Dual-curing polyurethane acrylate resin and preparation method thereof

Abstract

The invention discloses dual-curing polyurethane acrylate resin and a preparation method thereof. The formula of the dual-curing polyurethane acrylate resin comprises trihydric alcohol, dihydric alcohol, carbonyl-containing monobasic acid, isocyanate, a hydroxyl-containing monofunctional acrylic monomer, an amine neutralizer, a hydrazide compound and water. The preparation method comprises the following steps: step 1, preparing raw materials; step 2, synthesizing polyester glycol; step 3, synthesis of polyurethane acrylate; step 4, preparing resin; 5, follow-up treatment is carried out; step 6, detecting and storing; according to the invention, the hydrazide compound is added as a cross-linking agent, the hydrazide compound and carbonyl in the resin can form a stable chemical bond under a weak acidic condition to realize cross-linking, and the dual-cured polyurethane acrylate resin is obtained by combining ultraviolet curing; the defects that the curing process of single water-based ultraviolet curing polyurethane acrylate is easily influenced by oxygen in air, the curing speed is limited by the light source intensity and the curing time length, and the adaptability to complex shapes is insufficient are overcome.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane acrylate, in particular to a dual-curing polyurethane acrylate resin and a preparation method thereof. Background Art

[0002] Polyurethane acrylate resin, referred to as polyurethane acrylate (PUA), is a radiation-curing material with excellent comprehensive properties. The molecules of polyurethane acrylate contain acrylic functional groups and urethane bonds. The cured adhesive has a variety of excellent properties. Due to the presence of urethane bonds, a variety of hydrogen bonds can be formed between polymer molecular chains, which makes the polyurethane film have excellent mechanical wear resistance, good adhesion and flexibility, and high elongation at break. The cured adhesive has high peel strength, excellent low temperature resistance, and excellent optical properties and weather resistance of polyacrylate.

[0003] Existing polyurethane acrylate resins have the following defects: First, single water-based UV-curable polyurethane acrylate is easily affected by oxygen in the air during the curing process; oxygen will hinder the generation of free radicals and chain growth reactions, resulting in insufficient curing and affecting the overall performance of the material; in addition, this single UV curing mechanism is also limited by factors such as light source intensity and curing time, making the curing speed unsatisfactory; what is particularly tricky is that for those parts with complex shapes or obscured parts, UV light is often difficult to irradiate evenly, resulting in uneven curing or complete uncuring, showing insufficient adaptability to complex shapes; second, poor mechanical properties and insufficient water resistance are also a major shortcoming of this type of resin, which to a certain extent limits its application in fields requiring high strength and good water resistance; third, the price and application cost are relatively high, which to a large extent limits its market expansion and the breadth of its application fields. The higher product price not only increases the direct procurement cost, but may also lead to an increase in the overall application cost due to the increase in subsequent processing and maintenance needs, thereby hindering the widespread application of this material in multiple potential fields. Summary of the invention

[0004] The object of the present invention is to provide a dual-curing polyurethane acrylate resin and a preparation method thereof to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical scheme: a dual-curing polyurethane acrylate resin, the formula of which includes: diol, triol, dibasic acid, monobasic acid containing carbonyl group, isocyanate, water-based monomer containing carboxyl group, monofunctional acrylic monomer containing hydroxyl group, amine neutralizer, hydrazide compound and water, wherein the molar mass of each component in one raw material is: 1-2 mol of diol, 1-2 mol of triol, 1.5 mol-3 mol of dibasic acid, 0.5 mol-2 mol of monobasic acid containing carbonyl group, 2 mol-4 mol of isocyanate, 0.5 mol-1 mol of water-based monomer containing carboxyl group, 1 mol-2.5 mol of monofunctional acrylic monomer containing hydroxyl group, 0.4 mol-0.8 mol of amine neutralizer, 0.2 mol-0.6 mol of hydrazide compound and 85 mol-94 mol of water.

