An environmentally friendly corrugated paper with an antibacterial and antifouling coating

Abstract

The present invention relates to the field of corrugated paper, and discloses an environmentally friendly corrugated paper with an antibacterial and antifouling coating. The surface of the corrugated paper is coated with an antibacterial and antifouling coating, and the antibacterial and antifouling coating comprises the following raw materials in parts by weight: 45-70 parts of waterborne polyurethane, 10-20 parts of a modified additive, 5-15 parts of modified nano-silica, 0.1-0.5 part of a dispersant, 0.2-0.5 part of a leveling agent, 1-2 parts of an antifoaming agent, 0.5-1 part of a thickener, 1.5-2 parts of a film-forming auxiliary, and 5-8 parts of deionized water; the modified additive is prepared by blending modified polyvinyl alcohol and a chitosan solution, adopting an emulsion polymerization method, using glutaraldehyde as a crosslinking agent, introducing quaternary ammonium groups and loading titanium dioxide on the surface of quaternized chitosan; the modified nano-silica is obtained by grafting glycidyl neodecanoate on the surface of carboxylated nano-silica through a chemical reaction. The present invention endows the coating with excellent waterproof and antifouling properties and antibacterial effects by adding the modified additive and the modified silica.

Description

Technical Field

[0001] The present invention belongs to the technical field of corrugated paper, and particularly relates to an environmentally friendly corrugated paper with an antibacterial and antifouling coating. Background Art

[0002] Corrugated paper is a multi-layer cardboard composed of a flat paper and some corrugated cardboard. Its hollow corrugated structure gives it strong pressure resistance and seismic resistance, and it is used to manufacture various corrugated cartons, paper pallets, paper cushions, paper corner protectors, display racks, paper furniture, paper toys, lightweight building materials products, etc. The products show a diversified trend and have broad industrial application prospects. Taking single corrugated cardboard as an example, the basic structure of corrugated cardboard, that is, three-layer corrugated cardboard, is composed of a face paper, a lining paper and a layer of corrugated core paper bonded together. A corrugated carton is a paper container made of corrugated cardboard, which is an ideal packaging container with excellent properties such as good cushioning performance, light weight, firmness, high strength, sufficient raw materials, low cost, convenient for automated production, wide applicability, good printability, environmental friendliness, and recyclability. It has been used for transportation packaging and sales packaging for many years.

[0003] Due to the material of corrugated paper, the surface of corrugated paper is extremely easy to absorb water and adhere to bacteria and molds. After the corrugated carton absorbs water and gets damp, on the one hand, it will cause the corrugated cardboard to be easily deformed when stressed, affecting the use effect; on the other hand, bacteria and molds will reproduce on the corrugated paper, producing a large amount of plaque and mildew spots, with poor waterproof and antifouling performance, and various performances will drop significantly, and even the phenomenon of being unable to be used will occur. Moreover, contacting a moldy carton is not good for physical health. Therefore, there is an urgent need for an environmentally friendly corrugated paper with an antibacterial and antifouling coating to solve the problems of poor waterproof and antifouling performance of corrugated paper and the generation of bacteria and molds. Summary of the Invention

[0004] To solve the deficiencies mentioned in the above background art, the purpose of the present invention is to provide an environmentally friendly corrugated paper with an antibacterial and antifouling coating, which endows the coating with excellent waterproof and antifouling performance and antibacterial effect by adding a modified additive and modified silica.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] An environmentally friendly corrugated paper with an antibacterial and antifouling coating, wherein the surface of the corrugated paper is coated with an antibacterial and antifouling coating, and the antibacterial and antifouling coating comprises the following raw materials in parts by weight: 45-70 parts of waterborne polyurethane, 10-20 parts of a modified additive, 5-15 parts of modified nano-silica, 0.1-0.5 part of a dispersant, 0.2-0.5 part of a leveling agent, 1-2 parts of an antifoaming agent, 0.5-1 part of a thickening agent, 1.5-2 parts of a film-forming auxiliary agent, and 5-8 parts of deionized water;

[0007] The modified additive is prepared by blending modified polyvinyl alcohol with a chitosan solution, using emulsion polymerization method with glutaraldehyde as the crosslinking agent to introduce quaternary ammonium groups and load titanium dioxide on the surface of quaternized chitosan; the modified nano-silica is prepared by grafting glycidyl neodecanoate on the surface of carboxylated nano-silica through chemical reaction.

