CN115109550A - Antibacterial and antiviral polymer resin composition and adhesive film paper using same - Google Patents
Antibacterial and antiviral polymer resin composition and adhesive film paper using same Download PDFInfo
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- CN115109550A CN115109550A CN202211036514.3A CN202211036514A CN115109550A CN 115109550 A CN115109550 A CN 115109550A CN 202211036514 A CN202211036514 A CN 202211036514A CN 115109550 A CN115109550 A CN 115109550A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09J161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
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Abstract
The invention relates to an antibacterial and antiviral polymer resin composition and an adhesive film paper using the same, wherein the composition comprises polymer resin, an antibacterial and antiviral active auxiliary agent and aldehyde modified cellulose nanocrystalline, and the antibacterial and antiviral active auxiliary agent comprises aminated mesoporous SiO 2 A nano-particle carrier and an antibacterial and antiviral natural plant extract, wherein the antibacterial and antiviral natural plant extract is completely or partially loaded in aminated mesoporous SiO 2 In the pores of the nanoparticle support; use of aldehyde modified cellulose nanocrystal for improving amination mesoporous SiO 2 Surface properties of the nanoparticle carrier. The invention adopts amination-modified mesoporous SiO 2 The nano-particle loading ensures high loading rate of natural plant extract and keeps antibacterial and antiviral properties in a hot-pressing environment; through the compounding of the aldehyde cellulose nanocrystals and the specific antibacterial and antiviral active auxiliary agent, the dispersibility and stability of various components in the melamine resin adhesive are improved.
Description
Technical Field
The invention belongs to the field of polymer resin compositions and application of the polymer resin compositions in the technical field of functional paper products, and particularly relates to an antibacterial and antiviral resin composition and adhesive film paper using the same.
Background
Along with the improvement of living standard and environmental awareness of people, the requirements on the health and safety of the air environment of a room are higher and higher, and the artificial board for indoor home is beneficial to the existence of microorganisms and bacteria besides potential formaldehyde pollution caused by the adhesive used by the artificial board. Bacteria and viruses can enter a room along with dust, air and spray, daily household closely related to the life of people becomes a diffusion carrier of the bacteria and the viruses, and particularly, after people are impacted by SARS, influenza A and new coronavirus, the household product has higher requirements on the biological safety. The antibacterial and antiviral formaldehyde-free low-formaldehyde artificial board is a general demand.
As most of artificial board household products need to be decorated by melamine impregnated bond paper, the addition of the antibacterial and antiviral auxiliary agent in the impregnated bond becomes the most effective method for preparing the antibacterial and antiviral artificial board. At present, inorganic antibacterial auxiliaries are coated on the surface of the antibacterial plate in China, and the organic matters of bacteria or viruses are destroyed or changed by using the redox reaction of inorganic ions, so that the effects of resisting bacteria and inactivating viruses are achieved; the antiviral assistant is used in artificial board, and inorganic antiviral assistants, such as copper, silver, etc. are used in Japan to destroy virus organism through redox reaction. However, the inorganic antibacterial and antiviral additive has large addition amount, easily causes photocatalytic reaction to influence a substrate material, and is easy to cause heavy metal enrichment in a human body and damage to body health after long-term use and surface abrasion.
The method has the main reason that the melamine impregnated paper is alkaline, and the impregnated paper not only needs to be dried at high temperature after being impregnated, but also is paved in hard artificial boards such as shaving boards, fiber boards, plywood and core boards and needs to be processed at high temperature and high pressure to form boards, while the traditional natural plant extract has mild use environment and weak durability, and the high-temperature acid-base environment is easy to damage so as to reduce the timeliness.
Chinese patent CN 112477299A discloses a biological floor containing bioactive components, which adopts mesoporous nano-silica with low thermal conductivity as a molecular nest to protect active substances extracted from lavender and valerian. However, this method has not been applied to melamine impregnated bond paper for reasons including: firstly, the mesoporous silica entraps active substances, which are mainly adsorbed by hydrogen bonds of silicon hydroxyl groups to the active substances, and the active substances are easily separated from the mesoporous silica due to the weak hydrogen bond action, so that the lasting effect cannot be realized; in addition, because unsaturated residual bonds and hydroxyl groups in different bonding states exist on the surface of the silicon dioxide, the silicon dioxide has strong polarity, and a three-dimensional network structure is easily formed through hydrogen bonds, so that the silicon dioxide particles are agglomerated and are difficult to disperse into the melamine impregnating adhesive. The method not only causes the instability of the antibacterial and antiviral effects of the surfaces of wooden furniture, but also affects the appearance of the adhesive film paper and the appearance of the functional artificial board, the surfaces of the adhesive film paper are easy to wrinkle, bubble, white dot, stain, crack and the like, and the defects of dry flowers, scratches, indentations, bubbling, layering, corrugation and the like of the surfaces of the artificial boards are easy to cause after the surfaces of the artificial boards are veneered.
In order to improve the coating rate of the nano-silica, the surface of the mesoporous silica is often modified, and active groups are introduced, chinese patent CN 113969211 a discloses a triazine-modified mesoporous silica nanoparticle, which improves the coating rate of the perfume; chinese patent CN 113184861 a discloses a carboxylated modified mesoporous silica for improving the coating of curcumin and other drugs. It can be seen that the surface modification of the mesoporous silica requires differential adjustment for the surface groups of different coating materials.
