High-strength antibacterial decorative paper and preparation method thereof

Abstract

The invention relates to the technical field of decorative paper, and discloses high-strength antibacterial decorative paper and a preparation method thereof. The preparation method comprises the following steps: mixing and reacting a waterborne polyurethane prepolymer with antibacterial functional polyether to obtain a waterborne polyurethane-polyurea prepolymer; carrying out an imidazole end-capping reaction on the waterborne polyurethane-polyurea prepolymer, and neutralizing and emulsifying to obtain an antibacterial impregnation liquid; and dipping decorative raw paper in the antibacterial dipping liquid, taking out the decorative raw paper, and drying the decorative raw paper to obtain the high-strength antibacterial decorative paper. The decorative paper is high in strength, excellent in wear resistance and excellent in antibacterial property, and a veneer prepared from the decorative paper as a veneer material is high in bonding strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of decorative paper, in particular to a high-strength antibacterial decorative paper and a preparation method thereof. BACKGROUND

[0002] Impregnated paper faced artificial boards are widely used in the fields of furniture manufacturing and interior decoration of buildings. The impregnated paper faced artificial boards can effectively separate the external environment and the artificial board substrate, block the emission of harmful substances in the substrate to the environment, and improve the environmental protection of the veneer board.

[0003] At present, the impregnating resin used in the impregnated paper is mostly an adhesive containing formaldehyde, such as urea-formaldehyde resin, phenol-formaldehyde resin and melamine-formaldehyde resin. Such impregnated paper faced artificial boards will release formaldehyde in the process of use, affecting the safety of use, and the impregnating resin itself does not have antibacterial and mildew resistance, affecting the application of the impregnated paper. The prior art such as Chinese patent application CN117845656A discloses a formaldehyde-free antibacterial melamine impregnated paper and a preparation method thereof. The paper base material is impregnated with impregnating glue, hot pressed and pre-solidified to obtain the formaldehyde-free antibacterial melamine impregnated paper. The impregnating glue is composed of melamine-formaldehyde resin, modified sepiolite loaded de-aldehyde agent, cyclodextrin embedded antibacterial agent and chitin. Although the prepared decorative paper has the effect of adsorbing and purifying formaldehyde, the main component of the impregnating glue is melamine-formaldehyde resin, and a small amount of formaldehyde is still free. In addition, the melamine-formaldehyde resin used for paper impregnation is generally in the form of a low molecular weight prepolymer. After the prepolymer is solidified on the surface of the facing material, there are still many polar groups, which have strong hydrophilic ability, and are not conducive to the transportation and storage of the decorative paper. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art and provide a high-strength antibacterial decorative paper and a preparation method thereof. The decorative paper has high strength, excellent wear resistance and good antibacterial property, and the veneer board prepared by using the decorative paper as a facing material has high bonding strength.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a high-strength antibacterial decorative paper, comprising the following steps:

[0007] Step one, mixing polycaprolactone diol, polytetrahydrofuran ether diol, isophorone diisocyanate and dibutyltin dilaurate, reacting, adding 2,2-dimethylol propionic acid after the reaction is completed, continuing to react, and obtaining a water-based polyurethane prepolymer after the reaction is completed;

[0008] Mixing, reacting, after the reaction is completed, obtaining the water-based polyurethane-polyurea prepolymer; mixing the water-based polyurethane-polyurea prepolymer with imidazole, reacting, after the reaction is completed, cooling, adding triethylamine, neutralizing, after neutralizing, adding water emulsion, removing the solvent acetone by rotary evaporation, obtaining the antibacterial type impregnating solution;

[0009] The preparation of the antibacterial functional polyether includes the following steps:

[0010] Step (1), mixing sepiolite with water, ultrasonic dispersion, adding hydrochloric acid aqueous solution to adjust the pH value, stirring, dropwise adding titania sulfate aqueous solution, after dropwise adding is completed, adding ammonia water to adjust the pH value, reacting, after the reaction is completed, obtaining the reaction product, washing, drying, calcining, obtaining the titanium dioxide / sepiolite composite material;

[0011] Mixing the titanium dioxide / sepiolite composite material with silver nitrate aqueous solution, reacting, after the reaction is completed, filtering, taking the filter cake, drying, calcining, grinding and sieving, obtaining the silver-loaded titanium dioxide / sepiolite composite material;

[0012] Step (2), mixing γ-(2,3-epoxypropoxy) propyl trimethoxysilane, ethanol, water, adding a regulator to adjust the pH value, stirring, adding the silver-loaded titanium dioxide / sepiolite composite material, reacting, after the reaction is completed, centrifuging, filtering, taking the filter cake, washing, drying, obtaining the epoxy silver-loaded titanium dioxide / sepiolite composite material;

[0013] Step (3), mixing 1,2-benzisothiazolin-3-one, potassium carbonate, N,N-dimethylformamide, adding 1,3-dibromo-2-propanol, reacting, after the reaction is completed, cooling, obtaining the reaction product, purifying, obtaining the modified benzisothiazolinone; mixing the modified benzisothiazolinone, the epoxy silver-loaded titanium dioxide / sepiolite composite material, water, reacting, after the reaction is completed, filtering, taking the filter cake, washing, drying, obtaining the antibacterial agent;

[0014] Step (4), mixing polyether amine, the antibacterial agent, tetrahydrofuran, reacting, after the reaction is completed, adding p-phenylenediamine, diethylenetriamine, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, mixing uniformly, continuing to react; after the reaction is completed, removing the solvent tetrahydrofuran by rotary evaporation, drying, obtaining the antibacterial functional polyether;

[0015] Step two, immersing the decorative base paper in the antibacterial type impregnating solution, taking out after immersion, drying, obtaining the high-strength antibacterial decorative paper.

[0016] Preferably, in the step one: the molar ratio of polycaprolactone diol, polytetrahydrofuran ether diol, isophorone diisocyanate and 2,2-dimethylol propionic acid is 2-3:1-2:10:2; the amount of dibutyltin dilaurate is 0.5-0.6% of the mass of polycaprolactone diol, polytetrahydrofuran ether diol and isophorone diisocyanate; the reaction condition for preparing the water-based polyurethane prepolymer is: 4-5h under 80-85℃ in nitrogen atmosphere; the continuous reaction condition is: 4-5h under 55-65℃ in nitrogen atmosphere.

[0017] Preferably, in the step one: the mass ratio of water-based polyurethane prepolymer, antibacterial functional polyether and acetone is 75-80:20-25:10-20; the reaction condition for preparing the water-based polyurethane-polyurea prepolymer is: 4-5h under 80-85℃ in nitrogen atmosphere; the reaction condition for preparing the antibacterial type impregnating solution is: 100-120% of the amount of free isocyanate group in the water-based polyurethane-polyurea prepolymer, 3-4h under 50-60℃; the neutralization condition is: neutralized to pH 7 at room temperature; the emulsification condition is: 30-40min under 3500-4000r / min and 0-5℃; the solid content of the antibacterial type impregnating solution is 20-25%.

[0018] Preferably, in the step one for preparing the antibacterial functional polyether, in step (1): the mass ratio of sepiolite and water is 1:20-30; the hydrochloric acid aqueous solution is 36wt% hydrochloric acid aqueous solution, and the adjusted pH value is 4-4.5; the titania sulfate aqueous solution is 1mol / L titania sulfate aqueous solution, and the dropping condition is: 20-30min at room temperature, the mass ratio of sepiolite and 1mol / L titania sulfate aqueous solution is 1:5-6; the ammonia water is 30vol% ammonia water, and the adjusted pH value is 7-8; the reaction condition for preparing the titanium dioxide / sepiolite composite material is: 2-3h under 70-75℃, and the calcination condition is: 2-2.5h under 450-500℃ in nitrogen atmosphere.

