Composite board for highly antibacterial and mildew-proof furniture and its manufacturing process

Abstract

The present invention relates to the technical field of composite board processing, specifically to a composite board for high antibacterial and mildew-proof furniture and its manufacturing process. The present invention prepares a mercapto-modified hyaluronic acid, adds it to a green formaldehyde-free polyurethane adhesive, and mixes evenly to obtain a modified polyurethane adhesive for bonding composite boards. The two sides of the composite board of the present invention are covered with decorative paper. First, the decorative paper is impregnated in an epoxy resin impregnating solution. Vinyltrimethoxysilane in the epoxy resin impregnating solution can undergo a thiol-vinyl click reaction with the mercapto-modified hyaluronic acid in the modified polyurethane adhesive under the action of 2-hydroxy-2-methyl-1-phenyl-1-propanone photoinitiator, increasing the interfacial interaction force and enhancing the bonding force between the wood board and the decorative paper. The present invention first prepares a corn cob biochar, which can adsorb free formaldehyde and is green and environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of composite board processing, and specifically to a composite board for high antibacterial and mildew-proof furniture and its manufacturing process. Background Art

[0002] Composite board is a multi-layer board-shaped household material glued by adhesives. Composite boards have the characteristics of high strength and low cost, and are increasingly widely used in the fields of packaging, furniture, and building materials. In order to pursue the aesthetic effect of composite boards, manufacturers will adhere decorative surface materials on the composite boards, such as decorative paper or wood grain film, etc. However, due to reasons such as humid environment and bacterial growth, the surface of composite boards is often vulnerable to the invasion of mold and bacteria, resulting in hygiene problems and quality decline. To solve this problem, manufacturers will coat antibacterial and mildew-proof coatings and materials on the composite boards, but these coatings often lead to a decrease in material adhesion and also bring the problem of excessive formaldehyde content. For example, melamine resin impregnated decorative paper contains a small amount of formaldehyde, and excessive use poses a hazard of free formaldehyde. Traditional composite boards have been difficult to meet the increasing functional requirements and more demanding usage environments.

[0003] To solve the above problems and improve the antibacterial and mildew-proof effect of composite boards, the present invention provides a composite board for high antibacterial and mildew-proof furniture and its manufacturing process. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite board for high antibacterial and mildew-proof furniture and its manufacturing process to solve the problems raised in the above background art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] The manufacturing process of the composite board for high antibacterial and mildew-proof furniture includes the following steps:

[0007] Step 1: Take mercapto-modified hyaluronic acid and polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0008] Step 2: Take epoxy resin, silver-iron co-doped corn cob biochar, vinyltrimethoxysilane, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0009] Step 3: Immerse the decorative paper in the epoxy resin impregnating solution for 3 - 4 hours, take it out, introduce a horizontal magnetic field, and dry for 1 - 2 hours to obtain decorative paper A;

[0010] Step 4: Take a wooden board, spray a modified polyurethane adhesive on the surface of the wooden board, assemble the glued wooden boards, then cover decorative paper A on both sides, hot press at 100 - 110 °C and 1 - 1.5 MPa for 5 - 10 min, perform photo - reinforcement under an ultraviolet lamp for 30 - 40 min, and let it stand and cool for 2 - 3 h to obtain a composite board.

[0011] More preferably, the mass ratio of the mercapto - modified hyaluronic acid to the polyurethane adhesive is 1:(18 - 20).

[0012] More preferably, the preparation method of the mercapto - modified hyaluronic acid is as follows: It includes the following steps:

[0013] S1: Take 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide hydrochloride, cystamine dihydrochloride, N - hydroxysuccinimide, and deionized water, stir evenly, add hydrochloric acid and sodium hyaluronate, mix evenly, react at 3 - 4 °C for 70 - 74 h, and perform dialysis;

[0014] S2: Take dithiothreitol and deionized water, stir evenly, add the dialyzed gel, add sodium hydroxide to adjust the pH value, stir for 50 - 70 min, perform dialysis and freezing to obtain mercapto - modified hyaluronic acid.

