Bacteriostatic and antiviral bamboo pulp paper-based sanitary isolation bag as well as preparation method and application thereof

Abstract

The invention discloses a bacteriostatic and antiviral bamboo pulp paper-based sanitary isolation bag as well as a preparation method and application thereof, and belongs to the field of functional paper-based packaging materials. The isolation bag takes bamboo pulp fiber paper as a base material, and the surface of the isolation bag is coated with a water-based polyhydroxyalkanoate functional coating. According to the preparation method, a special polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor is introduced, and the problem of agglomeration of nano particles is effectively solved by utilizing the special bridging effect of polyphenol, so that high-density cation capture and oxidation inactivation sites are constructed on the surface of the coating. Compared with the prior art, the method has the advantages that the method does not need to depend on organic fluorine compounds, and the excellent waterproof and oil-proof barrier effect and the efficient inactivation of viruses can be achieved only through the extremely low coating amount. In addition, the isolation bag has unique environmental chemical responsiveness, can be efficiently dissociated under the alkaline condition to facilitate repulping recovery, can be completely biodegraded in the natural environment, and perfectly considers the requirements of biological safety protection and green environmental protection.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional paper-based packaging materials, and particularly relates to a bacteriostatic and antiviral bamboo pulp paper-based health isolation bag and a preparation method and application thereof. BACKGROUND

[0002] With the promotion of "plastic limit order" and green low-carbon development goals, the demand for paper-based packaging materials with cellulose as the matrix, which have barrier properties, reslurry properties and degradability, continues to grow in the hotel, catering and medical industries. Although traditional polyethylene (PE), polypropylene (PP) composite film bags and paper-plastic composite bags can provide certain waterproof and oil-proof performance, they are difficult to separate in the regeneration pulp line and are prone to form adhesives, and their biological safety protection ability is limited. In the prior art, in order to solve the problem of insufficient barrier properties of paper-based materials, various water-based dispersions or emulsion systems with polyhydroxyalkanoate (PHA) as the main film-forming body have appeared. For example, Chinese Patent CN119912795B discloses a pure bio-based water-based dispersion with PHA as the main film-forming material, which can be used for paper-based barrier coatings, adhesives and degradable films by stabilizing the emulsion with solid particles and surfactants. The product has both compostability and reslurry properties, but does not introduce an efficient inhibition or inactivation mechanism for enveloped viruses, nor does it limit bamboo pulp fiber paper-based materials. For another example, Chinese Patent CN120026524B discloses a ternary blended water-based emulsion of PHA, polybutylene adipate / terephthalate (PBAT) and polyvinyl alcohol (PVOH) and its application in paper-based barrier coatings. By forming a PHA, PBAT and PVOH composite film layer on the surface of the paper, the Cobb value and Kit oil-proof grade are improved, and the reslurry efficiency is improved by using the solubility of PVOH in an alkaline pulp tank at room temperature. This technology focuses on solving the balance problem of barrier property, toughness and recyclability, and does not involve bamboo pulp fiber paper as a special substrate and bacteriostatic and antiviral health isolation scenarios. Zhongke Union Chemical and other subjects also disclose a nano-scale paper-based barrier emulsion and a multi-layer controllable degradable coating composition with PHA and PVOH as the main film-forming resins, which further improve the water resistance, oil resistance and degradation properties of paper-based packaging materials, but also do not report a technical solution for synergistically constructing an antiviral active interface with chitosan quaternary ammonium salt (HACC), polyphenol derivatives and nano-zinc oxide (NanoZnO).

[0003] On the other hand, there are many technologies that use bamboo pulp or other plant fibers to improve the environmental friendliness of paper products. For example, there are disclosed graphene oxide antibacterial packaging papers, such as Chinese Patent CN108867189A, which uses wood pulp and bamboo pulp as fiber raw materials, and introduces graphene oxide during the papermaking stage to give the packaging paper the ability to inhibit common bacteria; there is also a utility model CN205443788U which discloses that the bamboo pulp fiber paper or other filter material is treated with antifungal and antibacterial to be used as a humidifying filter screen to improve the hygiene performance of the product. However, the above-mentioned technologies mainly use bamboo pulp fiber and inorganic nano filler to improve the antibacterial or antifungal ability of paper, and do not couple the bamboo pulp paper base with the water-based PHA barrier coating, nor do they systematically consider the synergistic mechanism of pulp separation and end-of-life composting. There are still a large number of antibacterial or antiviral materials based on chitosan, NanoZnO and polyphenols in the prior art. Some composite materials, such as Al-Naamani et al. in Innovative Food Science & Emerging Technologies, use chitosan to coat NanoZnO particles to improve the dispersion stability of NanoZnO and increase the inhibition effect on bacteria; some technologies, such as Bharathi et al. in International Journal of Biological Macromolecules, report that chitosan and NanoZnO hybrid materials can reduce the photocatalytic activity and retain the antibacterial performance by controlling the coating layer on the surface of NanoZnO, which are used for medical or nursing supplies. In addition, many papers, such as Yadav et al. in the journal Food Chemistry, propose a food packaging film based on chitosan as a matrix and modified NanoZnO composite particles loaded with gallic acid (GA), which uses the coordination of GA on the surface of NanoZnO and the film-forming property of chitosan to synergistically improve the antibacterial activity and antioxidant performance; there are also reports that GA or other polyphenols, quaternary ammonium polymers and metal oxides are combined to be applied to active packaging or antibacterial film systems. The above-mentioned technologies show that GA, chitosan and NanoZnO hybrid structures have a certain basis in efficient bacteriostasis, but are mostly based on self-supporting films or fabric coating systems, and chitosan is mostly non-quaternized chitosan or not coupled with the water-based PHA paper base barrier system, and is not integrated with water-based PHA emulsion and paper base repulping process. In addition, for the end-of-life disposal of packaging materials, some studies point out that pure PHA melt-coated paper is difficult to completely separate from the fiber surface under standard paper mill repulping conditions, and plastic particles are easily formed, which affects the stability of the paper machine; paper base coatings based on PVOH or nanocellulose have certain barrier properties, but they are easily lost under high humidity or long-term water vapor contact conditions, and do not take into account the contact inactivation function of enveloped viruses.

[0004] In summary, the prior art has made progress in water-based PHA paper-based barrier coating, bamboo pulp fiber paper antibacterial packaging, and GA, chitosan, NanoZnO hybrid antibacterial materials, but there is no water-based PHA barrier layer without PVOH film-forming resin on the bamboo pulp fiber paper base, and the introduction of GA-HACC-NanoZnO organic-inorganic hybrid factor and environmental chemical response interface structure in the same coating system, so as to realize the system solution of paper-based health isolation bag with high barrier property, high efficient bacteriostatic and antiviral, re-pulping separation and composting degradation ability under the condition of dry coating amount of 3-8g / m². SUMMARY

[0005] The purpose of the present application is to overcome the shortcomings of the prior art, provide a bacteriostatic and antiviral bamboo pulp paper-based health isolation bag and its preparation method and application, which has excellent barrier performance and high efficient bacteriostatic and antiviral ability, and can meet the environmental protection requirements of fluorine-free, re-pulping separation and composting degradation.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] A bacteriostatic and antiviral bamboo pulp paper-based health isolation bag, comprising a bag body made of a bamboo pulp fiber paper base and a sealing assembly, at least one side surface of the bamboo pulp fiber paper base is covered with a water-based PHA barrier bacteriostatic and antiviral coating; the coating is formed by curing a coating composition of PHA water-based dispersion and a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor, the coating forms a continuous and dense hydrophobic barrier layer on the surface of the bamboo pulp fiber, and the hybrid factor constructs cation capture and oxidation inactivation active sites on the surface of the coating through the bridging action of the polyphenol derivative, and the TOF content of the coating and the health isolation bag is less than 5mg / kg.

