High-weather-resistance antibacterial environment-friendly water-based woodworking glue and preparation method thereof

Abstract

The invention relates to the field of adhesives, and particularly discloses high-weather-resistance antibacterial environment-friendly water-based woodworking glue and a preparation method thereof. Comprising the following components in parts by weight: 50-70 parts of water-soluble antibacterial polyurethane modified acrylic resin; 0.3 to 0.6 part of a defoaming agent; 0.5 to 0.8 part of a dispersant; 0.2 to 0.5 part of a thickening agent; 5-8 parts of a cross-linking agent; 5-10 parts of a solvent; and 3-8 parts of microcapsules. The woodworking adhesive disclosed by the invention is environment-friendly, high in adhesive power, capable of realizing lasting antibacterial and weather-proof effects and 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 adhesive 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 into play 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 need to have long-lasting high weather resistance and antibacterial properties to meet long-term practical needs. However, existing wood products often suffer structural damage due to adhesive failure, requiring re-bonding or even irreparable structural damage. Water-based adhesives are often inferior to solvent-based adhesives in terms of weather resistance and antibacterial properties. Therefore, how to prepare a long-lasting, high-weather resistance and antibacterial adhesive is a problem that needs to be solved. Summary of the invention

[0004] In order to solve the problem that water-based adhesives have high weather resistance, antibacterial properties and strong adhesion, the present application provides a highly weather-resistant, antibacterial and environmentally friendly water-based woodworking 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] The present application prepares water-based glue by modifying acrylic resin with water-soluble antibacterial polyurethane, abandons the use of highly toxic oil-soluble solvents, and has positive environmental protection significance. At the same time, by modifying acrylic resin with antibacterial polyurethane, on the one hand, the prepared colloid has the excellent water resistance, chemical solvent resistance, and weather resistance of acrylic resin and polyurethane, solving the problem of poor compatibility between acrylic resin and polyurethane, and on the other hand, it gives the glue excellent antibacterial properties, which can meet the requirements of outdoor use. The addition of microcapsules to release antibacterial agents for a long time can achieve long-lasting antibacterial properties.

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

[0008] The preparation method of the antibacterial polyurethane comprises: vacuum dehydrating polyol, adding diisocyanate and catalyst to mix, reacting at 70-75° C. for 2-4 hours under nitrogen protection, adding organosilicon modified quaternary ammonium salt and catalyst, heating to 75-80° C. for insulation reaction for 1-3 hours, then adding diisocyanate and catalyst, cooling to 70-75° C. for continuous 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 mass ratio of the polyols is polyether diol, polyester diol and polybutadiene diol is: (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 conventional polymerization process of acrylic monomers, and then obtains polyurethane-modified acrylic resin by chemical grafting of isocyanate-terminated antibacterial polyurethane. 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 under a catalyst to form a prepolymer, then adding a silicone-modified quaternary ammonium salt to react and extend the chain, 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 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 monomer is too small, there are fewer acrylic 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 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, 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, the prepared polyurethane can provide better hydrophilicity, flexibility and adhesion, and therefore has 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 agents, the present application preferably uses organosilicon-modified quaternary ammonium salts. On the one hand, quaternary ammonium salts have excellent antibacterial properties and good water solubility, and can give resins better antibacterial properties and adhesion. On the other hand, appropriate organosilicon modification has the effect of migration. When prepared into antibacterial polyurethane modified acrylic resin, because of the migration effect of organosilicon, the antibacterial quaternary ammonium salt groups and the double bonds in the polyurethane can be enriched on the surface of the adhesive, thereby improving the antibacterial efficacy of the adhesive and providing a better effect of repairing adhesion. Therefore, the present application controls the mass ratio of acrylic monomer, functional monomer, and antibacterial polyurethane to (2-4): (2-4): 5. On the other hand, while ensuring good antibacterial properties and ensuring the adhesive force of the glue, the ability to further provide the repair adhesion of some adhesives can be provided. The organosilicon-modified quaternary ammonium salt of the present application can be prepared by conventional preparation technology or prepared by prior art.

