Anti-fog composition and anti-fog plastic prepared from same

Abstract

The invention relates to an antifogging composition, antifogging plastic prepared from the antifogging composition and related application. More specifically, the antifogging compositions of the present invention include a thermoplastic, at least one antifogging agent, a thermoplastic elastomer, and a porous copolymer carrier. The anti-fogging plastic prepared from the anti-fogging composition shows good mechanical properties and transparency, a more durable and cleanable anti-fogging effect and an unexpected surface bacterium repelling effect, is easy to continuously produce and low in cost, meets the food contact safety requirements, and can be widely applied to the fields of packaging, buildings, medical equipment, automobiles and the like.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, in particular to an anti-fog composition, an anti-fog plastic prepared therefrom and related applications. Background Art

[0002] Anti-fog plastics improve light transmittance and reduce water droplets, thereby protecting crop growth and preventing the accumulation of pathogenic microorganisms. Therefore, they are widely used in food packaging, agriculture, healthcare, and consumer goods. These industries are experiencing growing demand for anti-fog products, and the global anti-fog additive market is expected to grow from US$1.6 billion in 2019 to US$2.8 billion in 2027, with the market size of end-use anti-fog products reaching approximately US$200 billion.

[0003] Traditional anti-fog plastics are made by spraying or impregnating the plastic surface with a hydrophilic compound. However, the adhesion between the hydrophilic layer and the hydrophobic substrate is typically weak, resulting in only a short-term anti-fog effect and poor durability. Some have proposed and attempted to directly mix hydrophilic anti-fog agents into the polymer resin during plastic processing. However, due to the incompatibility of hydrophilic anti-fog agents with the polymer matrix resin, direct mixing of hydrophilic anti-fog agents with the polymer resin during plastic processing can lead to rapid detachment of the anti-fog agent. Others have proposed and attempted to use amphiphilic anti-fog agents during plastic processing to improve the compatibility of the anti-fog agent, but the porous carriers of the prior art do not have a significant adsorption effect on such anti-fog agents. Furthermore, the antibacterial effect of anti-fog plastics is typically achieved by adding antimicrobial agents. However, existing antimicrobial agents are mostly silver particles or quaternary ammonium salt cations, which directly affect the efficacy of the surfactant in the anti-fog agent, causing the anti-fog effect to disappear or weaken.

[0004] Therefore, there is still a need in the art for a more efficient and cost-effective novel anti-fog and antibacterial composition, which can provide plastics with more durable and washable anti-fog performance and antibacterial effects through built-in technology. Summary of the Invention

[0005] The present inventors have unexpectedly discovered that an amphiphilic antifog agent can be combined with at least one carrier resin comprising an elastomer and, optionally, a porous copolymer carrier to produce an antifog masterbatch. The resulting antifog masterbatch not only synergistically enhances the antifog agent loading capacity of the antifog masterbatch but also expands its capacity for loading different types of antifog agents. Antifog plastics produced from this antifog masterbatch exhibit significant and long-lasting antifog effects, good washability, low cost, and suitability for continuous manufacturing. This has led to the present invention.

[0006] Therefore, in a first aspect of the present invention, an anti-fog composition is provided, comprising, based on the total weight of the anti-fog composition:

[0007] - 30% to 50% of a first thermoplastic resin;

[0008] -25% to 40% thermoplastic elastomer;

[0009] - 10% to 30% of at least one anti-fog agent;

[0010] - 0% to 10% porous copolymer carrier.

[0011] In a second aspect of the present invention, an anti-fog plastic is provided, which is made of the anti-fog composition according to the first aspect of the present invention and a second thermoplastic resin.

[0012] The beneficial effects of the present invention include but are not limited to at least one of the following:

[0013] (1) By introducing at least one carrier resin including an elastomer and an optional porous copolymer carrier into an anti-fog composition such as an anti-fog masterbatch, not only the loading amount of the anti-fog agent in the anti-fog masterbatch is synergistically increased, but also the loading capacity of the anti-fog masterbatch for different types of anti-fog agents is expanded, thereby being able to simultaneously load a variety of anti-fog agents with different properties, such as anti-cold fog anti-fog agents, anti-hot fog anti-fog agents, etc., thereby achieving different properties of anti-fog plastics according to requirements.

[0014] (2) The anti-fog masterbatch of the present invention is suitable for the continuous production of anti-fog plastics. Existing film production lines, such as extrusion film casting or blown film processes, can be directly used for large-scale production without the need for production line modifications. Furthermore, the cost of the anti-fog plastic produced using the anti-fog masterbatch of the present invention is only increased by 10%-20% compared to the base resin, making it highly cost-effective.

