Mildew-proof, antibacterial and antiviral efficacy impregnated adhesive film paper and preparation process

Abstract

This invention provides an impregnated paper with anti-mildew, antibacterial, and antiviral properties, and its preparation process. The impregnated paper comprises the following raw materials by percentage: 0.8-1.4% plant extract, 45-57% film-forming resin, 1-1.5% calcium peroxide, 1-1.5% protamine, 0.5-0.8% capsid protein, 0.3-0.5% oligosaccharide chain protein, 3-4% nano-sepiolite, 0.8-1.2% calcium hypochlorite, 0.1-0.2% silver-loaded nanoparticles, 6-8% slow-release carrier, 0.6-0.8% photoinitiator, 0.3-0.5% surfactant, 3-4% plasticizer, 0.1-0.2% curing agent, 0.2-0.3% dispersant, 0.2-0.4% crosslinking agent, 0.2-0.3% moisture-proof agent, 0.2-0.4% antioxidant, 0.1-0.3% antistatic agent, and the balance being solvent. The combined effect of the components in this invention enables the impregnated film paper to possess excellent comprehensive properties such as mildew resistance, antibacterial properties, and antiviral properties, reducing the probability of bacterial and viral transmission and improving the practicality and safety of the impregnated film paper in decorative panels for underfloor heating environments, humid areas (such as bathroom cabinets), or medical facilities.

Description

Technical Field

[0001] This invention relates to the field of impregnated paper technology, specifically to an impregnated paper with anti-mildew, antibacterial and antiviral properties and its preparation process. Background Technology

[0002] Melamine-impregnated paper is a specially treated industrial paper primarily used for surface decoration in furniture and building materials. Its full name is melamine-impregnated paper, also known as "melamine" paper. Melamine-impregnated paper is mainly composed of non-woven wood pulp, polyethylene, and plant fibers. It features wear resistance, a wide variety of styles, impact resistance, stain resistance, moisture resistance, and environmental friendliness, and is widely used in furniture manufacturing, building decoration, and industrial materials.

[0003] Impregnated paper is an important material for the surface finish of engineered wood panels. It is typically made by impregnating patterned or solid-color decorative base paper with urea-formaldehyde resin or melamine-formaldehyde resin. It not only gives engineered wood panels an aesthetic appeal but also provides protection against wear, stains, corrosion, and scratches, making it widely used in furniture, flooring, and wall panels. However, impregnated paper performs poorly in terms of mold resistance, antibacterial properties, and antiviral activity. When used in underfloor heating environments, humid areas (such as bathroom cabinets), or in decorative panels for medical facilities, ordinary impregnated paper struggles to inhibit the growth of molds such as Aspergillus niger, leading to mold spots and discoloration on the surface layer, severely affecting aesthetics and structural strength. Furthermore, the surface of impregnated paper on interior decorative panels is prone to harboring pathogens such as Escherichia coli and Staphylococcus aureus, posing a risk of cross-infection. In addition, viruses can spread through aerosols attached to the surface of the impregnated paper on decorative panels, posing a threat to human safety. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention provides an impregnated paper with anti-mildew, antibacterial and antiviral properties, and its preparation process.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This application discloses an impregnated film paper with anti-mildew, antibacterial, and antiviral effects. The impregnated film paper comprises the following raw materials by percentage: 0.8-1.4% plant extract, 45-57% film-forming resin, 1-1.5% calcium peroxide, 1-1.5% protamine, 0.5-0.8% capsid protein, 0.3-0.5% oligosaccharide chain protein, 3-4% nano-sepiolite, 0.8-1.2% calcium hypochlorite, 0.1-0.2% silver-loaded nanoparticles, 6-8% slow-release carrier, 0.6-0.8% photoinitiator, 0.3-0.5% surfactant, 3-4% plasticizer, 0.1-0.2% curing agent, 0.2-0.3% dispersant, 0.2-0.4% crosslinking agent, 0.2-0.3% moisture-proof agent, 0.2-0.4% antioxidant, 0.1-0.3% antistatic agent, and the balance being solvent.

[0007] Preferably, the composition of the impregnated film paper, by percentage, includes the following raw materials: 1.1% plant extract, 51% film-forming resin, 1.2% calcium peroxide, 1.2% protamine, 0.6% capsid protein, 0.4% oligosaccharide chain protein, 3.5% nano-sepiolite, 1% calcium hypochlorite, 0.15% silver-loaded nanoparticles, 7% slow-release carrier, 0.7% photoinitiator, 0.4% surfactant, 3.5% plasticizer, 0.15% curing agent, 0.25% dispersant, 0.25% crosslinking agent, 0.25% moisture-proof agent, 0.3% antioxidant, 0.2% antistatic agent, and 26.85% solvent.