[0015] More preferably, in S2, add sodium hydroxide to adjust the pH value to 8 - 8.5.

[0016] More preferably, the preparation method of the silver - iron co - doped corn cob biochar is: Take silver nitrate solution, ferric nitrate nonahydrate solution, and citric acid solution, stir evenly to obtain a mixed solution, add corn cob biochar to the mixed solution, mix evenly, then dropwise add ascorbic acid solution, stir for 7 - 8 h, filter, wash, and dry, activate at 480 - 500 °C for 60 - 70 min, wash and dry to obtain silver - iron co - doped corn cob biochar.

[0017] More preferably, the preparation method of the corn cob biochar is: Take corn cobs, cut them into pieces, carbonize at 600 - 650 °C for 1.5 - 2 h, cool, grind and sieve to obtain corn cob biochar.

[0018] More preferably, the intensity of the magnetic field is 220 - 230 mT.

[0019] More preferably, the power of the ultraviolet lamp is 800 - 830 W.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] (1) The present invention first prepares a corncob biochar, which can adsorb free formaldehyde and is green and environmentally friendly. Secondly, the present invention loads silver nanoparticles and magnetite on the corncob biochar by adding silver nitrate solution and ferric nitrate nonahydrate solution. Silver nanoparticles have good antibacterial effects and can improve the antibacterial and mildew-proof properties of composite boards.

[0022] (2) The present invention prepares a mercapto-functionalized hyaluronic acid and adds it to a green formaldehyde-free polyurethane adhesive, and mixes them evenly to obtain a modified polyurethane adhesive for bonding composite boards. The two sides of the composite board of the present invention are covered with decorative paper. First, the decorative paper is impregnated in an epoxy resin impregnating solution. Vinyltrimethoxysilane in the epoxy resin impregnating solution can react with the mercapto-functionalized hyaluronic acid in the modified polyurethane adhesive under the action of 2-hydroxy-2-methyl-1-phenyl-1-propanone photoinitiator to produce a thiol-vinyl click reaction, increasing the interfacial force and enhancing the bonding strength between the wooden board and the decorative paper.

[0023] However, the silver-iron co-doped corncob biochar is prone to agglomeration in the epoxy resin, which affects the antibacterial and mildew-proof effects of the board. To solve this problem, after the decorative paper is impregnated in the epoxy resin impregnating solution, magnetic field treatment needs to be introduced. At this time, the magnetite on the corncob biochar is more evenly dispersed under the influence of magnetic force, solving the problem of performance degradation caused by agglomeration and enhancing the mildew-proof and antibacterial properties of the wooden board. Specific embodiments

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0025] There are no special restrictions on the purchase manufacturers of all raw materials involved in the present invention. Exemplarily, they include: polyurethane adhesive: can be purchased from Wanhua Chemical Group, model: CW20; decorative paper can be purchased from Schattdecor of Germany; sodium hyaluronate (1 million, Mw) can be purchased from Shandong Huaxi Freda Biopharmaceutical Co., Ltd.; corncob: can use the corncob in Luoyang area as raw material; epoxy resin can be purchased from Jinan Chuangshi Chemical Co., Ltd., model: E51; wooden board: pine wood, can be purchased from New Zealand.