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

[0020] By using microcapsules containing antimicrobial agents, polyhexamethyleneguanidine hydrochloride is released when the microcapsules are broken, so that the antimicrobial agent of the adhesive is strengthened, and the antimicrobial agent is compounded with the quaternary ammonium salt antimicrobial agent to achieve a better mixed antimicrobial effect and maintain a lasting antimicrobial effect. In addition, the core material of the antimicrobial agent of the present application also contains acrylates, and the wall material includes a photoinitiator 184. When the microcapsules are broken, the acrylates and the 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 the photoinitiator, the double bonds in the main resin-modified acrylic resin of the colloid are polymerized, and can be further cross-linked to achieve the repair of the adhesive adhesion performance. In the present application, through the migration of silicone, the quaternary ammonium salt is enriched on the surface of the adhesive, and 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 woodworking 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 woodworking 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 the present 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 and can meet the requirements of outdoor use.

[0024] 2. The present 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, which 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 improve the bonding strength, thereby achieving a 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, and the obtained resin has slightly poor weather resistance. If the content of acrylic monomer 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. In addition, 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 in conjunction with the examples. In Examples 1-11 and Comparative Examples 1-2, the defoamer BYK-024; the dispersant TEGO250; the thickener RHEOLATE299; the crosslinker CYMEL325 amino resin; the solvent is isopropanol / acetone in a volume ratio of 1:1; other experimental reagents in the preparation examples or examples, unless otherwise specified, are conventional commercial 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 mixed solution (acetone / toluene volume ratio 1:1) and stirred, 0.2g of chloroplatinic acid was added as catalyst, the temperature was raised to 75℃ for reaction for 1h, and then 50g of hydrogenated silicone oil was added to keep the temperature for reaction for 10h, and 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 temperature was raised to 55℃ in nitrogen atmosphere for reaction for 10h, and the solvent was removed and dried to obtain double-headed epoxy modified silicone oil; 10g of double-headed epoxy modified silicone oil and 0.5g of hexadecyl dimethylamine were added to anhydrous ethanol, refluxed and heated to 70℃ for reaction for 2h, pH was adjusted to neutral, reaction was carried out for 3h, and the solvent was removed and dried to obtain polyhydroxyl silicone modified quaternary ammonium salt. Among them, hydrogenated silicone oil CAS: 63148-57-2, molecular weight Mn: 600.

[0030] Preparation Example 2

[0031] 150g of itaconic acid was added to 500mL of mixed solution (acetone / toluene volume ratio 1:1) and stirred, 0.2g of chloroplatinic acid was added as catalyst, the temperature was raised to 75℃ for reaction for 1h, and then 50g of hydrogenated silicone oil was added to keep the temperature for reaction for 10h, and 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 temperature was raised to 55℃ in nitrogen atmosphere for reaction for 10h, and the solvent was removed and dried to obtain double-headed epoxy-modified silicone oil; 10g of double-headed epoxy-modified silicone oil and 0.5g of hexadecyl dimethylamine were added to anhydrous ethanol, refluxed and heated to 70℃ for reaction for 2h, the pH was adjusted to neutral, the reaction was carried out for 3h, and the solvent was removed and dried to obtain polyhydroxyl silicone-modified quaternary ammonium salt. Among them, hydrogenated silicone oil CAS: 63148-57-2, molecular weight Mn: 2500.

