A highly weather-resistant, antibacterial, and environmentally friendly water-based wood glue and its preparation method

Abstract

This application relates to the field of adhesives, specifically disclosing a highly weather-resistant, antibacterial, and environmentally friendly water-based wood adhesive and its preparation method. The adhesive comprises the following components by weight: 50-70 parts of a water-soluble antibacterial polyurethane-modified acrylic resin; 0.3-0.6 parts of a defoamer; 0.5-0.8 parts of a dispersant; 0.2-0.5 parts of a thickener; 5-8 parts of a cross-linking agent; 5-10 parts of a solvent; and 3-8 parts of microcapsules. This wood adhesive is environmentally friendly, exhibits strong adhesion, and offers long-lasting antibacterial and weather resistance, making it suitable for bonding outdoor wood products.

Description

Technical Field

[0001] The present application relates to the field of adhesives, and more specifically, to a highly weather-resistant, antibacterial, and environmentally friendly water-based woodworking adhesive and a preparation method thereof. Background Art

[0002] Solvent-based adhesives have always been the mainstream adhesives for woodworking substrates, but water-based adhesives have developed rapidly. Water-based acrylic adhesives and water-based polyurethane adhesives are conventional adhesive types. Water-based acrylic adhesives have good water resistance, weather resistance, adhesion, and heat resistance, but poor solvent resistance. Water-based polyurethane adhesives have high reactivity, alkali resistance, cold resistance, and good adhesion, but poor water resistance and high temperature resistance. The mixed use of water-based acrylic adhesives and water-based polyurethane adhesives can bring out the advantages of each resin, but the compatibility of acrylic resins and polyurethane resins is poor, resulting in poor physical properties and insufficient adhesion.

[0003] Wood products are often used indoors and outdoors, especially in harsh outdoor environments. The adhesives used to make them must possess long-lasting, high weather resistance and antibacterial properties to meet long-term practicality. However, existing wood products often suffer structural damage due to adhesive failure, requiring rebonding or even irreparable structural damage. Water-based adhesives are often inferior to solvent-based adhesives in terms of weather resistance and antibacterial properties. Therefore, the development of a durable, highly weather-resistant, and antibacterial adhesive is an urgent challenge. Summary of the Invention

[0004] In order to solve the problem that water-based adhesives have long-lasting high weather resistance, antibacterial properties and strong adhesion, the present application provides a highly weather-resistant, antibacterial and environmentally friendly water-based wood glue and a preparation method thereof.

[0005] In the first aspect, the present application provides a highly weather-resistant, antibacterial, and environmentally friendly water-based woodworking glue, comprising the following components in parts by weight: 50-70 parts of a water-soluble antibacterial polyurethane-modified acrylic resin; 0.3-0.6 parts of a defoaming agent; 0.5-0.8 parts of a dispersant; 0.2-0.5 parts of a thickener; 5-8 parts of a cross-linking agent; 5-10 parts of a solvent; and 3-8 parts of microcapsules.

[0006] This application uses a water-soluble antimicrobial polyurethane-modified acrylic resin to prepare a water-based adhesive, eliminating the use of highly toxic oil-soluble solvents and having positive environmental benefits. Furthermore, by modifying the acrylic resin with antimicrobial polyurethane, the resulting colloid possesses the excellent water resistance, chemical solvent resistance, and weather resistance of both acrylic resin and polyurethane, resolving the poor compatibility issue between acrylic resin and polyurethane. Furthermore, the adhesive is endowed with excellent antimicrobial properties, meeting the requirements for outdoor use. The addition of microcapsules allows for sustained release of the antimicrobial agent, achieving long-lasting antimicrobial properties.

[0007] Preferably, the preparation method of the water-soluble antibacterial polyurethane modified acrylic resin comprises: adding acrylic monomer and functional monomer to a solvent, introducing nitrogen, stirring, heating and refluxing, adding an initiator dropwise, and then keeping the temperature at 80-90°C for 3-6 hours to obtain an acrylic resin; then cooling the acrylic resin to 70-80°C, adding antibacterial polyurethane, keeping the temperature for 1-3 hours, and heating to 90-100°C for 1-3 hours to obtain a water-soluble antibacterial polyurethane modified acrylic resin.