[0008] Preferably, the dispersant is one of calcium stearate or oxidized polyethylene wax; the leveling agent is sodium polyacrylate; the defoaming agent is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether; the thickening agent is polyacrylamide; the film-forming aid is an alcohol ester compound.

[0009] Preferably, the preparation method of the modified additive comprises the following steps:

[0010] (1) Take polyvinyl alcohol and dissolve it in deionized water at 80-95 °C to obtain a polyvinyl alcohol solution. Add sodium methyl silicate to the polyvinyl alcohol solution and react at 80-95 °C for 1-3 h to obtain modified polyvinyl alcohol.

[0011] (2) Take chitosan and dissolve it in an acetic acid solution to obtain a chitosan solution. Heat the chitosan solution to 75-85 °C, add the modified polyvinyl alcohol and stir and mix for 30-45 min to obtain Component One.

[0012] (3) Take Span 80 and liquid paraffin and mix them evenly to obtain Component Two.

[0013] (4) Mix Component One and Component Two evenly, add a glutaraldehyde solution, and place it in a water bath at 50-85 °C for crosslinking reaction for 30-45 min. After the reaction is completed, wash and dry to obtain Component Three.

[0014] (5) Mix Component Three with isopropanol, add 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and react at 70-85 °C for 2-4 h. After the reaction is completed, wash and dry to obtain Component Four.

[0015] (6) Dissolve Component Four in deionized water, add urea and titanyl sulfate and stir evenly, then transfer it to a hydrothermal reaction kettle and react at 150-165 °C for 3-4 h. After the reaction is completed, wash and dry to prepare the modified additive.

[0016] Preferably, in the step (1), the mass fraction of the polyvinyl alcohol solution is 15-22%, and the mass ratio of the polyvinyl alcohol solution to sodium methyl silicate is 8-15:1.

[0017] Preferably, the mass fraction of the acetic acid solution is 1.5 - 5%; the mass fraction of the glutaraldehyde solution is 45 - 55%; the addition ratio of chitosan, acetic acid solution, modified polyvinyl alcohol, span 80, liquid paraffin and glutaraldehyde solution is 1.5 - 4 g: 100 - 150 mL: 30 - 50 mL: 12 - 20 mL: 180 - 220 mL: 0.4 - 1.2 mL.

[0018] Preferably, the addition ratio of component three and 3-chloro-2-hydroxypropyltrimethylammonium chloride in step (5) is 1 g: 4 - 6 mL; the mass fraction of 3-chloro-2-hydroxypropyltrimethylammonium chloride is 50 - 70%.

[0019] Preferably, the mass ratio of component four, urea and titanyl sulfate in step (6) is 0.15 - 0.3: 0.8 - 1.5: 0.08 - 0.2.

[0020] Preferably, the preparation method of the modified nano-silica includes the following steps:

[0021] A. Take nano-silica and ultrasonically disperse it in N, N-dimethylformamide to obtain a nano-silica suspension. Take γ-aminopropyltriethoxysilane and succinic anhydride, mix them, uniformly disperse them in N, N-dimethylformamide, stir for 2 - 4 h, then add the nano-silica suspension and deionized water, and continue to stir and react for 4 - 6 h. After the reaction is completed, wash and dry to obtain carboxylated nano-silica;

[0022] B. Take the carboxylated nano-silica and ultrasonically disperse it in butyl acetate, add triphenylphosphine, heat up to 90 - 105 °C, then add glycidyl neodecanoate and react for 8 - 12 h. After the reaction is completed, filter, wash and dry to prepare the modified nano-silica.