[0019] Preferably, in the step one for preparing the antibacterial functional polyether, in step (1): the mass ratio of titanium dioxide / sepiolite composite material and 0.05mol / L silver nitrate aqueous solution is 1:35-40, and the silver nitrate aqueous solution is 0.05mol / L silver nitrate aqueous solution; the reaction condition for preparing the titanium dioxide / sepiolite composite material is: 1.5-2h under 25-35℃ in the dark, and the calcination condition is: 0.5-1h under 200-220℃.

[0020] Further, the mesh number of the sieve is 300 mesh.

[0021] Preferably, in the preparation of the antibacterial functional polyether in step one, in step (2): the mass ratio of γ-(2,3-epoxypropoxy) propyl trimethoxysilane, ethanol, water, silver-loaded titanium dioxide / sea sponge composite material is 5.5-6:60-70:20-30:1-1.2; the stirring condition is stirring for 1.5-2h under the condition of pH value of 4-4.5; the reaction condition is reaction for 24-26h at room temperature.

[0022] Preferably, the adjusting agent comprises 1mol / L aqueous acetic acid.

[0023] Preferably, in the preparation of the antibacterial functional polyether in step one, in step (3): the mass ratio of 1,2-benzisothiazolin-3-one, potassium carbonate, N,N-dimethylformamide, 1,3-dibromo-2-propanol is 3-3.2:2.8-3:30-40:2.2-2.3; the reaction condition for preparing the modified benzisothiazolinone is reaction for 12-16h at a temperature of 60-70℃.

[0024] Preferably, the purification operation comprises: adding water with a mass of 3-4 times that of the reaction product into the reaction product and mixing uniformly, then adding ethyl acetate with a mass of 3-4 times that of the reaction product for extraction, taking the organic phase, adding anhydrous magnesium sulfate with a mass of 15-20% of the organic phase for drying, filtering, taking the filtrate, removing the solvent ethyl acetate by rotary evaporation at a temperature of 60-70℃, and passing through a column.

[0025] Further, the developing agent in the passing through a column operation is prepared by mixing dichloromethane and ethyl acetate at a volume ratio of 1:1.

[0026] Preferably, in the preparation of the antibacterial functional polyether in step one, in step (3): the mass ratio of modified benzisothiazolinone, epoxy-based silver-loaded titanium dioxide / sea sponge composite material, water is 3-3.1:1:80-100; the reaction condition for preparing the antibacterial agent is reaction for 3-4h at a temperature of 80-90℃.

[0027] Preferably, in the preparation of the antibacterial functional polyether in step one, in step (4): the mass ratio of polyether amine, antibacterial agent, tetrahydrofuran, terephthaldehyde, diethylenetriamine, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 18-20:1-1.2:90-100:13-13.4:2-2.1:2-2.2; the reaction condition is reaction for 4-5h at a temperature of 105-115℃; the continued reaction condition is continued reaction for 3-4h at a temperature of 55-65℃ in a nitrogen atmosphere.

[0028] Preferably, in the step two, the mass ratio of the decorative base paper to the antibacterial impregnating solution is 1:20-30, the impregnating condition is 3-5 min at room temperature, and the drying condition is 40-50 min at 80-90 DEG C under a vacuum degree of -0.08 MPa.

[0029] Preferably, the high-strength antibacterial decorative paper is prepared by the method.

[0030] Compared with the prior art, the high-strength antibacterial decorative paper has the following beneficial effects:

[0031] The blocked isocyanate refers to that a blocking agent is used to form a weak bond with the isocyanate group, so that the group is protected, and the isocyanate group is released again at a certain temperature, and the regenerated isocyanate group can react with the substrate containing a hydroxyl functional group to form a higher thermal stability bond. The present application prepares a blocked waterborne polyurethane with antibacterial property, and uses the blocked waterborne polyurethane as an impregnating solution to impregnate the decorative base paper. The obtained decorative paper has high strength, and the antibacterial property and wear resistance are improved. The decorative paper has high bonding strength when used as a veneer material to prepare a veneer board, and can be applied to veneer bonding.

[0032] The present application uses sepiolite as a carrier and titanyl sulfate as a titanium source to prepare a titanium dioxide / sepiolite composite material by a hydrolysis precipitation-calcination crystallization method. Then, the titanium dioxide / sepiolite composite material is used as a carrier and silver nitrate is used as a silver source to load silver oxide on the surface of the titanium dioxide / sepiolite composite material by impregnation and calcination to obtain a silver-loaded titanium dioxide / sepiolite composite material. The sepiolite is a silicate clay material with a large specific surface area and pore volume, and has good adsorption performance and can effectively adsorb formaldehyde. The titanium dioxide is a semiconductor photocatalyst material that has excellent degradation effect on formaldehyde and also has antibacterial property, and cooperates with silver oxide to improve the antibacterial performance of the composite material.

[0033] The present application uses 1,2-benzisothiazolin-3-one and 1,3-dibromo-2-propanol to undergo nucleophilic substitution reaction to obtain modified benzisothiazolinone with hydroxyl groups. The surface of the silver-loaded titanium dioxide / sepiolite composite material is grafted with an epoxy silane coupling agent. The epoxy group and the hydroxyl group of the modified benzisothiazolinone undergo ring-opening reaction to combine the modified benzisothiazolinone with the silver-loaded titanium dioxide / sepiolite composite material through a chemical bond to obtain an antibacterial agent. The benzisothiazolinone is a new type of bactericide with broad-spectrum and high efficiency and low toxicity. The modified benzisothiazolinone has a synergistic antibacterial effect with titanium dioxide and silver oxide, and the prepared antibacterial agent has more excellent antibacterial property.

[0034] The application mixes the antibacterial agent with the polyether amine, utilizes the end amino group of the polyether amine to react with the unreacted epoxy group in the antibacterial agent again to make the antibacterial agent graft in the polyether amine chain segment, improves the dispersibility and compatibility of the antibacterial agent in the matrix, and the silver-loaded titanium dioxide / sea sponges composite material in the antibacterial agent can be used as the wear-resistant inorganic filler to improve the wear resistance of the matrix; the antibacterial functionalized polyether containing Schiff base bonds and amine groups is prepared by adding p-xylylene glycol, diethylenetriamine and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane into the antibacterial agent modified polyether amine and utilizing the Schiff base reaction between the aldehyde group and the amino group; the water-based polyurethane-polyurea prepolymer is obtained by mixing and reacting the antibacterial functionalized polyether as the polyamine component with the water-based polyurethane prepolymer; the antibacterial type impregnating solution is obtained by capping the water-based polyurethane-polyurea prepolymer with imidazole as a capping agent and then neutralizing and emulsifying; the high-strength antibacterial decorative paper is obtained by impregnating the decorative base paper with the antibacterial type impregnating solution and then drying.