[0008] The basis weight of the bamboo pulp fiber paper base is 35-280g / m², which can be 35g / m², 40g / m², 45g / m², 50g / m², 60g / m², 70g / m², 80g / m², 100g / m², 120g / m², 150g / m², 180g / m², 200g / m², 250g / m² or 280g / m², and the mass fraction of bamboo pulp fiber is ≥70%, which can be 70%, 75%, 80%, 85%, 90%, 95% or 100%, and is treated by calendering or surface sizing.

[0009] The water-based PHA barrier bacteriostatic and antiviral coating is arranged on the inner surface of the bamboo pulp fiber paper base; or arranged on the inner surface and the outer surface at the same time.

[0010] The dry coating amount of the water-based PHA antibacterial and antiviral coating is 3-8 g / m2, and can be 3.0 g / m2, 3.5 g / m2, 4.0 g / m2, 4.5 g / m2, 5.0 g / m2, 5.5 g / m2, 6.0 g / m2, 6.5 g / m2, 7.0 g / m2, 7.5 g / m2 or 8.0 g / m2.

[0011] The PHA aqueous dispersion is prepared from PHA;

[0012] The PHA is selected from short-chain PHA, medium-chain PHA or a copolymer formed between short-chain PHA monomers and medium-chain PHA monomers; the short-chain PHA is selected from one or more of poly-3-hydroxybutyrate (PHB), poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (PHBH), poly-3-hydroxybutyrate-co-4-hydroxybutyrate (P34HB); the medium-chain PHA is selected from one or more of poly-3-hydroxyhexanoate, poly-3-hydroxyheptanoate, poly-3-hydroxyoctanoate, poly-3-hydroxynonanoate, poly-3-hydroxydecanoate, poly-3-hydroxyundecanoate, poly-3-hydroxydodecanoate, poly-3-hydroxylaurate, poly-3-hydroxystearate and copolymers thereof; the solid content of the PHA aqueous dispersion is 30-55 wt%, and can be 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% or 55 wt%. 50 The particle size is 0.2-2.0 μm, and can be 0.2 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm or 2.0 μm.

[0013] The polyphenol derivative is GA, the hybrid factor is a GA-HACC-NanoZnO hybrid network, and the preparation of the polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor comprises:

[0014] a) preparing an aqueous HACC solution and adjusting the pH to 5.0-7.5 to obtain an HACC solution;

[0015] b) slowly adding a polyphenol derivative solution to the HACC solution and stirring until a uniform and stable pre-complexing system is formed to obtain a pre-complexing system;

[0016] c) adding a NanoZnO aqueous dispersion to the pre-complexing system and performing shearing dispersion until a uniform and stable organic-inorganic hybrid colloid is formed to obtain a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor;

[0017] The mass ratio of the polyphenol derivative to HACC is 0.05-0.30:1, and specifically can be 0.05:1, 0.08:1, 0.10:1, 0.12:1, 0.15:1, 0.18:1, 0.20:1, 0.25:1 or 0.30:1; the mass ratio of NanoZnO to HACC is 0.10-0.60:1, and specifically can be 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1, 0.50:1, 0.55:1 or 0.60:1.

[0018] The water-based PHA barrier antibacterial and antiviral coating has environmental chemical responsiveness, including the following properties: an alkaline-induced interface dissociation property, which is that, under the conditions of pH≥9 and temperature≥40℃ in a water medium pulping condition, the PHA coating is hydrolyzed, swelled and embrittled, or the interfacial compatibilizer is ionized, swelled and induced to hydrate the interface, so that the coating is detached from the fiber surface in the form of particles or flakes, and the fiber interface dissociation rate measured under the conditions is≥95%; and an enzymatic mineralization property, which is that, in a biologically active soil or compost environment, the ester bond of PHA is broken under the action of PHA depolymerase, the glycosidic bond of bamboo pulp fiber is broken under the action of cellulase, and is further mineralized into carbon dioxide and water after microbial metabolism.

[0019] Under predetermined test conditions, the performance of the hygiene isolation bag simultaneously meets the following indexes: Cobb 60 ≤9g / m²; Kit oil-proof grade≥10; the blocking or inactivation rate for enveloped viruses≥99.9%; the total organic fluorine content measured according to the total organic fluorine test method is less than 5mg / kg.

[0020] The sealing assembly is a self-adhesive sealing strip, a pressure-sensitive adhesive sealing strip, a zipper sealing structure, or a direct heat sealing structure realized by the thermoplasticity of the water-based PHA barrier antibacterial and antiviral coating itself; if an adhesive is used, the pressure-sensitive adhesive or heat sealing adhesive is a water-based system or a biodegradable system.

[0021] The water-based PHA barrier antibacterial and antiviral coating further comprises an organic modified nano-montmorillonite and an interfacial compatibilizer, and the coating comprises, in terms of solid mass parts, PHA 70-85, specifically 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts or 85 parts; polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor 10-15 parts, specifically 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts; organic modified nano-montmorillonite 3-6 parts, specifically 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, 5.5 parts or 6.0 parts; interfacial compatibilizer 2-5 parts, specifically 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts or 5.0 parts.

[0022] The organic modified nano-montmorillonite has a sheet length-diameter ratio ≥ 50.

[0023] The interfacial compatibilizer contains ionized groups or hydrated groups, and is selected from PVOH and carboxylated derivatives thereof without organic fluorine structure, carboxymethyl cellulose (CMC), cationic starch, carboxylated starch or water-based resin containing carboxylate structure, and the amount of the interfacial compatibilizer in the coating is 2-5 parts by solid mass, specifically 2 parts, 3 parts, 4 parts or 5 parts.

[0024] The film-forming resin phase of the water-based PHA barrier antibacterial and antiviral coating is composed of PHA and a second film-forming polymer, and the PHA accounts for 40-95 wt% of the total mass of the film-forming resin phase, specifically 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt%, and the second film-forming polymer accounts for 5-60 wt%, specifically 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% or 60 wt%.

[0025] The second film-forming polymer is selected from one or more of the following types of polymers: acrylic polymers or copolymers obtained by emulsion polymerization of one or more monomers of acrylic acid, methacrylic acid and C1-C8 alkyl esters thereof, hydroxyalkyl acrylate or methacrylate, styrene, acrylonitrile; water-based polyurethane dispersions obtained by polyaddition of aliphatic or cycloaliphatic diisocyanates with polyester diols, polyether diols or polycarbonate diols and dispersed in water; water dispersions of bio-based polyesters or copolymers thereof obtained by polycondensation of one or more diacids of succinic acid, glutaric acid, adipic acid, oxalic acid with one or more diols of ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, isosorbide; water dispersions of polylactic acid (PLA) or copolymers thereof obtained by ring-opening polymerization of lactic acid; polyolefin dispersions obtained by emulsification or dispersion of ethylene, propylene or copolymers thereof; and water dispersions of cellulose derivatives or modified products thereof obtained by carboxymethylation, hydroxypropylation or quaternization modification of cellulose molecules; the second film-forming polymer does not include PVOH and copolymers thereof.

[0026] The second film-forming polymer is a bio-based polyester or an acrylic polymer; the phase state of the second film-forming polymer and the PHA in the coating is a continuous phase-dispersed phase structure or an interpenetrating network structure.

[0027] The application also provides a bacteriostatic and antiviral bamboo pulp paper-based coated paper, which comprises a bamboo pulp fiber paper base and an aqueous PHA barrier bacteriostatic and antiviral coating arranged on at least one side surface of the bamboo pulp fiber paper base; the coating is formed by curing a coating composition formed by a PHA aqueous dispersion and a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor.

[0028] The application also provides an aqueous film-forming coating composition for bamboo pulp paper-based hygiene isolation coating, which at least comprises a film-forming resin phase, a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor and water; the film-forming resin phase is composed of PHA and a second film-forming polymer, wherein the PHA accounts for 40-95wt% of the total mass of the film-forming resin phase, specifically 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt% or 95wt%, and the second film-forming polymer accounts for 5-60wt% of the total mass of the film-forming resin phase, specifically 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%; the second film-forming polymer is selected from one or more of the above-mentioned second film-forming polymers.