[0023] Preferably, the mass ratio of the carboxylated nano-silica and glycidyl neodecanoate in step B is 1: 3.5 - 5.

[0024] Preferably, the preparation method of the antibacterial and antifouling coating includes the following steps:

[0025] S1. Take deionized water, dispersant, modified additive, modified nano-silica in parts by weight and pour them into a mixer. After stirring and mixing evenly, a premix is obtained;

[0026] S2. Add waterborne polyurethane, leveling agent, defoaming agent, thickening agent in parts by weight to the premix and stir evenly, then add a film-forming aid and continue to stir and mix evenly to prepare the antibacterial and antifouling coating.

[0027] The beneficial effects of the present invention:

[0028] The present invention utilizes the cross-linking reaction between sodium methyl silicate and polyvinyl alcohol. The silanol groups in the structure of sodium methyl silicate are active groups and are prone to undergo dehydration cross-linking reactions with the hydroxyl groups in the structure of polyvinyl alcohol, resulting in modified polyvinyl alcohol containing Si-O-C functional groups. Among them, polyvinyl alcohol is a water-soluble polymer with good film-forming properties and elasticity, and has no toxic side effects. Sodium methyl silicate can improve the flexibility and hydrophobicity of the matrix, and has the characteristics of being green, environmentally friendly, and pollution-free. The prepared modified polyvinyl alcohol can form a dense protective film layer with excellent hydrophobic properties. The present invention blends the modified polyvinyl alcohol with a chitosan solution and uses emulsion polymerization with glutaraldehyde as the cross-linking agent to prepare Component Three. The amino and hydroxyl groups in the chitosan structure are connected by the aldehyde groups in the glutaraldehyde structure, promoting the cross-linking of sheet-like chitosan into spheres to increase its specific surface area. Then, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is introduced for the quaternization of chitosan, introducing quaternary ammonium groups into the chitosan structure. Then, titanium dioxide is loaded on the surface of quaternized chitosan by hydrothermal method. Among them, chitosan and quaternary ammonium groups have broad-spectrum antibacterial properties, and at the same time, titanium dioxide has antibacterial, deodorant, and mildew-proof effects, and the loading of titanium dioxide fills the pores of the matrix, improving the mechanical properties of the coating to a certain extent. The modified additive prepared by the present invention endows the coating with excellent waterproof and stain-resistant properties and antibacterial and mildew-proof effects.

[0029] The present invention carboxylates nano-silica using γ-aminopropyltriethoxysilane and succinic anhydride, and then grafts glycidyl neodecanoate. The carboxyl groups in the structure of carboxylated nano-silica react with the epoxy groups in the structure of glycidyl neodecanoate, thereby introducing tertiary carbonic acid hydrophobic groups on the surface of nano-silica, enhancing the hydrophobicity of the coating, and at the same time facilitating the dispersion of nano-silica, enabling the full play of the mechanical properties of nano-silica. The present invention uses the modified additive and modified nano-silica in combination, enabling the coating to form a superhydrophobic surface, which can play a role in isolating water vapor, avoiding providing conditions for the production and reproduction of bacteria, enabling the coating to achieve antibacterial and mildew-proof effects, and at the same time, the superhydrophobic surface can also endow the coating with anti-fouling and self-cleaning effects. Detailed implementation manners

[0030] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0031] Example 1 A preparation method of a modified additive includes the following steps:

[0032] (1) Dissolve polyvinyl alcohol in deionized water at 85 °C to prepare a polyvinyl alcohol solution with a mass fraction of 15%. Add 5 g of sodium methyl silicate to 50 g of the polyvinyl alcohol solution and react at 80 °C for 2 h to obtain modified polyvinyl alcohol;

[0033] (2) Dissolve 2 g of chitosan in 100 mL of acetic acid solution with a mass fraction of 2% to obtain a chitosan solution. Heat the chitosan solution to 80 °C, add 45 mL of modified polyvinyl alcohol and stir and mix for 40 min to obtain Component 1;

[0034] (3) Mix 15 mL of Span 80 and 185 mL of liquid paraffin evenly to obtain Component 2;