[0035] The Schiff base bond in the antibacterial functionalized polyether is a dynamic covalent bond with antibacterial property, which further improves the mechanical property and antibacterial property of the paper-based material; the urea group structure is easier to form stable hydrogen bonds between the solute molecules in the impregnating solution, the 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane can improve the water resistance of the matrix, and the comprehensive performance of the decorative paper is improved; the imidazole as the capping agent can temporarily cap the isocyanate groups in the water-based polyurethane-polyurea prepolymer, and the isocyanate groups can be released again at high temperature; when the decorative paper is hot-pressed to prepare a veneer, the isocyanate groups react with the surface of the decorative paper and the fiberboard, effectively improving the bonding strength between the decorative paper and the veneer. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is the process flow chart for preparing the high-strength antibacterial decorative paper in the application;

[0037] Figure 2 is the antibacterial rate column chart of the example 1-5 and the comparative example 1-2 in the antibacterial property test in the application;

[0038] Figure 3 is the wear resistance column chart of the sample 1-7 in the comprehensive performance test in the application. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0040] Example 1

[0041] The embodiment discloses a preparation method of high-strength antibacterial decorative paper, comprising the following steps:

[0042] Step one, poly (caprolactone) diol, poly (tetrahydrofuran ether) diol, isophorone diisocyanate, dibutyltin dilaurate are mixed, and the mixture is reacted at 80 DEG C for 5h in a nitrogen atmosphere; after the reaction is completed, 2, 2-dimethylol propionic acid is added, and the mixture is continuously reacted at 55 DEG C for 5h; after the reaction is completed, water-based polyurethane prepolymer is obtained;

[0043] The molar ratio of poly (caprolactone) diol, poly (tetrahydrofuran ether) diol, isophorone diisocyanate and 2, 2-dimethylol propionic acid is 2:2:10:2; the amount of dibutyltin dilaurate added is 0.5% of the mass of poly (caprolactone) diol, poly (tetrahydrofuran ether) diol and isophorone diisocyanate;

[0044] The water-based polyurethane prepolymer, the antibacterial functional polyether and acetone are mixed in a mass ratio of 80:20:20, and the mixture is reacted at 80 DEG C for 5h in a nitrogen atmosphere; after the reaction is completed, water-based polyurethane-polyurea prepolymer is obtained; the water-based polyurethane-polyurea prepolymer is mixed with imidazole, the amount of imidazole added is 100% of the amount of free isocyanate groups in the water-based polyurethane-polyurea prepolymer, the mixture is reacted at 50 DEG C for 4h, and then cooled to room temperature; triethylamine is added, and neutralized to pH 7 at room temperature; after neutralization, water is added to emulsify for 40min at a rotation speed of 3500r / min and a temperature of 0 DEG C; acetone is removed by rotary evaporation at a temperature of 50 DEG C to obtain an antibacterial type impregnating solution with a solid content of 20%;

[0045] The preparation of the antibacterial functional polyether comprises the following steps:

[0046] Step (1), sepiolite and water are mixed in a mass ratio of 1:25, ultrasonic dispersion is carried out, 36wt% hydrochloric acid aqueous solution is added to adjust the pH value to 4.5, stirring is carried out for 20min, 1mol / L titania sulfate aqueous solution is added dropwise at room temperature, the dropwise adding time is 25min, after the dropwise adding is completed, 30vol% ammonia water is added to adjust the pH value to 7.5, and the mixture is reacted at 70 DEG C for 3h; after the reaction is completed, the reaction product is obtained, the reaction product is washed with water for three times, and the mass of water used for washing is six times of the mass of the reaction product; the mixture is dried at 55 DEG C for 11h, and then calcined at 500 DEG C for 2h in a muffle furnace in a nitrogen atmosphere to obtain a titanium dioxide / sepiolite composite material; the mass ratio of sepiolite to 1mol / L titania sulfate aqueous solution is 1:5.5;

[0047] The titanium dioxide / sepiolite composite material was mixed with a 0.05 mol / L silver nitrate aqueous solution in a mass ratio of 1:35 under light-shielding conditions, and reacted at 30°C for 2 hours. After the reaction, the mixture was filtered, the filter cake was collected, dried at 55°C for 2 hours, calcined at 210°C for 0.5 hours, and ground through a 300-mesh sieve to obtain a silver-loaded titanium dioxide / sepiolite composite material.

[0048] Step (2), mixing γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, and water, adding 1 mol / L acetic acid aqueous solution to adjust the pH value to 4, stirring for 1.5 hours, adding silver-loaded titanium dioxide / sepiolite composite material, reacting at room temperature for 24 hours, centrifuging and filtering after the reaction, taking the filter cake, adding ethanol 6 times the mass of the filter cake, washing three times, and drying at 50° C. for 28 hours to obtain the epoxy-loaded silver titanium dioxide / sepiolite composite material;

[0049] The mass ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, water, and silver-loaded titanium dioxide / sepiolite composite material is 5.5:60:30:1;

[0050] Step (3), 1,2-benzisothiazolin-3-one, potassium carbonate, and N,N-dimethylformamide are mixed, 1,3-dibromo-2-propanol is added, and the mixture is reacted at 60°C for 16 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a reaction product, 3 times the mass of the reaction product is added with water and mixed evenly, and then 3 times the mass of the reaction product is added with ethyl acetate to extract the mixture, the organic phase is taken, anhydrous magnesium sulfate with an organic phase mass of 15% is added and dried, filtered, and the filtrate is taken, the solvent ethyl acetate is removed by rotary evaporation at 60°C, and the mixture is passed through a column to obtain a modified benzisothiazolinone;

[0051] The mass ratio of 1,2-benzisothiazolin-3-one, potassium carbonate, N,N-dimethylformamide, and 1,3-dibromo-2-propanol is 3:2.8:30:2.2, and the developing solvent in the column operation is prepared by mixing dichloromethane and ethyl acetate in a volume ratio of 1:1;

[0052] The modified benzisothiazolinone, epoxy-supported silver titanium dioxide / sepiolite composite material, and water were mixed in a mass ratio of 3:1:80, reacted at 80°C for 4 hours, filtered, and the filter cake was washed with water 5 times the mass of the filter cake, and dried at 50°C for 16 hours to obtain an antibacterial agent.

[0053] Step (4), the polyether amine, the antibacterial agent, the tetrahydrofuran are mixed, and the reaction is carried out at a temperature of 105 DEG C for 5h, after the reaction is completed, the p-xylylene glycol, the diethylene triamine, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane are added and uniformly mixed, the mass ratio of the polyether amine, the antibacterial agent, the tetrahydrofuran, the p-xylylene glycol, the diethylene triamine, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane is 18:1:90:13:2:2, the reaction is continuously carried out at a temperature of 55 DEG C under a nitrogen atmosphere for 4h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at a temperature of 35 DEG C, and the obtained product is dried at a temperature of 50 DEG C for 10h to obtain an antibacterial functional polyether;

[0054] Step two, the decorative base paper is dipped in the antibacterial type impregnating solution at room temperature, the mass ratio of the decorative base paper to the antibacterial type impregnating solution is 1:20, the dipping time is 3min, after dipping, the obtained product is taken out and dried at a temperature of 80 DEG C under a vacuum degree of-0.08MPa for 50min to obtain a high-strength antibacterial decorative paper.