The common method for improving the dispersibility of the nano silicon dioxide comprises physical ultrasonic treatment and surface chemical modification, and the ultrasonic treatment has short dispersion time and is difficult to meet the preparation process of the impregnated bond paper; the surface modification usually adopts a coupling agent for chemical bonding, however, the addition of a small amount of the coupling agent can cause poor dispersion effect, and the addition of a large amount of the coupling agent can enhance the brittleness of the melamine adhesive and influence the mechanical properties of the adhesive film paper. Therefore, in order to improve the dispersibility of the nano material in the melamine resin adhesive, not only the interface fusion with the melamine adhesive needs to be increased, but also the apparent performance and the mechanical property of the adhesive film paper need to be comprehensively optimized, and the flexibility of the adhesive film paper is improved.
Disclosure of Invention
The invention aims to provide a preparation method of natural antibacterial antiviral impregnated bond paper, and the natural plant extract provided by the invention is coated with aminated modified mesoporous silica nanoparticles to form an antibacterial antiviral active auxiliary agent, so that the natural plant extract has the characteristics of high temperature resistance and high pressure resistance, and can realize stable and lasting broad-spectrum antiviral efficacy; by means of hydroformylation of the cellulose nanocrystals, the hydroformylation cellulose nanocrystals are further cooperated with the antibacterial and antiviral active auxiliary agent, so that the dispersibility and stability of antibacterial and antiviral components in the melamine resin adhesive are improved, and the apparent performance and surface bonding strength of the adhesive film paper are improved.
In order to achieve the above object, the present invention firstly provides an antibacterial and antiviral polymeric resin composition comprising a polymeric resin, an antibacterial and antiviral co-agent comprising aminated mesoporous SiO, and an aldehyde-modified cellulose nanocrystal 2 A nano-particle carrier and an antibacterial and antiviral natural plant extract, wherein the antibacterial and antiviral natural plant extract is completely or partially loaded in aminated mesoporous SiO 2 In the pores of the nanoparticle support; use of aldehyde modified cellulose nanocrystal for improving amination mesoporous SiO 2 Surface properties of the nanoparticle support.
Preferably, the polymer resin is melamine resin. The antibacterial and antiviral active auxiliary agent is formed by aminationSiO pore 2 The antibacterial and antiviral natural plant extract nanometer particle is prepared from a natural plant extract mixture and sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution.
Preferably, the natural plant extract is a mixture of glycyrrhizic acid and sophoridine, and the weight ratio of glycyrrhizic acid to sophoridine is (2-4) to (3-5). Or preferably, the natural plant extract is a mixture of glycyrrhizic acid and chitin, and the weight ratio of glycyrrhizic acid to chitin is (2-4) to (1-3).
Preferably, the aminated mesoporous SiO 2 The nano particles are mesoporous silicon dioxide subjected to surface treatment by bisaminosilane, triaminosilane or silane containing amino and piperazinyl.
Preferably, the aldehyde modified cellulose nanocrystal is obtained by oxidizing cellulose with periodic acid under the catalysis of isopropanol.
Preferably, the aminated mesoporous SiO 2 The preparation process of the nano-particles comprises the following steps of a) preparing the mesoporous SiO 2 The nano particles are activated to be placed for 12-15h at the temperature of 250-300 ℃; b) subjecting the activated mesoporous SiO in step a) 2 Adding nanoparticles and bisaminosilane, triaminosilane or silane containing amino and piperazinyl into absolute ethanol, stirring at normal temperature, volatilizing ethanol, and preparing to obtain the aminated mesoporous SiO 2 And (3) nanoparticles.
Preferably, the aminated mesoporous SiO 2 The nano particles are the mesoporous silicon dioxide subjected to surface treatment by the 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane.
The invention also provides a preparation method of the natural antibacterial antiviral adhesive film paper, which comprises the following steps:
1) the antibacterial and antiviral polymer resin composition is prepared by the following steps: preparing aminated mesoporous silica, preparing an antibacterial and antiviral natural plant extract, loading all or part of the antibacterial and antiviral natural plant extract into the aminated mesoporous silica to obtain an antibacterial and antiviral active auxiliary agent, preparing aldehyde cellulose nanocrystalline, preparing an antibacterial and antiviral composite additive microsphere from the antibacterial and antiviral active auxiliary agent and the aldehyde cellulose nanocrystalline, and adding the antibacterial and antiviral composite additive microsphere into a high polymer resin adhesive;
2) dipping the paper into a urea-formaldehyde resin adhesive, controlling the dipping amount through roll coating, and then drying to obtain the one-time dipping dry adhesive film paper;
3) dipping the primary gum dipping dried adhesive film paper into the antibacterial and antiviral polymer resin composition obtained in the step 1), controlling gum dipping amount through roll coating, and then drying to obtain the natural antibacterial and antiviral adhesive film paper.
Preferably, the preparation of the antibacterial and antiviral polymeric resin composition comprises:
A) preparing aminated mesoporous silica;
B) preparing a mixture of natural plant extracts;
C) mixing the aminated mesoporous silica obtained in the step A) and the natural plant extract mixture obtained in the step B) with a sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution, stirring at normal temperature, and freeze-drying to obtain an antibacterial and antiviral active assistant;
D) adding the fiber nanocrystal, sodium periodate and isopropanol into water, stirring for 4-10 hours at 70-90 ℃ in a dark place, dialyzing to remove unreacted sodium periodate and isopropanol, and freeze-drying to obtain an aldehyde modified cellulose nanocrystal;
E) adding the antibacterial and antiviral active auxiliary agent obtained in the step C) and the aldehyde modified cellulose nanocrystalline obtained in the step D) into water for mixing to obtain an antibacterial and antiviral compound additive microsphere;
F) and E) adding the antibacterial and antiviral composite additive microspheres obtained in the step E) into a high-molecular resin adhesive to obtain the antibacterial and antiviral melamine resin composition.
Preferably, the antibacterial and antiviral co-agent: aldehyde modified cellulose nanocrystal: the weight ratio of the water is (2-5): 6-30): 100. The weight ratio of the aminated mesoporous silica obtained in the step A) to the natural plant extract mixture obtained in the step B) is 1: 1-3.