[0008] By employing the aforementioned technical solutions, the film-forming resin exhibits excellent mechanical strength and water resistance; calcium peroxide slowly releases oxygen and hydrogen peroxide, with hydrogen peroxide possessing strong oxidizing properties, capable of oxidizing and destroying the viral envelope and nucleic acid, thereby inactivating the virus; protamine, as a natural cationic antimicrobial peptide, can bind to anionic phospholipids on bacterial cell membranes, disrupting the cell membrane structure and causing leakage of bacterial contents, achieving broad-spectrum antibacterial activity; capsid proteins mimic the viral capsid structure, competitively binding to viral receptors on the host cell surface, blocking the adsorption process between the virus and the cell, thus preventing viral infection; oligosaccharide chain proteins can activate intracellular defense signaling pathways, inducing the production of antiviral proteins such as β-1,3-glucanase and chitinase, which can degrade the protective structure of the virus, inhibiting viral replication and spread; the unique porous structure of nano-sepiolite gives it a large specific surface area, allowing it to... It adsorbs microorganisms and can also serve as a carrier to load antibacterial components such as calcium hypochlorite and silver-loaded nanoparticles, achieving slow release and prolonging the antibacterial effect. Calcium hypochlorite releases hypochlorous acid upon contact with water. Hypochlorous acid has strong oxidizing properties and can oxidize the enzyme system, proteins, and nucleic acids of bacteria, rapidly killing bacteria and mold. Silver ions in the silver-loaded nanoparticles have broad-spectrum antiviral activity. They can bind to viral nucleic acids, interfering with viral genetic material replication and destroying the viral envelope, rendering it infective. The photoinitiator initiates the polymerization reaction of the film-forming resin under light conditions, causing the adhesive to quickly solidify into a film. The combined effect of these components gives the impregnated paper excellent comprehensive properties such as mildew resistance, antibacterial properties, and antiviral properties, reducing the probability of bacterial and viral transmission and improving the practicality and safety of impregnated paper in decorative panels for underfloor heating environments, humid areas (such as bathroom cabinets), or medical facilities.

[0009] Preferably, the plant extract is composed of the following raw materials according to the percentage of total components: betalain 0.3-0.5%, paeoniflorin 0.3-0.5% and linalool 0.2-0.4%.

[0010] By setting up the above technical solutions, betalain has antioxidant and antibacterial activities, can remove free radicals produced by microbial metabolism and inhibit microbial growth; paeoniflorin has inhibitory effects on a variety of fungi and can interfere with the physiological metabolic processes of fungal cells; linalool is volatile, and its odor can inhibit the germination and growth of mold spores, while also having a certain bactericidal effect.

[0011] The preferred method for extracting betaine is as follows:

[0012] a1. Take fresh beetroot, wash it, cut it into 2-3mm thin slices, dry it in a 50℃ oven until constant weight, and then crush it through a 60-mesh sieve.

[0013] a2. Using a 0.1% dilute hydrochloric acid solution, mix the finely powdered beetroot with 50% ethanol at a material-to-liquid ratio of 1:10, and ultrasonically extract for 30 minutes under the conditions of pH 4.5, temperature 50℃, power 400W, and frequency 40kHz.

[0014] a3. After cooling, the ultrasonic extract of beetroot is centrifuged at 3800 r / min for 10 min, and the supernatant is collected. The residue is extracted twice in the same way, and the supernatants are combined.

[0015] a4. The supernatant was concentrated to 1 / 5 of its original volume by a rotary evaporator at 45°C under reduced pressure. It was then filtered through a 0.45µm filter membrane and purified by macroporous adsorption resin column chromatography with a gradient elution of deionized water and ethanol to obtain betalain eluent.

[0016] The extraction method of paeoniflorin is as follows:

[0017] b1. Take peony root slices, pulverize them and pass them through a 50-mesh sieve, then dry them at 60℃ until the moisture content is <5%;

[0018] b2. A compound solution of 1.5% w / v cellulase and 0.8% w / v pectinase was used. The fine powder of peony root was mixed with the compound solution at a material-to-liquid ratio of 1:20. The mixture was treated for 2 hours at pH 4.5 and 50℃. Then, a 2.5% citric acid solution was used as the medium, and the mixture was treated intermittently with pulsed ultrasound at 40kHz and 400W for 30 minutes.

[0019] b3. Mix the enzymatic hydrolysate with 50% ethanol at a volume ratio of 1:15 and extract for 15 min at 60℃ and 600W microwave.

[0020] b4. Filter the extract while hot, concentrate the filtrate under reduced pressure until there is no alcohol odor, dissolve it in water, extract with ethyl acetate to remove impurities, pass the aqueous phase through a polyamide column, and elute with 20% ethanol to obtain the paeoniflorin eluent.

[0021] The extraction method of linalool is as follows:

[0022] c1. Take fresh lavender flowers, drain the water and chop them. Weigh 50g and place them in a distillation flask. Add 300mL of deionized water and heat with an electric heating mantle until boiling. Distill for 2 hours. Salt out the condensate with saturated NaCl solution.

[0023] c2. After the distillate is cooled, it is transferred to a separatory funnel to separate the oil phase. The oil phase is then transferred to a 20 mL headspace vial and extracted for 30 min under magnetic stirring at 40 °C and 500 r / min.

[0024] c3. The crude oil obtained by steam distillation is dried with anhydrous Na2SO4 and then distilled under reduced pressure at 4 kPa and 60-70℃ to collect the linalool fraction.

[0025] Preferably, the film-forming resin is composed of the following raw materials in terms of total component content: 25-30% polyethylene glycol diacrylate, 15-20% acrylic resin and 5-7% polyurethane resin.

[0026] By employing the aforementioned technical solutions, polyethylene glycol diacrylate can form a hydrophilic gel network through photo-initiated polymerization; acrylic resin imparts good mechanical strength and water resistance to the film paper; the combination of the two forms a high-performance film-forming matrix; the polyurethane resin molecular chain contains a large number of polar groups (such as urethane groups, urea groups, etc.), which can form hydrogen bonds or chemical bonds with the hydroxyl groups on the surface of paper fibers and substrates (such as wood, engineered wood), enhancing interfacial adhesion. The film-forming resin composed of polyethylene glycol diacrylate, acrylic resin, and polyurethane resin can effectively improve the comprehensive properties of impregnated film paper, including mechanical strength, flexibility, and water resistance.