[0032] Preparation Example 3:

[0033] 150g of itaconic acid was added to 500mL of mixed solution (acetone / toluene volume ratio 1:1) and stirred, 0.2g of chloroplatinic acid was added as catalyst, the temperature was raised to 75℃ for reaction for 1h, and then 50g of hydrogenated silicone oil was added to keep the temperature for reaction for 10h, and 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 temperature was raised to 55℃ in nitrogen atmosphere for reaction for 10h, and the solvent was removed and dried to obtain double-headed epoxy-modified silicone oil; 10g of double-headed epoxy-modified silicone oil and 0.5g of hexadecyl dimethylamine were added to anhydrous ethanol, refluxed and heated to 70℃ for reaction for 2h, the pH was adjusted to neutral, the reaction was carried out for 3h, and the solvent was removed and dried to obtain polyhydroxyl silicone-modified quaternary ammonium salt. Among them, hydrogenated silicone oil CAS: 63148-57-2, molecular weight Mn: 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 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 for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols, i.e., polyether diol, polyester diol and polybutadiene diol, was 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 for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was lowered to 73°C for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols, namely, polyether diol, polyester diol and polybutadiene diol, was 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 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 for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols, i.e., polyether diol, polyester diol and polybutadiene diol, was 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 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 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 for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols, namely, polyether diol, polyester diol and polybutadiene diol, was 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 for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was lowered to 73°C for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols, i.e., polyether diol, polyester diol and polybutadiene diol, was 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 for reaction for 2h. Then, 30g of excess diisocyanate and 0.2g of dimethyltin dioctanoate were added as catalyst, and the temperature was lowered to 73°C for reaction for 2h. Antibacterial polyurethane was obtained by lowering the temperature, wherein the mass ratio of polyols being polyether diol and polyester diol was 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 4 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 5 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 6 was added and kept for 2h, and the temperature was raised to 90°C for 2h to obtain 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 7 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 8 was added and kept for 2h, and the mixture was heated to 90°C and kept for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 9 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 8 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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, nitrogen was introduced, stirred, heated and refluxed, 0.2g of azobisisobutyronitrile and 20mL of ethyl acetate were added, and then the mixture was kept at 85°C for 4h to remove the solvent to obtain acrylic resin; the acrylic resin was cooled to 75°C, 50g of the antibacterial polyurethane of Preparation Example 8 was added and kept for 2h, and the temperature was raised to 90°C for 2h 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 Examples 10-17, the acrylic 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 the present 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 are added to 100 g of 4% gelatin aqueous solution, stirred at 40°C for 40 min, and then 4 g of 20% glutaraldehyde aqueous solution is added and stirred at 10°C for 1 h, separated, washed, and dried at low temperature to obtain an intermediate product; 0.1 g of photoinitiator 184 is added to 100 g of 6% gelatin aqueous solution, stirred at 40°C for 10 min, then the intermediate product is added and stirred for 10 min, and then 4 g of 20% glutaraldehyde aqueous solution is added and stirred at 10°C for 1 h, 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 woodworking adhesive.

[0073] Embodiment 1:

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

[0075] Embodiment 2:

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

[0077] Embodiment 3:

[0078] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 10; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0079] Embodiment 4:

[0080] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 11; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0081] Embodiment 5:

[0082] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 12; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0083] Embodiment 6:

[0084] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 13; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0085] Embodiment 7:

[0086] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 14; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0087] Embodiment 8:

[0088] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin in 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 in Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent and microcapsules according to the proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0089] Embodiment 9:

[0090] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 16; 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 proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0091] Embodiment 10:

[0092] Prepare raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin in 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 in Preparation Example 18; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent and microcapsules according to the proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0093] Embodiment 11:

[0094] Prepare the raw materials: 60g of the water-soluble antibacterial polyurethane modified acrylic resin of Preparation Example 10; 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 19; mix the water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent and microcapsules according to the proportion, stir evenly, then add the cross-linking agent and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0095] Comparative Example 1:

[0096] Prepare the raw materials: 55g of acrylic resin; 5g of 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 proportion and stir evenly, then add the cross-linking agent and mix evenly to obtain environmentally friendly water-based woodworking glue.