[0008] The preparation method of the antibacterial polyurethane comprises: vacuum dehydrating polyol, adding diisocyanate and a catalyst, mixing, reacting at 70-75° C. for 2-4 hours under nitrogen protection, adding organosilicon-modified quaternary ammonium salt and a catalyst, heating to 75-80° C. and keeping the temperature for reaction for 1-3 hours, then adding diisocyanate and the catalyst, cooling to 70-75° C. and continuing the reaction for 1-3 hours, and cooling to obtain the antibacterial polyurethane.

[0009] Preferably, the acrylic monomer is one or more of methyl methacrylate, butyl acrylate, and isooctyl acrylate; and the functional monomer is one or more of acrylic acid and hydroxyethyl acrylate.

[0010] Preferably, the mass ratio of the acrylic monomer, the functional monomer and the antibacterial polyurethane is: (2-4): (2-4): 5.

[0011] Preferably, the polyol is one or more of polyether diol, polyester diol, and polybutadiene diol.

[0012] Preferably, the polyol is polyether diol, polyester diol, and polybutadiene diol in a mass ratio of (4-8):(3-5):1.

[0013] Preferably, the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0014] The present application prepares and synthesizes acrylic resin containing active groups such as hydroxyl and carboxyl groups through the conventional polymerization process of acrylic monomers, and then chemically grafts antibacterial polyurethane terminated with isocyanate groups to obtain polyurethane-modified acrylic resin. The preparation process is simple and the raw materials are easily available.

[0015] The antibacterial polyurethane of the present application is prepared by reacting a polyol and a diisocyanate in the presence of a catalyst to form a prepolymer, then adding a silicone-modified quaternary ammonium salt to carry out chain extension reaction, and then obtaining an antibacterial polyurethane with isocyanate end-capping groups through the reaction of the diisocyanate.

[0016] At the same time, the mass ratio of acrylic acid monomer, functional monomer and antibacterial polyurethane in the preparation is: (2-4): (2-4): 5. The antibacterial polyurethane modified acrylic resin prepared within this range has good weather resistance and antibacterial properties. When the amount of acrylic acid monomer is too small, there are fewer acrylic acid polymer chains in the colloid and fewer cross-linkable active groups, and the obtained resin has slightly poor weather resistance. If the content of acrylic acid monomer is too much, the content of antibacterial polyurethane is less and the antibacterial property is weakened. In addition, the organosilicon-modified quaternary ammonium salt component of the present application is relatively less, the high temperature resistance is reduced, and the mutual cross-linking of polyurethane and acrylic resin to form a dense network structure is reduced, thereby reducing weather resistance. Within the above range of the present application, the obtained resin has better hydrophilicity, adhesion, weather resistance and antibacterial agent.

[0017] In addition, the polyurethane prepared when the mass ratio of the polyols of the present application is polyether diol, polyester diol, and polybutadiene diol is: (4-8): (3-5): 1 can provide better hydrophilicity, flexibility and adhesion, and therefore, better weather resistance. In addition, the polybutadiene diol makes the polyurethane contain unsaturated double bonds, providing reaction sites that can achieve long-lasting adhesion.

[0018] Compared to conventional antibacterial agent, the preferred organosilicon modified quaternary ammonium salt of the application, on the one hand, quaternary ammonium salt has excellent antibiotic property, and good water solubility, can give resin better antibiotic property, adhesive force, on the other hand, appropriate organosilicon modification has the effect of migration, when being prepared into antibacterial polyurethane modified acrylic resin, because of the migration effect of organosilicon, the double bond in antibiotic quaternary ammonium salt group and polyurethane can realize enrichment on the surface of adhesive, thus improve the antibacterial efficacy of adhesive and provide the effect of better repair adhesion, therefore the mass ratio of acrylic acid monomer, functional monomer, antibacterial polyurethane is controlled at (2-4) by the application: (2-4): 5 on the other hand is to ensure good antibiotic property, ensure the adhesive force of glue and can further provide the ability of repair adhesion of some adhesives. The organosilicon modified quaternary ammonium salt of the application can be prepared by conventional preparation process or prior art prepares and obtains.

[0019] Preferably, the core material of the microcapsule includes polyhexamethyleneguanidine hydrochloride and acrylate; and the wall material includes photoinitiator 184.