In addition, the invention also provides the adhesive film paper prepared by the preparation method.
It is preferable thatThe preparation of the antibacterial and antiviral active auxiliary agent comprises mesoporous SiO 2 Activating the nanoparticles, namely standing for 12-15h at 250-300 ℃, preferably for 13h at 260-280 ℃; the mesoporous SiO 2 The diameter of the nano particles is 20-100 nm, and the specific surface area is 200-600 m 2 (g) total pore volume of 0.2-0.6 cm 3 The preferred diameter is 50-60 nm, and the specific surface area is 400-500 m 2 (g) total pore volume of 0.3-0.4 cm 3 /g。
The aminated mesoporous SiO 2 Preparing nano particles by coupling aminosilane with activated mesoporous SiO 2 Dispersing the nano particles into absolute ethyl alcohol, amino silane coupling agent and mesoporous SiO 2 The mass ratio of the absolute ethyl alcohol is (2.5-4): 0.1-0.6): 100, stirring for 10-24h at normal temperature, recovering volatile ethyl alcohol, and drying to obtain aminated mesoporous silica;
the aminosilane coupling agent is bisaminosiloxane, triaminosiloxane or siloxane containing amino and piperazinyl, and comprises N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and N-2-aminoethyl-3-aminopropyltriethoxysilane, at least one of N-2-aminoethyl-3-aminopropyltrimethoxysilane, 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane, and 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane is most preferable.
Preferably, the step C) is to aminated mesoporous SiO 2 Mixing the mixture of nanoparticles and plant extract with sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with pH of 7.2-7.5 to obtain mixed solution, and amination to obtain mesoporous SiO 2 The mass ratio of the mixture of the nano particles and the plant extract to the buffer solution is (1-4): 20-40): 100, the mixture is stirred for 24-48 h at the normal temperature of 20-25 ℃ at 600-1200 rpm, and the antiviral active additive is obtained after freeze drying.
The step D) comprises the steps of mixing cellulose nanocrystal, sodium periodate, isopropanol and water in a beaker, stirring the cellulose nanocrystal, the sodium periodate, the isopropanol and the water in a mass ratio of (5-10): 0.5-1:100 at 50-80 ℃ in a dark place for 4-8 hours, for example, stirring the mixture in a mass ratio of (6-8): 0.5-1:100 at 60 ℃ in a dark place for 6 hours, dialyzing to remove unreacted sodium periodate and isopropanol, and freeze-drying to obtain the aldehyde cellulose nanocrystal;
the cellulose nanocrystal has a diameter of 5-20 nm, a length of 100-300 nm, preferably a diameter of 10-15 nm, and a length of 150-200 nm.
The coating of the aldehyde cellulose nanocrystals comprises mixing the aldehyde cellulose nanocrystals, an antibacterial and antiviral active assistant and water to prepare a mixed solution, wherein the mass ratio of the aldehyde cellulose nanocrystals to the antibacterial and antiviral active assistant to the water is (2-5): 6-30): 100, and preferably 4: (20-25): 100; homogenizing at high speed for 1-3 min, wherein the homogenizing speed is 10000-20000 revolutions/min;
preferably, the step 2) includes immersing the paper in a urea-formaldehyde resin adhesive (with a solid content of 30-50wt%), controlling the gum dipping amount to be 110-150% of the weight of the paper by roll coating, and then drying at 110-130 ℃ for 5-10 min;
preferably, in the step 3), the polymer resin is melamine resin, and the method comprises the steps of dipping the once-dipped and dried adhesive film paper in the antibacterial and antiviral melamine resin composition obtained in the step 1), wherein the solid content of the melamine resin composition is 0.5-2 wt%, preferably 0.7-1 wt%, stirring at 800-1200 rpm for 1-2 min, controlling the dipping amount to be 110-150% of the weight of the adhesive film paper through roll coating, and then drying at 110-130 ℃ for 5-10 min.
The invention also provides application of the natural antibacterial antiviral adhesive film paper in the artificial board.
The invention has the following technical effects:
firstly, the antibacterial and antiviral composition is obtained by synergistic compounding of compound plant extracts, and has inhibition and killing effects of different degrees on a plurality of pathogenic bacteria such as common proteus, staphylococcus aureus, staphylococcus epidermidis, streptococcus mutans, clostridium botulinum, lactobacillus, vibrio cholerae, oral mutans, intestinal pathogenic bacteria and the like; in addition, glycyrrhizic acid extracted from licorice realizes the inhibition effect on viruses such as HIV, influenza virus, SARS coronavirus and the like by inhibiting virus replication; sophoridine extracted from herba Sophorae Alopecuroidis belongs to an alkaloid, and has inhibitory effect on hepatitis B virus, human herpesvirus, enterovirus and other common viruses, and strong acting force between glycyrrhizic acid and Sophoridine is also beneficial to the stable release of glycyrrhizic acid and Sophoridine. In addition, the compound of glycyrrhizic acid and chitin also has similar effect. The single plant extract has selectivity on the inhibition of viruses, and the patent realizes the broad-spectrum antiviral effect through the compound action of the natural plant extracts.
Then, the invention selects mesoporous SiO 2 Nano particles are used as adsorption carriers and are aminated, and the aminated mesoporous SiO obtained in the way 2 The nano particles can act between glycyrrhizic acid and sophoridine or between glycyrrhizic acid and chitin, so that the loading rate and stability of bioactive substances are improved, the activity of the biological extract in the hot pressing process of resin or paper is protected from being damaged, particularly, the reaction activity of amino can be improved by adopting a diamino and triamino silane coupling agent or a silane coupling agent containing amino and piperazinyl, and the loading rate and stability of the natural plant extract can be effectively improved.