[0097] The preparation method of acrylic resin is as follows: 30 g of acrylic acid monomer and 30 g of functional monomer are added to 200 mL of ethyl acetate, nitrogen is introduced, stirred, heated and refluxed, 0.2 g of azobisisobutyronitrile and 20 mL of ethyl acetate mixed solution are added, and then the mixture is kept at 85° C. for 4 hours 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 defoamer; 0.6g of dispersant; 0.3g of thickener; 6g of cross-linker; 8g of solvent; 5g of microcapsules prepared in Example 18; mix the antibacterial polyurethane, defoamer, dispersant, thickener, solvent and microcapsules according to the proportions, stir evenly, then add the cross-linker and mix evenly to obtain the environmentally friendly water-based woodworking glue.

[0100] Comparative Example 3

[0101] Prepare 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 proportion and stir evenly, then add the cross-linking agent and mix evenly to obtain environmentally friendly water-based woodworking 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, the test environment RT: 23±1℃, RH: 50%, 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, the test environment RT: 23±1℃, RH: 50%, the peeling speed was 100mm / min; the peeling force N2 was recorded; the adhesion retention rate (N1 / N3)*100%.

[0104] 2. High temperature resistance test: The woodworking glue of Examples 1-11 and Comparative Examples 1-2 was subjected to an antibacterial test 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 using a water-soluble antibacterial polyurethane-modified acrylic resin. 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 weather resistance test to obtain the adhesion retention rate.

[0110] Table 2: Adhesion test results

[0111]

[0112] Tests show that, by adding acrylate and initiator to microcapsules and combining with polyurethane-modified acrylic resin containing double bonds, the adhesion of the adhesive has a certain repair function, providing more lasting weather resistance and antibacterial effects. In addition, the colloid prepared from the modified resin with a molecular weight of 1200 as the raw material hydrogen silicone oil has the best repair performance, indicating that the quaternary ammonium salt polyol modified by silane chain 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 on the surface to a certain extent, and the moderate silane chain length can achieve migration on the basis of ensuring a good adhesion effect, which is conducive to light-curing repair and further improves the 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 modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly weather-resistant, antibacterial and environmentally friendly water-based woodworking glue, characterized in that: The invention comprises 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.

2. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 1, characterized in that: The preparation method of the water-soluble antibacterial polyurethane modified acrylic resin comprises: adding acrylic monomer and functional monomer into a solvent, introducing nitrogen, stirring, heating and refluxing, dropping an initiator, and then keeping the temperature at 80-90° C. for 3-6 hours to remove the solvent to obtain acrylic resin; cooling the acrylic resin to 70-80° C., adding antibacterial polyurethane and keeping the temperature for 1-3 hours, and heating to 90-100° C. and keeping the temperature for 1-3 hours to obtain the water-soluble antibacterial polyurethane modified acrylic resin.

3. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 2, characterized in that: The preparation method of the antibacterial polyurethane comprises: vacuum dehydrating polyol, adding diisocyanate and catalyst to mix, reacting at 70-75° C. for 2-4 hours under nitrogen protection, adding organosilicon modified quaternary ammonium salt and catalyst, heating to 75-80° C. for insulation reaction for 1-3 hours, then adding diisocyanate and catalyst, cooling to 70-75° C. for continuous reaction for 1-3 hours, and cooling to obtain the antibacterial polyurethane.

4. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 2, 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.

5. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 2, characterized in that: The mass ratio of the acrylic monomer, the functional monomer and the antibacterial polyurethane is: (2-4):(2-4):

5.

6. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 3, characterized in that: The polyol is one or more of polyether diol, polyester diol and polybutadiene diol.

7. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 6, characterized in that: The mass ratio of the polyols, which are polyether diol, polyester diol and polybutadiene diol, is (4-8):(3-5):

1.

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

9. The highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to claim 1, characterized in that: The core material of the microcapsule includes polyhexamethyleneguanidine hydrochloride and acrylate; the wall material includes a photoinitiator 184.

10. A method for preparing the highly weather-resistant, antibacterial and environmentally friendly water-based woodworking adhesive according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing water-soluble antibacterial polyurethane modified acrylic resin, defoamer, dispersant, thickener, solvent and microcapsule evenly according to the proportion, and then adding cross-linking agent and mixing evenly to obtain environmentally friendly water-based woodworking glue.

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