[0020] By containing microcapsules of antimicrobial agents, polyhexamethyleneguanidine hydrochloride is released when the microcapsules rupture, thereby strengthening the antimicrobial agent in the adhesive. The antimicrobial agent is compounded with the quaternary ammonium salt antimicrobial agent to achieve a better mixed antimicrobial effect and maintain a long-lasting antimicrobial effect. In addition, the core material of the antimicrobial agent of the present application also contains acrylates, and the wall material includes photoinitiator 184. When the microcapsules rupture, the acrylates and photoinitiator are released. The double bonds in the adhesive and the acrylic acid can be further polymerized by simple ultraviolet light curing in the presence of the photoinitiator. In the presence of acrylates and photoinitiators, the double bonds in the main resin-modified acrylic resin of the colloid are polymerized, which can be further cross-linked to achieve repair of the adhesive's adhesion properties. In the present application, through the migration of silicone, the quaternary ammonium salt is enriched on the adhesive surface while the double bonds are also enriched on the surface, which is more conducive to achieving further cross-linking repair and improving the repair ability.

[0021] On the other hand, the present application provides a method for preparing highly weather-resistant, antibacterial and environmentally friendly water-based wood glue, comprising the following steps: mixing and stirring water-soluble antibacterial polyurethane modified acrylic resin, defoaming agent, dispersant, thickener, solvent and microcapsule according to a proportion, and then adding a cross-linking agent and mixing evenly to obtain environmentally friendly water-based wood glue.

[0022] In summary, this application has at least the following beneficial effects:

[0023] 1. The water-soluble antibacterial polyurethane-modified acrylic resin prepared in this application has, on the one hand, the excellent water resistance, chemical solvent resistance, and weather resistance of acrylic resin and polyurethane, which solves the problem of poor compatibility between acrylic resin and polyurethane. On the other hand, it gives the glue excellent antibacterial properties, which can meet the requirements of outdoor use.

[0024] 2. This application prepares antibacterial polyurethane by adding polybutadiene diol and silicone-modified quaternary ammonium salt, and then modifies acrylic resin to prepare water-soluble antibacterial polyurethane-modified acrylic resin. The resin contains double bonds and silicone quaternary ammonium salt groups. At the same time, the microcapsule core material includes polyhexamethyleneguanidine hydrochloride and acrylate; the wall material includes photoinitiator 184. On the one hand, it can enrich the antibacterial agent on the surface of the adhesive to improve the antibacterial function. On the other hand, when the bonding performance of the adhesive is reduced, the monomers released by the microcapsules continue to participate in the polymerization and cross-linking of the double bonds in the modified resin to further repair and enhance the adhesion, thereby achieving a long-lasting antibacterial and weather-resistant effect.

[0025] 3. The present application regulates the mass ratio of acrylic monomer, functional monomer, and antibacterial polyurethane within the range of (2-4): (2-4): 5. When the amount of acrylic monomer is too small, there are fewer acrylic polymer chains in the colloid and fewer cross-linkable active groups. The obtained resin has slightly poor weather resistance. If the acrylic monomer content is too high, the content of antibacterial polyurethane is less and the antibacterial property is weakened. In addition, the organosilicon-modified quaternary ammonium salt component of the present application is relatively less, and the high temperature resistance is reduced. Within the above range of the present application, the obtained resin has better hydrophilicity, adhesion, weather resistance and antibacterial agent. Moreover, due to the enrichment of double bonds and antibacterial agents, by controlling the above content, it is possible to ensure better antibacterial property and ensure the adhesion of the glue while further providing some adhesive repair adhesion capabilities. DETAILED DESCRIPTION

[0026] The present application is further described in detail below with reference to the examples. In Examples 1-11 and Comparative Examples 1-2, the defoamer BYK-024, the dispersant TEGO 250, the thickener RHEOLATE 299, the crosslinker CYMEL 325 amino resin, and the solvent are isopropyl alcohol / acetone in a 1:1 volume ratio. All other experimental reagents in the preparation examples or examples, unless otherwise specified, are commercially available brands or obtained through conventional preparation processes.