[0015] (3) The built-in anti-fog plastic prepared in this manner exhibits excellent mechanical properties and transparency, a durable and washable anti-fog effect, complies with the GB / T 31726 standard, is suitable for repeated use, and can be widely used in packaging, construction, medical equipment, automotive, and other fields. The anti-fog plastic of the present invention has passed the food contact safety assessment conducted by SGS in accordance with FDA and EU regulations, thus meeting food contact safety requirements. Even more surprisingly, the anti-fog plastic of the present invention exhibits a surface repellency with a bacterial adhesion rate exceeding 90%, even without the addition of any antimicrobial substances.

[0016] (4) The anti-fog plastic of the present invention can simultaneously exhibit, for example, short-term and long-term anti-fog effects, and / or simultaneously exhibit anti-cold fog and hot fog anti-fog effects due to the loading of different types of anti-fog agents in the anti-fog masterbatch. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings are included to provide a further understanding of the present invention and are incorporated into and constitute a part of this specification. The drawings described herein are for illustration purposes only and are not intended to limit the scope of the disclosure in any way.

[0018] Figure 1 The following is a preparation process of an anti-fog masterbatch according to one embodiment of the present invention.

[0019] Figure 2 The following is a preparation process of an anti-fog plastic film according to one embodiment of the present invention.

[0020] Figure 3 Schematic diagram showing the water bath hot fog test method according to GB / T 31726 "Test method for anti-fog performance of plastic films".

[0021] Figure 4 Shows a 5-level rating based on GB / T 31726 "Test method for anti-fog performance of plastic films".

[0022] Figure 5 Shown are the results of water bath hot mist testing of AFPE plastic films AF08_MB#2_3% and AF08_MB#2_5% according to one embodiment of the present invention.

[0023] Figure 6 Shown are cold fog test results for an AFPE plastic film AF03_MB#1_5% according to one embodiment of the present invention.

[0024] Figure 7 The graph shows the bacteria repellency of the AFPE plastic film AF08_MB#2_5% according to one embodiment of the present invention against Escherichia coli and Staphylococcus aureus, with a PE film as a control.

[0025] FIG8 shows the bacteria repellency report of the AFPE plastic film AF08_MB#2_5% against Staphylococcus aureus (A) and Escherichia coli (B) according to one embodiment of the present invention.

[0026] Figure 9 It is shown that the AFPE plastic film AF08_MB#2_5% according to one embodiment of the present invention has passed the food contact safety assessment report conducted by SGS according to FDA and EU regulations and its Chinese translation.

[0027] Figure 10 Shown are the results of a water bath hot mist test of AF_MB#1_7% according to one embodiment of the present invention and the results of a water bath hot mist test after 100 water washes. DETAILED DESCRIPTION

[0028] The following detailed description is merely exemplary and is in no way intended to limit the invention or its application or uses.

[0029] While the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0030] Furthermore, it should be understood that any numerical range recited herein is intended to include all subranges contained therein. For example, a range of "1 to 10" is intended to include all subranges between the recited minimum value of 1 and the recited maximum value of 10 (including the end values), i.e., the minimum value is equal to or greater than 1 and the maximum value is equal to or less than 10.

[0031] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0032] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably to indicate that there is at least one of the specified element, material, component, or method step, unless the context clearly dictates otherwise.

[0033] As used herein, the terms "about" and "substantially" are used herein to describe measurable values ​​and ranges due to expected variations known to those skilled in the art (e.g., limitations and variability in measurements). The term "about" also indicates that the numerical value allows for some slight imprecision (precision of the value obtained using some method; close or reasonably close to the value; almost close). If the imprecision provided by the term "about" is not otherwise understood in the art to have this ordinary meaning, the term "about" as used herein at least indicates differences that may arise from ordinary methods of measuring and using such parameters. In addition, the disclosure of a range includes the disclosure of all values ​​and further divided ranges within the entire range.

[0034] As used herein, the terms "include," "comprising," and their grammatical variations are synonymous with the term "comprises" and its grammatical variations. The term "comprising" and its grammatical variations are open-ended expressions and, in the context of the present invention, should be understood to include not only the specified elements, materials, components, or method steps, but also other unspecified elements, materials, components, or method steps.