[0027] Preferably, the sustained-release carrier is a β-cyclodextrin inclusion complex, the photoinitiator is benzoin dimethyl ether or Irgacure 184, the desiccant is silica aerogel, and the solvent is composed of water and ethanol in a volume ratio of 7:3.

[0028] By employing the aforementioned technical solutions, the sustained-release carrier (β-cyclodextrin inclusion complex) can encapsulate volatile or easily decomposable components such as linalool, paeoniflorin, betaine, and calcium hypochlorite, reducing their loss during preparation and storage, achieving slow release, and prolonging the duration of action. Silica aerogel can effectively absorb moisture, improving the moisture-proof performance of the film paper.

[0029] Preferably, the surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium diisooctyl succinate sulfonate; the plasticizer is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized linseed oil, polyethylene glycol, and sorbitol; the curing agent is one or more of ethylenediamine, diethylenetriamine, phthalic anhydride, maleic anhydride, and m-phenylenediamine; the dispersant is one or more of sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium silicate; the crosslinking agent is one of environmentally friendly citric acid, tea polyphenols, or N,N'-methylenebisacrylamide; the antioxidant is one or more of di-tert-butyl-p-cresol, dibutylhydroxytoluene, ascorbate palmitate, and propyl gallate; and the antistatic agent is one of octadecyltrimethylammonium chloride, dodecyl dimethyl benzyl ammonium chloride, or hexadecyltrimethylammonium chloride.

[0030] By setting up the above technical solution, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium diisooctyl succinate sulfonate are all anionic surfactants, which can reduce the surface tension of the system, improve the dispersibility of components, and promote the wetting of the adhesive to the substrate. Epoxidized soybean oil, epoxy fatty acid methyl ester, and epoxy linseed oil are epoxy plasticizers with good heat resistance and weather resistance, which can improve the stability of the film paper; polyethylene glycol and sorbitol are polyol plasticizers, which can increase the flexibility and hygroscopicity of the film paper. Ethylenediamine, diethylenetriamine, and m-phenylenediamine are amine curing agents that can undergo curing reactions with film-forming resins and other components; sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium silicate are inorganic dispersants that uniformly disperse the components in the system through electrostatic repulsion. Antioxidants can effectively prevent the oxidation and deterioration of plant extracts and various protein components, and improve the storage stability of the product. Antistatic agents can reduce the electrostatic adsorption of dust on the surface of the film paper, avoiding affecting the antibacterial and antiviral properties.

[0031] This application also discloses a preparation process for an impregnated paper with anti-mildew, antibacterial, and antiviral properties, comprising the following steps:

[0032] S1. Linalool, paeoniflorin, betaine, calcium hypochlorite, silver-loaded nanoparticles, and β-cyclodextrin inclusion complex are mixed, and an appropriate amount of 50°C warm water is added. The mixture is stirred for 1.5 hours and then spray-dried to obtain the inclusion complex powder.

[0033] S2. Mix calcium peroxide and nano sepiolite, add an appropriate amount of ethanol, disperse under ultrasonic conditions of 250W for 25min, and then dry at 60℃ to constant weight to obtain nano sepiolite composite.

[0034] S3. Add polyethylene glycol diacrylate, acrylic resin, and polyurethane resin to a mixed solvent of water and ethanol, and stir at 75°C until completely dissolved. Then add photoinitiator, surfactant, plasticizer, crosslinking agent, curing agent, and dispersant in sequence, and continue stirring for 30 minutes to ensure that all components are fully mixed.

[0035] S4. Add nano-sepiolite complex, protamine, capsid protein and oligosaccharide chain protein to the film-forming matrix solution obtained in S3, disperse under ultrasonic conditions of 300W for 40min to form a uniform and stable composite solution, control the solid content of the solution to be 28-30%, then add moisture-proof agent, antioxidant and antistatic agent, and stir evenly.

[0036] S5. Select 40g / m² polyester fiber nonwoven fabric as the substrate, dry it at 60℃ for 2h to remove moisture, and then perform corona treatment to improve the hydrophilicity and adhesion of the substrate surface. Immerse the pretreated substrate in the composite adhesive solution for 4min, and then roll off the excess adhesive solution with a roller at a pressure of 0.8MPa to make the roll-off rate 65-67%.

[0037] S6. Dry the impregnated substrate in a 65℃ hot air circulating oven for 8 minutes to remove most of the solvent. Irradiate it with a 365nm wavelength, 1200W ultraviolet lamp, and control the conveyor belt speed of the substrate to 1.5m / min to allow the polyethylene glycol diacrylate to crosslink and cure. Bake the UV-cured film paper at 85℃ for 15 minutes to completely cure the acrylic resin, thus obtaining the anti-mildew, antibacterial and antiviral impregnated film paper.

[0038] Preferably, in the spray drying method of step S1, the inlet air temperature is 180°C and the outlet air temperature is 80°C.

[0039] The beneficial effects of this invention are as follows:

[0040] The combined effect of the components in this invention enables the impregnated film paper to possess excellent comprehensive properties such as mildew resistance, antibacterial properties, and antiviral properties, reducing the probability of bacterial and viral transmission and improving the practicality and safety of the impregnated film paper in decorative panels for underfloor heating environments, humid areas (such as bathroom cabinets), or medical facilities.