[0035] (4) Mix Component 1 and Component 2 evenly, add 0.7 mL of glutaraldehyde solution with a mass fraction of 50%, and place it in a water bath at 85 °C for cross-linking reaction for 30 min. After the reaction is completed, wash and dry to obtain Component 3;

[0036] (5) Mix 1 g of Component 3 with 20 mL of isopropyl alcohol, add 5 mL of 3-chloro-2-hydroxypropyltrimethylammonium chloride with a mass fraction of 65%, and react at 80 °C for 3 h. After the reaction is completed, wash and dry to obtain Component 4;

[0037] (6) Dissolve 0.2 g of Component 4 in 50 mL of deionized water, add 1.2 g of urea and 0.15 g of titanium oxysulfate and stir evenly, then transfer it to a hydrothermal reaction kettle and react at 160 °C for 4 h. After the reaction is completed, wash and dry to prepare the modified additive.

[0038] Example 2 A preparation method of modified nano-silica includes the following steps:

[0039] A. Ultrasonically disperse 1 g of nano-silica in 100 mL of N,N-dimethylformamide to obtain a nano-silica suspension. Mix 1.2 g of γ-aminopropyltriethoxysilane and 0.87 g of succinic anhydride, evenly disperse them in 100 mL of N,N-dimethylformamide, stir for 4 h, then add the nano-silica suspension and 10 mL of deionized water, and continue to stir and react for 5 h. After the reaction is completed, wash and dry to obtain carboxylated nano-silica;

[0040] B. Ultrasonically disperse 1 g of carboxylated nano-silica in 40 mL of butyl acetate, add 0.007 g of triphenylphosphine, heat to 95 °C, then add 4.8 g of glycidyl neodecanoate and react for 12 h. After the reaction is completed, filter, wash and dry to prepare the modified nano-silica.

[0041] Example 3: An environmentally friendly corrugated paper with an antibacterial and antifouling coating. The surface of the corrugated paper is coated with an antibacterial and antifouling coating, which comprises the following raw materials in parts by weight: 47 parts of waterborne polyurethane, 10 parts of the modified additive prepared in Example 1, 5 parts of the modified nano-silica prepared in Example 2, 0.2 part of dispersant calcium stearate, 0.2 part of leveling agent sodium polyacrylate, 1 part of defoaming agent fatty alcohol polyoxyethylene ether, 0.5 part of thickening agent polyacrylamide, 1.5 parts of film-forming auxiliary TEXANOL, and 5 parts of deionized water.

[0042] The preparation method of the above antibacterial and antifouling coating comprises the following steps:

[0043] S1. Take the deionized water, dispersant, modified additive, and modified nano-silica in parts by weight and pour them into a mixer. After stirring and mixing evenly, a premix is obtained.

[0044] S2. Add the waterborne polyurethane, leveling agent, defoaming agent, and thickening agent in parts by weight to the premix and stir evenly. Then add the film-forming auxiliary and continue to stir and mix evenly to prepare the antibacterial and antifouling coating.

[0045] Example 4: An environmentally friendly corrugated paper with an antibacterial and antifouling coating. The surface of the corrugated paper is coated with an antibacterial and antifouling coating, which comprises the following raw materials in parts by weight: 62 parts of waterborne polyurethane, 15 parts of the modified additive prepared in Example 1, 10 parts of the modified nano-silica prepared in Example 2, 0.4 part of dispersant oxidized polyethylene wax, 0.3 part of leveling agent sodium polyacrylate, 1.5 parts of defoaming agent alkylphenol polyoxyethylene ether, 1 part of thickening agent polyacrylamide, 2 parts of film-forming auxiliary TEXANOL, and 7 parts of deionized water.

[0046] The preparation method of the above antibacterial and antifouling coating is the same as that of Example 3.