[0035] As used herein, the term "consisting of and its grammatical variations should be understood in the context of the present invention to exclude the presence of any unspecified elements, ingredients, or process steps. As used herein, the term "consisting essentially of and its grammatical variations should be understood in the context of the present invention to include the specified elements, materials, ingredients, or process steps, as well as those elements, materials, ingredients, or process steps that do not materially affect the basic and novel characteristics of the content being described. It should be understood that if the term "comprising" and its grammatical variations are used, and other elements, materials, ingredients, or process steps that may materially affect the basic and novel characteristics of the content being described are not included, the term "comprising" can be replaced with the term "including" or "consisting essentially of and its grammatical variations.

[0036] In the context of the present invention, the proportions of the various components are all weight percentages.

[0037] Although specific aspects of the present invention will be described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to these details can be developed based on the overall teachings of the present invention. Therefore, the specific configurations disclosed are for illustrative purposes only and are not intended to limit the scope of the disclosure, that is, the full scope of the appended claims and any and all equivalents thereof.

[0038] As mentioned above, the present invention provides a new anti-fog composition, and the anti-fog plastic prepared therefrom exhibits significant and long-lasting anti-fog effect, good washability, surface bacteria repellency, low cost and is suitable for continuous manufacturing.

[0039] In a first aspect of the present invention, an anti-fog composition is provided, comprising, based on the total weight of the anti-fog composition:

[0040] - 30% to 50% by weight of a first thermoplastic resin;

[0041] - 25% to 40% by weight of thermoplastic elastomer;

[0042] - 10% to 30% by weight of at least one antifogging agent;

[0043] - 0 to 10 wt% of a porous copolymer support.

[0044] Thermoplastic resin

[0045] In the context of the present invention, the term "thermoplastic resin" refers to a class of polymers that have the property of softening into a liquid when heated and hardening when cooled, but do not undergo chemical reactions.

[0046] The first thermoplastic resin used in the anti-fog composition of the present invention can be made of common plastic materials, such as polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate (EVA) and polyvinyl chloride (PVC), so as to be applied to common plastic masterbatch to make anti-fog plastic.

[0047] In a specific embodiment, the first thermoplastic resin may be one or more of polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA) and polyvinyl chloride (PVC).

[0048] In a specific embodiment, the weight average molecular weight of the polyethylene (PE) may be 40,000-120,000; the molecular weight of the polypropylene (PP) may be 80,000-150,000; the molecular weight of the ethylene-vinyl acetate copolymer (EVA) may be 20,000-50,000; and the molecular weight of the polyvinyl chloride (PVC) may be 50,000-110,000.

[0049] In a preferred embodiment, the first thermoplastic resin may be polyethylene (PE).

[0050] In a more preferred embodiment, the first thermoplastic resin may be low density polyethylene (LDPE).

[0051] In the context of the present invention, the term "low density polyethylene (LDPE)" refers to polyethylene with a density in the range of 0.910-0.940 g / cm 3 of polyethylene.

[0052] In another specific embodiment, the first thermoplastic resin may be present in the anti-fog composition of the present invention in an amount of 35% to 45%, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44% or 45% or a range consisting of any two values ​​therein.

[0053] In a preferred embodiment, the first thermoplastic resin may be present in the anti-fog composition of the present invention at 35% to 40%.

[0054] anti-fog agent

[0055] As used herein, the anti-fog agent used in the anti-fog composition of the present invention is an amphiphilic compound comprising a super-hydrophilic portion having an anti-fog function and a hydrophobic portion compatible with the base plastic (i.e., polymer matrix) suitable for manufacturing anti-fog plastics. The super-hydrophilic portion may be, for example, but not limited to, a group comprising multiple -OH end groups (e.g., ethylene oxide), which can reduce the surface tension of the anti-fog plastic, allowing water mist to migrate to the plastic surface to form a water layer or hydration layer, preventing the formation of mist droplets and biofilms on the surface, and preventing bacteria from adhering to and growing on the plastic surface. The hydrophobic portion may be, for example, a C-terminal portion that is easily compatible with the polymer matrix. 12 -C 14 Alkyl ether.

[0056] In a specific embodiment, the at least one anti-fog agent is present in the anti-fog composition of the present invention in an amount of 15% to 30% by weight, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% by weight, or a range consisting of any two values ​​therein.

[0057] In a preferred embodiment, the at least one anti-fog agent is present in the anti-fog composition of the present invention in an amount of 20% to 30%, based on the total weight of the anti-fog plastic.

[0058] In yet another specific embodiment, the at least one anti-fog agent is an amphiphilic compound having multiple hydroxyl end groups and a long-chain hydrophobic aliphatic group.