[0006] As a further technical solution of the present invention, the diol is one or more of neopentyl glycol, methyl propane diol, propylene glycol, and ethylene glycol; the triol is one or more of trimethylolpropane, glycerol, propylene glycol, and trimethylolethane; the dibasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, maleic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, and cyclohexanedicarboxylic acid; the carbonyl-containing monobasic acid is one or a mixture of two or more of acetyl C1-C8 carboxylic acids; and the isocyanate is one or more of IPDI, MDI, TDI, and XDI.

[0007] As a further technical solution of the present invention, the carboxyl-containing aqueous monomer is one or both of dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA), the hydroxyl-containing monofunctional acrylic monomer is one or more of HEMA, HPMA and PETA, the amine neutralizer is one or more of triethylamine, dimethylethanolamine and ammonia water, and the hydrazide compound is one or more of adipic acid dihydrazide, sebacic acid dihydrazide and succinic acid hydrazide.

[0008] As a further technical solution of the present invention, the molar masses of the components in one portion of the raw material are: 1 mol of triol, 2 mol of diol, 2 mol of dibasic acid, 1 mol of monobasic acid containing carbonyl group, 2.6 mol of isocyanate, 0.65 mol of water-based monomer containing carboxyl group, 2 mol of monofunctional acrylic monomer containing hydroxyl group, 0.6 mol of amine neutralizer, 0.5 mol of hydrazide compound and 90.5 mol of water.

[0009] As a further technical solution of the present invention, the molar masses of the components in one portion of the raw material are: 1.5 mmol triol, 2 mol diol, 2.4 mol dibasic acid, 0.8 mol monobasic acid containing carbonyl group, 3 mol isocyanate, 0.8 mol water-based monomer containing carboxyl group, 1.4 mol monofunctional acrylic monomer containing hydroxyl group, 0.5 mol amine neutralizer, 0.45 mol hydrazide compound and 93.5 mol water.

[0010] As a further technical solution of the present invention, the molar masses of the components in one portion of the raw material are: 1.2 mol of triol, 1.4 mol of diol, 1.8 mol of dibasic acid, 1.3 mol of monobasic acid containing carbonyl group, 3.2 mol of isocyanate, 0.6 mol of water-based monomer containing carboxyl group, 1.6 mol of monofunctional acrylic monomer containing hydroxyl group, 0.7 mol of amine neutralizer, 0.3 mol of hydrazide compound and 88 mol of water.

[0011] A method for preparing a dual-curing polyurethane acrylate resin, comprising step 1, raw material preparation; step 2, polyester diol synthesis; step 3, polyurethane acrylate synthesis; step 4, resin preparation; step 5, subsequent treatment; step 6, detection and storage;

[0012] In the above step 1, raw materials required for preparing dual-curing polyurethane acrylate resin are prepared;

[0013] In the above step 2, polyester diol is synthesized by using diol, triol, dibasic acid and monobasic acid containing carbonyl group;

[0014] In the above step 3, polyurethane acrylate is synthesized by synthesizing polyester diol, carboxyl-containing aqueous monomer, isocyanate and hydroxyl-containing monofunctional acrylic monomer;

[0015] wherein in the above step 4, an amine neutralizer, water and a hydrazide compound are added to obtain a waterborne polyurethane acrylate resin having dual curing;

[0016] In the above step 5, unreacted raw materials and impurities are removed by filtering to improve the purity of the resin;

[0017] In the above step six, the solid content, acid value, viscosity and other performance indicators of the resin are tested to ensure that the product quality meets the requirements, and the prepared waterborne polyurethane acrylate resin is stored in a cool and dry place, avoiding direct sunlight and high temperature.

[0018] As a further technical solution of the present invention, in the step 2, diol, triol, dibasic acid and carbonyl-containing monobasic acid are put into a reaction container for esterification reaction under nitrogen protection to avoid oxidation, the stirring speed is 200-300r / min, the reaction temperature is gradually increased to 150-200°C, the temperature required for the esterification reaction is maintained, the reaction synthesis time is 6-8h, until the acid value drops to a predetermined range, and the reaction is cooled to room temperature after the reaction is completed to obtain polyester diol.