[0047] Example 5: An environmentally friendly corrugated paper with an antibacterial and antifouling coating. The surface of the corrugated paper is coated with an antibacterial and antifouling coating, which comprises the following raw materials in parts by weight: 68 parts of waterborne polyurethane, 20 parts of the modified additive prepared in Example 1, 14 parts of the modified nano-silica prepared in Example 2, 0.5 part of dispersant calcium stearate, 0.5 part of leveling agent sodium polyacrylate, 2 parts of defoaming agent fatty alcohol polyoxyethylene ether, 1 part of thickening agent polyacrylamide, 2 parts of film-forming auxiliary TEXANOL, and 8 parts of deionized water.

[0048] The preparation method of the above antibacterial and antifouling coating is the same as that of Example 3.

[0049] Comparative Example 1: The preparation method of a modified additive comprises the following steps:

[0050] (1) Take 2 g of chitosan and dissolve it in 100 mL of acetic acid solution with a mass fraction of 2%, to obtain Component 1.

[0051] (2) Take 15 mL of Span 80 and 185 mL of liquid paraffin, mix them evenly to obtain Component Two.

[0052] (3) Mix Component One and Component Two evenly, add 0.7 mL of a 50% glutaraldehyde solution, place it in a water bath at 85 °C for cross-linking reaction for 30 min. After the reaction is completed, wash and dry to obtain Component Three.

[0053] (4) Mix 1 g of Component Three with 20 mL of isopropanol, add 5 mL of 3-chloro-2-hydroxypropyltrimethylammonium chloride with a mass fraction of 65%, place it at 80 °C for reaction for 3 h. After the reaction is completed, wash and dry to obtain Component Four.

[0054] (5) Dissolve 0.2 g of Component Four in 50 mL of deionized water, add 1.2 g of urea and 0.15 g of titanium oxysulfate, stir evenly, then transfer it to a hydrothermal reaction kettle, place it at 160 °C for reaction for 4 h. After the reaction is completed, wash and dry to prepare the modified additive.

[0055] Comparative Example 2 A preparation method of a modified additive includes the following steps:

[0056] (1) Take polyvinyl alcohol and dissolve it in deionized water at 85 °C to prepare a polyvinyl alcohol solution with a mass fraction of 15%. Add 5 g of sodium methyl silicate to 50 g of the polyvinyl alcohol solution, place it at 80 °C for reaction for 2 h to obtain modified polyvinyl alcohol.

[0057] (2) Take 2 g of chitosan and dissolve it in 100 mL of an acetic acid solution with a mass fraction of 2% to obtain a chitosan solution. Heat the chitosan solution to 80 °C, add 45 mL of modified polyvinyl alcohol and stir and mix for 40 min to obtain Component One.

[0058] (3) Take 15 mL of Span 80 and 185 mL of liquid paraffin, mix them evenly to obtain Component Two.

[0059] (4) Mix Component One and Component Two evenly, add 0.7 mL of a 50% glutaraldehyde solution, place it in a water bath at 85 °C for cross-linking reaction for 30 min. After the reaction is completed, wash and dry to prepare the modified additive.

[0060] Comparative Example 3 An environmentally friendly corrugated paper with an antibacterial and antifouling coating. The surface of the corrugated paper is coated with an antibacterial and antifouling coating. The antibacterial and antifouling coating includes the following raw materials in parts by weight: 68 parts of waterborne polyurethane, 20 parts of the modified additive prepared in Comparative Example 1, 14 parts of the modified nano-silica prepared in Example 2, 0.5 part of dispersant calcium stearate, 0.5 part of leveling agent sodium polyacrylate, 2 parts of defoaming agent fatty alcohol polyoxyethylene ether, 1 part of thickener polyacrylamide, 2 parts of film-forming aid TEXANOL, and 8 parts of deionized water.

[0061] The preparation method of the above antibacterial and antifouling coating is the same as that in Example 3.