[0059] In a preferred embodiment, the at least one antifog agent can be selected from fatty acid glycerides such as glyceryl stearate and glyceryl monooleate, fatty alcohol polyoxyethylene ethers such as polyoxyethylene lauryl ether, oleic acid alcohol esters, sorbitan monostearate, polyether oligomers such as polypropylene glycol, polyethylene glycol, and octadecyl diethanolamine. Among the above antifog agents, fatty acid glycerides are long-acting antifog agents that can provide long-term antifog performance, while polyoxyethylene lauryl ether is a short-acting antifog agent that can provide immediate or short-term antifog performance.

[0060] In a more preferred embodiment, the anti-fog composition comprises fatty acid glyceride and / or fatty alcohol polyoxyethylene ether.

[0061] In a most preferred embodiment, the at least one anti-fog agent can be selected from fatty acid glycerides having a structure of formula I, or polyoxyethylene lauryl ether having a structure of formula II:

[0062]

[0063] As used herein, the antifog composition can include a combination of two or more antifog agents. The two or more antifog agents can each have different antifog properties, thereby providing complementary or all-round antifog effects when combined. For example, a short-acting antifog agent such as polyoxyethylene lauryl ether and a long-acting antifog agent such as fatty acid glyceride can be loaded simultaneously, thereby providing an immediate and long-lasting antifog effect. For another example, a cold mist antifog agent such as fatty acid glyceride and a hot mist antifog agent such as polyoxyethylene lauryl ether can be loaded simultaneously, thereby providing an effect of preventing both hot mist and cold mist from being generated. It can also be understood that a kind of antifog agent can have different antifog properties at the same time. For example, fatty acid glyceride has both long-lasting antifog properties and antifog properties that prevent cold mist from being generated, while polyoxyethylene lauryl ether has both immediate antifog properties and antifog properties that prevent hot mist from being generated. When these two antifog agents are used in combination, the all-round antifog requirements of plastics can be achieved.

[0064] In a preferred embodiment, the anti-fog composition comprises a combination of fatty acid glyceride and fatty alcohol polyoxyethylene ether.

[0065] Thermoplastic elastomers

[0066] In the context of this invention, the term "thermoplastic elastomer" refers to a class of elastomeric materials that exhibit rubber-like elasticity at room temperature and can be plasticized and molded at high temperatures. As used herein, the inclusion of a thermoplastic elastomer in an anti-fog composition allows for expansion and adsorption through its flexible and rigid structure, thereby loading the added anti-fog agent via adsorption. This significantly increases the anti-fog agent loading capacity while also improving the process conditions for preparing anti-fog plastics from anti-fog masterbatch.

[0067] In a specific embodiment, the thermoplastic elastomer may be present in the anti-fog composition of the present invention in an amount of 30 wt % to 35 wt %, for example, 31 wt %, 32 wt %, 33 wt %, 34 wt % or 35 wt % or a range consisting of any two values ​​therein.

[0068] In another specific embodiment, the thermoplastic elastomer used in the anti-fog composition of the present invention is selected from ethylene-octene copolymer (POE), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene (SEBS), and styrene-ethylene-propylene-styrene (SEPS).

[0069] In a preferred embodiment, the thermoplastic elastomer is styrene-ethylene-butylene-styrene (SEBS).

[0070] Porous copolymer support

[0071] Those skilled in the art will appreciate that the porous copolymer carrier can be combined with the antifogging agent through adsorption to achieve loading of the antifogging agent.

[0072] In a specific embodiment, the porous copolymer carrier can be present in the anti-fog composition of the present invention in an amount of 3 wt % to 7 wt %, for example, 3 wt %, 4 wt %, 5 wt %, 6 wt % or 7 wt %, or a range consisting of any two values ​​therein.

[0073] In yet another specific embodiment, the porous copolymer support may be selected from ethylene butyl acrylate (EBA) porous copolymer support, linear low density polyethylene (LLDPE) porous copolymer support, low density polyethylene (LDPE) porous copolymer support.

[0074] In a preferred embodiment, the porous copolymer support may be a low-density polyethylene (LDPE) porous copolymer support.

[0075] Anti-fog composition

[0076] In a specific embodiment, the anti-fog composition can be prepared in the form of anti-fog masterbatch.