[0019] As a further technical solution of the present invention, in the step three, the polyester diol synthesized in the step two is first reacted with a carboxyl-containing aqueous monomer and isocyanate at 40-80°C, with a stirring speed of 400-600r / min, to ensure that the isocyanate fully reacts with the polyester diol and the carboxyl-containing aqueous monomer, and the reaction is carried out until the NCO content reaches the theoretical value. After the reaction is completed, a hydroxyl-containing monofunctional acrylic monomer is added to continue the reaction until the NCO content is less than 0.1wt%.

[0020] As a further technical solution of the present invention, in the step 4, the polyurethane acrylate obtained by the reaction is cooled to 40-60° C., an amine neutralizer is added to neutralize the carboxyl groups in the resin, and then water is added to complete emulsification to obtain an aqueous emulsion, and then a hydrazide compound is added to obtain an aqueous polyurethane acrylate resin.

[0021] Compared with the prior art, the present invention has the following beneficial effects: the present invention adds a hydrazide compound as a cross-linking agent, which can form a stable chemical bond with the carbonyl group in the resin under weakly acidic conditions to achieve cross-linking, and combines with ultraviolet light curing to obtain a dual-cured polyurethane acrylate resin, thereby solving the shortcomings of single water-based ultraviolet light-cured polyurethane acrylate being easily affected by oxygen in the air during curing, the curing speed being limited by the light source intensity, the curing time, and the insufficient adaptability to complex shapes. The polyurethane acrylate resin combines the high strength of polyurethane with the weather resistance of acrylate, and through the dual curing mechanism, the tensile strength and tear strength of the cured resin are significantly improved. The acrylate segment has good water resistance and can effectively resist the erosion of water molecules, preventing the resin from swelling, softening or degrading due to water absorption. The dual curing mechanism makes the cross-linking network inside the resin tighter, further improving its water resistance. At the same time, the dual curing mechanism makes the production process of the resin more flexible and efficient. Compared with the traditional single curing mechanism, the production process of the dual-cured waterborne polyurethane acrylate resin does not require additional curing equipment or process steps, thereby reducing its production cost and expanding its application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The present invention is a flow chart of the method. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] See also Figure 1 , a technical solution provided by the present invention:

[0025] Embodiment 1:

[0026] A dual-curing polyurethane acrylate resin, the formula of which includes: diol, triol, dibasic acid, monobasic acid containing carbonyl group, isocyanate, water-based monomer containing carboxyl group, monofunctional acrylic monomer containing hydroxyl group, amine neutralizer, hydrazide compound and water, the molar mass of each component in one raw material is: 1 mol of triol, 2 mol of diol, 2 mol of dibasic acid, 1 mol of monobasic acid containing carbonyl group, 2.6 mol of isocyanate, 0.65 mol of water-based monomer containing carboxyl group Monomers, 2 mol of a monofunctional acrylic monomer containing a hydroxyl group, 0.6 mol of an amine neutralizer, 0.5 mol of a hydrazide compound and 90.5 mol of water; the triol is trimethylolpropane, the diol is neopentyl glycol, the dibasic acid is isophthalic acid, the monobasic acid containing a carbonyl group is levulinic acid, and the isocyanate is IPDI; the water-based monomer containing a carboxyl group is DMPA, the monofunctional acrylic monomer containing a hydroxyl group is hydroxyethyl acrylate, the amine neutralizer is triethylamine, and the hydrazide compound is adipic acid dihydrazide.

[0027] A method for preparing a dual-curing polyurethane acrylate resin, comprising step 1, raw material preparation; step 2, polyester diol synthesis; step 3, polyurethane acrylate synthesis; step 4, resin preparation; step 5, subsequent treatment; step 6, detection and storage;

[0028] In the above step 1, raw materials required for preparing dual-curing polyurethane acrylate resin are prepared;

[0029] In the above step 2, diol, triol, dibasic acid and monobasic acid containing carbonyl are put into a reaction vessel for esterification reaction under nitrogen protection to avoid oxidation, the stirring speed is 200-300r / min, the reaction temperature is gradually increased to 150-200°C, the temperature required for the esterification reaction is maintained, the reaction synthesis time is 6-8h, until the acid value drops to a predetermined range, and the reaction is cooled to room temperature after the reaction is completed to obtain polyester diol;