Subsequently, the aminated mesoporous silica composite material adopting the aldehyde modified cellulose nanocrystal to load the natural plant extract improves the dispersibility and stability of the antibacterial and antiviral components in the melamine resin adhesive, and simultaneously improves the apparent performance and surface bonding strength of the adhesive film paper. The Cellulose Nanocrystalline (CNC) is a natural nano material with the diameter of less than one hundred nanometers and the length of hundreds of nanometers, not only has the characteristics of nano particles, unique strength and optical performance, but also has rich surface hydroxyl groups, and is easy to be mixed with SiO in the high-speed stirring process 2 The hydroxyl on the surface of the nano-particles and unsaturated residual bonds form a stable hydrogen bond structure, so that the dispersibility of the nano-particles in the adhesive is improved, compared with the non-porous coating of an organic high polymer, the coating mode has higher porosity, is favorable for desorption and release of active substances, and plays antibacterial and antiviral effects through surface contact; in addition, the surface of the partially formylated cellulose nanocrystalline not only has a large number of hydroxyl groups, but also increases aldehyde groups, and the partially formylated cellulose nanocrystalline can be mixed with melamine resin in the hot pressing processThe methylol forms hydrogen bonds and forms stable ether bonds through aldol condensation, the mechanical property of the resin is enhanced, meanwhile, the aldehyde group and free amino in the melamine resin are subjected to Schiff base reaction, so that the branched cellulose is achieved, the curing speed of the melamine resin is improved, the flexibility of the material can be improved, and simultaneously, the cellulose aldehyde group and the melamine resin are crosslinked, so that the mechanical property of the impregnated film paper is enhanced.
Drawings
FIG. 1 is a surface structure of the antibacterial and antiviral composite additive microspheres obtained in step (6) of example 1.
Detailed Description
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention has no special requirements on the specific type of the paper for the impregnated bond paper.
In order to further illustrate the present invention, the following embodiments are provided to describe the technical solutions provided by the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Preparation example 1
(1) The diameter is 50-100 nm, and the specific surface area is 400-600 m 2 (g) total pore volume of 0.4-0.6 cm 3 (g) mesoporous SiO 2 The nano particles are placed for 15 hours at the temperature of 300 ℃ to obtain activated mesoporous SiO 2 A nanoparticle;
(2) 4 parts of 4-aminoethyl-3-piperazinyl propyl methyl dimethoxy silane and mesoporous SiO 2 0.6 part of nano-particles are added into 100 parts of absolute ethyl alcohol, stirred for 24 hours at normal temperature, volatilized ethyl alcohol is recovered, and aminated mesoporous SiO is obtained after drying 2 A nanoparticle;
(3) 4 parts of glycyrrhizic acid and 5 parts of sophoridine are uniformly mixed to prepare a natural plant extract mixture;
(4) the aminated mesoporous SiO obtained in the step (2) is 2 Mixing 40 parts of nano particles, 40 parts of the natural plant extract mixture obtained in the step (3) and 100 parts of sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 7.21, stirring at the normal temperature of 1200 rpm for 48 hours, and freeze-drying to obtain the antibioticThe active assistant microsphere for bacteria and virus resistance.
(5) 10 parts of cellulose nanocrystal with the diameter of 10-20 nm and the length of 200-300 nm, 10 parts of sodium periodate, 1 part of isopropanol and 100 parts of water are mixed in a beaker, stirred at 80 ℃ in the dark for 8 hours, dialyzed to remove unreacted sodium periodate and isopropanol, and freeze-dried to obtain the aldehyde modified cellulose nanocrystal.
(6) 4 parts of aldehyde modified cellulose nanocrystalline obtained in the step (5), 20 parts of antibacterial and antiviral active auxiliary agent microsphere obtained in the step (4) and 100 parts of water are mixed and homogenized at a high speed of 20000 revolutions per minute for 3min to obtain antibacterial and antiviral composite additive microsphere, the surface structure of which is shown in figure 1, and the nanocrystalline attached to the surface can be obviously seen;
(7) and (3) adding 100 parts of the antibacterial and antiviral composite additive microspheres obtained in the step (6) into 6000 parts of melamine resin adhesive (purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., solid content of 55%, viscosity of 19-21 mPa · s, pH value of 8-9.5 and melamine molecular weight of 126 g/mol), and stirring at 1200 rpm for 2min to obtain the antibacterial and antiviral melamine resin composition.
Example 1 preparation of adhesive film paper
1) Dipping ordinary paper (with the thickness of 0.15mm and the gram weight of 90 g/square meter) in a urea-formaldehyde resin adhesive (urea-formaldehyde resin is purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., the molecular weight is about 10000, the solid content is 48%, the pH value is 7-7.5, the viscosity is 10-12 mPa & s, and the curing time is 180 s), controlling the dipping amount to be 150% of the weight of the paper by roll coating, and then drying at 130 ℃ for 10min to obtain the one-time dipped and dried adhesive film paper I;
2) the one-time dip dried adhesive film paper is dipped in the antibacterial and antiviral melamine resin composition obtained in preparation example 1, the dip amount is controlled to be 130% of the weight of the adhesive film paper I by roll coating, and then the adhesive film paper is dried at 130 ℃ for 10 min.
Preparation example 2 preparation of antibacterial and antiviral Melamine resin composition
(1) 20 to 50nm in diameter and 200 to 400m in specific surface area 2 (ii) a total pore volume of 0.2 to 0.4cm 3 (iv) g mesoporous SiO 2 The nanoparticles are left at 250 ℃ for 12h to obtain activated nanoparticlesMesoporous SiO 2 And (3) nanoparticles.