[0077] In another specific embodiment, the anti-fog composition of the present invention can be prepared by mixing the components in a weight ratio and then subjecting them to twin-screw composite extrusion. More specifically, the anti-fog agent, the thermoplastic elastomer, and the porous copolymer carrier can be fully mixed to form a first mixture; the first mixture obtained is then fully mixed with first thermoplastic resin particles using, for example, a high-speed mixer to obtain a second mixture; the second mixture is then placed in a twin-screw extruder and compounded at a processing temperature of 110°C to 200°C (e.g., 150°C to 190°C) at a screw speed of, for example, 200-600 rpm; and the composite material is finally pelletized.

[0078] The anti-fog masterbatch of the present invention is suitable for the continuous production of anti-fog plastics. Existing film production lines, such as extrusion film casting or blown film processes, can be directly used for large-scale production without requiring modifications. Furthermore, the cost of the anti-fog plastic produced using the anti-fog masterbatch of the present invention increases by only 10%-20% compared to the base resin, making it highly cost-effective.

[0079] Those skilled in the art can improve the above preparation method according to actual needs without affecting the performance of the final product, and the anti-fog masterbatch prepared does not exceed the scope of the present invention.

[0080] In a second aspect of the present invention, an anti-fog plastic is provided, which is made of the anti-fog composition according to the first aspect and a second thermoplastic resin.

[0081] In a specific embodiment, the anti-fog composition may be added in an amount of 1 wt % to 10 wt % based on the total weight of the anti-fog plastic.

[0082] In a preferred embodiment, based on the total weight of the anti-fog plastic, the addition amount of the anti-fog composition can be 3 wt % to 8 wt %, for example, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt % or 8 wt %, or a range consisting of any two of these values.

[0083] In a preferred embodiment, the anti-fog composition may be added in an amount of no more than 5 wt % based on the total weight of the anti-fog plastic.

[0084] In a more preferred embodiment, the anti-fog composition may be added in an amount of 3 wt % to 5 wt % based on the total weight of the anti-fog plastic.

[0085] In another specific embodiment, the anti-fog plastic exhibits a surface bacteria repellency with a bacteria repellency rate of more than 90% against bacterial adhesion. The bacteria are, for example, Escherichia coli and Staphylococcus aureus, but are not limited thereto.

[0086] In yet another specific embodiment, the second thermoplastic may be selected from polyethylene (PE), polypropylene (PP), ethylene vinyl acetate copolymer (EVA) and polyvinyl chloride (PVC).

[0087] In a further specific embodiment, the molecular weight of the polyethylene (PE) may be 40,000-120,000; the molecular weight of the polypropylene (PP) may be 80,000-150,000; the molecular weight of the ethylene-vinyl acetate copolymer (EVA) may be 20,000-50,000; and the molecular weight of the polyvinyl chloride (PVC) may be 50,000-110,000.

[0088] In a preferred embodiment, the second thermoplastic may be polyethylene (PE).

[0089] In a more preferred embodiment, the second thermoplastic may be low-density polyethylene (LDPE). In a more preferred embodiment, the second thermoplastic may be the same as the first thermoplastic, so that the anti-fog masterbatch prepared by the anti-fog composition of the present invention has better compatibility with the second thermoplastic (i.e., matrix plastic resin).

[0090] The anti-fog plastic of the present invention can be manufactured into various forms, such as sheets and films, as needed. The steps for preparing the anti-fog plastic from the anti-fog composition of the present invention and the second thermoplastic resin can employ methods and procedures well known to those skilled in the art. For example, in the case of preparing an anti-fog plastic film, the anti-fog composition and the second thermoplastic resin can be premixed in a weight ratio, extruded through a twin-screw extruder, and then extruded through a blown film extrusion process to obtain a built-in anti-fog plastic film. Those skilled in the art can modify the above-mentioned preparation method as needed without affecting the performance of the final product, and the resulting anti-fog plastic product does not exceed the scope of the present invention.

[0091] The anti-fog plastic of the present invention exhibits excellent mechanical properties and transparency, as well as a durable and washable anti-fog effect. It complies with the GB / T 31726 standard, is suitable for repeated use, and can be widely used in packaging, construction, medical equipment, automotive, and other fields. The anti-fog plastic of the present invention has passed the food contact safety assessment conducted by SGS in accordance with FDA and EU regulations, thus meeting food contact safety requirements. Even more surprisingly, the anti-fog plastic of the present invention exhibits a surface bacteria repellency exceeding 90% without the addition of any antimicrobial substances.

[0092] Example

[0093] In this specification, embodiments are described in a manner that provides for a clear and concise description, but it is intended and will be understood that the embodiments may be combined in various ways or individually without departing from the scope of the present invention. For example, it will be understood that all preferred properties described herein apply to all aspects of the present invention described herein.