[0062] Comparative Example 4 An environmentally friendly corrugated paper with an antibacterial and antifouling coating, the surface of the corrugated paper is coated with an antibacterial and antifouling coating, and the antibacterial and antifouling coating comprises the following raw materials in parts by weight: 68 parts of waterborne polyurethane, 20 parts of the modified additive prepared in Comparative Example 2, 14 parts of the modified nano-silica prepared in Example 2, 0.5 part of dispersant calcium stearate, 0.5 part of leveling agent sodium polyacrylate, 2 parts of defoaming agent fatty alcohol polyoxyethylene ether, 1 part of thickener polyacrylamide, 2 parts of film-forming aid TEXANOL, and 8 parts of deionized water.

[0063] The preparation method of the above antibacterial and antifouling coating is the same as that in Example 3.

[0064] Comparative Example 5 An environmentally friendly corrugated paper with an antibacterial and antifouling coating, the surface of the corrugated paper is coated with an antibacterial and antifouling coating, and the antibacterial and antifouling coating comprises the following raw materials in parts by weight: 68 parts of waterborne polyurethane, 20 parts of the modified additive prepared in Example 1, 14 parts of nano-silica, 0.5 part of dispersant calcium stearate, 0.5 part of leveling agent sodium polyacrylate, 2 parts of defoaming agent fatty alcohol polyoxyethylene ether, 1 part of thickener polyacrylamide, 2 parts of film-forming aid TEXANOL, and 8 parts of deionized water.

[0065] The preparation method of the above antibacterial and antifouling coating is the same as that in Example 3.

[0066] Performance testing

[0067] a. Place the coatings prepared in Examples 3-5 and Comparative Examples 3-5 in a coater and perform roll-type quantitative coating on both sides of the corrugated paper. The designed single-sided coating amount is 2.5 g / m in terms of dry film. 2 ;

[0068] b. In a room temperature environment with a temperature of 23 °C and a relative humidity of 65%, after the coated corrugated paper is completely dried, put it into a constant temperature and humidity box (relative humidity is 50%, temperature is 23 °C) and maintain it for 24 h to obtain the environmentally friendly corrugated paper with an antibacterial and antifouling coating.

[0069] c. Perform performance testing on the obtained corrugated paper: Refer to GB / T 6546-1998 to test the edge crush strength; refer to GB / T6545-1998 to determine the bursting strength; refer to GB / T 2679.7-2005 to test the puncture strength; refer to GB / T 21866-2008 to conduct the antibacterial rate test; use a PZ-200SD type contact angle measuring instrument to conduct the water contact angle test, and the test results are shown in Table 1.

[0070] Table 1 Test results of sample performance

[0071]

[0072]

[0073] As can be seen from the data in Table 1, the mechanical properties of the corrugated paper prepared in Examples 3-5 of the present invention, such as edge crush strength, burst strength and puncture strength, are improved compared with those in Comparative Examples 3-5. Moreover, the corrugated paper prepared in Examples 3-5 has excellent antibacterial effects, and its water contact angles are all greater than 150°, with superhydrophobic surfaces. Among them, the modified additive added in Comparative Example 3 does not contain the modified polyvinyl alcohol component, and the measured water contact angle is less than 150°, not meeting the requirements of superhydrophobicity; the modified additive added in Comparative Example 4 does not contain quaternary ammonium groups and is not loaded with titanium dioxide, and its measured mechanical properties and antibacterial effects are worse than those in Examples 3-5; in Comparative Example 5, the nano-silica is not modified, and its measured mechanical properties are slightly worse than those in Examples 3-5, which may be due to the agglomeration phenomenon of nano-silica resulting in the reduction of its mechanical properties, and its hydrophobicity performance is poor.