[0027] Preparation of organosilicon-modified quaternary ammonium salt

[0028] Preparation Example 1

[0029] 150g of itaconic acid was added to 500mL of a mixed solution (acetone / toluene ratio, 1:1, by volume) and stirred. 0.2g of chloroplatinic acid was added as a catalyst, and the mixture was heated to 75°C for 1h. 50g of hydrogenated silicone oil was then added and the mixture was kept warm for 10h. The solvent was removed and dried to obtain carboxylic acid silicone oil. 16g of carboxylic acid silicone oil was added to 300mL of DMF and stirred. 80mL of glycidol and 6g of p-toluenesulfonic acid were added. The mixture was heated to 55°C under a nitrogen atmosphere for 10h. The solvent was removed and dried to obtain a double-headed epoxy-modified silicone oil. 10g of the double-headed epoxy-modified silicone oil and 0.5g of hexadecyldimethylamine were added to anhydrous ethanol, refluxed, heated to 70°C for 2h, the pH was adjusted to neutral, and the mixture was allowed to react for 3h. The solvent was removed and dried to obtain a polyhydroxyl-modified organosilicon quaternary ammonium salt. The hydrogenated silicone oil has a CAS number of 63148-57-2 and a molecular weight of 600.

[0030] Preparation Example 2

[0031] 150g of itaconic acid was added to 500mL of a mixed solution (acetone / toluene ratio, 1:1, by volume) and stirred. 0.2g of chloroplatinic acid was added as a catalyst, and the mixture was heated to 75°C for 1h. 50g of hydrogenated silicone oil was then added and the mixture was kept warm for 10h. The solvent was removed and dried to obtain carboxylic acid silicone oil. 16g of carboxylic acid silicone oil was added to 300mL of DMF and stirred. 80mL of glycidol and 6g of p-toluenesulfonic acid were added. The mixture was heated to 55°C under a nitrogen atmosphere for 10h. The solvent was removed and dried to obtain a double-headed epoxy-modified silicone oil. 10g of the double-headed epoxy-modified silicone oil and 0.5g of hexadecyldimethylamine were added to anhydrous ethanol, refluxed, heated to 70°C for 2h, the pH was adjusted to neutral, and the mixture was allowed to react for 3h. The solvent was removed and dried to obtain a polyhydroxyl-modified organosilicon quaternary ammonium salt. The hydrogenated silicone oil has a CAS number of 63148-57-2 and a molecular weight of 2500.

[0032] Preparation Example 3:

[0033] 150g of itaconic acid was added to 500mL of a mixed solution (acetone / toluene ratio, 1:1, by volume) and stirred. 0.2g of chloroplatinic acid was added as a catalyst, and the mixture was heated to 75°C for 1h. 50g of hydrogenated silicone oil was then added and the mixture was kept warm for 10h. The solvent was removed and dried to obtain carboxylic acid silicone oil. 16g of carboxylic acid silicone oil was added to 300mL of DMF and stirred. 80mL of glycidol and 6g of p-toluenesulfonic acid were added. The mixture was heated to 55°C under a nitrogen atmosphere for 10h. The solvent was removed and dried to obtain a double-headed epoxy-modified silicone oil. 10g of the double-headed epoxy-modified silicone oil and 0.5g of hexadecyldimethylamine were added to anhydrous ethanol, refluxed, heated to 70°C for 2h, the pH was adjusted to neutral, and the mixture was allowed to react for 3h. The solvent was removed and dried to obtain a polyhydroxyl-modified organosilicon quaternary ammonium salt. The hydrogenated silicone oil has a CAS number of 63148-57-2 and a molecular weight of 1500.

[0034] Preparation of antibacterial polyurethane:

[0035] Preparation Example 4:

[0036] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C for 3h under nitrogen protection. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 1 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling. The polyol was polyether diol, polyester diol, and polybutadiene diol in a mass ratio of 3:2:1.

[0037] Preparation Example 5:

[0038] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C for 3h under nitrogen protection. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 2 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling. The polyol was polyether diol, polyester diol, and polybutadiene diol in a mass ratio of 3:2:1.

[0039] Preparation Example 6:

[0040] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C for 3h under nitrogen protection. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 3 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling. The polyol was polyether diol, polyester diol, and polybutadiene diol in a mass ratio of 3:2:1.