[0055] Example 2

[0056] The embodiment discloses a preparation method of a high-strength antibacterial decorative paper, and comprises the following steps:

[0057] Step one, the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the dibutyl tin dilaurate are mixed, and the reaction is carried out at a temperature of 80 DEG C under a nitrogen atmosphere for 4.5h, after the reaction is completed, the 2,2-dimethylol propionic acid is added, and the reaction is continuously carried out at a temperature of 60 DEG C for 4.5h, after the reaction is completed, the obtained product is a water-based polyurethane prepolymer;

[0058] The molar ratio of the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the 2,2-dimethylol propionic acid is 2.2:1.8:10:2; the added amount of the dibutyl tin dilaurate is 0.5% of the mass sum of the polycaprolactone diol, the polytetrahydrofuran ether diol and the isophorone diisocyanate;

[0059] The water-based polyurethane-polyurea prepolymer is mixed with the imidazole, the added amount of the imidazole is 105% of the amount of substance of the free isocyanate group in the water-based polyurethane-polyurea prepolymer, the reaction is carried out at a temperature of 55 DEG C for 3.5h, after the reaction is completed, the obtained product is cooled to room temperature, the triethylamine is added, and the obtained product is neutralized to a pH value of 7 at room temperature, after neutralization, the obtained product is emulsified by adding water at a rotating speed of 3600r / min and a temperature of 0 DEG C for 35min, the solvent acetone is removed by rotary evaporation at a temperature of 55 DEG C to obtain an antibacterial type impregnating solution with a solid content of 22%;

[0060] Preparation of the antibacterial functionalized polyether comprises the following steps:

[0061] Step (1), γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water are mixed, 1 mol / L aqueous acetic acid solution is added to adjust the pH value to 4, stirred for 1.5 h, silver-loaded titanium dioxide / sepiolite composite material is added, and the reaction is carried out at room temperature for 24 h. After the reaction is completed, centrifugation, filtration, taking the filter cake, adding 6 times the mass of ethanol to wash three times, and drying at 55℃ for 25 h to obtain an epoxy silver-loaded titanium dioxide / sepiolite composite material;

[0062] The preparation of the silver-loaded titanium dioxide / sepiolite composite material is the same as in Example 1; the mass ratio of γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water, and silver-loaded titanium dioxide / sepiolite composite material is 5.6:62:22:1.05;

[0063] Step (2), 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide are mixed, 1, 3-dibromo-2-propanol is added, and the reaction is carried out at 65℃ for 14 h. After the reaction is completed, it is cooled to room temperature to obtain a reaction product. Water is added to the reaction product in an amount of 3 times the mass of the reaction product, mixed uniformly, and then ethyl acetate is added to the reaction product in an amount of 3 times the mass of the reaction product. The organic phase is taken, anhydrous magnesium sulfate is added in an amount of 15% of the mass of the organic phase, dried, filtered, and the filtrate is taken. The solvent ethyl acetate is removed by rotary evaporation at 65℃, and the product is obtained by column chromatography;

[0064] The mass ratio of 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide, and 1, 3-dibromo-2-propanol is 3.05:2.85:32:2.22, and the developing agent in the column chromatography operation is prepared by mixing dichloromethane and ethyl acetate in a volume ratio of 1:1;

[0065] The modified benzisothiazolinone, epoxy silver-loaded titanium dioxide / sepiolite composite material, and water are mixed in a mass ratio of 3.03:1:85, and the reaction is carried out at 85℃ for 3.5 h. After the reaction is completed, filtration is carried out, the filter cake is taken, and the filter cake is washed with 6 times the mass of water at 55℃ for 14 h to obtain an antibacterial agent;

[0066] Step (3), the polyether amine, the antibacterial agent, the tetrahydrofuran are mixed, and the reaction is carried out at 110 DEG C for 4.5 h; after the reaction is completed, the p-xylylene glycol, the diethylene triamine, the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane are added and uniformly mixed, and the mass ratio of the polyether amine, the antibacterial agent, the tetrahydrofuran, the p-xylylene glycol, the diethylene triamine and the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is 18.5:1.05:93:13.1:2.03:2.05; the reaction is continued at 60 DEG C under a nitrogen atmosphere for 3.5 h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 40 DEG C, and the product is dried at 55 DEG C for 9 h to obtain the antibacterial functional polyether;

[0067] Step two, the decorative base paper is dipped in the antibacterial type impregnating solution at room temperature, the mass ratio of the decorative base paper to the antibacterial type impregnating solution is 1:20, the dipping time is 3 min, and the product is taken out after dipping, dried at 85 DEG C under a vacuum degree of -0.08 MPa for 45 min to obtain the high-strength antibacterial decorative paper.

[0068] Example 3

[0069] The embodiment discloses a preparation method of a high-strength antibacterial decorative paper, comprising the following steps:

[0070] Step one, the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the dibutyltin dilaurate are mixed, and the reaction is carried out at 82 DEG C under a nitrogen atmosphere for 4.5 h; after the reaction is completed, the 2,2-dimethylol propionic acid is added, and the reaction is continued at 60 DEG C for 4.5 h; after the reaction is completed, the water-based polyurethane prepolymer is obtained;

[0071] The molar ratio of the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the 2,2-dimethylol propionic acid is 2.5:1.5:10:2; the amount of the dibutyltin dilaurate added is 0.5% of the mass sum of the polycaprolactone diol, the polytetrahydrofuran ether diol and the isophorone diisocyanate;

[0072] The water-based polyurethane-polyurea prepolymer is mixed with the imidazole, the amount of the imidazole added is 110% of the amount of substance of the free isocyanate group in the water-based polyurethane-polyurea prepolymer, the reaction is carried out at 55 DEG C for 3.5 h, the product is cooled to room temperature after the reaction is completed, the triethylamine is added, the product is neutralized to a pH value of 7 at room temperature, the product is emulsified by adding water at a rotating speed of 3800 r / min and a temperature of 2 DEG C for 35 min, the solvent acetone is removed by rotary evaporation at 55 DEG C to obtain the antibacterial type impregnating solution with a solid content of 23%.

[0073] Preparation of the antibacterial functionalized polyether comprises the following steps:

[0074] Step (1), γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water are mixed, 1 mol / L aqueous acetic acid is added to adjust the pH value to 4, stirred for 2 h, silver-loaded titanium dioxide / sepiolite composite material is added, and the reaction is carried out at room temperature for 25 h. After the reaction is completed, centrifugation, filtration, taking the filter cake, adding 7 times the mass of ethanol to wash the filter cake for three times, and drying at 55℃ for 25 h to obtain an epoxy group silver-loaded titanium dioxide / sepiolite composite material;

[0075] Preparation of the silver-loaded titanium dioxide / sepiolite composite material is the same as in Example 1; the mass ratio of γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water, and silver-loaded titanium dioxide / sepiolite composite material is 5.8:65:25:1.1;

[0076] Step (2), 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide are mixed, 1, 3-dibromo-2-propanol is added, and the reaction is carried out at 65℃ for 14 h. After the reaction is completed, the reaction product is obtained by cooling to room temperature. Water is added to the reaction product in an amount of 3 times the mass of the reaction product, mixed uniformly, and then ethyl acetate is added to the reaction product in an amount of 3 times the mass of the reaction product. The organic phase is obtained, anhydrous magnesium sulfate is added in an amount of 15% of the mass of the organic phase, dried, filtered, and the filtrate is obtained. The solvent ethyl acetate is removed by rotary evaporation at 65℃, and the modified benzisothiazolinone is obtained by column chromatography;

[0077] The mass ratio of 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide, and 1, 3-dibromo-2-propanol is 3.1:2.9:35:2.25, and the developing agent in the column chromatography operation is prepared by mixing dichloromethane and ethyl acetate in a volume ratio of 1:1;

[0078] The modified benzisothiazolinone, epoxy group silver-loaded titanium dioxide / sepiolite composite material, and water are mixed in a mass ratio of 3.05:1:90, and the reaction is carried out at 85℃ for 3.5 h. After the reaction is completed, filtration is carried out, the filter cake is obtained, and the filter cake is washed with water in an amount of 6 times the mass of the filter cake. Drying is carried out at 55℃ for 14 h to obtain an antibacterial agent;