[0094] Example 1: Preparation of anti-fog masterbatch containing a single anti-fog agent

[0095] According to the weight ratio shown in Table 1 below, an anti-fog masterbatch containing only one anti-fog agent was prepared by a twin-screw compounding process, wherein anti-fog agent 1 (AF03) is monoolein (paste), anti-fog agent 2 (AF04) is a fatty acid glyceride (paste) shown by the compound of formula I, and anti-fog agent 3 (AF08) is a polyoxyethylene lauryl ether (liquid) shown by the compound of formula II.

[0096]

[0097] The reagents used in the examples can be obtained commercially. For example, low-density polyethylene (LDPE) was purchased from BASF GmbH (Mw: 94,000), and low-density polyethylene porous copolymer carrier (porous PE) was purchased from Graft Polymer LTD.

[0098] The specific general steps are as follows: first, the anti-fog agent, thermoplastic elastomer (if any) and porous copolymer carrier material (if any) are thoroughly mixed; then, the mixture is thoroughly mixed with low-density polyethylene (LDPE) particles using a high-speed mixer; finally, all the mixed materials are put into a twin-screw extruder, and the processing temperature of the extruder is 150°C to 190°C and the screw speed is 200 rpm (such as Figure 1 After granulation, the anti-fog masterbatch (AFMB) was stored dry at room temperature.

[0099] Table 1: Formula of anti-fog masterbatch with single anti-fog agent

[0100]

[0101] The results in Table 1 show that compared to porous PE, the use of SEBS effectively increases the absorption rate of the anti-fog agent in the anti-fog masterbatch, thereby improving the processability of the anti-fog masterbatch. Later tests found that the combination of SEBS and porous PE, such as AF08_MB#2, showed a synergistic effect and had the best processability.

[0102] Example 2: Preparation of anti-fog masterbatch containing dual anti-fog agents

[0103] According to the weight ratio shown in Table 2 below, an anti-fog masterbatch containing two anti-fog agents was prepared by twin-screw compounding. The preparation method of the anti-fog masterbatch containing two anti-fog agents is the same as the preparation method of the anti-fog masterbatch containing a single anti-fog agent, except that two anti-fog agents are added, and the LDPE, SEBS, anti-fog agent 1, and anti-fog agent 3 are the same as those in Example 1.

[0104] Table 2: Formula of anti-fog masterbatch with double anti-fog agents

[0105]

[0106] The results in Table 2 show that, due to the use of the thermoplastic elastomer SEBS as the carrier for the antifog agent, Antifog Agent 1 and Antifog Agent 3 can be used together to prepare a composite antifog masterbatch. SEBS can effectively adsorb the combination of the two antifog agents and improve the processability of the antifog masterbatch.

[0107] Example 3: Preparation and anti-fog test of AFPE plastic film

[0108] According to the weight ratio shown in Table 3 below, low density polyethylene resin (LDPE) and anti-fog masterbatch (AFMB) prepared in Example 1 were used to prepare anti-fog polyethylene (AFPE) plastic film by blown film extrusion. The general steps are as follows: Figure 2 As shown, the extrusion step is divided into four stages, the corresponding extrusion temperatures are 80°C, 180°C, 190°C and 180°C, and the screw speed is 110 rpm.

[0109] After film formation, the anti-fog effect of the AFPE plastic film prepared above was tested according to the industrial standard GB / T 31726 "Test method for anti-fog performance of plastic films", and the selected test methods were water bath hot fog test and cold fog test.

[0110] Figure 3 Shows a schematic diagram of the water bath hot fog test, Figure 4 The figure shows a 5-level rating system based on GB / T31726. The water bath hot fog test is performed at 60°C for 15 minutes. Specifically, an AFPE plastic film (e.g., 120 mm x 120 mm, 0.6 mm thick) is placed on a glass beaker (e.g., 250 mL) filled with 60°C hot water. A logarithmic visual acuity chart is placed at the bottom of the beaker. After 15 minutes, the anti-fog performance is evaluated by comparing the clarity of the vertical observation result with the image shown in the anti-fog rating chart.

[0111] The AFPE plastic film prepared in Example 3 was further subjected to a cold fog test according to the industry standard GB / T 31726. The cold fog test conditions were 3°C and the test duration was 5 minutes. Specifically, the AFPE plastic film was placed on a glass beaker filled with 23°C Grade III water that complies with GB / T 6682-2008. The beaker was then placed in a 3°C constant temperature and humidity chamber or refrigerator. After 5 minutes, the eye chart at the bottom of the beaker was observed.