[0041] Betalain has antioxidant and antibacterial activities, and can scavenge free radicals produced by microbial metabolism and inhibit microbial growth; paeoniflorin has inhibitory effects on a variety of fungi and can interfere with the physiological metabolic processes of fungal cells; linalool is volatile, and its odor can inhibit the germination and growth of mold spores, while also having a certain bactericidal effect. The plant extract composed of these three components has good antibacterial and bacteriostatic properties, which improves the anti-mildew and antibacterial properties of the prepared impregnated film paper.

[0042] Polyethylene glycol diacrylate (PEG) can form a hydrophilic gel network through photo-initiated polymerization; acrylic resin imparts good mechanical strength and water resistance to the film paper; the combination of the two can form a high-performance film-forming matrix; polyurethane resin molecules contain a large number of polar groups (such as urethane groups, urea groups, etc.), which can form hydrogen bonds or chemical bonds with the hydroxyl groups on the surface of paper fibers and substrates (such as wood, engineered wood products), enhancing interfacial adhesion. The film-forming resin composed of PEG, acrylic resin, and polyurethane resin can effectively improve the overall properties of impregnated film paper, such as mechanical strength, flexibility, and water resistance.

[0043] The sustained-release carrier (β-cyclodextrin inclusion complex) can encapsulate volatile or easily decomposed components such as linalool, paeoniflorin, betaine, and calcium hypochlorite, reducing their loss during preparation and storage, achieving slow release, and prolonging the duration of action. Silica aerogel can effectively absorb moisture, improving the moisture-proof performance of the film paper. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] Example 1: This example discloses an impregnated paper with anti-mildew, antibacterial, and antiviral properties. The impregnated paper comprises the following raw materials by percentage: betaine 0.3%, paeoniflorin 0.3%, linalool 0.2%, polyethylene glycol diacrylate 25%, acrylic resin 15%, polyurethane resin 5%, calcium peroxide 1%, protamine sulfate 1%, capsid protein 0.5%, oligosaccharide chain protein 0.3%, nano-sepiolite 3%, calcium hypochlorite 0.8%, silver-loaded nanoparticles 0.1%, β-cyclodextrin inclusion complex 6%, benzoin dimethyl ether 0.6%, surfactant 0.3%, plasticizer 3%, curing agent 0.1%, dispersant 0.2%, crosslinking agent 0.2%, silica aerogel 0.2%, antioxidant 0.2%, antistatic agent 0.1%, and solvent 36.6%.

[0046] The solvent is composed of water and ethanol in a volume ratio of 7:3.

[0047] The surfactant is sodium dodecyl sulfate, the plasticizer is epoxidized soybean oil, the curing agent is ethylenediamine, the dispersant is [missing information], the crosslinking agent is environmentally friendly citric acid, the antioxidant is di-tert-butyl-p-cresol, and the antistatic agent is octadecyltrimethylammonium chloride.

[0048] The extraction method for betalains is as follows:

[0049] a1. Take fresh beetroot, wash it, cut it into 2-3mm thin slices, dry it in a 50℃ oven until constant weight, and then crush it through a 60-mesh sieve.

[0050] a2. Using a 0.1% dilute hydrochloric acid solution, mix the finely powdered beetroot with 50% ethanol at a material-to-liquid ratio of 1:10, and ultrasonically extract for 30 minutes under the conditions of pH 4.5, temperature 50℃, power 400W, and frequency 40kHz.

[0051] a3. After cooling, the ultrasonic extract of beetroot is centrifuged at 3800 r / min for 10 min, and the supernatant is collected. The residue is extracted twice in the same way, and the supernatants are combined.

[0052] a4. The supernatant was concentrated to 1 / 5 of its original volume by a rotary evaporator at 45°C under reduced pressure. It was then filtered through a 0.45µm filter membrane and purified by macroporous adsorption resin column chromatography with a gradient elution of deionized water and ethanol to obtain betalain eluent.

[0053] The extraction method of paeoniflorin is as follows:

[0054] b1. Take peony root slices, pulverize them and pass them through a 50-mesh sieve, then dry them at 60℃ until the moisture content is <5%;

[0055] b2. A compound solution of 1.5% w / v cellulase and 0.8% w / v pectinase was used. The fine powder of peony root was mixed with the compound solution at a material-to-liquid ratio of 1:20. The mixture was treated for 2 hours at pH 4.5 and 50℃. Then, a 2.5% citric acid solution was used as the medium, and the mixture was treated intermittently with pulsed ultrasound at 40kHz and 400W for 30 minutes.

[0056] b3. Mix the enzymatic hydrolysate with 50% ethanol at a volume ratio of 1:15 and extract for 15 min at 60℃ and 600W microwave.

[0057] b4. Filter the extract while hot, concentrate the filtrate under reduced pressure until there is no alcohol odor, dissolve it in water, extract with ethyl acetate to remove impurities, pass the aqueous phase through a polyamide column, and elute with 20% ethanol to obtain the paeoniflorin eluent.

[0058] The extraction method of linalool is as follows:

[0059] c1. Take fresh lavender flowers, drain the water and chop them. Weigh 50g and place them in a distillation flask. Add 300mL of deionized water and heat with an electric heating mantle until boiling. Distill for 2 hours. Salt out the condensate with saturated NaCl solution.

[0060] c2. After the distillate is cooled, it is transferred to a separatory funnel to separate the oil phase. The oil phase is then transferred to a 20 mL headspace vial and extracted for 30 min under magnetic stirring at 40 °C and 500 r / min.