[0029] The application also provides a preparation method of the hygiene isolation bag, which comprises the following steps:

[0030] Step 1. Provide a bamboo pulp fiber paper base raw paper, which is a raw paper treated by calendering and / or surface sizing, or a raw bamboo pulp fiber paper base raw paper is treated by calendering or surface sizing pretreatment to obtain a pretreated bamboo pulp fiber paper base raw paper;

[0031] Step 2. Prepare a water-based PHA barrier antibacterial and antiviral coating, mix a PHA water-based dispersion with a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor, and add a nano-layered barrier filler and an interfacial compatibilizer, and then disperse by shearing to obtain a stable coating, thereby obtaining a water-based PHA barrier antibacterial and antiviral coating; wherein the film-forming resin phase of the stable coating is PHA, or a blend system of PHA and a second film-forming polymer;

[0032] Step 3. The water-based PHA barrier antibacterial and antiviral coating is applied to the surface of the pretreated bamboo pulp fiber paper base raw paper by means of flexographic coating, gravure coating, blade coating or microgravure coating to obtain a wet coating layer;

[0033] Step 4. Dry the wet coating layer under a segmented hot air or infrared drying condition, so that the polyhydroxyalkanoate water-based dispersion particles coalesce into a film and undergo short-range leveling in a setting temperature zone to form a continuous and dense barrier layer and a surface hydrophobic microstructure, thereby obtaining a coated paper material, wherein the drying temperature is higher than the minimum film-forming temperature of the polyhydroxyalkanoate water-based dispersion particles and lower than the crystalline melting temperature thereof;

[0034] Step 5. Fold, edge seal and composite the coated paper material to obtain a sanitary isolation bag.

[0035] The application also provides the use of the sanitary isolation bag in the packaging of disposable toiletries for hotels and homestays, the sanitary isolation storage of guest rooms and long-term rental apartments, the temporary storage of disposable toiletries and disposable personal care products after use, the packaging and temporary storage of toiletry sets for travel vehicles, and the packaging of disposable sanitary products for visitors and caregivers in medical or nursing institutions.

[0036] Compared with the prior art, the following significant beneficial effects can be obtained by using the application:

[0037] The application utilizes a polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor and a water-based PHA to construct an active barrier coating, the dual bridging effect of the polyphenol derivative (such as GA) effectively solves the agglomeration problem of inorganic nanoparticles in the polymer matrix, and a high-density cation capture site (from HACC) and an oxidation inactivation site (from NanoZnO) are formed on the surface of the coating, thereby realizing efficient synergistic blocking and inactivation of bacteria and enveloped viruses, and the inactivation rate for enveloped viruses can be more than 99.9%.

[0038] This invention, through water-based coating formulation design, abandons traditional fluorinated oil repellents. Utilizing the hydrophobicity and high crystallinity of PHA itself, combined with the tortuous path constructed by nano-layered barrier fillers, it achieves Cobb coating at a relatively low coating weight (3–8 g / m²). 60 It boasts excellent barrier properties with a concentration of ≤9g / m² and a Kit oil resistance rating of ≥10, while its TOF content is less than 5mg / kg, meeting increasingly stringent environmental protection requirements for fluorine-free products.

[0039] The sanitary isolation bag of the present invention has excellent environmental adaptability and end-of-life disposal performance. The interface compatibilizer and PHA structure in the coating endow the material with environmental chemical responsiveness, enabling it to achieve efficient interface dissociation (dissociation rate ≥95%) under alkaline hydraulic pulping conditions, which facilitates the recycling of paper-based fibers.

[0040] Compared with Chinese patents CN119912795B and CN120026524B, this invention simultaneously defines a polyhydroxy fatty acid ester without PVOH in the film-forming resin phase and a second film-forming polymer system in the same bamboo pulp fiber paper-based system. It allows the introduction of only a small amount of PVOH and its carboxylated derivatives into the interface compatibilizer. Combined with the synergistic design of gallic acid-chitosan quaternary ammonium salt-nano zinc oxide hybrid antiviral structure and alkali-induced interface dissociation and composting degradation mechanism, and limiting the total organic fluorine content of the coating and sanitary isolation bag to less than 5 mg / kg, it achieves high water resistance, high oil resistance and high antiviral performance through non-fluorinated materials. Attached Figure Description

[0041] Figure 1 This is a schematic cross-sectional view of the microstructure of the coated paper used in the antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag of the present invention.

[0042] In the figure, 1-bamboo pulp fiber paper base; 2-interfacial compatibilizer; 3-waterborne PHA barrier antibacterial and antiviral coating; 4-cation capture and oxidative inactivation active sites; 5-polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor; 6-polyhydroxy fatty acid ester; 7-nano-layered barrier filler. Detailed Implementation

[0043] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention. Unless otherwise stated, the raw materials used in this embodiment are commercially available industrial products or can be prepared by conventional methods. Unless otherwise specified, performance testing methods are performed according to the standards described in the invention summary section.

[0044] Figure 1 This diagram illustrates the cross-sectional microstructure of the coated paper material used in the antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag of this invention. As shown, the bottom layer of the material is an interwoven bamboo pulp fiber paper base 1. A thin interfacial compatibilizer 2 is placed on top of the paper base to enhance the interlayer bonding force. At the top is a functional aqueous PHA barrier antibacterial and antiviral coating 3. Inside this aqueous PHA barrier antibacterial and antiviral coating 3, a continuous polyhydroxy fatty acid ester 6 serves as the matrix phase, in which sheet-like nanolayered barrier fillers 7, tending to align parallel to the surface, are dispersed, constructing a tortuous path to provide excellent barrier effect. Simultaneously, a network-structured polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor 5 is embedded in the coating matrix. This hybrid factor effectively constructs cation capture and oxidative inactivation active sites 4 (indicated by surface micro-markers in the figure) on the exposed surface of the coating, thereby achieving highly efficient antibacterial and antiviral functions through a contact mechanism.

[0045] Main reagents and raw materials:

[0046] Table 1. Main reagent and raw material names, product models and manufacturers:

[0047]

[0048] Table 2 Main analytical and testing instruments:

[0049]

[0050] Main testing standards:

[0051] Cobb 60 Value: The value was determined in accordance with GB / T 1540-2002 "Determination of water absorption of paper and paperboard (Cobb method)".

[0052] Kit oil repellency rating: Measured according to TAPPI T 559 cm-22; For film-forming or non-fluorine-containing oil-repellent paper-based barrier layers, this method can still be used as a general comparison index, and the test can be conducted under the same batch of control sample conditions.

[0053] Virus inactivation rate: When a continuous, dense coating forms on the sample surface, allowing it to be treated as a non-porous material, the test should be conducted according to GB / T43355-2023 "Determination of antiviral activity of plastics and other non-porous materials" (equivalent to ISO 21702:2019); when the sample surface still exhibits a clearly porous / fibrous structure, the test should be conducted according to ISO 18184:2025 or GB / T 43823-2024 "Determination of antiviral activity of textiles". H1N1 influenza virus was used as a representative enveloped virus. Test conditions were performed according to the selected standard; under the example conditions in this specification, the exposure time was 2 hours, the host cells were Martin-Darby canine kidney cells (MDCK), and the virus titer was determined using the 50% tissue culture infectious dose (TCID50) method.

[0054] Antibacterial performance: Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 8739 were selected as test strains; Staphylococcus aureus was tested according to GB / T 21866-2025 "Determination of Antiviral Activity and Antibacterial Properties of Coatings", and Escherichia coli was tested according to GB / T 21866-2008 "Determination of Antibacterial Properties and Antibacterial Effects of Antibacterial Coatings (Films)"; in this invention, an antibacterial rate of ≥99% calculated according to the test method is considered as qualified antibacterial performance.

[0055] Barrier performance qualification criteria: Cobb 60 ≤9g / m² and Kit oil resistance rating ≥10 are considered to be qualified for barrier performance.

[0056] Criteria for passing antiviral performance test: A blocking or inactivation rate of ≥99.9% against enveloped viruses is considered to be passing antiviral performance test.