(2) 2.5 parts of N-2-aminoethyl-3-aminopropyltriethoxysilane, and the activated mesoporous SiO obtained in step (1) 2 0.1 part of nano-particles are added into 100 parts of absolute ethyl alcohol, stirred for 24 hours at normal temperature, volatilized ethyl alcohol is recovered, and aminated mesoporous SiO is obtained after drying 2 And (3) nanoparticles.
(3) And (3) uniformly mixing 2 parts of glycyrrhizic acid and 3 parts of sophoridine to obtain a natural plant extract mixture.
(4) Amination mesoporous SiO obtained in step (2) 2 And (3) mixing 15 parts of nano particles, 20 parts of the natural plant extract mixture obtained in the step (3) and 100 parts of sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 7.21 to prepare a mixed solution, stirring at the normal temperature of 600 rpm for 24 hours, and freeze-drying to obtain the antibacterial and antiviral activity aid microspheres.
(5) Mixing 5 parts of cellulose nanocrystal with the diameter of 5-10 nm and the length of 100-200 nm, 5 parts of sodium periodate, 1 part of isopropanol and 100 parts of water in a beaker, stirring for 4 hours at 60 ℃ in the dark, dialyzing to remove unreacted sodium periodate and isopropanol, and freeze-drying to obtain the aldehyde cellulose nanocrystal.
(6) 4 parts of aldehyde cellulose nanocrystalline obtained in the step (5), 20 parts of antibacterial and antiviral auxiliary agent microsphere obtained in the step (4) and 100 parts of water are mixed to prepare a mixed solution, and the mixed solution is homogenized at a high speed of 10000 r/min for 1min to obtain the antibacterial and antiviral composite additive microsphere.
(7) And (3) adding 100 parts of the antibacterial and antiviral composite additive microspheres obtained in the step (6) into 6000 parts of melamine resin adhesive (purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., solid content of 55%, viscosity of 19-21 mPa · s, pH value of 8-9.5, curing time of 600s, and melamine molecular weight of 126 g/mol), and stirring for 2min at 1000 r/min to obtain the antibacterial and antiviral melamine resin composition.
Example 2 preparation of adhesive film paper
1) The paper (thickness is 0.15mm, gram weight is 90 g/square meter) is soaked in a urea-formaldehyde resin adhesive (urea-formaldehyde resin is purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., molecular weight is about 10000, solid content is 48%, pH value is 7-7.5, viscosity is 10-12 mPa & s, curing time is 180 s), the gum dipping amount is controlled to be 120% of the weight of the paper by roll coating, and then the paper is dried at 110 ℃ for 5min to obtain the one-time gum dipping and drying adhesive film paper I.
2) The one-time dip dried adhesive film paper is dipped in the antibacterial and antiviral melamine resin composition obtained in preparation example 2, the dip amount is controlled to be 115% of the weight of the adhesive film paper I by roll coating, and then the adhesive film paper is dried for 5min at 110 ℃.
Preparation example 3 preparation of antibacterial and antiviral Melamine resin composition
(1) The diameter is 50-60 nm, and the specific surface area is 400-500 m 2 (g) total pore volume of 0.3-0.4 cm 3 (g) mesoporous SiO 2 The nano particles are placed for 14 hours at 270 ℃ to obtain activated mesoporous SiO 2 And (3) nanoparticles.
(2) 3 parts of 3-diethylenetriaminopropyltrimethoxysilane, and the activated mesoporous SiO obtained in the step (1) 2 0.4 part of nano-particles are added into 100 parts of absolute ethyl alcohol, stirred for 24 hours at normal temperature, volatilized ethyl alcohol is recovered, and aminated mesoporous SiO is obtained after drying 2 And (3) nanoparticles.
(3) Uniformly mixing 3 parts of glycyrrhizic acid and 4 parts of sophoridine to prepare a natural plant extract mixture;
(4) and (3) mixing 30 parts of aminated mesoporous SiO2 nanoparticles obtained in the step (2), 30 parts of natural plant extract mixture obtained in the step (3) and 100 parts of sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 7.21, stirring for 30 hours at the normal temperature at 1000 rpm, and freeze-drying to obtain the antibacterial and antiviral active aid microspheres.
(5) Mixing 7 parts of cellulose nanocrystal with the diameter of 10-15 nm and the length of 200nm, 7 parts of sodium periodate, 1 part of isopropanol and 100 parts of water in a beaker, stirring for 6 hours at 60 ℃ in a dark place, dialyzing to remove unreacted sodium periodate and isopropanol, and freeze-drying to obtain the aldehyde cellulose nanocrystal.
(6) 4 parts of aldehyde cellulose nanocrystalline obtained in the step (5), 23 parts of antibacterial and antiviral auxiliary agent microsphere obtained in the step (4) and 100 parts of water are mixed to prepare a mixed solution, and the mixed solution is homogenized at a high speed of 15000 r/min for 2min to obtain the antibacterial and antiviral composite additive microsphere.
(7) And (3) adding 100 parts of the antibacterial and antiviral composite additive microspheres obtained in the step (6) into 6000 parts of melamine resin adhesive (purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., solid content of 55%, viscosity of 19-21 mPa · s, pH value of 8-9.5, curing time of 600s, and melamine molecular weight of 126 g/mo), and stirring at 1000 r/min for 1.5min to obtain the antibacterial and antiviral melamine resin composition.