[0079] Step (3), the polyether amine, the antibacterial agent, the tetrahydrofuran are mixed, and the reaction is carried out at 110 DEG C for 4.5 h; after the reaction is completed, the p-xylylene glycol, the diethylene triamine, the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane are mixed uniformly, and the mass ratio of the polyether amine, the antibacterial agent, the tetrahydrofuran, the p-xylylene glycol, the diethylene triamine, the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is 19:1.1:95:13.2:2.05:2.1; the reaction is continued at 60 DEG C under the nitrogen atmosphere for 3.5 h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 40 DEG C, and the product is dried at 55 DEG C for 9 h, to obtain the antibacterial functional polyether;

[0080] Step two, the decorative base paper is dipped in the antibacterial type impregnating solution at room temperature, the mass ratio of the decorative base paper and the antibacterial type impregnating solution is 1:25, the dipping time is 4 min, and the product is taken out after dipping, dried at 85 DEG C under the vacuum degree of-0.08 MPa for 45 min, to obtain the high-strength antibacterial decorative paper.

[0081] Example 4

[0082] The embodiment discloses a preparation method of a high-strength antibacterial decorative paper, comprising the following steps:

[0083] Step one, the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate, the dibutyl tin dilaurate are mixed, and the reaction is carried out at 85 DEG C under the nitrogen atmosphere for 4 h; after the reaction is completed, the 2,2-dimethylol propionic acid is added, and the reaction is continued at 60 DEG C for 4.5 h; after the reaction is completed, the water-based polyurethane prepolymer is obtained;

[0084] The molar ratio of the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the 2,2-dimethylol propionic acid is 2.8:1.2:10:2; the added amount of the dibutyl tin dilaurate is 0.6% of the mass sum of the polycaprolactone diol, the polytetrahydrofuran ether diol and the isophorone diisocyanate;

[0085] The water-based polyurethane-polyurea prepolymer is mixed with the imidazole, the added amount of the imidazole is 115% of the amount of substance of the free isocyanate group in the water-based polyurethane-polyurea prepolymer, the reaction is carried out at 55 DEG C for 3.5 h, the product is cooled to room temperature after the reaction is completed, the triethylamine is added, the product is neutralized to the pH value of 7 at room temperature, the product is emulsified by adding water at the rotation speed of 4000 r / min and the temperature of 2 DEG C for 35 min, the solvent acetone is removed by rotary evaporation at 55 DEG C, to obtain the antibacterial type impregnating solution with the solid content of 24%;

[0086] The preparation of the antibacterial functionalized polyether comprises the following steps:

[0087] Step (1), γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, and water are mixed, 1 mol / L acetic acid aqueous solution is added to adjust the pH value to 4.5, and the mixture is stirred for 2 hours. The silver-loaded titanium dioxide / sepiolite composite material is added, and the reaction is carried out at room temperature for 25 hours. After the reaction is completed, the mixture is centrifuged and filtered to obtain a filter cake, which is washed three times with ethanol having a mass of 8 times that of the filter cake, and dried at 55° C. for 25 hours to obtain an epoxy-loaded silver titanium dioxide / sepiolite composite material;

[0088] The preparation of the silver-loaded titanium dioxide / sepiolite composite material is the same as that in Example 1; the mass ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, water, and the silver-loaded titanium dioxide / sepiolite composite material is 5.9:68:28:1.15;

[0089] Step (2), 1,2-benzisothiazolin-3-one, potassium carbonate, and N,N-dimethylformamide are mixed, 1,3-dibromo-2-propanol is added, and the mixture is reacted at a temperature of 65°C for 14 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a reaction product, 3 times the mass of the reaction product is added with water and mixed evenly, and then 3 times the mass of the reaction product is added with ethyl acetate to extract the mixture, the organic phase is taken, anhydrous magnesium sulfate is added with 20% of the mass of the organic phase, and dried, filtered, and the filtrate is taken, the solvent ethyl acetate is removed by rotary evaporation at a temperature of 65°C, and the mixture is passed through a column to obtain a modified benzisothiazolinone;

[0090] The mass ratio of 1,2-benzisothiazolin-3-one, potassium carbonate, N,N-dimethylformamide, and 1,3-dibromo-2-propanol is 3.15:2.95:38:2.28, and the developing solvent in the column operation is prepared by mixing dichloromethane and ethyl acetate in a volume ratio of 1:1.

[0091] The modified benzisothiazolinone, epoxy-supported silver titanium dioxide / sepiolite composite material, and water were mixed in a mass ratio of 3.08:1:95, reacted at 85°C for 3.5 hours, filtered, and the filter cake was washed with water 6 times the mass of the filter cake, and dried at 55°C for 14 hours to obtain an antibacterial agent.

[0092] Step (3), the polyether amine, the antibacterial agent, the tetrahydrofuran are mixed, and the reaction is carried out at a temperature of 115 DEG C for 4.5 h; after the reaction is completed, the p-xylylene glycol, the diethylene triamine and the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane are uniformly mixed, and the mass ratio of the polyether amine, the antibacterial agent, the tetrahydrofuran, the p-xylylene glycol, the diethylene triamine and the 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is 19.5:1.15:98:13.3:2.08:2.15; the reaction is continuously carried out at a temperature of 60 DEG C for 3.5 h in a nitrogen atmosphere; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at a temperature of 40 DEG C, and the obtained product is dried at a temperature of 55 DEG C for 9 h to obtain an antibacterial functional polyether;

[0093] Step two, the decorative base paper is immersed in the antibacterial type impregnating solution at room temperature, the mass ratio of the decorative base paper to the antibacterial type impregnating solution is 1:30, the immersion time is 4 min, and the obtained product is dried at a temperature of 85 DEG C for 45 min under a vacuum degree of-0.08 MPa to obtain a high-strength antibacterial decorative paper.

[0094] Example 5

[0095] The embodiment discloses a preparation method of a high-strength antibacterial decorative paper, and the method comprises the following steps:

[0096] Step one, the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the dibutyl tin dilaurate are mixed, and the reaction is carried out at a temperature of 85 DEG C for 4 h in a nitrogen atmosphere; after the reaction is completed, the 2,2-dimethylol propionic acid is added, and the reaction is continuously carried out at a temperature of 65 DEG C for 4 h; after the reaction is completed, the obtained product is a water-based polyurethane prepolymer;

[0097] The molar ratio of the polycaprolactone diol, the polytetrahydrofuran ether diol, the isophorone diisocyanate and the 2,2-dimethylol propionic acid is 3:1:10:2; the added amount of the dibutyl tin dilaurate is 0.6% of the mass sum of the polycaprolactone diol, the polytetrahydrofuran ether diol and the isophorone diisocyanate;

[0098] The water-based polyurethane prepolymer, the antibacterial functional polyether and the acetone are mixed at a mass ratio of 75:25:10, and the reaction is carried out at a temperature of 85 DEG C for 4 h in a nitrogen atmosphere; after the reaction is completed, the obtained product is a water-based polyurethane-polyurea prepolymer; the water-based polyurethane-polyurea prepolymer is mixed with the imidazole, the added amount of the imidazole is 120% of the amount of substance of the free isocyanate group in the water-based polyurethane-polyurea prepolymer, the reaction is carried out at a temperature of 60 DEG C for 3 h, the obtained product is cooled to room temperature, the triethylamine is added, the obtained product is neutralized to a pH value of 7 at room temperature, the obtained product is emulsified by adding water at a rotation speed of 4000 r / min and a temperature of 5 DEG C for 30 min, the solvent acetone is removed by rotary evaporation at a temperature of 60 DEG C to obtain an antibacterial type impregnating solution with a solid content of 25%;