[0057] Fiber interface dissociation rate: Take 10.0g of the cut coated paper sample by oven-dry weight, add deionized water to a total mass of 500g (pulp concentration 2.0wt%), and adjust the pH of the system to 9.0±0.2 with 1mol / L sodium hydroxide solution; place the system under constant temperature of 45℃ and pulp for 20min using a high-speed shear disperser. The high-speed shear disperser model is IKAT25 digital, the matching disperser head specification is S25N-25G, and the speed is set to 10000±500rpm; during the pulping process, the system temperature is maintained at 45℃±2℃ by a constant temperature water bath or a container with a temperature control jacket. After pulping, the pulp is sieved using a 0.20mm sieve. The residue on the sieve is thoroughly rinsed with deionized water, collected, and dried at 105℃ to constant weight. The percentage of the oven-dry mass of the residue on the sieve relative to the oven-dry mass of the sample is calculated. The fiber interface dissociation rate is calculated as (1 - mass of residue on the sieve / mass of the sample) × 100%. A fiber interface dissociation rate ≥ 95% is considered to be qualified for repulping and separation performance.

[0058] Final aerobic biodegradation rate: Referring to GB / T 19277.1-2025 "Determination of final aerobic biodegradation capacity of materials under controlled composting conditions by means of determination of carbon dioxide released - Part 1: General method", the final aerobic biodegradation rate was determined under controlled composting conditions for 90 days. The obtained "90-day final aerobic biodegradation rate" is used as an indicator to characterize the degradation performance under composting conditions in the application example. A 90-day final aerobic biodegradation rate ≥90% is judged as qualified biodegradation performance under composting conditions.

[0059] TOF content: The test was conducted according to T / CNFIA 190—2024 "Determination of Total Organic Fluorine Content in Food Contact Paper, Paperboard and Paper Products by Ion Chromatography" or equivalent standards. Samples were pretreated and measured according to the standard specifications. The fluoride ion content in the solution was determined by ion chromatography and converted to TOF content. In this invention, the limit of quantitation for the TOF test method is set at 5 mg / kg. A measured value less than 5 mg / kg is considered undetectable, and a TOF content less than 5 mg / kg is considered to meet the requirement of being free of organic fluorine.

[0060] Sample conditioning: Sample conditioning was performed in accordance with GB / T 10739-2023 "Standard atmospheric conditions for the treatment and testing of paper, paperboard and pulp specimens".

[0061] General preparation method for PHA aqueous dispersions:

[0062] Unless otherwise stated, the PHA aqueous dispersions used in the embodiments of this invention are all prepared according to the following method:

[0063] Step 1. Add SDS to deionized water as an emulsifying dispersant. The amount of SDS is 0.3 wt% based on the mass of the aqueous phase. Stir until completely dissolved to obtain an aqueous phase.

[0064] Step 2. Add the PHA powder to the aqueous phase in batches under stirring conditions to avoid agglomeration caused by adding it all at once. Disperse the powder at 10,000 rpm for 45 minutes using a high-speed shear disperser at 70-85°C to obtain a coarse dispersion system.

[0065] Step 3. The coarse dispersion system is homogenized twice using a high-pressure homogenizer at a working pressure of 60 MPa. During homogenization, the temperature of the liquid is controlled at 45°C by cooling. After homogenization, it is cooled to room temperature, and the solid content of the dispersion is adjusted to 45 wt% by adding deionized water and / or adjusting the ratio of PHA resin to the aqueous phase, thus obtaining an aqueous PHA dispersion. The solid content of the aqueous PHA dispersion is determined using the constant gravimetric method at 105°C; D 50The particle size distribution of the emulsion was determined using a dynamic light scattering particle size analyzer at 25℃ and calculated based on the cumulative distribution. Before testing, the emulsion sample was diluted with deionized water to 0.07wt% and stirred thoroughly. 50 It is controlled at 0.6μm.

[0066] General preparation method of interface compatibilizer solution:

[0067] Step 1. Weigh PVOH-COOH and CMC separately at a solid mass ratio of 2:1. First, add PVOH-COOH to deionized water and heat and stir at 90°C until PVOH-COOH is completely dissolved. Then cool to 40°C to obtain PVOH-COOH solution.

[0068] Step 2. Under stirring conditions, CMC is added in batches to the PVOH-COOH solution and stirring is continued for 60 minutes until the system is homogeneous. Finally, deionized water is added to make the total solid content of PVOH-COOH and CMC 3.5wt%. The mixture is allowed to stand at room temperature to remove bubbles and obtain the interface compatibilizer solution.

[0069] Preparation process of homemade PE coated paper:

[0070] Step 1. Select bamboo pulp base paper with a basis weight of 45 g / m² as the paper base, and low-density polyethylene (LDPE) resin as the coating resin. On a laboratory extrusion coating laminator, the extruded polyethylene melt is uniformly coated on one or both sides of the paper base. The basis weight of the polyethylene extrusion coating layer is controlled to be 15 g / m² to obtain the composite material.

[0071] Step 2. Cool and shape the composite material to obtain PE coated paper.

[0072] Except for Comparative Example 3, which uses the PE coated paper listed in Table 1 as the substrate, Examples 1 to 6, as well as Comparative Examples 1, 2 and 4, all use the bamboo pulp base paper listed in Table 1 as the paper base.

[0073] Description of sealing components and processes for sanitary isolation bags:

[0074] Step 1. Regarding water-based pressure-sensitive adhesive: Since the sealing component is not a key innovative part of the coating system of this invention, if an adhesive is used, the water-based pressure-sensitive adhesive shall be a commercially available water-based acrylic pressure-sensitive adhesive dispersion with a solid content of 45wt% and a pH of 7.5, or a water-based pressure-sensitive adhesive prepared by emulsion polymerization according to the prior art.

[0075] Step 2. Regarding the direct heat-sealing structure: When the direct heat-sealing structure is achieved by utilizing the thermoplasticity of the water-based PHA barrier antibacterial and antiviral coating itself, the bag opening or sealing area is heat-sealed at 135°C, 0.3MPa, and 1.0s to form a heat-sealed edge with a width of 10mm, thereby obtaining the direct heat-sealing structure.

[0076] Example:

[0077] Example 1:

[0078] Preparation of the GA-HACC-NanoZnO hybrid factor: Weigh HACC powder and add it to deionized water. Stir magnetically or mechanically at room temperature until completely dissolved to prepare a 1.0 wt% HACC aqueous solution. Adjust the pH to 6.0 using 0.1 mol / L dilute hydrochloric acid and / or 0.1 mol / L sodium hydroxide aqueous solution. Under mechanical stirring at 500 rpm, first prepare a 0.3 wt% GA solution with deionized water (stirring until completely dissolved). Then, slowly add the GA solution to the HACC solution at a dropping rate of 1.0 mL / min until the mass ratio of GA (on a dry basis) to HACC (on a dry basis) reaches 0.15:1. During the dropping process, maintain the pH of the system at 6.0 by adding the above dilute acid / base solution. After the dropping is completed, continue stirring for 30 min to form a homogeneous and stable pre-complexed system. Then add NanoZnO aqueous dispersion (as listed in the main reagents and raw materials table). The solid content of the NanoZnO aqueous dispersion was determined by constant gravimetric analysis at 105℃, and the dry weight of NanoZnO was calculated accordingly. The required amount of NanoZnO aqueous dispersion was calculated based on a mass ratio of NanoZnO (on a dry basis) to HACC (on a dry basis) of 0.35:1. When the NanoZnO aqueous dispersion was a high-solids system, it was first diluted with deionized water to 5.0 wt% to reduce the system viscosity and improve the shear dispersion efficiency. The dispersion was then performed using a high-speed shear disperser at 10,000 rpm for 20 min to obtain the GA-HACC-NanoZnO hybrid factor aqueous dispersion.