EXAMPLE 3 preparation of adhesive film paper
1) Soaking paper (with the thickness of 0.15mm and the gram weight of 90 g/square meter) in a urea-formaldehyde resin adhesive (urea-formaldehyde resin is purchased from Zhejiang sublimation Yunfeng New materials Co., Ltd., the molecular weight is about 10000, the solid content is 48%, the pH value is 7-7.5, the viscosity is 10-12 mPa & s, and the curing time is 180 s), controlling the gum dipping amount to be 120% of the weight of the paper by roll coating, and then drying at 120 ℃ for 8min to obtain the one-time gum dipping dried adhesive film paper I;
2) dipping the dried film paper subjected to primary gum dipping into the antibacterial and antiviral melamine resin composition obtained in the preparation example 3, dipping the dried film paper subjected to primary gum dipping into a secondary gum dipping adhesive system, controlling the gum dipping amount to be 130% of the weight of the film paper I by roll coating, and then drying at 120 ℃ for 7 min.
Preparation example 4 preparation of antibacterial and antiviral Melamine resin composition
The other conditions are the same as those of preparation example 1, except that step 1 is omitted, and the material with the diameter of 50-100 nm and the specific surface area of 400-600 m is directly adopted 2 (g) total pore volume of 0.4-0.6 cm 3 (ii) mesoporous silica per gram.
EXAMPLE 4 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in production example 4 was used instead of the antibacterial and antiviral melamine resin composition obtained in production example 1.
Preparation example 5 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that 3 parts of chitin was used instead of 5 parts of sophoridine in step (3) of preparation example 1.
EXAMPLE 5 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in production example 5 was used instead of the antibacterial and antiviral melamine resin composition obtained in production example 1.
Preparation example 6 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that in step (2), N-2-aminoethyl-3-aminopropyltriethoxysilane was used in place of 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane.
EXAMPLE 6 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in production example 6 was used instead of the antibacterial and antiviral melamine resin composition obtained in production example 1.
Preparation example 7 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that 3-divinyltriaminopropyltrimethoxysilane was used in place of 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane in step (2).
Example 7 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in production example 7 was used in place of the antibacterial and antiviral melamine resin composition obtained in production example 1.
Preparation example 8 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that in step (2), γ -aminopropyltriethoxysilane was used in place of 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane.
EXAMPLE 8 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in production example 8 was used in place of the antibacterial and antiviral melamine resin composition obtained in production example 1.
Comparative preparation example 1 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that 9 parts of glycyrrhizic acid was used instead of the natural plant extract mixture obtained by mixing 4 parts of glycyrrhizic acid and 5 parts of sophoridine in preparation example 1.
Comparative example 1 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in comparative preparation example 1 was used in place of the antibacterial and antiviral melamine resin composition obtained in preparation example 1.
Comparative preparation example 2 preparation of antibacterial and antiviral Melamine resin composition
The other conditions were the same as in preparation example 1 except that 9 parts of sophoridine was used instead of the mixture of natural plant extracts prepared by mixing 4 parts of glycyrrhizic acid and 5 parts of sophoridine in preparation example 1.
Comparative example 2 preparation of adhesive film paper
The other conditions were the same as in example 1 except that the antibacterial and antiviral melamine resin composition obtained in comparative preparation example 2 was used in place of the antibacterial and antiviral melamine resin composition obtained in preparation example 1.
Comparative preparation example 3 preparation of antibacterial and antiviral Melamine resin composition
(1) The size is 50-100 nm, and the specific surface area is 400-600 m 2 (g) total pore volume of 0.4-0.6 cm 3 (g) mesoporous SiO 2 Placing the nanoparticles at 300 ℃ for 15 h;
(2) 4 parts of glycyrrhizic acid and 5 parts of sophoridine are uniformly mixed to prepare a natural plant extract mixture;
(3) subjecting the mesoporous SiO obtained in the step (1) to 2 And (3) mixing 4 parts of nano particles, 40 parts of the natural plant extract mixture obtained in the step (2) and 100 parts of sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 7.21, stirring at the normal temperature of 1200 rpm for 48 hours, and freeze-drying to obtain the antibacterial and antiviral active auxiliary agent.
(4) 10 parts of cellulose nanocrystal with the diameter of 10-20 nm and the length of 200-300 nm, 10 parts of sodium periodate, 1 part of isopropanol and 100 parts of water are mixed in a beaker, stirred at 80 ℃ in the dark for 8 hours, dialyzed to remove unreacted sodium periodate and isopropanol, and freeze-dried to obtain the aldehyde modified cellulose nanocrystal.
(5) 5 parts of aldehyde modified cellulose nanocrystalline obtained in the step (4), 30 parts of antibacterial and antiviral active additive obtained in the step (3) and 100 parts of water are mixed, and the mixture is homogenized at a high speed for 3min, wherein the homogenization speed is 20000 revolutions per minute, so that the antibacterial and antiviral compound additive is obtained;
(6) and (3) adding 100 parts of the antibacterial and antiviral composite additive obtained in the step (5) into 6000 parts of melamine resin adhesive (purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., solid content of 55%, viscosity of 19-21 mPa · s, pH value of 8-9.5, curing time of 600s, and melamine molecular weight of 126 g/mo), and stirring at 1200 r/min for 2min to obtain the antibacterial and antiviral melamine resin composition.
Comparative example 3 preparation of adhesive film paper
1) Dipping ordinary paper (with the thickness of 0.15mm and the gram weight of 90 g/square meter) in a urea-formaldehyde resin adhesive (urea-formaldehyde resin is purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., the molecular weight is about 10000, the solid content is 48%, the pH value is 7-7.5, the viscosity is 10-12 mPa & s, and the curing time is 180 s), controlling the dipping amount to be 150% of the weight of the paper by roll coating, and then drying at 130 ℃ for 10min to obtain the one-time dipped and dried adhesive film paper;
2) the gummed paper after the primary gumming drying is dipped in the antibacterial and antiviral melamine resin composition obtained in the comparative preparation example 3, the gumming amount is controlled to be 150% of the weight of the gummed paper by roll coating, and then the gummed paper is dried for 10min at 130 ℃.