[0099] Preparation of the antibacterial functionalized polyether comprises the following steps:

[0100] Step (1), γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water are mixed, 1 mol / L aqueous acetic acid solution is added to adjust the pH value to 4.5, stirred for 2 h, silver-loaded titanium dioxide / sea soapstone composite material is added, and the reaction is carried out at room temperature for 26 h. After the reaction is completed, centrifugation, filtration, taking the filter cake, adding 8 times the mass of ethanol to wash three times, and drying at 60℃ for 24 h, the epoxy silver-loaded titanium dioxide / sea soapstone composite material is obtained;

[0101] The preparation of the silver-loaded titanium dioxide / sea soapstone composite material is the same as in Example 1; the mass ratio of γ-(2, 3-epoxypropoxy) propyl trimethoxysilane, ethanol, water, and silver-loaded titanium dioxide / sea soapstone composite material is 6:70:20:1.2;

[0102] Step (2), 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide are mixed, 1, 3-dibromo-2-propanol is added, and the reaction is carried out at 70℃ for 12 h. After the reaction is completed, it is cooled to room temperature to obtain a reaction product. The reaction product is mixed with 4 times the mass of water, and then 4 times the mass of ethyl acetate is added for extraction. The organic phase is taken, anhydrous magnesium sulfate is added to the organic phase in an amount of 20%, dried, filtered, and the filtrate is obtained. The solvent ethyl acetate is removed by rotary evaporation at 70℃, and the modified benzisothiazolinone is obtained by column chromatography.

[0103] The mass ratio of 1, 2-benzisothiazolin-3-one, potassium carbonate, N, N-dimethylformamide, and 1, 3-dibromo-2-propanol is 3.2:3:40:2.3, and the developing agent in the column chromatography operation is prepared by mixing dichloromethane and ethyl acetate in a volume ratio of 1:1;

[0104] The modified benzisothiazolinone, epoxy silver-loaded titanium dioxide / sea soapstone composite material, and water are mixed in a mass ratio of 3.1:1:100, and the reaction is carried out at 90℃ for 3 h. After the reaction is completed, filtration is carried out, the filter cake is taken, 8 times the mass of water is added to wash, and drying is carried out at 60℃ for 12 h to obtain the antibacterial agent.

[0105] Step (3), the polyether amine, antibacterial agent, tetrahydrofuran are mixed, and the reaction is carried out at a temperature of 115 DEG C for 4h; after the reaction is completed, p-xylylene glycol, diethylene triamine, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane are added and uniformly mixed; the mass ratio of the polyether amine, antibacterial agent, tetrahydrofuran, p-xylylene glycol, diethylene triamine, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane is 20:1.2:100:13.4:2.1:2.2; the reaction is continued at a temperature of 65 DEG C under a nitrogen atmosphere for 3h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at a temperature of 45 DEG C, and drying is carried out at a temperature of 60 DEG C for 8h to obtain an antibacterial functional polyether;

[0106] Step two, the decorative base paper is immersed in the antibacterial type impregnating solution at room temperature; the mass ratio of the decorative base paper to the antibacterial type impregnating solution is 1:30, and the immersion time is 5min; after immersion, the decorative base paper is taken out and dried at a vacuum degree of-0.08MPa and a temperature of 90 DEG C for 40min to obtain a high-strength antibacterial decorative paper.

[0107] Comparative example 1

[0108] The present comparative example discloses a preparation method of a decorative paper, comprising the following steps:

[0109] Step one, poly (caprolactone) diol, poly (tetrahydrofuran ether) diol, isophorone diisocyanate, dibutyltin dilaurate are mixed, and the reaction is carried out at a temperature of 80 DEG C under a nitrogen atmosphere for 5h; after the reaction is completed, 2,2-dimethylol propionic acid is added, and the reaction is continued at a temperature of 55 DEG C for 5h; after the reaction is completed, an aqueous polyurethane prepolymer is obtained;

[0110] The molar ratio of the poly (caprolactone) diol, poly (tetrahydrofuran ether) diol, isophorone diisocyanate, and 2,2-dimethylol propionic acid is 2:2:10:2; the amount of dibutyltin dilaurate added is 0.5% of the mass of the poly (caprolactone) diol, poly (tetrahydrofuran ether) diol, and isophorone diisocyanate;

[0111] The aqueous polyurethane prepolymer, the antibacterial functional polyether, and acetone are mixed at a mass ratio of 80:20:20, and the reaction is carried out at a temperature of 80 DEG C under a nitrogen atmosphere for 5h; after the reaction is completed, an aqueous polyurethane-polyurea prepolymer is obtained; the aqueous polyurethane-polyurea prepolymer is mixed with imidazole, and the amount of imidazole added is 100% of the amount of substance of free isocyanate groups in the aqueous polyurethane-polyurea prepolymer; the reaction is carried out at a temperature of 50 DEG C for 4h; after the reaction is completed, the mixture is cooled to room temperature; triethylamine is added, and neutralization is carried out at room temperature until the pH value is 7; after neutralization, water is added and emulsified at a rotation speed of 3500r / min and a temperature of 0 DEG C for 40min; the solvent acetone is removed by rotary evaporation at a temperature of 50 DEG C to obtain an antibacterial type impregnating solution with a solid content of 20%;

[0112] Preparation of the antibacterial functional polyether includes the following steps:

[0113] The polyether amine, silver-loaded titanium dioxide / sepiolite composite material, tetrahydrofuran, p-xylylene glycol, diethylene triamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are mixed uniformly, and the mass ratio of the polyether amine, silver-loaded titanium dioxide / sepiolite composite material, tetrahydrofuran, p-xylylene glycol, diethylene triamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 18:1:90:13:2:2. The reaction is continued at 55°C under a nitrogen atmosphere for 4h. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 35°C, and the product is dried at 50°C for 10h to obtain the antibacterial functional polyether.

[0114] The silver-loaded titanium dioxide / sepiolite composite material is prepared in the same manner as in Example 1.

[0115] Step two, the decorative base paper is immersed in the antibacterial impregnating solution at room temperature, the mass ratio of the decorative base paper to the antibacterial impregnating solution is 1:20, the immersion time is 3min, and the decorative paper is obtained after drying at a vacuum degree of-0.08MPa and a temperature of 80°C for 50min.

[0116] Comparative Example 2

[0117] This comparative example discloses a preparation method of decorative paper, including the following steps:

[0118] Step one, the polycaprolactone diol, polytetrahydrofuran ether diol, isophorone diisocyanate, and dibutyltin dilaurate are mixed and reacted at 80°C under a nitrogen atmosphere for 5h. After the reaction is completed, 2,2-dimethylolpropionic acid is added, and the reaction is continued at 55°C for 5h. After the reaction is completed, the water-based polyurethane prepolymer is obtained.

[0119] The molar ratio of the polycaprolactone diol, polytetrahydrofuran ether diol, isophorone diisocyanate, and 2,2-dimethylolpropionic acid is 2:2:10:2. The amount of dibutyltin dilaurate added is 0.5% of the mass of the polycaprolactone diol, polytetrahydrofuran ether diol, and isophorone diisocyanate.