[0030] In the above step 3, the polyester diol synthesized in step 2 is first reacted with a carboxyl-containing aqueous monomer and isocyanate at 40-80° C., and the stirring speed is 400-600 r / min to ensure that the isocyanate, the polyester diol and the carboxyl-containing aqueous monomer are fully reacted, and the reaction is carried out until the NCO content reaches the theoretical value. After the reaction is completed, a hydroxyl-containing monofunctional acrylic monomer is added to continue the reaction until the NCO content is less than 0.1wt%;

[0031] In the above step 4, the polyurethane acrylate obtained by the reaction is cooled to 40-60° C., an amine neutralizer is added to neutralize the carboxyl groups in the resin, and then water is added to complete emulsification to obtain an aqueous emulsion, and then a hydrazide compound is added to obtain an aqueous polyurethane acrylate resin;

[0032] In the above step 5, unreacted raw materials and impurities are removed by filtering to improve the purity of the resin;

[0033] In the above step six, the solid content, acid value, viscosity and other performance indicators of the resin are tested to ensure that the product quality meets the requirements, and the prepared waterborne polyurethane acrylate resin is stored in a cool and dry place, avoiding direct sunlight and high temperature.

[0034] Embodiment 2:

[0035] A dual-curing polyurethane acrylate resin, the formula of which includes: diol, triol, dibasic acid, monobasic acid containing carbonyl group, isocyanate, water-based monomer containing carboxyl group, monofunctional acrylic monomer containing hydroxyl group, amine neutralizer, hydrazide compound and water, the mol weight of each component in one raw material is: 1.5mmol triol, 2mol diol, 2.4mol dibasic acid, 0.8mol monobasic acid containing carbonyl group, 3mol isocyanate, 0.8mol water-based monomer containing carboxyl group, 1.4 mol of a hydroxyl-containing monofunctional acrylic monomer, 0.5 mol of an amine neutralizer, 0.45 mol of a hydrazide compound and 93.5 mol of water; the triol is trimethylolpropane, the diol is neopentyl glycol, the dibasic acid is isophthalic acid, the monobasic acid containing a carbonyl group is levulinic acid, and the isocyanate is IPDI; the carboxyl-containing aqueous monomer is DMPA, the hydroxyl-containing monofunctional acrylic monomer is hydroxyethyl acrylate, the amine neutralizer is triethylamine, and the hydrazide compound is adipic acid dihydrazide, and the preparation method is consistent with that in Example 1.

[0036] Embodiment 3:

[0037] A dual-curing polyurethane acrylate resin, the formula of which includes: diol, triol, dibasic acid, monobasic acid containing carbonyl group, isocyanate, water-based monomer containing carboxyl group, monofunctional acrylic monomer containing hydroxyl group, amine neutralizer, hydrazide compound and water, the mol weight of each component in one raw material is: 1.2 mol of triol, 1.4 mol of neopentyl glycol, 1.8 mol of dibasic acid, 1.3 mol of monobasic acid containing carbonyl group, 3.2 mol of isocyanate, 0.6 mol of water-based monomer containing carboxyl group The invention relates to a polyol comprising: a polyol comprising trimethylolpropane and neopentyl glycol, a dibasic acid comprising isophthalic acid, a monobasic acid comprising a carbonyl group comprising levulinic acid, and an isocyanate comprising IPDI; a carboxyl-containing aqueous monomer comprising DMPA, a hydroxyl-containing monofunctional acrylic monomer comprising hydroxyethyl acrylate, an amine neutralizer comprising triethylamine, and a hydrazide compound comprising adipic acid dihydrazide. The preparation method thereof is the same as that of Example 1.