[0041] Preparation Example 7:

[0042] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C under nitrogen protection for 3h. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 3 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling. The polyol was polyether diol, polyester diol, and polybutadiene diol in a mass ratio of 10:7:1.

[0043] Preparation Example 8:

[0044] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C for 3h under nitrogen protection. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 3 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling. The polyol was polyether diol, polyester diol, and polybutadiene diol in a mass ratio of 6:4:1.

[0045] Preparation Example 9:

[0046] 150g of polyol was vacuum dehydrated, 10g of diisocyanate and 0.2g of dimethyltin dioctanoate were added and mixed, and the mixture was reacted at 73°C for 3h under nitrogen protection. Then, 5g of the organosilicon-modified quaternary ammonium salt of Preparation Example 1 and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was raised to 78°C and kept for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate as catalyst were added, and the temperature was lowered to 73°C and the reaction was continued for 2h. Antibacterial polyurethane was obtained by cooling, wherein the polyol was a polyether diol and a polyester diol in a mass ratio of 6:4.

[0047] The diisocyanate in Preparation Example 4-9 is toluene diisocyanate.

[0048] Preparation of water-soluble antibacterial polyurethane modified acrylic resin.

[0049] Preparation Example 10:

[0050] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 4 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0051] Preparation Example 11:

[0052] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 5 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0053] Preparation Example 12:

[0054] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent, thereby obtaining an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 6 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0055] Preparation Example 13:

[0056] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 7 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0057] Preparation Example 14:

[0058] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 8 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0059] Preparation Example 15:

[0060] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 9 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:1.

[0061] Preparation Example 16:

[0062] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 8 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 1:1:5.

[0063] Preparation Example 17:

[0064] 30g of acrylic acid monomer and 30g of functional monomer were added to 200mL of ethyl acetate, stirred and heated under reflux with nitrogen, and a mixture of 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate was added. The mixture was then kept at 85°C for 4 hours to remove the solvent to obtain an acrylic resin. The acrylic resin was cooled to 75°C, and 50g of the antibacterial polyurethane prepared in Preparation Example 8 was added and kept at this temperature for 2 hours. The temperature was then raised to 90°C and kept at this temperature for 2 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin. The mass ratio of acrylic acid monomer, functional monomer, and antibacterial polyurethane was 3:3:5.

[0065] In Preparation Example 10-17, the acrylic acid monomer is methyl methacrylate and butyl acrylate in a mass ratio of 1:1; and the functional monomer is acrylic acid and hydroxyethyl acrylate in a mass ratio of 1:3.

[0066] Preparation of microcapsules:

[0067] The microcapsules used in this application are prepared by selecting gelatin as the wall material and using conventional microcapsule preparation technology.

[0068] Preparation Example 18:

[0069] 2 g of polyhexamethyleneguanidine hydrochloride and 2 g of acrylate were added to 100 g of a 4% gelatin aqueous solution and stirred at 40°C for 40 minutes. Then, 4 g of a 20% glutaraldehyde aqueous solution was added and stirred at 10°C for 1 hour. The mixture was separated, washed, and dried at low temperature to obtain an intermediate product. 0.1 g of photoinitiator 184 was added to 100 g of a 6% gelatin aqueous solution and stirred at 40°C for 10 minutes. Then, the intermediate product was added and stirred for 10 minutes. Then, 4 g of a 20% glutaraldehyde aqueous solution was added and stirred at 10°C for 1 hour. The mixture was filtered, washed, and dried at low temperature to obtain microcapsules.

[0070] Preparation Example 19:

[0071] 2 g of polyhexamethyleneguanidine hydrochloride was added to 100 g of 4% gelatin aqueous solution and stirred at 40° C. for 40 min. Then 4 g of 20% glutaraldehyde aqueous solution was added and stirred at 10° C. for 1 h. The microcapsules were separated, washed, and dried at low temperature.

[0072] Preparation of highly weather-resistant, antibacterial and environmentally friendly water-based wood glue.