[0061] c3. The crude oil obtained by steam distillation is dried with anhydrous Na2SO4 and then distilled under reduced pressure at 4 kPa and 60-70℃ to collect the linalool fraction.

[0062] This embodiment also discloses a preparation process for an impregnated paper with anti-mildew, antibacterial, and antiviral properties, comprising the following steps:

[0063] S1. Linalool, paeoniflorin, betaine, calcium hypochlorite, silver-loaded nanoparticles, and β-cyclodextrin inclusion complex are mixed, and an appropriate amount of 50°C warm water is added. The mixture is stirred for 1.5 hours and then the inclusion complex powder is obtained by spray drying. The inlet air temperature is 180°C and the outlet air temperature is 80°C.

[0064] S2. Mix calcium peroxide and nano sepiolite, add an appropriate amount of ethanol, disperse under ultrasonic conditions of 250W for 25min, and then dry at 60℃ to constant weight to obtain nano sepiolite composite.

[0065] S3. Add polyethylene glycol diacrylate, acrylic resin, and polyurethane resin to a mixed solvent of water and ethanol, and stir at 75°C until completely dissolved. Then add photoinitiator, surfactant, plasticizer, crosslinking agent, curing agent, and dispersant in sequence, and continue stirring for 30 minutes to ensure that all components are fully mixed.

[0066] S4. Add nano-sepiolite complex, protamine, capsid protein and oligosaccharide chain protein to the film-forming matrix solution obtained in S3, disperse under ultrasonic conditions of 300W for 40min to form a uniform and stable composite solution, control the solid content of the solution to be 28-30%, then add moisture-proof agent, antioxidant and antistatic agent, and stir evenly.

[0067] S5. Select 40g / m² polyester fiber nonwoven fabric as the substrate, dry it at 60℃ for 2h to remove moisture, and then perform corona treatment (voltage 15kV, treatment time 30s) to improve the hydrophilicity and adhesion of the substrate surface. Immerse the pretreated substrate in the composite adhesive solution for 4min, and then roll off the excess adhesive solution with a roller at a pressure of 0.8MPa to achieve a roll-off rate of 65-67%.

[0068] S6. Dry the impregnated substrate in a 65℃ hot air circulating oven for 8 minutes to remove most of the solvent. Irradiate it with a 365nm wavelength, 1200W ultraviolet lamp, and control the conveyor belt speed of the substrate to 1.5m / min to allow the polyethylene glycol diacrylate to crosslink and cure. Bake the UV-cured film paper at 85℃ for 15 minutes to completely cure the acrylic resin, thus obtaining the anti-mildew, antibacterial and antiviral impregnated film paper.

[0069] Example 2: This example discloses an impregnated paper with anti-mildew, antibacterial, and antiviral properties. The differences compared to Example 1 are as follows:

[0070] The composition of this impregnated film paper, by percentage, includes the following raw materials: betaine 0.5%, paeoniflorin 0.5%, linalool 0.4%, polyethylene glycol diacrylate 30%, acrylic resin 20%, polyurethane resin 7%, calcium peroxide 1.5%, protamine 1.5%, capsid protein 0.8%, oligosaccharide chain protein 0.5%, nano sepiolite 4%, calcium hypochlorite 1.2%, silver-loaded nanoparticles 0.2%, β-cyclodextrin inclusion complex 8%, Irgacure 184 0.8%, surfactant 0.5%, plasticizer 4%, curing agent 0.2%, dispersant 0.3%, crosslinking agent 0.4%, silica aerogel 0.3%, antioxidant 0.4%, antistatic agent 0.3%, and solvent 16.7%.

[0071] The solvent is composed of water and ethanol in a volume ratio of 7:3.

[0072] The surfactant is sodium dodecylbenzenesulfonate, the plasticizer is epoxy fatty acid methyl ester, the curing agent is diethylenetriamine, the dispersant is sodium pyrophosphate, the crosslinking agent is tea polyphenols, the antioxidant is butylated hydroxytoluene, and the antistatic agent is dodecyl dimethyl benzyl ammonium chloride.

[0073] Example 3: This example discloses an impregnated paper with anti-mildew, antibacterial, and antiviral properties. Compared with Example 1, the differences are as follows:

[0074] The composition of this impregnated film paper, by percentage, includes the following raw materials: betaine 0.4%, paeoniflorin 0.4%, linalool 0.3%, polyethylene glycol diacrylate 27.5%, acrylic resin 17.5%, polyurethane resin 6%, calcium peroxide 1.2%, protamine 1.2%, capsid protein 0.6%, oligosaccharide chain protein 0.4%, nano sepiolite 3.5%, calcium hypochlorite 1%, silver-loaded nanoparticles 0.15%, β-cyclodextrin inclusion complex 7%, benzoin dimethyl ether 0.7%, surfactant 0.4%, plasticizer 3.5%, curing agent 0.15%, dispersant 0.25%, crosslinking agent 0.25%, moisture-proof agent 0.25%, antioxidant 0.3%, antistatic agent 0.2%, and solvent 26.85%.

[0075] The solvent is composed of water and ethanol in a volume ratio of 7:3.

[0076] The surfactant is sodium oleate, the plasticizer is epoxy linseed oil, the curing agent is phthalic anhydride, the dispersant is sodium tripolyphosphate, the crosslinking agent is N,N'-methylenebisacrylamide, the antioxidant is ascorbate palmitate, and the antistatic agent is hexadecyltrimethylammonium chloride.