[0079] Coating preparation: A coating with a solid content of 45 wt% and D was prepared using the PHBV resin listed in the main reagents and raw materials table. 50A PHBV aqueous dispersion of approximately 0.6 μm was used as the film-forming resin, and the film-forming resin phase was composed solely of this PHBV aqueous dispersion. By solids mass: 80 parts PHBV, 12 parts hybridizing agent, 5 parts organically modified nano-montmorillonite, and 3 parts PVOH-COOH / CMC (solids mass ratio 2:1) interfacial compatibilizer. The interfacial compatibilizer solution was prepared according to the "General Preparation Method for Interfacial Compatibilizer Solutions" (total solids content of the solution 5.0 wt%). The amount of each component added was calculated based on its solids content and weighed accordingly. The solids content was measured using the constant weight method at 105℃. In coating preparation, the interfacial compatibilizer solution and the hybrid factor aqueous dispersion were first mixed for 10 min under mechanical stirring at 500 rpm. Then, organically modified nano-montmorillonite was added under high-speed shear dispersion conditions and sheared at 10000 rpm for 10 min (if necessary, the nano-montmorillonite could be pre-wetted with a small amount of deionized water before addition to reduce agglomeration). Finally, the PHBV aqueous dispersion was added and sheared at 10000 rpm for 20 min to obtain a homogeneous coating. The pH was adjusted to 7.5 using 0.1 mol / L dilute hydrochloric acid or 0.1 mol / L sodium hydroxide aqueous solution. The coating viscosity was measured at 25℃ using a rotational viscometer (rotor No. 3, 60 rpm), and the viscosity was 800 mPa·s.

[0080] Coating and Film Formation: The coating was applied to the bamboo pulp base paper using a laboratory blade coating method at a speed of 10 m / min. The solid content of the coating was measured at 105℃ using the constant weight method. The required wet coating amount was calculated according to the formula "target dry coating amount = target wet coating amount × coating solid content" to control the dry coating amount at 5 g / m². The wet coating amount was verified by weighing the paper sample before and after coating and dividing by the coated area. After coating, the paper was dried sequentially at 95℃, 115℃, and 125℃ to form a film, with a dwell time of 2 minutes at each temperature. After exiting the drying stage, the paper was allowed to stand at 23℃ and 50% relative humidity for 24 hours before subsequent testing.

[0081] Example 2: The only difference from Example 1 is the composition of the film-forming resin phase. The film-forming resin is composed of a blend of PHBV aqueous dispersion and acrylic copolymer emulsion. By solid mass, PHBV accounts for 70 wt% and the acrylic copolymer accounts for 30 wt%. By solid mass: PHBV 56 parts, acrylic copolymer 24 parts, GA-HACC-NanoZnO hybridizing agent 12 parts, organic modified nano-montmorillonite 5 parts, and PVOH-COOH / CMC (solid mass ratio 2:1) interface compatibilizer 3 parts. The remaining process conditions are the same as in Example 1.

[0082] Example 3: The difference from Example 1 lies in the composition of the film-forming resin phase. By solid mass, PHBV accounts for 95 wt%, and the acrylic copolymer accounts for 5 wt%. By solid mass parts: PHBV 76 parts, acrylic copolymer 4 parts, GA-HACC-NanoZnO hybridizing factor 12 parts, organically modified nano-montmorillonite 5 parts, and PVOH-COOH / CMC (solid mass ratio 2:1) interface compatibilizer 3 parts. Other conditions remain unchanged.

[0083] Example 4: The difference from Example 1 lies in the composition of the film-forming resin phase. By solid mass, PHBV accounts for 40 wt%, and the acrylic copolymer accounts for 60 wt%. By solid mass parts: PHBV 32 parts, acrylic copolymer 48 parts, GA-HACC-NanoZnO hybridizing factor 12 parts, organically modified nano-montmorillonite 5 parts, and PVOH-COOH / CMC (solid mass ratio 2:1) interface compatibilizer 3 parts. Other conditions remain unchanged.

[0084] Example 5: The difference from Example 1 is that PHBH aqueous dispersion is used instead of PHBV aqueous dispersion in the film-forming resin phase, and the film-forming resin phase is composed solely of PHA aqueous dispersion; in the preparation of the hybrid factor, the GA:HACC mass ratio is 0.30:1, and the NanoZnO:HACC mass ratio is 0.60:1. Other conditions remain unchanged. This example verifies the high loading endpoint of the hybrid factor.

[0085] Example 6: The difference from Example 1 is that in the preparation of the hybridization factor, the GA:HACC mass ratio is 0.05:1, and the NanoZnO:HACC mass ratio is 0.10:1. Other conditions remain unchanged. This example verifies the low-loading endpoint of the hybridization factor.

[0086] Comparative example:

[0087] Comparative Example 1: The difference from Example 1 is that no GA-HACC-NanoZnO hybrid factor is added to the coating. By solid mass: 92 parts PHBV, 5 parts organic modified nano-montmorillonite, 3 parts PVOH-COOH / CMC (solid mass ratio 2:1) interface compatibilizer, and the remaining process conditions are the same as in Example 1.

[0088] Comparative Example 2: The difference from Example 1 is that physical blending is used instead of pre-complexing hybridization. The total amount of active components remains unchanged at 12 parts by solid mass, and the components are prepared according to the proportions of Example 1: 8.0 parts HACC, 1.2 parts GA, and 2.8 parts NanoZnO (corresponding to GA:HACC = 0.15:1 and NanoZnO:HACC = 0.35:1). In Comparative Example 2, the pre-complexation step between GA and HACC, and the pre-complexation step between the GA-HACC system and NanoZnO, were not performed. Instead, the active components were added directly during the coating preparation process: first, the interface compatibilizer solution and the GA aqueous solution were mixed for 10 min under mechanical stirring at 500 rpm; then, the HACC aqueous solution was added and stirring was continued for 20 min; next, the NanoZnO aqueous dispersion was added and sheared at 10000 rpm for 20 min under high-speed shear dispersion conditions to obtain a uniform dispersion system; then, the nano-layered barrier filler was added and dispersed according to the shear dispersion conditions of Example 1; finally, the PHA aqueous dispersion was added and sheared and dispersed according to Example 1 for 20 min; the pH was adjusted to 7.5 with 0.1 mol / L dilute hydrochloric acid or 0.1 mol / L sodium hydroxide aqueous solution. The remaining components and coating and drying film-forming conditions were the same as in Example 1.

[0089] Comparative Example 3: Self-made PE coated paper. The substrate of Comparative Example 3 is bamboo pulp base paper with a basis weight of 45 g / m². Low-density polyethylene (LDPE) resin is used to form a polyethylene extrusion coating layer with a basis weight of 15 g / m² on one side of the bamboo pulp base paper by extrusion coating method to simulate the structure and performance of common bamboo pulp paper-based PE coated paper.

[0090] Comparative Example 4: Uncoated bamboo pulp base paper.

[0091] Application example:

[0092] Application Example 1: Performance testing of hotel toiletries packaging bags.

[0093] Using the coated paper materials prepared in Examples 1 to 6 and Comparative Examples 1 to 4, toothbrush hygiene isolation packaging bags were prepared as follows: The coated paper material was cut into 120mm × 180mm pieces, and the inner coated side was folded inward to form a bag shape; a water-based acrylic pressure-sensitive adhesive dispersion was coated in strips on the two sides and bottom sealing areas (10mm wide), with the wet coating amount being 30g / m² based on the actual area of ​​the adhesive coating; the bags were dried in a 60℃ forced-air drying oven for 2 minutes until surface dry, then pressed with a rubber roller and left at room temperature for 1 hour to obtain the bag body; a self-adhesive water-based pressure-sensitive adhesive sealing strip was laminated to the bag opening. The resulting packaging bags were then subjected to comprehensive performance tests under a simulated hotel usage environment. Except for the fiber interface dissociation rate and controlled composting tests, which were performed directly using the coated paper material samples according to the corresponding methods, Cobb... 60, The Cobb test for the oil-proof grade, virus inactivation rate, and antibacterial performance of the Kit was carried out by cutting flat samples from the non-sealed edge area of the bag body (avoiding adhesives and heat seals); all samples were conditioned at 23 °C and 50% relative humidity for 24 h according to GB / T 10739-2023 before performing the Cobb 60 and Kit tests, and the virus / antibacterial tests were carried out after conditioning (if the relevant standards have other regulations on the conditioning conditions, follow their regulations). The test conditions include: Cobb 60 test at 23 °C, 50% relative humidity, oil-proof test, anti-H1N1 influenza virus test, fiber interface dissociation test under alkaline hydropulping conditions at pH 9, 45 °C, 20 min, and controlled composting test according to GB / T 19277.1-2025.