[0026] Example 1: The manufacturing process of a high antibacterial and mildew-proof furniture composite board includes the following steps:

[0027] Step 1: Preparation of mercapto-functionalized hyaluronic acid:

[0028] Take 0.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.6 g of cystamine dihydrochloride, 0.3 g of N-hydroxysuccinimide, and 20 mL of deionized water. Stir evenly, add 1 M hydrochloric acid to adjust the pH value to 5.5, add 1 g of sodium hyaluronate, mix evenly, react at 3 °C for 70 h, place the gel in a 0.2 M phosphate buffer solution with a pH value of 7.2 and dialyze until the gel weight is constant to obtain the dialyzed gel; take 0.4 g of dithiothreitol and 10 mL of deionized water, stir evenly, add 10 g of the dialyzed gel, add 1 M sodium hydroxide to adjust the pH value to 8, stir for 60 min, dialyze with 0.3 mM HCl and 0.1 M NaCl solution, and freeze to obtain thiolated hyaluronic acid;

[0029] Step 2: Preparation of silver-iron co-doped corn cob biochar:

[0030] Take corn cobs, chop them, carbonize at 630 °C for 1.7 h, cool, grind and pass through a 2 mm sieve to obtain corn cob biochar;

[0031] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution. Add 1 g of corn cob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 26 °C for 7.5 h, filter, wash, dry, activate at 490 °C for 65 min, wash and dry to obtain silver-iron co-doped corn cob biochar;

[0032] Step 3: Preparation of modified polyurethane adhesive:

[0033] Take 5 g of thiolated hyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0034] Step 4: Preparation of epoxy resin impregnating solution:

[0035] Take 50 g of epoxy resin, 8 g of silver-iron co-doped corn cob biochar, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0036] Step 5: Preparation of composite board:

[0037] Immerse the decorative paper at 120 g / m 2 in the epoxy resin impregnating solution for 3.5 h, take it out, introduce a horizontal magnetic field with a magnetic field intensity of 220 mT, and dry for 1.5 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0038] Take wooden boards, dry them until the water content is 5%, spray a modified polyurethane adhesive on the surface of the wooden boards, and the single-sided glue application amount is 150 g / m 2 ; Stack 5 layers of glued wooden boards according to the principle that the textures between adjacent layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 105 °C and 1 MPa for 7 min, photo-reinforce under an 810 W ultraviolet lamp for 35 min, and let it stand and cool for 2.5 h to obtain a composite board with a thickness of 9 mm.

[0039] Example 2: The manufacturing process of a composite board for high antibacterial and mildew-proof furniture, comprising the following steps:

[0040] Step 1: Preparation of mercapto-modified hyaluronic acid:

[0041] Take 0.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.6 g of cystamine dihydrochloride, 0.3 g of N-hydroxysuccinimide, 20 mL of deionized water, stir evenly, add 1 M hydrochloric acid to adjust the pH value to 5.5, add 1 g of sodium hyaluronate, mix evenly, react at 3 °C for 70 h, place the gel in a 0.2 M phosphate buffer solution with a pH value of 7.2 and dialyze until the gel weight is constant to obtain the dialyzed gel; take 0.4 g of dithiothreitol, 10 mL of deionized water, stir evenly, add 10 g of the dialyzed gel, add 1 M sodium hydroxide to adjust the pH value to 8, stir for 50 min, dialyze with 0.3 mM HCl and 0.1 M NaCl solutions, and freeze to obtain mercapto-modified hyaluronic acid;

[0042] Step 2: Preparation of silver-iron co-doped corn cob biochar:

[0043] Take corn cobs, cut them into pieces, carbonize at 600 °C for 1.5 h, cool, grind and pass through a 2 mm sieve to obtain corn cob biochar;

[0044] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution, add 1 g of corn cob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 25 °C for 7 h, filter, wash, dry, activate at 480 °C for 60 min, wash, and dry to obtain silver-iron co-doped corn cob biochar;

[0045] Step 3: Preparation of modified polyurethane adhesive:

[0046] Take 5 g of mercapto-modified hyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0047] Step 4: Preparation of epoxy resin impregnating solution:

[0048] Take 50 g of epoxy resin, 8 g of silver-iron co-doped corn cob biochar, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0049] Step Five: Preparation of composite board:

[0050] Immerse the decorative paper at 120 g / m 2 in the epoxy resin impregnating solution for 3 h, take it out, introduce a horizontal magnetic field with a magnetic field strength of 220 mT, dry for 1 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0051] Take wooden boards, dry them to a water content of 5%, spray modified polyurethane adhesive on the surface of the wooden boards, and the single-sided glue application amount is 150 g / m 2 ; Assemble 5 layers of sized wooden boards according to the principle that the textures between adjacent two layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 100 °C and 1 MPa for 5 min, photo-reinforce under an 800 W ultraviolet lamp for 30 minutes, and let it stand and cool for 2 h to obtain a composite board with a thickness of 9 mm.