[0077] Comparative Example 1: An impregnated paper with anti-mildew, antibacterial and antiviral effects. The only difference between this impregnated paper and Example 3 is that betalain is not added and an equal proportion of solvent is used instead.

[0078] Comparative Example 2: An impregnated paper with anti-mildew, antibacterial and antiviral effects. The only difference between this impregnated paper and Example 3 is that paeoniflorin was not added, and an equal proportion of solvent was used instead.

[0079] Comparative Example 3: An impregnated paper with anti-mildew, antibacterial and antiviral properties. The only difference between this impregnated paper and Example 3 is that linalool is not added, and an equal proportion of solvent is used instead.

[0080] Comparative Example 4: An impregnated paper with anti-mildew, antibacterial and antiviral properties. The only difference between this impregnated paper and Example 3 is that polyethylene glycol diacrylate is not added, and an equal proportion of solvent is used instead.

[0081] Comparative Example 5: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that: no acrylic resin is added, and an equal proportion of solvent is used instead.

[0082] Comparative Example 6: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that: no polyurethane resin is added, and an equal proportion of solvent is used instead.

[0083] Comparative Example 7: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that calcium peroxide is not added, and an equal proportion of solvent is used instead.

[0084] Comparative Example 8: An impregnated paper with anti-mildew, antibacterial and antiviral effects, the only difference between this impregnated paper and Example 3 is that: no protamine was added, and an equal proportion of solvent was used instead.

[0085] Comparative Example 9: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that: no capsid protein is added, and an equal proportion of solvent is used instead.

[0086] Comparative Example 10: An impregnated paper with anti-mildew, antibacterial and antiviral effects, the only difference between this impregnated paper and Example 3 is that: no oligosaccharide chain protein is added, and an equal proportion of solvent is used instead.

[0087] Comparative Example 11: An impregnated paper with anti-mildew, antibacterial and antiviral effects. The only difference between this impregnated paper and Example 3 is that: no nano sepiolite was added, and an equal proportion of solvent was used instead.

[0088] Comparative Example 12: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that calcium hypochlorite is not added, and an equal proportion of solvent is used instead.

[0089] Comparative Example 13: An impregnated paper with anti-mildew, antibacterial and antiviral effects. The only difference between this impregnated paper and Example 3 is that silver nanoparticles are not added, and an equal proportion of solvent is used instead.

[0090] Comparative Example 14: An impregnated paper with anti-mildew, antibacterial and antiviral properties, the only difference between this impregnated paper and Example 3 is that: no β-cyclodextrin inclusion complex was added, and an equal proportion of solvent was used instead.

[0091] This application conducted tests on the impregnated films obtained in Examples 1-3 and Comparative Examples 1-14 regarding their anti-mildew, antibacterial, and antiviral properties, as detailed below:

[0092] I. Anti-mildew performance test

[0093] 1. Testing standard: Refer to GB / T 2423.16-2008 "Environmental testing of electrical and electronic products - Part 2: Test methods and guidelines: Mold growth".

[0094] 2. Testing Methods

[0095] Preparation of test samples: Cut the impregnated paper of Examples 1-3 and Comparative Examples 1-14 into 50mm×50mm samples, and prepare 3 parallel samples for each group.

[0096] Inoculation with mold: Select common mold strains such as Aspergillus niger, Penicillium cordifolium, and budding short-stemmed mold, and prepare a solution with a concentration of 10. 6 -10 8 A spore suspension of CFU / mL was prepared and evenly sprayed onto the sample surface using a sterile sprayer.

[0097] Culture: The inoculated samples were placed in a constant temperature and humidity incubator at a temperature of 28±1℃ and a relative humidity of 95±2% for 28 days.

[0098] Observation and rating: After the culture is completed, the growth of mold on the sample surface is observed by the naked eye and rated according to the 0-4 standard (0: no mold growth; 1: mold coverage area <10%; 2: mold coverage area 10-30%; 3: mold coverage area 30-60%; 4: mold coverage area >60%).

[0099] II. Antibacterial Performance Test

[0100] 1. Testing standard: Refer to GB / T 21551.2-2010 "Special requirements for antibacterial materials with antibacterial, sterilization and purification functions for household and similar electrical appliances".

[0101] 2. Testing Methods

[0102] Bacterial strains selected: Escherichia coli and Staphylococcus aureus.

[0103] Preparation of bacterial suspension: Inoculate the bacterial strain into nutrient broth medium, incubate at 37°C for 24 hours, and dilute with sterile physiological saline to a concentration of approximately 10. 5 -10 6 CFU / mL.

[0104] Sample preparation: Cut the samples into 25mm × 25mm pieces, with 3 replicates per group, and place them in sterile petri dishes. Add 2mL of bacterial suspension to the petri dish to completely saturate the sample. The control group is prepared with the same volume of bacterial suspension but without the sample.

[0105] Culture: Place the petri dish in a 37℃ constant temperature incubator and culture for 24 hours.

[0106] Colony counting: After incubation, place the sample into a test tube containing 10 mL of sterile physiological saline and shake for 2 min to elute the bacteria. Count the colonies in the eluent using the dilution plating method and calculate the antibacterial rate. Antibacterial rate (%) = (number of colonies in the control group - number of colonies in the experimental group) / number of colonies in the control group × 100%.

[0107] III. Antiviral Performance Test

[0108] 1. Testing standard: Refer to ISO 18184:2019 "Determination of antiviral properties of textiles".

