sheet shape.

Melt Flow Index (MFI) testing was performed at 265 ℃ and 5.0kg according to ASTM D1238-10. The MFI of the PET antibacterial plastic (E) was + 24.1% compared with unmodified PET (control 5).

It is to be understood that only the embodiments in which the present invention may be practiced have been shown and described, and that modifications and/or changes may be made thereto without departing from the spirit of the invention.

It is also to be understood that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be used in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

Publications, references, etc., specifically cited herein are hereby incorporated by reference in their entirety. However, neither use alone nor in combination is an admission of their usefulness and/or relevance as prior art.