[0074] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0075] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art of this industry should understand that the present invention is not limited by the above embodiments, and the above embodiments and the descriptions in the specification only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. An environmentally friendly corrugated paper with an antibacterial and antifouling coating, characterized in that: The surface of the corrugated paper is coated with an antibacterial and antifouling coating, which comprises the following raw materials in parts by weight: 45-70 parts of waterborne polyurethane, 10-20 parts of modified additives, 5-15 parts of modified nano-silicon dioxide, 0.1-0.5 parts of dispersant, 0.2-05 parts of leveling agent, 1-2 parts of defoamer, 0.5-1 parts of thickener, 1.5-2 parts of film-forming aid, and 5-8 parts of deionized water; The preparation method of the modified additive comprises the following steps: (1) dissolving polyvinyl alcohol in deionized water at 80-95° C. to obtain a polyvinyl alcohol solution, adding sodium methyl silicate to the polyvinyl alcohol solution, and reacting the solution at 80-95° C. for 1-3 hours to obtain modified polyvinyl alcohol; (2) dissolving chitosan in acetic acid solution to obtain a chitosan solution, heating the chitosan solution to 75-85° C., adding modified polyvinyl alcohol and stirring for 30-45 minutes to obtain component 1; (3) Mix Span 80 and liquid paraffin evenly to obtain component 2; (4) Mix component one and component two evenly, add glutaraldehyde solution, place in a water bath at 50-85°C for cross-linking reaction for 30-45 minutes, wash and dry after the reaction is completed, and obtain component three; (5) Mixing component three with isopropanol, adding 3-chloro-2-hydroxypropyltrimethylammonium chloride, reacting at 70-85°C for 2-4 hours, washing and drying after the reaction is completed, to obtain component four; (6) Dissolve component 4 in deionized water, add urea and titanyl sulfate, stir evenly, then transfer to a hydrothermal reactor, place at 150-165° C. for reaction for 3-4 hours, wash and dry after the reaction is completed, and prepare a modified additive; The preparation method of the modified nano silicon dioxide comprises the following steps: A. Ultrasonic dispersion of nano-silica in N, N-dimethylformamide to obtain a nano-silica suspension, γ-aminopropyltriethoxysilane and succinic anhydride were mixed and uniformly dispersed in N, N-dimethylformamide, and the nano-silica suspension and deionized water were added after stirring for 2-4 hours, and the stirring reaction was continued for 4-6 hours. After the reaction was completed, the nano-silica was washed and dried to obtain carboxylated nano-silica; B. Ultrasonic dispersion of carboxylated nano-silica in butyl acetate, adding triphenylphosphine, heating to 90-105°C, then adding glycidyl neodecanoate to react for 8-12 hours. After the reaction is completed, filtering, washing and drying are performed to prepare modified nano-silica.

2. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: The dispersant is one of calcium stearate or oxidized polyethylene wax; the leveling agent is sodium polyacrylate; the defoaming agent is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether; the thickener is polyacrylamide; and the film-forming aid is an alcohol ester compound.

3. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: The mass fraction of the polyvinyl alcohol solution in step (1) is 15-22%, and the mass ratio of the polyvinyl alcohol solution to sodium methyl silicate is 8-15:

1.

4. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: The mass fraction of the acetic acid solution is 1.5-5%; the mass fraction of the glutaraldehyde solution is 45-55%; the addition ratio of the chitosan, acetic acid solution, modified polyvinyl alcohol, Span 80, liquid paraffin and glutaraldehyde solution is 1.5-4g: 100-150mL: 30-50mL: 12-20mL: 180-220mL: 0.4-1.2mL.

5. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: In the step (5), the addition ratio of component three and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1 g: 4-6 mL; the mass fraction of the 3-chloro-2-hydroxypropyltrimethylammonium chloride is 50-70%.

6. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: In the step (6), the mass ratio of component 4, urea and titanyl sulfate is 0.15-0.3: 0.8-1.5: 0.08-0.

2.

7. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: In the step B, the mass ratio of carboxylated nano-silica to glycidyl neodecanoate is 1:3.5-5.

8. The environmentally friendly corrugated paper with antibacterial and antifouling coating according to claim 1, characterized in that: The method for preparing the antibacterial and antifouling coating comprises the following steps: S1, pouring parts by weight of deionized water, dispersant, modified additive, and modified nano-silica into a mixer, stirring and mixing them evenly to obtain a premix; S2. Add parts by weight of water-based polyurethane, leveling agent, defoamer, and thickener to the premix and stir evenly, then add film-forming aid and continue stirring to mix evenly to prepare an antibacterial and antifouling coating.

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