[0112] In addition, a 100-wash test was conducted in a dishwasher with an automatic wash program set to 100 cycles. The test used tap water without detergent at room temperature to rinse the AFPE plastic film. The results are shown in Table 3.

[0113] Table 3: AFPE plastic film ratio and anti-fog test results

[0114]

[0115] The results in Table 3 above show that the anti-fog performance of the anti-fog film varies with the amount of anti-fog masterbatch added. AF08_MB#1_5% (5% by weight of AF08_MB#1), AF08_MB#1_10% (10% by weight of AF08_MB#1), AF08_MB#2_3% (3% by weight of AF08_MB#2), and AF08_MB#2_5% (5% by weight of AF08_MB#2) all demonstrate immediate and washable anti-fog performance. All achieve an anti-fog grade of G2+ according to the water bath hot fog test method according to industry standard GB / T 31726.

[0116] On this basis, the AFPE plastic films AF08_MB#2_3% (AF08_MB#B_3%) and AF08_MB#2_5% (AF08_MB#B_5%) that performed well in the aforementioned anti-fog test were also subjected to a rapid hot fog test according to the industry standard GB / T 31726 under more stringent conditions (85°C for 1 minute), using LDPE as a control. The test results are as follows: Figure 5 shown.

[0117] Depend on Figure 5 It can be seen that the AFPE plastic films AF08_MB#2_3% and AF08_MB#2_5% of the present invention can still maintain the second-level anti-fog standard (G2) after being placed at 85° C. for 1 minute, demonstrating the anti-fog ability to resist high temperatures.

[0118] In addition, a cold fog test was conducted on the AFPE plastic film AF03_MB#1_5% of the present invention, and the process and results are shown in FIG. Figure 6 After being placed at 3°C ​​for 5 minutes, the AFPE plastic film exhibits anti-fog performance (G2).

[0119] Example 4: Transparency and mechanical properties testing of AFPE plastic film

[0120] In this example, according to the industry standard GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics", the light transmittance of pure LDPE plastic film (control), AFPE plastic films AF08_MB#2_3% and AF08_MB#2_5% were characterized using a haze meter, and the tensile strength of the three plastic films was tested according to the industry standard ASTM D638 "Standard Test Method for Tensile Properties of Plastics". The results are shown in Table 4 below.

[0121] Table 4: Test results of transparency and tensile strength of AFPE plastic film

[0122]

[0123] As shown in Table 4, compared to pure LDPE plastic films, the AFPE plastic films AF08_MB#B_3% and AF08_MB#B_5% of the present invention exhibit superior light transmittance, indicating that the addition of the anti-fog masterbatch does not affect the transparency of the polyethylene film. Furthermore, the tensile strength of the AFPE plastic films AF08_MB#B_3% and AF08_MB#B_5% of the present invention is also improved, likely due to the addition of SEBS, an elastomer with excellent mechanical properties.

[0124] Example 5: Bacteria repellency test of AFPE film

[0125] In this example, a pure LDPE plastic film (control) and an AFPE plastic film AF08_MB#2_5% were used for a bacterial repellency test. The test standard is ASTM E3371-22, and the specific steps are as follows: First, prepare an AFPE plastic film sample and place it in a bacterial culture dish. Simultaneously, culture a bacterial liquid. Prepare a bacterial inoculum, take the bacterial liquid and place it on the film sample, and then place a cover film. Place the film in a 37°C oven for 24 hours, remove the cover film, and gently rinse the film with saline. Collect the bacteria on the sample using ultrasound and culture the bacteria on an agar plate. After 24 hours, determine the antimicrobial adhesion (bacterial reduction rate).

[0126] The results are as follows Figure 7 and Figures 8A-8B As shown, compared with the LDPE control film, the AF08_MB#2_5% film of the present invention has significant bacteriostasis to both Escherichia coli and Staphylococcus aureus, wherein the bacteriostasis to Escherichia coli reaches 98.33%±0.02%, and the bacteriostasis to Staphylococcus aureus reaches 96.64%±0.04%.

[0127] Example 6: Food contact safety assessment test

[0128] In this example, a food contact safety assessment was conducted in accordance with FDA and EU regulations. Specifically, the AFPE plastic film AF08_MB#2_5% of the present invention was placed in different simulated liquids (3% acetic acid solution, 10% ethanol solution, 95% ethanol solution) and subjected to simulated leaching experiments at a fixed test temperature (40°C). The migration rates of the components specified in the safety assessment were calculated. Figure 9 It can be seen that the AFPE plastic film AF08_MB#2_5% of the present invention has passed the food contact safety assessment of EU and FDA at SGS.