[0038] The specific composition ratios of each embodiment are shown in the following table:

[0039]

[0040]

[0041] Based on the above, the advantages of the present invention are: the present invention adds a hydrazide compound as a cross-linking agent, which can form a stable chemical bond with the carbonyl group in the resin under weak acid conditions to achieve cross-linking. During the resin film-forming process, the amine neutralizer volatilizes, the resin becomes weakly acidic, and the hydrazide compound and the carbonyl group undergo a cross-linking reaction. Combined with ultraviolet light curing, a dual-cured polyurethane acrylate resin is obtained, which solves the shortcomings of single water-based ultraviolet light-cured polyurethane acrylate being easily affected by oxygen in the air during the curing process, the curing speed being limited by the intensity of the light source, the curing time, and the lack of adaptability to complex shapes. The polyurethane acrylate resin combines the high strength of polyurethane with the weather resistance of acrylate. Through the dual curing mechanism, the tensile strength and tear strength of the resin after curing are significantly improved. The polyester diol is used as the main chain to provide good flexibility and toughness, further enhancing the mechanical properties of the resin. The acrylate segment has good water resistance and can effectively resist the erosion of water molecules to prevent the resin from swelling, softening or degradation due to water absorption. The dual curing mechanism makes the cross-linking network inside the resin more The double-curing waterborne polyurethane acrylate resin has a significant advantage in the application scenarios that need to be exposed to water or humid environment for a long time. At the same time, the double-curing mechanism makes the production process of the resin more flexible and efficient. Compared with the traditional single-curing mechanism, the production process of the double-curing waterborne polyurethane acrylate resin does not require additional curing equipment or process steps, thereby reducing its production cost and expanding its application range. Due to its excellent mechanical properties and water resistance, the double-curing waterborne polyurethane acrylate resin has broad application prospects in the fields of coatings, adhesives, elastomers, plastic products, etc. The wide range of applications enables the production cost of the resin to be further shared, thereby reducing the cost of the unit product. In summary, the double-curing waterborne polyurethane acrylate resin shows significant advantages in mechanical properties, water resistance and cost. These advantages make the resin have broad application potential and market competitiveness in many fields.

[0042] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A dual-curing polyurethane acrylate resin, the formula comprising: The invention relates to a method for preparing a raw material of the present invention. The method comprises the following steps: a diol, a triol, a dibasic acid, a monobasic acid containing a carbonyl group, an isocyanate, an aqueous monomer containing a carboxyl group, a monofunctional acrylic monomer containing a hydroxyl group, an amine neutralizer, a hydrazide compound and water. The method is characterized in that the molar masses of the components in one portion of the raw material are: 1 to 2 mol of the diol, 1 to 2 mol of the triol, 1.5 to 3 mol of the dibasic acid, 0.5 to 2 mol of the monobasic acid containing a carbonyl group, 2 to 4 mol of the isocyanate, 0.5 to 1 mol of the aqueous monomer containing a carboxyl group, 1 to 2.5 mol of the monofunctional acrylic monomer containing a hydroxyl group, 0.4 to 0.8 mol of the amine neutralizer, 0.2 to 0.6 mol of the hydrazide compound and 85 to 94 mol of water.

2. A dual-cure polyurethane acrylate resin according to claim 1, characterized in that: The diol is one or more of neopentyl glycol, methyl propanediol, propylene glycol, and ethylene glycol; the triol is one or more of trimethylolpropane, glycerol, propylene glycol, and trimethylolethane; the dibasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, maleic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, and cyclohexanedicarboxylic acid; the carbonyl-containing monobasic acid is one or a mixture of two or more of acetyl C1-C8 carboxylic acids; and the isocyanate is one or more of IPDI, MDI, TDI, and XDI.

3. A dual-cure polyurethane acrylate resin according to claim 1, characterized in that: The carboxyl-containing aqueous monomer is one or both of dimethylol propionic acid (DMPA) and dimethylol butyric acid (DMBA); the hydroxyl-containing monofunctional acrylic monomer is one or more of HEMA, HPMA and PETA; the amine neutralizer is one or more of triethylamine, dimethylethanolamine and ammonia water; and the hydrazide compound is one or more of adipic acid dihydrazide, sebacic acid dihydrazide and succinic acid hydrazide.

4. A dual-cure polyurethane acrylate resin according to claim 1, characterized in that: The molar masses of the components in one portion of the raw material are: 1 mol of triol, 2 mol of diol, 2 mol of dibasic acid, 1 mol of monobasic acid containing carbonyl group, 2.6 mol of isocyanate, 0.65 mol of water-based monomer containing carboxyl group, 2 mol of monofunctional acrylic monomer containing hydroxyl group, 0.6 mol of amine neutralizer, 0.5 mol of hydrazide compound and 90.5 mol of water.