[0073] Example 1:

[0074] Prepare the raw materials: 50 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 10; 0.3 g of defoaming agent; 0.8 g of dispersant; 0.5 g of thickener; 5 g of cross-linking agent; 5 g of solvent; 6 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoaming agent, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0075] Example 2:

[0076] Prepare the raw materials: 70 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 10; 0.6 g of defoamer; 0.5 g of dispersant; 0.2 g of thickener; 8 g of cross-linking agent; 10 g of solvent; 3 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0077] Example 3:

[0078] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 10; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linker and mix evenly to obtain the environmentally friendly water-based wood glue.

[0079] Example 4:

[0080] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 11; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0081] Example 5:

[0082] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 12; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linker and mix evenly to obtain the environmentally friendly water-based wood glue.

[0083] Example 6:

[0084] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 13; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linker and mix evenly to obtain the environmentally friendly water-based wood glue.

[0085] Example 7:

[0086] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 14; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0087] Example 8:

[0088] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 15; 0.4g of defoamer; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linking agent; 8g of solvent; 5g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0089] Example 9:

[0090] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 16; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0091] Example 10:

[0092] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 17; 0.4g of defoamer; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linking agent; 8g of solvent; 5g of microcapsules of Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0093] Example 11:

[0094] Prepare the raw materials: 60 g of the water-soluble antibacterial polyurethane-modified acrylic resin of Preparation Example 10; 0.4 g of defoamer; 0.6 g of dispersant; 0.3 g of thickener; 6 g of cross-linking agent; 8 g of solvent; 5 g of microcapsules of Preparation Example 19; mix the water-soluble antibacterial polyurethane-modified acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linker and mix evenly to obtain an environmentally friendly water-based wood glue.

[0095] Comparative Example 1:

[0096] Prepare the raw materials: 55g of acrylic resin; 5g of the silicone-modified quaternary ammonium salt of Preparation Example 1; 0.4g of defoamer; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linking agent; 8g of solvent; 5g of microcapsules of Preparation Example 18; mix the acrylic resin, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain an environmentally friendly water-based woodworking glue.

[0097] The preparation method of acrylic resin is as follows: 30g of acrylic acid monomer and 30g of functional monomer are added to 200mL of ethyl acetate, nitrogen is introduced, stirred, and the temperature is refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate are added, and then the mixture is kept at 85°C for 4h to obtain acrylic resin.

[0098] Comparative Example 2:

[0099] Prepare the raw materials: 60g of the antibacterial polyurethane prepared in Example 4; 0.4g of defoaming agent; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linking agent; 8g of solvent; 5g of the microcapsules prepared in Example 18; mix the antibacterial polyurethane, defoaming agent, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based wood glue.

[0100] Comparative Example 3

[0101] Prepare the raw materials: 30g of acrylic resin in Comparative Example 1, 30g of antibacterial polyurethane in Preparation Example 4; 0.4g of defoamer; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linking agent; 8g of solvent; 5g of microcapsules in Preparation Example 18; mix the antibacterial polyurethane, defoamer, dispersant, thickener, solvent, and microcapsules according to the ratio and stir evenly, then add the cross-linking agent and mix evenly to obtain environmentally friendly water-based wood glue.

[0102] Performance testing:

[0103] 1. Weather resistance test: The samples of Examples 1-11 and Comparative Examples 1-3 were applied to a wooden substrate, with a sizing of 15 g / m 2 After curing, the peeling force test was carried out in the test environment RT: 23±1℃, RH: 50%, and the peeling speed was 100mm / min; the peeling force N1 was recorded; the sample was placed at a temperature of 70℃ and a humidity of 80% for 1200h (aging), and the peeling force was tested in the test environment RT: 23±1℃, RH: 50%, and the peeling speed was 100mm / min; the peeling force N2 was recorded; the adhesion retention rate (N1 / N3) was 100%.

[0104] 2. High temperature resistance test: The wood glues of Examples 1-11 and Comparative Examples 1-2 were subjected to antibacterial tests to detect the antibacterial rates of Staphylococcus aureus and Escherichia coli.