[0094] Table 3 Test results of Application Example 1:

[0095]

[0096] Analysis: This application example comprehensively evaluated the barrier properties, biosafety, and environmental friendliness of various samples. Among them, a 90-day ultimate aerobic biodegradation rate ≥ 90% was judged as qualified biodegradation performance under composting conditions, and a fiber interface dissociation rate ≥ 95% was judged as qualified interface dissociation performance under repulping conditions. From the data, it can be seen that the Cobb 60 values of Examples 1 to 6 were all controlled below 9 g / m², and the oil-proof grades of the Kit all reached Grade 10, meeting the requirements of high water and oil barrier properties for disposable packaging of hotel toiletries and related scenarios. Among them, when the acrylic copolymer content in Example 4 was 60%, the Cobb 60 was 6.5 g / m², and the oil-proof grade of the Kit was Grade 10; compared with Examples 1 to 3 (Cobb 60 was 7.8 - 8.2 g / m² and the oil-proof grades of the Kit were all Grade 10), the Cobb 60 of Example 4 decreased by 1.3 - 1.7 g / m². The fiber interface dissociation rate of Example 4 was 95.0%, and the 90-day ultimate aerobic biodegradation rate was 90.2%, both near the lower limits of the repulping separation qualification criterion (≥ 95%) and the composting biodegradation qualification criterion (≥ 90%). The PE laminated paper in Comparative Example 3 showed excellent performance in Cobb 60 and Kit indicators, but basically did not have the ability of repulping separation and composting degradation, and it was difficult to meet the needs of green substitution of disposable products. In terms of antiviral, all examples containing hybrid factors showed extremely high inactivation rates, and the inactivation rates against enveloped viruses were not less than 99.9%.

[0097] Application Example 2: Surface hydrophobicity and adaptability test in high-humidity bathroom environment.

[0098] The toothbrush packaging bags prepared in Application Example 1 (Examples 1 to 6) and Comparative Examples 1 to 4 (Comparative Examples 1 to 4) were cut into 40mm × 60mm flat pieces and conditioned for 24 hours at 23°C and 50% relative humidity according to GB / T 10739-2023 "Standard Atmospheric Conditions for the Treatment and Testing of Paper, Paperboard and Pulp Specimens". The static water contact angle θ0 of the sample front was then measured at room temperature using a contact angle meter: deionized water was used as the test droplet, with a drop volume of 3.0 ± 0.2 μL. The contact angle was read within 5 seconds after the droplet contacted the sample surface. Five points at different locations were selected for each sample, and the average value was taken. The samples were then treated in a constant temperature and humidity chamber at 40°C and 90% relative humidity for 24 hours, and the water contact angle θ24h was measured using the same drop volume and reading time.

[0099] Table 4 shows the test results of Application Example 2:

[0100]

[0101] Analysis: This application example aims to simulate the surface performance stability of packaging materials in high-humidity environments such as bathrooms. Examples 1 to 6 all had initial water contact angles greater than 100°, and after 24 hours of high-humidity treatment at 40°C and 90% relative humidity, the angle remained above 98°, indicating that the waterborne PHA coating can maintain a stable hydrophobic surface in the high-humidity environment of a bathroom, which is beneficial for inhibiting water film formation and contaminant adhesion. Example 4, with its high acrylic copolymer content, achieved an initial contact angle of 112°, which remained at 108° after high-humidity treatment, demonstrating its excellent Cobb properties. 60 This data corroborates the findings of the Kit. Comparative Example 4, the uncoated bamboo pulp base paper, initially had a contact angle of only 47°, which decreased to 30° after high humidity, exhibiting significant hydrophilicity and moisture sensitivity, which is detrimental to hygiene in practical bathroom settings. Comparative Example 3, although a PE-coated paper, had a contact angle of around 92° that remained essentially unchanged after high humidity, its non-re-pulping and non-compostable nature limited its environmental friendliness.

[0102] Application Example 3: Antibacterial Performance Test.

[0103] Cut the toothbrush sanitary isolation packaging bags of Examples 1 to 6 and Comparative Examples 1 to 4 prepared in Application Example 1 into 50 mm × 50 mm flat pieces. Among them, the test of Staphylococcus aureus was carried out according to GB / T 21866-2025, and the test of Escherichia coli was carried out according to GB / T 21866-2008; The antibacterial properties of the samples against Staphylococcus aureus ATCC6538 and Escherichia coli ATCC 8739 were tested by the film coating method. The brief process is as follows: Drop the bacterial suspension of a specified concentration on the surfaces of the control sample and the test sample. After acting for 24 h under the conditions of 35 ± 1 °C and relative humidity ≥ 90%, wash and count the number of surviving colonies respectively, and calculate the antibacterial rate according to the standard formula. In this invention, when the antibacterial rate ≥ 99%, it is judged that the antibacterial performance is qualified. The test results are shown in Table 5.

[0104] Table 5 Test results of antibacterial properties of Application Example 3:

[0105]

[0106] Experimental description and analysis: As can be seen from Table 5, the antibacterial rates of Examples 1 to 6 against Staphylococcus aureus are 99.95% - 99.99%, and the antibacterial rates against Escherichia coli are 99.92% - 99.99%, all meeting the "Antibacterial performance qualification criterion (antibacterial rate ≥ 99%)" in this specification. It shows that under the condition of dry coating amount of 5 g / m², the coating of this invention can achieve efficient inhibition of the two representative bacteria tested. In Comparative Example 1, the GA-HACC-NanoZnO organic-inorganic hybrid factor was not added, and the antibacterial rates were all less than 10%, hardly showing antibacterial properties; Although Comparative Example 2 contains GA, HACC and NanoZnO at the same time, it is only a simple physical blending structure, and the nanoparticles are easy to agglomerate and partially embedded by the film-forming resin completely, and its antibacterial rate is about 70%, significantly lower than the hybrid network structure of this invention; Comparative Examples 3 and 4 are PE coated paper and uncoated bamboo pulp base paper respectively, and the antibacterial rates are both less than 10%. The above results further verify the decisive contribution of the GA-HACC-NanoZnO organic-inorganic hybrid factor to the antibacterial performance in the system of this invention.

[0107] Application Example 4: Test of organofluorine content.

[0108] Using the toothbrush sanitary isolation packaging bag samples prepared in Examples 1 to 6 and Comparative Examples 1 to 4, the TOF content of the coated paper was measured at 23 °C according to the TOF content test method described in the "Main test standard", and the average value was taken after measuring each sample 3 times. The test results are shown in Table 6.

[0109] Table 6 Test results of organofluorine content:

[0110]

[0111] Analysis: This application example verifies whether the coating system and comparative samples of this invention contain organofluorine compounds. According to the TOF test method, a value less than the detection limit of 5 mg / kg is considered undetectable. In this application example, the TOF content of all examples and comparative samples is less than 5 mg / kg, and is therefore considered undetectable. This indicates that the PHA, aqueous secondary film-forming polymer, HACC, GA, NanoZnO, nanolayered barrier filler, interface compatibilizer, and sealing components used do not introduce organofluorine structures, thus meeting the requirements for organofluorine-free paper-based disposable hygienic isolation packaging. This verifies the significant advantages of this invention in terms of environmental protection and fluorine-free properties.