5. A dual-cure polyurethane acrylate resin according to claim 4, characterized in that: The molar mass of each component in one portion of the raw material is: 1.5 mmol of triol, 2 mol of diol, 2.4 mol of dibasic acid, 0.8 mol of monobasic acid containing carbonyl group, 3 mol of isocyanate, 0.8 mol of a carboxyl-containing aqueous monomer, 1.4 mol of a hydroxyl-containing monofunctional acrylic monomer, 0.5 mol of an amine neutralizer, 0.45 mol of a hydrazide compound and 93.5 mol of water.

6. A dual-cure polyurethane acrylate resin according to claim 4, characterized in that: The molar mass of each component in one portion of the raw material is: 1.2 mol of triol, 1.4 mol of diol, 1.8 mol of dibasic acid, 1.3 mol of monobasic acid containing carbonyl group, 3.2 mol of isocyanate, 0.6 mol of a carboxyl-containing aqueous monomer, 1.6 mol of a hydroxyl-containing monofunctional acrylic monomer, 0.7 mol of an amine neutralizer, 0.3 mol of a hydrazide compound and 88 mol of water.

7. A method for preparing a dual-curing polyurethane acrylate resin, comprising step 1, raw material preparation; step 2, polyester diol synthesis; step 3, polyurethane acrylate synthesis; step 4, resin preparation; step 5, subsequent treatment; step 6, detection and storage; characterized in that: In the above step 1, raw materials required for preparing dual-curing polyurethane acrylate resin are prepared; In the above step 2, polyester diol is synthesized by using diol, triol, dibasic acid and monobasic acid containing carbonyl group; In the above step 3, polyurethane acrylate is synthesized by synthesizing polyester diol, carboxyl-containing aqueous monomer, isocyanate and hydroxyl-containing monofunctional acrylic monomer; wherein in the above step 4, an amine neutralizer, water and a hydrazide compound are added to obtain a waterborne polyurethane acrylate resin having dual curing; In the above step 5, unreacted raw materials and impurities are removed by filtering to improve the purity of the resin; In the above step six, the solid content, acid value, viscosity and other performance indicators of the resin are tested to ensure that the product quality meets the requirements, and the prepared waterborne polyurethane acrylate resin is stored in a cool and dry place, avoiding direct sunlight and high temperature.

8. The method for preparing a dual-curing polyurethane acrylate resin according to claim 7, characterized in that: In the step 2, diol, triol, dibasic acid and carbonyl-containing monobasic acid are put into a reaction container for esterification reaction under nitrogen protection to avoid oxidation. The stirring speed is 200-300 r / min, and the reaction temperature is gradually increased to 150-200° C. The temperature required for the esterification reaction is maintained. The reaction synthesis time is 6-8 hours until the acid value drops to a predetermined range. After the reaction is completed, it is cooled to room temperature to obtain a polyester diol.

9. The method for preparing a dual-curing polyurethane acrylate resin according to claim 7, characterized in that: In the step 3, the polyester diol synthesized in the step 2 is first reacted with a carboxyl-containing aqueous monomer and isocyanate at 40-80° C., and the stirring speed is 400-600 r / min to ensure that the isocyanate, the polyester diol and the carboxyl-containing aqueous monomer are fully reacted, and the reaction is carried out until the NCO content reaches the theoretical value. After the reaction is completed, a hydroxyl-containing monofunctional acrylic monomer is added to continue the reaction until the NCO content is less than 0.1wt%.

10. The method for preparing a dual-curing polyurethane acrylate resin according to claim 7, characterized in that: In the step 4, the polyurethane acrylate obtained by the reaction is cooled to 40-60° C., an amine neutralizer is added to neutralize the carboxyl groups in the resin, and then water is added to complete emulsification to obtain an aqueous emulsion, and then a hydrazide compound is added to obtain an aqueous polyurethane acrylate resin.

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