[0120] The water-based polyurethane prepolymer, the antibacterial functional polyether, and the acetone are mixed in a mass ratio of 80:20:20, and reacted at 80°C for 5h in a nitrogen atmosphere. After the reaction is completed, the water-based polyurethane-polyurea prepolymer is obtained. The water-based polyurethane-polyurea prepolymer is mixed with imidazole, and the amount of imidazole added is 100% of the amount of substance of free isocyanate groups in the water-based polyurethane-polyurea prepolymer. The mixture is reacted at 50°C for 4h. After the reaction is completed, the mixture is cooled to room temperature, and triethylamine is added. The mixture is neutralized to a pH value of 7 at room temperature. After neutralization, the mixture is emulsified by adding water at a rotation speed of 3500r / min and a temperature of 0°C for 40min. The solvent acetone is removed by rotary evaporation at a temperature of 50°C. An antibacterial type impregnating solution with a solid content of 20% is obtained.

[0121] The preparation of the antibacterial functional polyether includes the following steps:

[0122] The polyether amine and tetrahydrofuran are mixed, and p-xylylene glycol, diethylene triamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl disiloxane are added and uniformly mixed. The mass ratio of the polyether amine, tetrahydrofuran, p-xylylene glycol, diethylene triamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl disiloxane is 18:90:13:2:2. The mixture is continuously reacted at 55°C for 4h in a nitrogen atmosphere. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at a temperature of 35°C. The mixture is dried at a temperature of 50°C for 10h. The antibacterial functional polyether is obtained.

[0123] Step two, the decorative base paper is immersed in the antibacterial type impregnating solution at room temperature. The mass ratio of the decorative base paper to the antibacterial type impregnating solution is 1:20. The immersion time is 3min. After immersion, the decorative base paper is taken out and dried at a vacuum degree of -0.08MPa and a temperature of 80°C for 50min. The decorative paper is obtained.

[0124] In the above examples and comparative examples: the sepiolite was from Hebei Mingzhe Mining Products Co., Ltd., with a particle size of 300 mesh; the γ-(2,3-epoxypropoxy) propyl trimethoxysilane was from Shandong Xiya Chemical Co., Ltd., CAS No.: 2530-83-8; the 1,2-benzisothiazolin-3-one was from Shanghai Aladdin Biochem Technology Co., Ltd., CAS No.: 2634-33-5; the 1,3-dibromo-2-propanol was from Alfa Aesar Company, CAS No.: 96-21-9; the polyetheramine was from Hubei Langbomwany Biological Medicine Co., Ltd., model polyetheramine D-230; the p-phenylenedimethanol was from Shanghai Maikelin Biochemical Technology Co., Ltd., CAS No.: 623-27-8; the diethylenetriamine was from Alfa Aesar Company, CAS No.: 111-40-0; the 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was from Shanghai Aladdin Biochem Technology Co., Ltd., CAS No.: 2469-55-8; the polycaprolactone diol was from Jiangsu Haolong Chemical Co., Ltd., model PCL-1000; the polytetrahydrofuran ether diol was from Xuzhou Yihuiyang New Material Co., Ltd., model PTMG-1000; the isophorone diisocyanate was from Shanghai Aladdin Biochem Technology Co., Ltd., CAS No.: 4098-71-9; the 2,2-dimethylol propionic acid was from Sigma-Aldrich Company, CAS No.: 4767-03-7; the imidazole was from Shanghai Aladdin Biochem Technology Co., Ltd., CAS No.: 288-32-4; the decorative base paper had a specification of 70 g / m 2 .

[0125] Test Example

[0126] The decorative papers prepared in Examples 1-5 and Comparative Examples 1-2 were hot-pressed with artificial medium-density fiberboards to obtain samples 1-7, wherein the artificial medium-density fiberboards had a specification of 2440 mm x 1220 mm x 12 mm, the hot-pressing temperature was 180℃, the time was 180 s, and the pressure was 2.5 MPa.

[0127] The antibacterial performance of Examples 1-5 and Comparative Examples 1-2 was tested, and the comprehensive performance of sample 1-7 was tested, and the specific test results are shown in Table 1:

[0128] Table 1

[0129]

[0130] The detection of each index in Table 1 was respectively based on the following standards: the bacteriostatic rate was determined according to GB / T 42702-2023 “Determination of antibacterial property of paper, paperboard and paper products”; the surface bonding strength and wear resistance were determined according to GB / T 17657-2013 “Test methods of physicochemical properties of artificial boards and veneered artificial boards”.

[0131] According to the test results of Table 1, it can be seen that the decorative paper prepared by the present application has good antibacterial property and excellent wear resistance, and the veneer board prepared by using the decorative paper as a facing material has high bonding strength.

[0132] The present application prepares an antibacterial agent with silver-loaded titanium dioxide / sepiolite composite material and modified benzisothiazolinone, wherein the titanium dioxide in the silver-loaded titanium dioxide / sepiolite composite material has antibacterial property, the benzisothiazolinone is a new type of bactericide with broad-spectrum and high efficiency and low toxicity, the modified benzisothiazolinone has synergistic antibacterial effect with titanium dioxide and silver oxide, the prepared antibacterial agent has more excellent antibacterial property, and the silver-loaded titanium dioxide / sepiolite composite material in the antibacterial agent can be used as a wear-resistant inorganic filler to improve the wear resistance of the substrate; the present application prepares an antibacterial functionalized polyether with antibacterial agent and Schiff base bond, which is mixed with a waterborne polyurethane prepolymer as a polyamine component to generate a urea group structure, to obtain a waterborne polyurethane-polyurea prepolymer, and then the waterborne polyurethane-polyurea prepolymer is capped with imidazole and emulsified to obtain an antibacterial type impregnating solution; wherein the Schiff base bond is a dynamic covalent bond with antibacterial property, which further improves the antibacterial performance of the decorative paper; imidazole as a capping agent can temporarily cap the isocyanate groups in the waterborne polyurethane-polyurea prepolymer, and the isocyanate groups can be released again at high temperature; when the decorative paper is hot-pressed to prepare a veneer board, the isocyanate groups react with the surface of the decorative paper and fiber board material, effectively improving the bonding strength between the decorative paper and the veneer.

[0133] The silver-loaded titanium dioxide / sepiolite composite material in Comparative Example 1 is not surface-modified, has low dispersibility in the matrix resin, and lacks the synergistic antibacterial effect of the modified benzisothiazolinone with titanium dioxide and silver oxide, so the antibacterial performance of Comparative Example 1 is lower than that of the examples, and the bonding strength and wear resistance of Sample 6 prepared from Comparative Example 1 are lower than those of the examples.

[0134] No antibacterial agent is added in Comparative Example 2, lacking the antibacterial effect of the antibacterial agent and the improvement of the wear resistance of the substrate as a wear-resistant inorganic filler, so the antibacterial property of Comparative Example 2 is lower than that of the examples, and the wear resistance of Sample 7 prepared from Comparative Example 2 is lower than that of the examples.

