An epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration

Abstract

The present invention provides an epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration. The surface adhesive comprises a waterborne photocurable epoxy vinyl ester resin, a gloss enhancing and hardening agent, and an auxiliary agent. The gloss enhancing and hardening agent is an emulsion formed by dispersing paraffin wax, polyethylene oxide wax, and Fischer-Tropsch wax composition in an emulsifier and deionized water. The mass of the gloss enhancing and hardening agent is 5-20% of the mass of the waterborne photocurable epoxy vinyl ester resin. By using the waterborne photocurable epoxy vinyl ester resin, the hydrolysis stability of the cured product of the epoxy vinyl ester resin is greatly improved. By using the emulsion formed by dispersing paraffin wax, polyethylene oxide wax, and Fischer-Tropsch wax composition in an emulsifier and deionized water as the gloss enhancing and hardening agent, the glossiness can be improved while significantly imparting greater hardness to the colloid.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable materials, and particularly to an epoxy vinyl-based waterborne photocurable stone decoration surface glue. Background Art

[0002] At present, most of the stone surface glues on the market are epoxy resin systems, which are relatively expensive, have a long curing time, and require a long waiting time during the construction process, are not suitable for flow operation, and affect work efficiency; in addition, the epoxy resin has a high viscosity, and the method of adding a diluent is often used in the market to reduce the product viscosity, but this method will cause the product to have a high VOC content, which is harmful to the atmosphere and human health, damages the ecological environment of mankind, and will reduce the mechanical properties of the product after adding the diluent, resulting in many defects such as weak adhesion to the stone surface; and after the epoxy resin is cured, a dense protective film will be formed on the stone surface, completely blocking the micropores of the stone, hindering the air permeability of the stone, and making the moisture inside the stone or the moisture at the bottom of the stone unable to be discharged normally, which is extremely easy to form stone "diseases" such as water stains, wet marks, efflorescence, and mildew on the stone.

[0003] The patent application with the publication number of CN110903799A discloses a waterborne photocurable stone decoration surface glue, which can solve the problems of slow curing speed and weak adhesion to the stone to a certain extent, but the acrylate-based resin often has a pungent smell, and due to the development of the construction industry, higher requirements are put forward for the stone decoration surface glue. The waterborne photocurable stone decoration surface glue disclosed in CN110903799A can no longer meet the market requirements for the brightness and strength of the waterborne photocurable stone decoration surface glue. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides an epoxy vinyl-based waterborne photocurable stone decoration surface glue to further improve its brightness and strength.

[0005] The present invention provides an epoxy vinyl-based waterborne photocurable stone decoration surface glue, which includes a waterborne photocurable epoxy vinyl ester resin, a brightening and hardening agent, and an auxiliary agent. The brightening and hardening agent is an emulsion formed by dispersing paraffin wax, polyethylene oxide wax, and Fischer-Tropsch wax composition in an emulsifier and deionized water; the mass of the brightening and hardening agent is 5-20% of the mass of the waterborne photocurable epoxy vinyl ester resin.

[0006] The present invention selects a waterborne photocurable epoxy vinyl ester resin, in which the ester bonds in the main chain are 35-50% less than those in the main chain of unsaturated polyester resin, greatly improving the hydrolysis stability of the cured product of the epoxy vinyl ester resin. In addition, the present invention selects a paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition as the main component of the polishing and hardening agent, which can not only improve the gloss of the surface glue for stone decoration, but also endow the colloid with greater hardness. Moreover, the present invention makes the wax into an emulsion and adds it to the resin in the form of emulsified wax. The particle size of the wax emulsion is only in the nanometer to micrometer range and will not affect the air permeability of the colloid.

[0007] For the surface glue for stone decoration of epoxy vinyl type waterborne photocurable provided by the present invention, the mass ratio of paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax is (0.5-1.5):(0.5-1.5):1; the mass of the paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition accounts for 25-30% of the mass of the polishing and hardening agent.