Comparative preparation example 4
(1) The diameter is 50-100 nm, and the specific surface area is 400-600 m 2 (g) total pore volume of 0.4-0.6 cm 3 (g) mesoporous SiO 2 The nano particles are placed for 15 hours at the temperature of 300 ℃ to obtain activated mesoporous SiO 2 A nanoparticle;
(2) 4 parts of 4-aminoethyl-3-piperazinyl propyl methyl dimethoxy silane and mesoporous SiO 2 0.6 part of nano-particles are added into 100 parts of absolute ethyl alcohol, stirred for 24 hours at normal temperature, volatilized ethyl alcohol is recovered, and aminated mesoporous SiO is obtained after drying 2 A nanoparticle;
(3) 4 parts of glycyrrhizic acid and 5 parts of sophoridine are uniformly mixed to prepare a natural plant extract mixture;
(4) the aminated mesoporous SiO obtained in the step (2) is 2 4 parts of nano particles, 40 parts of the natural plant extract mixture obtained in the step (3) and 100 parts of sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 7.21 are mixed, stirred at the normal temperature of 1200 rpm for 48 hours, and freeze-dried to obtain the antibacterial and antiviral active auxiliary agent;
(5) mixing 25 parts of the antibacterial and antiviral active additive obtained in the step (4) with 100 parts of water, and homogenizing at a high speed of 20000 revolutions per minute for 3min to obtain an antibacterial and antiviral compound additive;
(6) adding 100 parts of the antibacterial and antiviral composite additive obtained in the step (5) into 6000 parts of melamine resin adhesive (purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., solid content of 55%, viscosity of 19-21 mPa · s, pH value of 8-9.5, curing time of 600s, and melamine molecular weight of 126 g/mol), and stirring at 1200 r/min for 2min to obtain the antibacterial and antiviral melamine resin composition.
Comparative example 4 preparation of adhesive film paper
1) Dipping ordinary paper (with the thickness of 0.15mm and the gram weight of 90 g/square meter) in a urea-formaldehyde resin adhesive (urea-formaldehyde resin is purchased from Zhejiang sublimation cloud peak new materials Co., Ltd., the molecular weight is about 10000, the solid content is 48%, the pH value is 7-7.5, the viscosity is 10-12 mPa & s, and the curing time is 180 s), controlling the dipping amount to be 150% of the weight of the paper by roll coating, and then drying at 130 ℃ for 10min to obtain the one-time dipped and dried adhesive film paper I;
2) the one-time dip dried adhesive film paper is dipped in the antibacterial and antiviral melamine resin composition obtained in preparation example 1, the dip amount is controlled to be 130% of the weight of the adhesive film paper I by roll coating, and then the adhesive film paper is dried at 130 ℃ for 10 min.
Comparative example 5
The other conditions were the same as in example 1, except that in the preparation of the antibacterial and antiviral melamine resin composition, the step (5) was omitted, that is, the cellulose nanocrystals were not subjected to the hydroformylation modification, and were directly used in the subsequent steps.
Test example 1
The initial virus inactivation rates of the natural plant antibacterial and antiviral impregnated adhesive film papers prepared in examples 1 to 8 and comparative examples 1 to 3 were tested, and the samples were immersed in water at 25 ℃ for 24 hours. After being taken out, the sample is irradiated for 100 hours by using an ultraviolet lamp which is 30W and has the wavelength of 253.7nm and is in accordance with GB19258 at a distance of 0.8m from the sample, and then a virus inactivation rate test is carried out, so that the virus inactivation durability is recorded as the durable inactivation rate, and the test results are shown in Table 1.
And (3) antibacterial testing: reference JC/T2039-
Virus fire extinguishing rate and durability: reference T/GDTL 011 and 2020 Standard
TABLE 1 Table of the results of the tests of the antibacterial rate, virus inactivation rate and durability of the impregnated bond paper
As can be seen from the data in Table 1, the broad-spectrum antibacterial and antiviral abilities of examples 1-8 are significantly improved and the antibacterial and antiviral durability is good as seen from the comparison between examples 1-8 and comparative examples 1-4. Comparative example 1 does not use sophoridine and has poor inactivation of hepatitis B and enteroviruses. Comparative example 2 does not use glycyrrhizic acid and has poor differential activity against influenza virus and staphylococcus. Comparative example 3 does not aminate mesoporous silica, and may have poor binding and loading capacity to natural plant extracts, resulting in poor antiviral properties and poor stability. Comparative example 4 no aldehyde-based nanocrystal was added, and the dispersibility was poor, resulting in poor antiviral properties and slightly poor stability. In addition, it can be seen from the comparison of example 1 with examples 2-3 and 6-8 that the antiviral durability is better when mesoporous silica is treated with 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane.
Test example 2
The natural plant antibacterial and antiviral impregnated bond paper prepared in the examples 1-8 and the comparative examples 4-5 is subjected to hot-pressing veneering to prepare an ecological plate, the apparent performance of the bond paper is determined according to the requirement of GB/T28995-2012012 for appearance quality (Table 2), and the apparent quality of the ecological plate is determined according to the requirement of GB/T34722-2017 for appearance quality (Table 3).