[0112] Experimental Results and Analysis:

[0113] Based on the test data and phenomena observed in Application Examples 1 to 4 above, the performance of the antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag prepared by the present invention is comprehensively analyzed as follows:

[0114] Analysis of the key role of hybrid factors in antibacterial and antiviral performance: Data from Examples 1 to 6 show that the coatings incorporating the polyphenol derivative-HACC-NanoZnO organic-inorganic hybrid factor achieved an inactivation rate of over 99.90% against enveloped viruses (such as H1N1) and an antibacterial rate of over 99.92% against Staphylococcus aureus and Escherichia coli. In contrast, Comparative Example 1, which did not contain this hybrid factor, had almost no antiviral ability; while Comparative Example 2, although containing the same total amount of GA, HACC, and NanoZnO, used a simple physical blending method, and its antiviral inactivation rate was only 65.40%, and its antibacterial rate was about 70%. This significant difference confirms the core advantage of the "organic-inorganic hybrid network structure" of this invention: the polyphenol derivative (GA) acts as a molecular bridge, coordinating with NanoZnO through polyphenol hydroxyl groups on the one hand, and forming hydrogen bonds or grafting with HACC on the other hand, effectively inhibiting the aggregation of NanoZnO and keeping it highly dispersed on the coating surface. This structure not only maximizes the exposure area of ​​active sites, but also constructs a synergistic killing mechanism of "cation capture (HACC)" and "oxidative inactivation (NanoZnO)," thereby achieving high efficiency at low addition levels.

[0115] Barrier mechanism and performance advantages of the fluorine-free system: All examples achieved Cobb protection with a TOF content of less than 5 mg / kg (i.e., undetectable). 60The high barrier properties, ≤8.5 g / m² and Kit oil-resistant rating 10, are primarily due to the high crystallinity and strong hydrophobicity of PHA itself, as well as the "maze effect" created by nano-layered barrier fillers (such as nano-montmorillonite) in the coating, which prolongs the penetration path of water and oil molecules. Compared to Comparative Example 3 (PE coated paper), although the Cobb value of the PE coated paper is lower (2.1 g / m²), the barrier properties of this invention fully meet the single-use requirements of sanitary isolation bags and completely solve the problems of non-degradability, difficulty in re-sizing, and potential fluorinated additives in PE materials.

[0116] Environmental chemical responsiveness and repulping degradation performance: Data from the examples confirm the excellent "life-cycle environmental friendliness" of the coating of this invention. Under alkaline hydraulic pulping conditions (pH 9, 45°C), the fiber interface dissociation rate of the examples was above 95.0%. This is because the interfacial compatibilizer (such as carboxyl-containing components) and PHA resin in the coating swell or hydrolyze under alkaline and warm conditions, destroying the bonding force between the coating and bamboo pulp fibers, causing the coating to detach in the form of tiny fragments, thus achieving paper-plastic separation. Under composting conditions, the final aerobic biodegradation rate after 90 days exceeded 90%, confirming the complete biodegradability of the PHA substrate and natural bamboo pulp fibers. This contrasts sharply with the "double failure" of Comparative Example 3 (PE coated paper) in both repulping and degradation tests.

[0117] Trend analysis of the impact of changes in the content of key components on performance: Based on the above embodiments and further verification experiments on the numerical ranges in the invention, the trend analysis of the impact of changes in the content of each component on performance is as follows:

[0118] 1) Effect of coating amount: Within the range of 3–8 g / m², as the dry coating amount increases, Cobb… 60 The value shows a downward trend, and the oil resistance level tends to stabilize. When the coating amount is less than 3 g / m², the coating is difficult to completely cover the fiber pores on the surface of bamboo pulp paper, and pinholes are prone to occur, resulting in a significant decrease in barrier properties. When the coating amount exceeds 8 g / m², the improvement in barrier performance slows down, and it also increases costs and may affect the flexibility of the coating. The preferred coating amount of around 5 g / m² in this invention achieves the best balance between performance and cost.

[0119] 2) Effect of hybrid factor addition: Within the range of 10-15 parts, the antiviral and antibacterial efficiencies increase with the increase of hybrid factor content. When the content is less than 10 parts, the density of active sites on the surface is insufficient, and the inactivation time is prolonged; when the content is more than 15 parts, it may slightly interfere with the film-forming continuity of PHA, resulting in a slight increase in Cobb value (decreased barrier properties), and the increased viscosity of the coating affects the coating leveling properties.

[0120] 3) Effect of PHA to Second Film-Forming Polymer Ratio: As the proportion of the second film-forming polymer (such as acrylic copolymer) increases (as in Example 4), the flexibility and initial film-forming properties of the coating improve (Cobb value decreases), but the biodegradation rate is slightly delayed (from >90% to 90.2%). This indicates that within the PHA content range of 40–95 wt%, the barrier properties, mechanical properties, and degradation properties can be balanced by adjusting the ratio to suit different application scenarios.

[0121] 4) Effect of the internal ratio of hybrid factors: When the mass ratio of GA to HACC is in the range of 0.05 to 0.30:1, the increase of GA content helps to improve the stability of the hybrid system and prevent NanoZnO precipitation; when the mass ratio of NanoZnO to HACC is in the range of 0.10 to 0.60:1, the increase of NanoZnO ratio directly enhances the oxidation and inactivation ability, but sufficient HACC is required for coating and dispersion, otherwise excessive NanoZnO will agglomerate and lead to a decrease in efficiency.

[0122] In summary, this invention successfully solves the technical challenge of traditional paper-based packaging in achieving a balance between fluorine-free barrier properties, high-efficiency antiviral properties, and re-pulping and biodegradability by constructing an aqueous PHA coating containing specific organic-inorganic hybrid factors on the surface of bamboo pulp fiber paper base. It provides a safe, efficient, and green hygienic isolation solution.

[0123] Those skilled in the art should understand that the above embodiments are merely exemplary and are not intended to limit the scope of the present invention. Any modifications, equivalent substitutions, improvements, etc., made to the technical solutions of the present invention within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A sanitary isolation bag based on bamboo pulp and paper, comprising a bag body and a sealing assembly made of bamboo pulp fiber paper base, characterized in that: At least one side of the bamboo pulp fiber paper base is coated with a water-based polyhydroxy fatty acid ester barrier antibacterial and antiviral coating. The coating is formed by curing a coating composition consisting of an aqueous dispersion of polyhydroxy fatty acid esters and a coating composition of polyphenol derivatives, chitosan quaternary ammonium salt, and nano zinc oxide organic-inorganic hybrid factors. The coating forms a continuous and dense hydrophobic barrier layer on the surface of bamboo pulp fiber, and the hybrid factor constructs cation capture and oxidative inactivation active sites on the coating surface through the bridging effect of polyphenol derivatives, and the total organic fluorine content of the coating and the sanitary isolation bag is less than 5 mg / kg.

2. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The basis weight of the bamboo pulp fiber paper base is 35-280 g / m², the mass ratio of bamboo pulp fiber is ≥70%, and it is subjected to calendering or surface sizing treatment.

3. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The water-based polyhydroxy fatty acid ester barrier antibacterial and antiviral coating is disposed on the inner surface of the bamboo pulp fiber paper base; or simultaneously disposed on the inner and outer surfaces.

4. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The dry coating amount of the waterborne polyhydroxy fatty acid ester barrier antibacterial and antiviral coating is 3-8 g / m².

5. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The aqueous dispersion of the polyhydroxy fatty acid ester is prepared from polyhydroxy fatty acid ester; The polyhydroxy fatty acid ester is selected from short-chain polyhydroxy fatty acid esters, medium- and long-chain polyhydroxy fatty acid esters, or copolymers that form short-chain polyhydroxy fatty acid ester monomers and medium- and long-chain polyhydroxy fatty acid ester monomers. The short-chain polyhydroxy fatty acid ester is selected from one or more of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). The medium- and long-chain polyhydroxy fatty acid esters are selected from one or more of poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxynonanoate), poly(3-hydroxydecanoate), poly(3-hydroxyundecanoate), poly(3-hydroxydodecanoate), poly(3-hydroxydoranoate), poly(3-hydroxypalmitate), poly(3-hydroxystearate), and copolymers thereof. The solid content of the aqueous dispersion of the polyhydroxy fatty acid ester is 30-55 wt%, D 50 The range is 0.2–2.0 μm.

6. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The polyphenol derivative is gallic acid, and the hybridization factor is a gallic acid-chitosan quaternary ammonium salt-nano zinc oxide hybrid network. The preparation of the polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybridization factor includes: a) Prepare an aqueous solution of chitosan quaternary ammonium salt and adjust the pH to 5.0–7.5 to obtain the chitosan quaternary ammonium salt solution; b) Slowly add the polyphenol derivative solution to the chitosan quaternary ammonium salt solution and stir until a uniform and stable pre-complexed system is formed to obtain the pre-complexed system; c) Add the nano zinc oxide aqueous dispersion to the pre-complexed system and perform shear dispersion until a uniform and stable organic-inorganic hybrid colloid is formed to obtain the polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor. The mass ratio of polyphenol derivatives to chitosan quaternary ammonium salt is 0.05–0.30:1, and the mass ratio of nano zinc oxide to chitosan quaternary ammonium salt is 0.10–0.60:

1.

7. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The waterborne polyhydroxyalkanoate barrier antibacterial and antiviral coating possesses environmental chemical responsiveness, including the following properties: alkali-induced interfacial dissociation performance, wherein under aqueous media pulping conditions of pH ≥ 9 and temperature ≥ 40℃, the polyhydroxyalkanoate coating undergoes hydrolysis, swelling, and embrittlement, or the interfacial compatibilizer undergoes ionization, swelling, and induces interfacial hydration, causing the coating to desorb from the fiber surface in the form of particles or flakes, with a fiber interfacial dissociation rate ≥ 95% measured under the aforementioned conditions; It also exhibits enzymatic mineralization properties, which involve the breaking of ester bonds in polyhydroxy fatty acid esters under the action of polyhydroxy fatty acid ester depolymerization enzymes in bioactive soil or compost environments, and the breaking of glycosidic bonds in bamboo pulp fibers under the action of cellulases. After microbial metabolism, these are further mineralized into carbon dioxide and water.

8. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: Under predetermined test conditions, its performance simultaneously meets the following specifications: Cobb 60 ≤9g / m²; Kit oil resistance rating ≥10; blocking or inactivation rate against enveloped viruses ≥99.9%; total organic fluoride content measured by the total organic fluoride test method is less than 5mg / kg.

9. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The sealing component is a self-adhesive sealing strip, a pressure-sensitive adhesive sealing strip, a zipper-type sealing structure, or a direct heat-sealing structure achieved by utilizing the thermoplasticity of the water-based polyhydroxyalkanoate barrier antibacterial and antiviral coating itself; wherein, if an adhesive is used, the pressure-sensitive adhesive or heat-sealing adhesive is a water-based system or a biodegradable system.

10. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The waterborne polyhydroxy fatty acid ester barrier antibacterial and antiviral coating also includes organically modified nano-montmorillonite and an interface compatibilizer. Based on solid mass, the coating comprises: 70-85 parts polyhydroxy fatty acid ester; 10-15 parts polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor; 3-6 parts organically modified nano-montmorillonite; and 2-5 parts interface compatibilizer. The organically modified nano-montmorillonite has a lamellar aspect ratio ≥ 50; The interface compatibilizer contains ionization groups or hydration groups, selected from polyvinyl alcohol and its carboxylated derivatives without organofluorine structures, carboxymethyl cellulose, cationic starch, carboxylated starch, or aqueous resins containing carboxylates.

11. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1, characterized in that: The film-forming resin phase of the aqueous polyhydroxyalkanoate barrier antibacterial and antiviral coating is composed of polyhydroxyalkanoate and a second film-forming polymer. Relative to the total mass of the film-forming resin phase, the polyhydroxyalkanoate accounts for 40-95 wt%, and the second film-forming polymer accounts for 5-60 wt%. The second film-forming polymer is selected from one or more of the following polymers: acrylic polymers or copolymers thereof obtained by emulsion polymerization of one or more monomers selected from acrylic acid, methacrylic acid and their C1-C8 alkyl esters, hydroxyalkyl acrylates or methacrylates, styrene, and acrylonitrile; Aqueous polyurethane dispersions obtained by addition polymerization of aliphatic or alicyclic diisocyanates with polyester diols, polyether diols, or polycarbonate diols and then dispersion in water; An aqueous dispersion of a bio-based polyester or its copolymer obtained by polycondensation of one or more dicarboxylic acids selected from succinic acid, glutaric acid, adipic acid, and oxalic acid with one or more diols selected from ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, and isosorbide; An aqueous dispersion of polylactic acid or its copolymers obtained by ring-opening polymerization of lactic acid; A polyolefin dispersion obtained by emulsification or dispersion of ethylene, propylene or their copolymers; And aqueous dispersions of cellulose derivatives or their modified forms obtained by carboxylation, hydroxypropylation or quaternization of cellulose molecules; The second film-forming polymer is a bio-based polyester or an acrylic polymer, and its phase state with the polyhydroxyalkanoate in the coating is a continuous phase-dispersed phase structure or an interpenetrating network structure.

12. A method for preparing an antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to any one of claims 1 to 11, characterized in that... Includes the following steps: Step 1. Provide bamboo pulp fiber paper base paper, wherein the bamboo pulp fiber paper base paper is base paper that has been calendered and / or surface sizing treated, or untreated bamboo pulp fiber paper base paper is pretreated by calendering or surface sizing to obtain pretreated bamboo pulp fiber paper base paper; Step 2. Prepare a waterborne polyhydroxy fatty acid ester barrier antibacterial and antiviral coating. Mix the waterborne polyhydroxy fatty acid ester dispersion with a polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor, and add nano-layered barrier filler and interfacial compatibilizer. After shear dispersion, a stable coating is obtained, thus obtaining a waterborne polyhydroxy fatty acid ester barrier antibacterial and antiviral coating. The film-forming resin phase of the stabilized coating is a polyhydroxy fatty acid ester, or a blend of a polyhydroxy fatty acid ester and a second film-forming polymer. Step 3. Apply the water-based polyhydroxyalkanoate barrier antibacterial and antiviral coating to the surface of the pretreated bamboo pulp fiber paper base paper using flexographic coating, gravure coating, doctor blade coating or microgravure coating to obtain a wet coating. Step 4. The wet coating is dried under segmented hot air or infrared drying conditions to cause the polyhydroxy fatty acid ester aqueous dispersion particles to aggregate into a film and undergo short-path leveling in the shaping temperature zone, forming a continuous dense barrier layer and a hydrophobic microstructure on the surface, thereby obtaining coated paper. The drying temperature is higher than the minimum film-forming temperature of the polyhydroxy fatty acid ester aqueous dispersion particles and lower than their crystallization melting temperature. Step 5. Fold and seal the coated paper material, and then attach a sealing assembly to obtain a sanitary isolation bag.

13. A bamboo pulp-based coated paper material with antibacterial and antiviral properties, characterized in that: It includes a bamboo pulp fiber paper base and an aqueous polyhydroxy fatty acid ester barrier antibacterial and antiviral coating disposed on at least one side of the bamboo pulp fiber paper base. The coating is formed by curing a coating composition consisting of an aqueous dispersion of polyhydroxy fatty acid esters and a polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor.

14. An aqueous film-forming coating composition for coating sanitary barriers on bamboo pulp paper base, characterized in that: It includes at least the film-forming resin phase, polyphenol derivative-chitosan quaternary ammonium salt-nano zinc oxide organic-inorganic hybrid factor and water; The film-forming resin phase is composed of polyhydroxyalkanoate and a second film-forming polymer, wherein, relative to the total mass of the film-forming resin phase, the polyhydroxyalkanoate accounts for 40-95 wt% and the second film-forming polymer accounts for 5-60 wt%; The second film-forming polymer is selected from one or more of the second film-forming polymers of claim 11.

15. The antibacterial and antiviral bamboo pulp paper-based sanitary isolation bag according to claim 1 is used in the disposable packaging of toiletries in hotels and homestays, the sanitary isolation and storage of guest rooms and long-term rental apartments, the recycling and temporary storage of disposable toiletries and disposable personal care products after use, the packaging and temporary storage of toiletries kits distributed on tourist transportation vehicles, and the packaging of disposable sanitary products used by visitors and caregivers in medical or nursing institutions.

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