[0135] Although the embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high-strength antibacterial decorative paper, characterized in that: The following steps are involved: Step 1: mixing polycaprolactone diol, polytetramethylene glycol, isophorone diisocyanate, and dibutyltin dilaurate, and reacting them. After the reaction is completed, adding 2,2-dimethylolpropionic acid, and continuing the reaction. After the reaction is completed, a waterborne polyurethane prepolymer is obtained; A waterborne polyurethane prepolymer, an antibacterial functionalized polyether, and acetone are mixed and reacted to obtain a waterborne polyurethane-polyurea prepolymer after the reaction is completed; the waterborne polyurethane-polyurea prepolymer is mixed with imidazole and reacted to obtain a waterborne polyurethane-polyurea prepolymer after the reaction is completed, cooled, and triethylamine is added to neutralize the mixture. After neutralization, water is added to emulsify the mixture, and the solvent acetone is removed by rotary evaporation to obtain an antibacterial impregnation solution; The preparation of the antibacterial functionalized polyether comprises the following steps: Step (1), mixing 1,2-benzisothiazolin-3-one, potassium carbonate, and N,N-dimethylformamide, adding 1,3-dibromo-2-propanol, reacting, cooling after the reaction is completed, obtaining a reaction product, purifying to obtain a modified benzisothiazolinone; mixing the modified benzisothiazolinone, epoxy-supported silver titanium dioxide / sepiolite composite material, and water, reacting, filtering after the reaction is completed, taking a filter cake, washing, and drying to obtain an antibacterial agent; Step (2), mixing the polyetheramine, antibacterial agent, and tetrahydrofuran, reacting, after the reaction is completed, adding terephthalaldehyde, diethylenetriamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, mixing evenly, and continuing the reaction; after the reaction is completed, removing the solvent tetrahydrofuran by rotary evaporation, and drying to obtain an antibacterial functionalized polyether; Step 2: Immerse the decorative base paper in the antibacterial impregnation liquid, take it out after immersion, and dry it to obtain high-strength antibacterial decorative paper.

2. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: In step 1, the molar ratio of polycaprolactone diol, polytetramethylene glycol, isophorone diisocyanate, and 2,2-dimethylolpropionic acid is 2-3:1-2:10:2; the amount of dibutyltin dilaurate added is 0.5-0.6% of the total mass of polycaprolactone diol, polytetramethylene glycol, and isophorone diisocyanate; when preparing the waterborne polyurethane prepolymer, the reaction conditions are: reaction at 80-85°C in a nitrogen atmosphere for 4-5 hours, and the continued reaction conditions are: reaction at 55-65°C in a nitrogen atmosphere for 4-5 hours.

3. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: In the step 1, the mass ratio of the waterborne polyurethane prepolymer, the antibacterial functionalized polyether, and acetone is 75-80:20-25:10-20; when preparing the waterborne polyurethane-polyurea prepolymer, the reaction conditions are: reaction for 4-5 hours at a temperature of 80-85°C in a nitrogen atmosphere; when preparing the antibacterial impregnation liquid, the amount of imidazole added is 100-120% of the amount of free isocyanate groups in the waterborne polyurethane-polyurea prepolymer, and the reaction conditions are: reaction for 3-4 hours at a temperature of 50-60°C; neutralization conditions are: neutralization at room temperature to a pH of 7; emulsification conditions are: adding water at a rotation speed of 3500-4000 r / min and a temperature of 0-5°C and emulsifying for 30-40 minutes; and the solid content of the antibacterial impregnation liquid is 20-25%.

4. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: When preparing the antibacterial functionalized polyether in step 1, the epoxy-based silver-loaded titanium dioxide / sepiolite composite material comprises the following steps: S1, mixing sepiolite with water, ultrasonically dispersing, adding aqueous hydrochloric acid to adjust the pH value, stirring, adding titanyl sulfate aqueous solution, after the addition is complete, adding ammonia water to adjust the pH value, reacting, after the reaction is completed, obtaining a reaction product, washing, drying, and calcining to obtain a titanium dioxide / sepiolite composite material; The titanium dioxide / sepiolite composite material is mixed with a silver nitrate aqueous solution, reacted, filtered, and the filter cake is dried, calcined, ground, and sieved to obtain a silver-loaded titanium dioxide / sepiolite composite material; S2. Mix γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, and water, add a regulator to adjust the pH value, stir, add silver-loaded titanium dioxide / sepiolite composite material, react, and after the reaction is completed, centrifuge, filter, take the filter cake, wash, and dry to obtain the epoxy-loaded silver titanium dioxide / sepiolite composite material.

5. The method for preparing high-strength antibacterial decorative paper according to claim 4, characterized in that: In S1, the mass ratio of sepiolite to water is 1:20-30; the hydrochloric acid aqueous solution is a 36 wt% hydrochloric acid aqueous solution, and the adjusted pH value is 4-4.5; the titanyl sulfate aqueous solution is a 1 mol / L titanyl sulfate aqueous solution, and the dropwise addition conditions are: dropwise addition at room temperature for 20-30 minutes, and the mass ratio of sepiolite to the 1 mol / L titanyl sulfate aqueous solution is 1:5-6; the ammonia water is 30 vol% ammonia water, and the adjusted pH value is 7-8; when preparing the titanium dioxide / sepiolite composite material, the reaction conditions are: reaction at a temperature of 70-75°C for 2-3 hours, and the calcination conditions are: calcination at a temperature of 450-500°C for 2-2.5 hours in a nitrogen atmosphere; The mass ratio of the titanium dioxide / sepiolite composite material to a 0.05 mol / L silver nitrate aqueous solution is 1:35-40, and the silver nitrate aqueous solution is a 0.05 mol / L silver nitrate aqueous solution. When preparing the titanium dioxide / sepiolite composite material, the reaction conditions are: reacting for 1.5-2 hours at a temperature of 25-35°C in the dark, and the calcination conditions are: calcining for 0.5-1 hour at a temperature of 200-220°C.

6. The method for preparing high-strength antibacterial decorative paper according to claim 4, characterized in that: In S2, the mass ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ethanol, water, and silver-loaded titanium dioxide / sepiolite composite material is 5.5-6:60-70:20-30:1-1.2; the stirring conditions are: stirring for 1.5-2 hours at a pH value of 4-4.5; and the reaction conditions are: reacting at room temperature for 24-26 hours.

7. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: When preparing the antibacterial functionalized polyether in step 1, in step (1), the mass ratio of 1,2-benzisothiazolin-3-one, potassium carbonate, N,N-dimethylformamide, and 1,3-dibromo-2-propanol is 3-3.2:2.8-3:30-40:2.2-2.3; when preparing the modified benzisothiazolinone, the reaction conditions are: reacting at a temperature of 60-70°C for 12-16 hours; the mass ratio of the modified benzisothiazolinone, epoxy-loaded silver titanium dioxide / sepiolite composite material, and water is 3-3.1:1:80-100; when preparing the antibacterial agent, the reaction conditions are: reacting at a temperature of 80-90°C for 3-4 hours.

8. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: When preparing the antibacterial functionalized polyether in step 1, in step (2), the mass ratio of polyetheramine, antibacterial agent, tetrahydrofuran, terephthalaldehyde, diethylenetriamine, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 18-20:1-1.2:90-100:13-13.4:2-2.1:2-2.2; the reaction conditions are: reacting at a temperature of 105-115° C. for 4-5 hours; and the continued reaction conditions are: continuing the reaction at a temperature of 55-65° C. for 3-4 hours in a nitrogen atmosphere.

9. The method for preparing high-strength antibacterial decorative paper according to claim 1, characterized in that: In the step 2, the mass ratio of the decorative base paper to the antibacterial impregnation liquid is 1:20-30, the impregnation conditions are: impregnation at room temperature for 3-5 minutes; and the drying conditions are: drying at a vacuum degree of -0.08 MPa and a temperature of 80-90° C. for 40-50 minutes.

10. A high-strength antibacterial decorative paper prepared by the method for preparing a high-strength antibacterial decorative paper according to any one of claims 1 to 9.

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