Table 2 apparent property test results of the adhesive film paper
Table 3 test results of the apparent performance of the ecological plate
As can be seen from the data in Table 2, the natural plant antibacterial and antiviral impregnated bond paper prepared in the embodiments 1-8 completely meets the requirement of GB/T28995-2012012 appearance quality, and the prepared ecological plate meets the requirement of GB/T34722-2017 appearance quality. The comparative example 4 does not adopt cellulose nanocrystals for coating, the surface of the adhesive film paper has obvious adhesive powder, adhesive bubbles and white spots, the number of cracks is increased, the ecological plate has dry flowers, surface scratches and indentations, uneven gloss and slight surface ripples, and the dispersibility of the silicon dioxide nanoparticles influences the apparent performance of the adhesive film paper and the veneered ecological plate; compared with the comparative example 4, the apparent performance of the cellulose nano-crystal coated by the cellulose nano-crystal which is not modified by dialdehyde (comparative example 5) is greatly improved, but the adhesive film paper still has tiny rubber bubbles and rubber powder, and the ecological plate has a small amount of dry flowers, tiny surface scratches and indentations.
Test example 3
The natural plant antibacterial and antiviral impregnated bond paper prepared in examples 1 to 8 and comparative examples 4 to 5 was subjected to hot pressing and veneering to prepare a laminated wood board, and the surface bonding strength was measured according to the standard requirements of GB/T5849 and 2016 laminated wood board (Table 4).
TABLE 4 surface bond Strength test of antiviral joinery board
As can be seen from the data in table 4, the surface bonding strength of the natural plant antiviral blockboard prepared in examples 1 to 8 is far higher than the standard, the scheme of adding cellulose nanocrystals is higher than comparative example 4, and the scheme of adding cellulose nanocrystals is higher than comparative example 5, and the cellulose nanocrystals are not subjected to dialdehyde modification, which indicates that the aldehyde modification plays a role in improving the mechanical properties and the bonding properties of the adhesive film paper.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The antibacterial and antiviral polymer resin composition is characterized by comprising polymer resin, an antibacterial and antiviral active auxiliary agent and aldehyde modified cellulose nanocrystalline, wherein the antibacterial and antiviral active auxiliary agent comprises aminated mesoporous SiO 2 A nano-particle carrier and an antibacterial and antiviral natural plant extract, wherein the antibacterial and antiviral natural plant extract is completely or partially loaded in aminated mesoporous SiO 2 In the pores of the nanoparticle support.
2. The antibacterial and antiviral polymeric resin composition as claimed in claim 1, wherein said polymeric resin is a melamine resin.
3. The antibacterial and antiviral polymeric resin composition as claimed in claim 1, wherein said natural plant extract is a mixture of glycyrrhizic acid and sophoridine, and the weight ratio of glycyrrhizic acid to sophoridine is (2-4) to (3-5); or the natural plant extract is a mixture of glycyrrhizic acid and chitin, and the weight ratio of glycyrrhizic acid to chitin is (2-4) to (1-3).
4. The antibacterial and antiviral polymeric resin composition as claimed in claim 1, wherein said aminated mesoporous SiO is 2 The nano particles are mesoporous silicon dioxide subjected to surface treatment by bisaminosilane, triaminosilane or silane containing amino and piperazinyl.
5. The antibacterial and antiviral polymeric resin composition as claimed in claim 1, wherein the aldehyde modified cellulose nanocrystals are obtained by periodic acid oxidation of cellulose under the catalysis of isopropanol.
6. The antibacterial and antiviral polymeric resin composition as claimed in claim 4, wherein said aminated mesoporous SiO is 2 The nano particles are mesoporous silicon dioxide subjected to surface treatment by 4-aminoethyl-3-piperazinylpropylmethyldimethoxysilane.
7. A preparation method of natural antibacterial antiviral adhesive film paper is characterized by comprising the following steps:
1) preparing the antibacterial and antiviral polymeric resin composition according to any one of claims 1 to 6: loading all or part of an antibacterial and antiviral natural plant extract into the aminated mesoporous silica to obtain antibacterial and antiviral active auxiliary agent microspheres, preparing antibacterial and antiviral composite additive microspheres from the antibacterial and antiviral active auxiliary agent microspheres and the aldehyde cellulose nanocrystals, and adding the antibacterial and antiviral composite additive microspheres into a high-molecular resin adhesive;
2) dipping the paper into a urea-formaldehyde resin adhesive, controlling the dipping amount through roll coating, and then drying to obtain the one-time dipping dry adhesive film paper;
3) dipping the primary gum dipping dried adhesive film paper into the antibacterial and antiviral polymer resin composition obtained in the step 1), controlling gum dipping amount through roll coating, and then drying to obtain the natural antibacterial and antiviral adhesive film paper.
8. The method of claim 7, wherein the antibacterial and antiviral polymeric resin composition is prepared by: A) preparing aminated mesoporous silica, B) preparing a natural plant extract mixture, C) mixing the aminated mesoporous silica obtained in the step A) and the natural plant extract mixture obtained in the step B) with a sodium hydrogen phosphate-disodium hydrogen phosphate buffer solution, stirring at normal temperature, and freeze-drying to obtain the antibacterial and antiviral activity aid; D) adding the fiber nanocrystal, sodium periodate and isopropanol into water, stirring for 4-10 hours at 70-90 ℃ in a dark place, dialyzing to remove unreacted sodium periodate and isopropanol, and freeze-drying to obtain the aldehyde modified cellulose nanocrystal; E) adding the antibacterial and antiviral active auxiliary agent obtained in the step C) and the aldehyde modified cellulose nanocrystalline obtained in the step D) into water for mixing to obtain an antibacterial and antiviral compound additive microsphere; F) and E) adding the antibacterial and antiviral composite additive microspheres obtained in the step E) into a high polymer resin adhesive to obtain an antibacterial and antiviral high polymer resin composition.
9. The method of claim 8, wherein the antimicrobial and antiviral co-agent: aldehyde modified cellulose nanocrystal: the weight ratio of the water is (2-5): 6-30): 100.
10. The adhesive film paper prepared by the preparation method of any one of claims 7 to 9.
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