[0052] Example 3: Manufacturing process of a composite board for highly antibacterial and mildew-proof furniture, including the following steps:

[0053] Step One: Preparation of mercapto-modified hyaluronic acid:

[0054] Take 0.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.6 g of cystamine dihydrochloride, 0.3 g of N-hydroxysuccinimide, 20 mL of deionized water, stir evenly, add 1 M hydrochloric acid to adjust the pH value to 5.5, add 1 g of sodium hyaluronate, mix evenly, react at 4 °C for 74 h, place the gel in a 0.2 M phosphate buffer solution with a pH value of 7.2 and dialyze until the gel weight is constant to obtain the dialyzed gel; take 0.4 g of dithiothreitol, 10 mL of deionized water, stir evenly, add 10 g of the dialyzed gel, add 1 M sodium hydroxide to adjust the pH value to 8, stir for 70 min, dialyze with 0.3 mM HCl and 0.1 M NaCl solutions, and freeze to obtain mercapto-modified hyaluronic acid;

[0055] Step Two: Preparation of silver-iron co-doped corn cob biochar:

[0056] Take corn cobs, cut them into pieces, carbonize at 650 °C for 2 h, cool, grind and pass through a 2 mm sieve to obtain corn cob biochar;

[0057] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution. Add 1 g of corncob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 27 °C for 8 h, filter, wash, and dry. Activate at 500 °C for 70 min, wash and dry to obtain silver-iron co-doped corncob biochar;

[0058] Step 3: Preparation of modified polyurethane adhesive:

[0059] Take 5 g of mercapto-modified hyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0060] Step 4: Preparation of epoxy resin impregnating solution:

[0061] Take 50 g of epoxy resin, 8 g of silver-iron co-doped corncob biochar, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0062] Step 5: Preparation of composite board:

[0063] Immerse the decorative paper at 120 g / m 2 in the epoxy resin impregnating solution for 4 h, take it out, introduce a horizontal magnetic field with a magnetic field strength of 230 mT, dry for 2 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0064] Take wooden boards, dry them to a moisture content of 5%, spray the modified polyurethane adhesive on the surface of the wooden boards, and the single-sided glue application amount is 150 g / m 2 ; Assemble 5 layers of sized wooden boards according to the principle that the textures between adjacent two layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 110 °C and 1.5 MPa for 10 min, photo-reinforce under an 820 W ultraviolet lamp for 40 min, and let it stand and cool for 3 h to obtain a composite board with a thickness of 9 mm.

[0065] Comparative Example 1: Use hyaluronic acid instead of mercapto-modified hyaluronic acid, and the rest is the same as in Example 1:

[0066] Step 1: Preparation of silver-iron co-doped corncob biochar:

[0067] Take corncobs, cut them into pieces, carbonize at 630 °C for 1.7 h, cool, grind and pass through a 2 mm sieve to obtain corncob biochar;

[0068] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution. Add 1 g of corncob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 26 °C for 7.5 h, filter, wash, and dry, activate at 490 °C for 65 min, wash and dry to obtain silver and iron co-doped corncob biochar;

[0069] Step 2: Preparation of modified polyurethane adhesive:

[0070] Take 5 g of hyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0071] Step 4: Preparation of epoxy resin impregnating solution:

[0072] Take 50 g of epoxy resin, 8 g of silver and iron co-doped corncob biochar, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0073] Step 5: Preparation of composite board:

[0074] Immerse the decorative paper at 120 g / m 2 in the epoxy resin impregnating solution for 3.5 h, take it out, introduce a horizontal magnetic field with a magnetic field intensity of 220 mT, dry for 1.5 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0075] Take a wooden board, dry it to a water content of 5%, spray the modified polyurethane adhesive on the surface of the wooden board, and the single-sided glue application amount is 150 g / m 2 ; Assemble 5 layers of sized wooden boards according to the principle that the textures between adjacent two layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 105 °C and 1 MPa for 7 min, photo-reinforce under an 810 W ultraviolet lamp for 35 min, and let it stand and cool for 2.5 h to obtain a composite board with a thickness of 9 mm.

[0076] Comparative Example 2: Without introducing a magnetic field, the rest is the same as in Example 1:

[0077] Step 1: Preparation of mercapto-functionalized hyaluronic acid:

[0078] Take 0.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.6 g of cystamine dihydrochloride, 0.3 g of N-hydroxysuccinimide, and 20 mL of deionized water. Stir evenly, add 1 M hydrochloric acid to adjust the pH value to 5.5, add 1 g of sodium hyaluronate, mix evenly, react at 3 °C for 70 h, place the gel in a 0.2 M phosphate buffer solution with a pH value of 7.2 for dialysis until the gel weight is constant to obtain the dialyzed gel; take 0.4 g of dithiothreitol and 10 mL of deionized water, stir evenly, add 10 g of the dialyzed gel, add 1 M sodium hydroxide to adjust the pH value to 8, stir for 60 min, dialyze with 0.3 mM HCl and 0.1 M NaCl solution, and freeze to obtain thiolated hyaluronic acid;

[0079] Step 2: Preparation of silver-iron co-doped corn cob biochar:

[0080] Take corn cobs, chop them, carbonize at 630 °C for 1.7 h, cool, grind through a 2 mm sieve to obtain corn cob biochar;

[0081] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution. Add 1 g of corn cob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 26 °C for 7.5 h, filter, wash, and dry, activate at 490 °C for 65 min, wash and dry to obtain silver-iron co-doped corn cob biochar;

[0082] Step 3: Preparation of modified polyurethane adhesive:

[0083] Take 5 g of thiolated hyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0084] Step 4: Preparation of epoxy resin impregnating solution:

[0085] Take 50 g of epoxy resin, 8 g of silver-iron co-doped corn cob biochar, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0086] Step 5: Preparation of composite board:

[0087] Immerse the decorative paper with a weight of 120 g / m 2 in the epoxy resin impregnating solution for 3.5 h, take it out and dry for 1.5 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0088] Take the wooden board and dry it until the water content is 5%. Spray the modified polyurethane adhesive on the surface of the wooden board, and the single-sided glue application amount is 150 g / m 2 ; Stack 5 layers of the sized wooden boards according to the principle that the textures between adjacent layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 105 °C and 1 MPa for 7 min, perform photo-reinforcement under an 810 W ultraviolet lamp for 35 min, and let it stand and cool for 2.5 h to obtain a composite board with a thickness of 9 mm.

[0089] Comparative Example 3: The mass ratio of mercaptohyaluronic acid to polyurethane adhesive is 1:15, and the rest is the same as in Example 1:

[0090] Step 1: Preparation of mercaptohyaluronic acid:

[0091] Take 0.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.6 g of cystamine dihydrochloride, 0.3 g of N-hydroxysuccinimide, and 20 mL of deionized water, stir evenly, add 1 M hydrochloric acid to adjust the pH value to 5.5, add 1 g of sodium hyaluronate, mix evenly, react at 3 °C for 70 h, place the gel in a 0.2 M phosphate buffer solution with a pH value of 7.2 for dialysis until the gel weight is constant to obtain the dialyzed gel; take 0.4 g of dithiothreitol and 10 mL of deionized water, stir evenly, add 10 g of the dialyzed gel, add 1 M sodium hydroxide to adjust the pH value to 8, stir for 60 min, dialyze with 0.3 mM HCl and 0.1 M NaCl solution, and freeze to obtain mercaptohyaluronic acid;