[0109] 2. Testing Methods

[0110] Virus selection: Influenza A virus (H1N1).

[0111] Preparation of virus suspension: In a biosafety laboratory, the virus is cultured in a suitable cell line, the virus suspension is harvested, and diluted to an appropriate concentration with phosphate-buffered saline (PBS).

[0112] Sample preparation: Cut the samples to a suitable size, with 3 parallel samples per group, and place them in the wells of a sterile culture plate. Add an appropriate amount of virus suspension to the wells to completely saturate the samples. The control group is prepared with the same volume of virus suspension but without the sample.

[0113] Function: Place the culture plate in a 37℃, 5% CO2 incubator for 2 hours.

[0114] Virus inactivation assay: After the reaction, the sample was placed in a test tube containing an appropriate amount of cell maintenance medium and shaken to elute the virus. The virus titer was determined using the plaque reduction method, and the virus inactivation rate was calculated as follows: Virus inactivation rate (%) = (Control group virus titer - Experimental group virus titer) / Control group virus titer × 100%.

[0115] III. Test Results

[0116] The results are shown in Table 1.

[0117] Table 1 Performance parameters of the impregnated paper obtained in Examples 1-3 and Comparative Examples 1-14

[0118]

[0119] As shown in Table 1:

[0120] As can be seen from Comparative Examples 1-2 and Example 3, the absence of betaine and paeoniflorin has a certain impact on the anti-mildew and antibacterial properties of the impregnated paper, but has no significant impact on the antiviral properties of the impregnated paper.

[0121] As can be seen from Comparative Example 3 and Example 3, the absence of linalool significantly affects the mildew resistance of the impregnated paper, and has a certain impact on both the mildew resistance and antibacterial properties of the impregnated paper, but has no significant impact on the antiviral properties of the impregnated paper.

[0122] As can be seen from Comparative Examples 4-6 and Example 3, the absence of polyethylene glycol diacrylate, acrylic resin and polyurethane resin has no significant impact on the antifungal, antibacterial and antiviral properties of the impregnated film paper.

[0123] As shown in Comparative Examples 7-10, Comparative Example 14, and Example 3, the absence of calcium peroxide, protamine, capsid protein, oligosaccharide chain protein, and β-cyclodextrin inclusion complex all have a certain impact on the antifungal properties of the impregnated paper. Specifically, the absence of β-cyclodextrin inclusion complex has a certain impact on the antibacterial properties of the impregnated paper; the absence of calcium peroxide, capsid protein, and oligosaccharide chain protein has a significant impact on the antiviral properties of the impregnated paper; and the absence of protamine has a significant impact on the antibacterial properties of the impregnated paper.

[0124] As can be seen from Comparative Examples 11-13 and Example 3, the absence of nano-sepiolite, calcium hypochlorite and silver-loaded nanoparticles significantly affects the anti-mildew and antibacterial properties of the impregnated paper, and the absence of silver-loaded nanoparticles also significantly affects the antiviral properties of the impregnated paper.

[0125] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A type of impregnated paper with anti-mildew, antibacterial, and antiviral properties, characterized in that, Using polyester fiber nonwoven fabric as the base material, it is impregnated with a composite adhesive that is mildew-proof, antibacterial, and antiviral. The composite adhesive comprises the following raw materials by percentage: 0.8-1.4% plant extracts, 45-57% film-forming resin, 1-1.5% calcium peroxide, 1-1.5% protamine, 0.5-0.8% capsid protein, 0.3-0.5% oligosaccharide chain protein, 3-4% nano-sepiolite, 0.8-1.2% calcium hypochlorite, 0.1-0.2% silver-loaded nanoparticles, 6-8% slow-release carrier, 0.6-0.8% photoinitiator, 0.3-0.5% surfactant, 3-4% plasticizer, 0.1-0.2% curing agent, 0.2-0.3% dispersant, 0.2-0.4% crosslinking agent, 0.2-0.3% moisture-proof agent, 0.2-0.4% antioxidant, 0.1-0.3% antistatic agent, with the remainder being solvent. Based on the percentage of total components, the plant extract consists of the following raw materials: betaine 0.3-0.5%, paeoniflorin 0.3-0.5%, and linalool 0.2-0.4%; Based on the total component content, the film-forming resin is composed of the following raw materials: 25-30% polyethylene glycol diacrylate, 15-20% acrylic resin, and 5-7% polyurethane resin; The sustained-release carrier is a β-cyclodextrin inclusion complex, the photoinitiator is benzoin dimethyl ether or Irgacure 184, the desiccant is silica aerogel, and the solvent is composed of water and ethanol in a volume ratio of 7:

3.

2. The anti-mildew, antibacterial, and antiviral impregnated paper according to claim 1, characterized in that: The extraction method for betalains is as follows: a1. Take fresh beetroot, wash it, cut it into 2-3mm thin slices, dry it in a 50℃ oven until constant weight, and then crush it through a 60-mesh sieve. a2. Using a 0.1% dilute hydrochloric acid solution, mix finely powdered beetroot with 50% ethanol at a material-to-liquid ratio of 1:10, and ultrasonically extract for 30 minutes under the conditions of pH 4.5, temperature 50℃, power 400W, and frequency 40kHz. a3. After cooling, the ultrasonic extract of beetroot is centrifuged at 3800 r / min for 10 min, and the supernatant is collected. The residue is extracted twice in the same way, and the supernatants are combined. a4. The supernatant was concentrated to 1 / 5 of its original volume under reduced pressure at 45°C using a rotary evaporator, filtered through a 0.45µm filter membrane, and purified by macroporous adsorption resin column chromatography with a gradient elution of deionized water and ethanol to obtain betalain eluent. The extraction method of paeoniflorin is as follows: b1. Take peony root slices, pulverize them and pass them through a 50-mesh sieve, then dry them at 60℃ until the moisture content is <5%; b2. A compound solution of 1.5% w / v cellulase and 0.8% w / v pectinase was used. The fine powder of peony root was mixed with the compound solution at a material-to-liquid ratio of 1:

20. The mixture was treated for 2 hours at pH 4.5 and 50℃. Then, a 2.5% citric acid solution was used as the medium, and the mixture was treated intermittently with pulsed ultrasound at 40kHz and 400W for 30 minutes. b3. Mix the enzymatic hydrolysate with 50% ethanol at a volume ratio of 1:15 and extract for 15 min at 60℃ and 600W microwave. b4. Filter the extract while hot, concentrate the filtrate under reduced pressure until there is no alcohol odor, dissolve it in water, extract with ethyl acetate to remove impurities, pass the aqueous phase through a polyamide column, and elute with 20% ethanol to obtain the paeoniflorin eluent. The extraction method of linalool is as follows: c1. Take fresh lavender flowers, drain the water and chop them. Weigh 50g and place them in a distillation flask. Add 300mL of deionized water and heat with an electric heating mantle until boiling. Distill for 2 hours. Salt out the condensate with saturated NaCl solution. c2. After the distillate is cooled, it is transferred to a separatory funnel to separate the oil phase. The oil phase is then transferred to a 20 mL headspace vial and extracted for 30 min under magnetic stirring at 40 °C and 500 r / min. c3. The crude oil obtained by steam distillation is dried with anhydrous Na2SO4 and then distilled under reduced pressure at 4 kPa and 60-70℃ to collect the linalool fraction.

3. The mildew-proof, antibacterial and antiviral efficacy impregnated gum film paper as claimed in claim 1, wherein, The surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium diisooctyl succinate sulfonate; the plasticizer is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized linseed oil, polyethylene glycol, and sorbitol; the curing agent is one or more of ethylenediamine, diethylenetriamine, phthalic anhydride, maleic anhydride, and m-phenylenediamine; the dispersant is one or more of sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium silicate; the crosslinking agent is one of environmentally friendly citric acid, tea polyphenols, or N,N'-methylenebisacrylamide; the antioxidant is one or more of di-tert-butyl-p-cresol, dibutylhydroxytoluene, ascorbate palmitate, and propyl gallate; and the antistatic agent is one of octadecyltrimethylammonium chloride, dodecyl dimethyl benzyl ammonium chloride, or hexadecyltrimethylammonium chloride.

4. A preparation process for an impregnated paper with anti-mildew, antibacterial, and antiviral properties as described in claim 3, characterized in that, The preparation process includes the following steps: S1. Linalool, paeoniflorin, betaine, calcium hypochlorite, silver-loaded nanoparticles, and β-cyclodextrin inclusion complex are mixed, and an appropriate amount of 50°C warm water is added. The mixture is stirred for 1.5 hours and then spray-dried to obtain the inclusion complex powder. S2. Mix calcium peroxide and nano sepiolite, add an appropriate amount of ethanol, disperse under ultrasonic conditions of 250W for 25min, and then dry at 60℃ to constant weight to obtain nano sepiolite composite. S3. Add polyethylene glycol diacrylate, acrylic resin, and polyurethane resin to a mixed solvent of water and ethanol, and stir at 75°C until completely dissolved. Then add photoinitiator, surfactant, plasticizer, crosslinking agent, curing agent, and dispersant in sequence, and continue stirring for 30 minutes to ensure that all components are fully mixed. S4. Add nano-sepiolite complex, protamine, capsid protein and oligosaccharide chain protein to the film-forming matrix solution obtained in S3, disperse under ultrasonic conditions of 300W for 40min to form a uniform and stable composite solution, control the solid content of the solution to be 28-30%, then add moisture-proof agent, antioxidant and antistatic agent, and stir evenly. S5. Select 40g / m² polyester fiber nonwoven fabric as the substrate, dry it at 60℃ for 2h to remove moisture, and then perform corona treatment to improve the hydrophilicity and adhesion of the substrate surface. Immerse the pretreated substrate in the composite adhesive solution for 4min, and then roll off the excess adhesive solution with a roller at a pressure of 0.8MPa to make the roll-off rate 65-67%. S6. Dry the impregnated substrate in a 65℃ hot air circulating oven for 8 minutes to remove most of the solvent. Irradiate it with a 365nm wavelength, 1200W ultraviolet lamp, and control the conveyor belt speed of the substrate to 1.5m / min to crosslink and cure the polyethylene glycol diacrylate. Bake the UV-cured film paper at 85℃ for 15 minutes to completely cure the acrylic resin, thus obtaining the anti-mildew, antibacterial and antiviral impregnated film paper.

5. The process for the preparation of anti-mildew, anti-bacterial, anti-viral efficacy impregnated gum film paper as claimed in claim 4, wherein, In the spray drying method of step S1, the inlet air temperature is 180℃ and the outlet air temperature is 80℃.

6. The preparation process of the anti-mildew, antibacterial, and antiviral impregnated film paper according to claim 4, characterized in that, In step S5, the voltage for corona treatment is 15kV and the treatment time is 30s.

Images