[0105] Table 1: Performance test results

[0106]

[0107]

[0108] From Examples 1-11 of the present application and Comparative Examples 1-3, it can be seen that the present application achieves excellent weather resistance and antibacterial properties by preparing a colloid by modifying an acrylic resin with a water-soluble antibacterial polyurethane. From Examples 5-10, it can be seen that the weather resistance and antibacterial properties of the colloid can be improved by adjusting the proportion of polyols and the proportion of acrylic monomers, functional monomers, and antibacterial polyurethane; from Examples 3-5, it can be seen that adjusting the molecular weight of silane is beneficial to improving weather resistance and antibacterial properties. This may be because silicone oil with a moderate molecular weight improves the antibacterial effect and high temperature resistance of the adhesive through migration while ensuring the adhesion of the adhesive to the substrate, and therefore is more conducive to improving weather resistance.

[0109] The samples of Example 3, Example 8, Example 11 and Example 5 were placed at a temperature of 80°C and a humidity of 80% for 1500 hours and then irradiated with ultraviolet light with a radiation intensity of 40-50 mW / cm 2 , time 2min; record the peeling force before and after aging repair in the same way as in the weathering test to obtain the adhesion retention rate.

[0110] Table 2: Adhesion test results

[0111]

[0112] Tests show that by adding acrylates and initiators to microcapsules and combining them with polyurethane-modified acrylic resins containing double bonds, the adhesive's adhesion has a certain repair function, providing more lasting weather resistance and antibacterial effects. In addition, the colloid prepared from a modified resin with a molecular weight of 1200 containing hydrogenated silicone oil as the raw material has the best repair performance, indicating that the quaternary ammonium salt polyol modified by silane chains in the present application participates in the preparation of polyurethane, so that the quaternary ammonium salt and double bond groups in the colloid of the present application are enriched to a certain extent on the surface, and the moderate silane chain length can ensure a good adhesion effect on the basis of migration, which is conducive to light-curing repair and further improves the long-lasting weather resistance.

[0113] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A highly weather-resistant, antibacterial and environmentally friendly water-based woodworking glue, characterized in that: The invention is composed of the following components in parts by weight: 50-70 parts of water-soluble antibacterial polyurethane modified acrylic resin; 0.3-0.6 parts of defoaming agent; 0.5-0.8 parts of dispersant; 0.2-0.5 parts of thickener; 5-8 parts of crosslinking agent; 5-10 parts of solvent; and 3-8 parts of microcapsules. The preparation method of the water-soluble antibacterial polyurethane-modified acrylic resin comprises: adding acrylic monomer and functional monomer to a solvent, introducing nitrogen, stirring, heating and refluxing, adding an initiator dropwise, and then keeping the temperature at 80-90° C. for 3-6 hours to remove the solvent to obtain an acrylic resin; cooling the acrylic resin to 70-80° C., adding antibacterial polyurethane, keeping the temperature for 1-3 hours, and then heating to 90-100° C. for 1-3 hours to obtain a water-soluble antibacterial polyurethane-modified acrylic resin; The preparation method of the antibacterial polyurethane comprises: vacuum dehydrating a polyol, adding a diisocyanate and a catalyst, mixing, reacting at 70-75° C. for 2-4 hours under nitrogen protection, then adding an organosilicon-modified quaternary ammonium salt and a catalyst, heating to 75-80° C. and keeping the temperature for reaction for 1-3 hours, then adding the diisocyanate and the catalyst, cooling to 70-75° C. and continuing the reaction for 1-3 hours, and then cooling to obtain the antibacterial polyurethane; The mass ratio of the acrylic monomer, functional monomer and antibacterial polyurethane is 3:3:5; The polyols are polyether diol, polyester diol and polybutadiene diol, and the mass ratio of polyether diol, polyester diol and polybutadiene diol is: (4-8): (3-5): 1; the core material of the microcapsule includes polyhexamethyleneguanidine hydrochloride and acrylate; the wall material includes photoinitiator 184.

2. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking glue according to claim 1, characterized in that: The acrylic monomer is one or more of methyl methacrylate, butyl acrylate, and isooctyl acrylate; the functional monomer is one or more of acrylic acid and hydroxyethyl acrylate.

3. The highly weather-resistant, antibacterial and environmentally friendly water-based wood glue according to claim 1, characterized in that: The diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

4. A method for preparing the highly weather-resistant, antibacterial and environmentally friendly water-based wood glue according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: mixing water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent and microcapsule according to a proportion and stirring evenly, then adding a crosslinking agent and mixing evenly to obtain environmentally friendly water-based wood glue.

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