[0092] Step 2: Preparation of silver-iron co-doped corn cob biochar:

[0093] Take corn cobs, cut them into pieces, carbonize at 630 °C for 1.7 h, cool, grind and pass through a 2 mm sieve to obtain corn cob biochar;

[0094] Take a silver nitrate solution with a concentration of 1.5 mmol / L, a ferric nitrate nonahydrate solution with a concentration of 1 mmol / L, and a citric acid solution with a concentration of 1 mmol / L, stir evenly to obtain a mixed solution. Add 1 g of corn cob biochar to 30 mL of the mixed solution, mix evenly, then dropwise add 10 mL of a 10 mmol / L ascorbic acid solution, stir at 26 °C for 7.5 h, filter, wash, and dry, activate at 490 °C for 65 min, wash and dry to obtain silver-iron co-doped corn cob biochar;

[0095] Step 3: Preparation of modified polyurethane adhesive:

[0096] Take 6.33 g of mercaptohyaluronic acid and 95 g of polyurethane adhesive, stir evenly to obtain a modified polyurethane adhesive;

[0097] Step 4: Preparation of epoxy resin impregnating solution:

[0098] Take 50 g of epoxy resin, 8 g of corn cob biochar co-doped with silver and iron, 2 g of vinyltrimethoxysilane, 0.3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 30 g of ethyl acetate, stir evenly to obtain an epoxy resin impregnating solution;

[0099] Step Five: Preparation of composite board:

[0100] Immerse the decorative paper of 120 g / m 2 in the epoxy resin impregnating solution for 3.5 h, take it out, introduce a horizontal magnetic field with a magnetic field strength of 220 mT, and dry it for 1.5 h to make the resin content (impregnation amount) 150% to obtain decorative paper A;

[0101] Take a wooden board, dry it until the water content is 5%, spray a modified polyurethane adhesive on the surface of the wooden board, and the single-sided glue application amount is 150 g / m 2 ; Assemble 5 layers of sized wooden boards according to the principle that the textures between adjacent two layers of wooden boards are perpendicular to each other, then cover decorative paper A on both sides, hot press at 105 °C and 1 MPa for 7 min, photo-reinforce under an ultraviolet lamp of 810 W for 35 min, and let it stand and cool for 2.5 h to obtain a composite board with a thickness of 9 mm.

[0102] Experiment:

[0103] Perform performance tests on the composite boards prepared in Examples 1-3 and Comparative Examples 1-3. According to GB / T17657, test the bonding strength between the decorative paper and the wooden board of the composite board; cut the composite board into specimens of 200 mm × 200 mm, place them in an environment of 25 °C and a humidity of 65% for 12 weeks, and test the anti-mold performance according to GB / T18261. Take Gram-positive Staphylococcus aureus for antibacterial performance testing, and the concentration of Gram-positive Staphylococcus aureus is 5×10 6 cfu / mL. Drop the mixed bacterial solution on the composite board specimen, incubate it at a constant temperature of 37 °C for 24 h, measure the bacteriostatic rate, and the obtained data are as follows:

[0104] Gluing strength / MPa Mildew area of composite board Antibacterial rate / % Example 1 3.9 The surface mildew area is 0 - 5%. 99.9 Example 2 3.7 The surface mildew area is 0 - 5%. 99.8 Example 3 3.9 The surface mildew area is 0 - 5%. 99.9 Comparative Example 1 3.2 The surface mildew area is 0 - 5%. 99.9 Comparative Example 2 3.8 The surface mildew area is 5 - 15%. 94.4 Comparative Example 3 3.5 The surface mildew area is 0 - 5%. 99.7