[0129] Example 7: Preparation of plastic film with double antifogging agents and related tests

[0130] An anti-fog polyethylene (AFPE) plastic film was prepared by blown film extrusion using a low-density polyethylene resin (LDPE) with a weight ratio of 93%:7% and the anti-fog masterbatch AF_MB#1 containing dual anti-fog agents prepared in Example 2. The prepared plastic film was subjected to a water bath hot fog test according to the industrial standard GB / T 31726 "Test method for anti-fog performance of plastic films". The results showed that the anti-fog film AF_MB#1_7% can achieve an immediate anti-fog effect (G2-G3), and can still achieve an anti-fog effect of G2 in the water bath hot fog test after 100 water washes, showing water washability. The specific results are as follows: Figure 10As shown. 100 water washes can remove excess antifog agent from the plastic film surface, thereby making the water layer on the plastic film more evenly distributed. Therefore, the antifog grade of the antifog film after 100 water washes increased from G2-G3 to G2. In addition, the tensile strength at break of the AFPE plastic film prepared with this formula was 22.8±1.8MPa (n=5), the transparency of the AFPE plastic film was 89.3±0.5 (n=3), and the haze was 20.7±0.6 (n=3).

Claims

1. An anti-fog composition comprising, based on the total weight of the anti-fog composition: - 30% to 50%, preferably 35% to 45% of a first thermoplastic resin; - 10% to 30%, preferably 15% to 30%, of at least one antifogging agent; - 25% to 40%, preferably 30% to 35% of thermoplastic elastomer; - 0% to 10%, preferably 3% to 7% of a porous copolymer support.

2. The anti-fog composition according to claim 1, wherein The first thermoplastic resin is selected from one or more of polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA) and polyvinyl chloride (PVC), preferably polyethylene (PE), more preferably low-density polyethylene (LDPE).

3. The anti-fog composition according to claim 1 or 2, wherein The at least one anti-fog agent is an amphiphilic compound having multiple hydroxyl groups and a long-chain hydrophobic aliphatic group, preferably selected from fatty acid glycerides such as stearic acid glyceryl, monooleic acid glyceryl, fatty alcohol polyoxyethylene ethers such as polyoxyethylene lauryl ether, oleic acid alcohol esters, monostearate sorbitol, polyether oligomers such as polypropylene glycol, polyethylene glycol, octadecyl diethanolamine, more preferably fatty acid glycerides and fatty alcohol polyoxyethylene ethers, most preferably an amphiphilic compound having a structure of formula I or II:

4. The anti-fog composition according to any one of claims 1 to 3, wherein The anti-fog composition comprises a combination of two or more anti-fog agents, such as a combination of fatty acid glyceride and fatty alcohol polyoxyethylene ether.

5. The anti-fog composition according to any one of claims 1 to 4, wherein The thermoplastic elastomer is selected from ethylene-octene copolymer (POE), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene (SEPS), preferably styrene-ethylene-butylene-styrene (SEBS).

6. The anti-fog composition according to any one of claims 1 to 5, wherein The porous copolymer carrier is selected from ethylene butyl acrylate (EBA) porous copolymer carrier, linear low density polyethylene (LLDPE) porous copolymer carrier, low density polyethylene (LDPE) porous copolymer carrier, preferably low density polyethylene (LDPE) porous copolymer carrier.

7. The anti-fog composition according to any one of claims 1 to 6, wherein The anti-fog composition is prepared by mixing the components in a weight ratio and then subjecting them to twin-screw composite extrusion; preferably, the anti-fog composition is prepared in the form of anti-fog masterbatch.

8. An anti-fog plastic, made from the anti-fog composition according to any one of claims 1 to 7 and a second thermoplastic resin.

9. The anti-fog plastic according to claim 8, wherein Based on the total weight of the anti-fog plastic, the addition amount of the anti-fog composition is 1% to 10%, preferably 3% to 8%, and more preferably 3% to 5%.

10. The anti-fog plastic according to claim 8 or 9, wherein: The anti-fog plastic exhibits a surface bacteria-repellent effect with a bacteria-repellent rate of more than 90% against bacterial adhesion.

11. The anti-fog plastic according to claim 8 or 9, wherein: The second thermoplastic is selected from polyethylene (PE), polypropylene (PP), polyethylene vinyl acetate (EVA) and polyvinyl chloride (PVC), preferably polyethylene (PE), and more preferably the same as the first thermoplastic.

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