[0105] Conclusion: It can be seen from the data comparison in the table that in Comparative Example 1, hyaluronic acid was used instead of thiolated hyaluronic acid, and the bonding strength between the decorative paper and the wooden board was poor. In Comparative Example 2, no magnetic field was introduced, and the silver-iron co-doped corncob biochar was prone to agglomeration in the epoxy resin, affecting the antibacterial and mildew-proof effects of the board. At this time, the mildew area of the composite board increased and the antibacterial rate decreased. In Comparative Example 3, the amount of thiolated hyaluronic acid added decreased, and the bonding strength of the composite board decreased. The decorative papers of the composite boards prepared in Examples 1 to 3 were impregnated in the epoxy resin impregnating solution. Vinyltrimethoxysilane in the epoxy resin impregnating solution can react with the thiolated hyaluronic acid in the modified polyurethane adhesive under the action of 2-hydroxy-2-methyl-1-phenyl-1-propanone photoinitiator to produce a thiol-vinyl click reaction. At this time, the bonding strength between the decorative paper and the wooden board is the best.

[0106] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. Manufacturing process of composite board for highly antibacterial and mildew-proof furniture, Characterized in that: It includes the following steps: Step 1: Take mercaptohyaluronic acid and polyurethane adhesive, stir evenly to obtain modified polyurethane adhesive; Step 2: Take epoxy resin, silver-iron co-doped corn cob biochar, vinyltrimethoxysilane, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and ethyl acetate, stir evenly to obtain epoxy resin impregnating solution; Step 3: Immerse the decorative paper in the epoxy resin impregnating solution for 3-4 h, take it out, introduce a horizontal magnetic field, and dry for 1-2 h to obtain decorative paper A; Step 4: Take a wooden board, spray the modified polyurethane adhesive on the surface of the wooden board, assemble the sized wooden boards, then cover decorative paper A on both sides, hot press for 5-10 min, and photo-reinforce under an ultraviolet lamp for 30-40 min, and let it stand and cool to obtain the composite board.

2. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 1, Characterized in that: The mass ratio of the mercaptohyaluronic acid to the polyurethane adhesive is 1:(18-20).

3. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 2, Characterized in that: The preparation method of the mercaptohyaluronic acid is: It includes the following steps: S1: Take 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, cystamine dihydrochloride, N-hydroxysuccinimide, and deionized water, stir evenly, add hydrochloric acid and sodium hyaluronate, mix evenly, react at 3-4 °C for 70-74 h, and dialyze; S2: Take dithiothreitol and deionized water, stir evenly, add the dialyzed gel, add sodium hydroxide to adjust the pH value, stir for 50-70 min, dialyze and freeze to obtain mercaptohyaluronic acid.

4. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 3, Characterized in that: In S2, add sodium hydroxide to adjust the pH value to 8-8.

5.

5. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 1, Characterized in that: The preparation method of the silver-iron co-doped corn cob biochar is: Take silver nitrate solution, ferric nitrate nonahydrate solution, and citric acid solution, stir evenly to obtain a mixed solution, add corn cob biochar to the mixed solution, mix evenly, then dropwise add ascorbic acid solution, stir for 7-8 h, filter, wash, and dry, activate at 480-500 °C for 60-70 min, wash and dry to obtain silver-iron co-doped corn cob biochar.

6. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 5, Characterized in that: The preparation method of the corn cob biochar is: Take corn cobs, cut them into pieces, carbonize at 600-650 °C for 1.5-2 h, cool, grind and sieve to obtain corn cob biochar.

7. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 1, Characterized in that: The intensity of the magnetic field is 220-230 mT.

8. The manufacturing process of the composite board for highly antibacterial and mildew-proof furniture according to claim 1, Characterized in that: The power of the ultraviolet lamp is 800-830 W.

9. A composite board produced by the manufacturing process of the high antibacterial and mildew-proof furniture composite board according to any one of claims 1-8.