[0008] For the surface glue for stone decoration of epoxy vinyl type waterborne photocurable provided by the present invention, the emulsifier is composed of span-80 and tween-80 with a mass ratio of (0.9-1.1):1; the mass of the emulsifier accounts for 8-10% of the mass of the polishing and hardening agent.

[0009] The selection of the emulsifier affects the emulsification and dispersion degree of the polishing and hardening agent, and further affects the appearance and performance of the colloid after curing. The present invention has found through research that emulsifying with a specific ratio of span-80 and tween-80 has a better effect.

[0010] For the surface glue for stone decoration of epoxy vinyl type waterborne photocurable provided by the present invention, the preparation method of the polishing and hardening agent includes: adding paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition and the emulsifier to a high-shear dispersion emulsifier, heating to the emulsification temperature of 80-100°C, and dropping deionized water at the same temperature, followed by high-shear dispersion emulsification. After the dropping is completed, it is naturally cooled to obtain the polishing and hardening agent.

[0011] For the surface glue for stone decoration of epoxy vinyl type waterborne photocurable provided by the present invention, the surface glue for stone decoration of epoxy vinyl type waterborne photocurable further includes a reinforcing material, and the reinforcing material includes whisker materials and light-transmitting fibers. The length of the whisker materials is 10-25μm, and the length of the light-transmitting fibers is 10-25μm.

[0012] For the surface glue for stone decoration of epoxy vinyl type waterborne photocurable provided by the present invention, the whisker materials are one or more of aluminum borate whiskers, alumina whiskers, calcium sulfate whiskers, and calcium carbonate whiskers.

[0013] According to the epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration provided by the present invention, the light-transmitting fiber is one or more of poly(diallyl diglycol carbonate) fiber and styrene acrylonitrile copolymer fiber.

[0014] The addition of the reinforcing material has certain improvements on various indexes such as the hardness, impact toughness and flexural modulus of elasticity of the cured surface adhesive.

[0015] A whisker refers to a fiber that is formed naturally or grown in the form of a single crystal under artificially controlled conditions (the main form). Its diameter is very small (in the micron order of magnitude), and it does not contain defects (grain boundaries, dislocations, holes, etc.) that exist in ordinary materials. Its atomic arrangement is highly ordered, so its strength is close to the theoretical value of a perfect crystal, and its mechanical strength is equal to the force between adjacent atoms; the highly oriented structure of the whisker not only endows it with high strength, high modulus and high elongation rate, but also has electrical, optical, magnetic, dielectric, conductive and superconducting properties; the strength of the whisker is much higher than that of other chopped fibers.

[0016] The light-transmitting fiber includes fibers that transmit visible light (wavelength 0.39 - 0.76 μm), infrared light (wavelength 1 - 1000 μm) and ultraviolet light (wavelength 0.01 - 0.4 μm). The preferred poly(diallyl diglycol carbonate) fiber and styrene acrylonitrile copolymer fiber of the present invention both have high transparency, and the visible light transmittance is more than 90%. They have high mechanical strength and good toughness. It is found that during the curing process of the colloid, internal stress will be generated due to volume shrinkage. Once the stress exceeds the tensile strength of the colloid, microscopic cracks will be caused inside the colloid, resulting in cracking, deformation or even damage. Compared with powder materials, the fiber has high tensile strength. After it is added to the surface adhesive, the shrinkage of the cured surface adhesive can be reduced. When the surface adhesive cracks, the randomly distributed fibers form a supporting force across the crack site. The fibers bear the stress when the surface adhesive cracks, which plays a role in delaying and preventing the crack from continuing to expand; when the surface adhesive is subjected to external force, the fibers and the surface adhesive act together, thereby improving the tensile strength, flexural strength and fatigue strength of the surface adhesive and enhancing the impact resistance.

[0017] In the present invention, the whisker material and the light-transmitting fiber are compounded. The whisker material can be closely combined with the light-transmitting fiber and intertwined with each other to form a "whisker-light-transmitting fiber" network structure, forming a tight structure with good rigidity, good uniformity and higher strength after curing; in addition, this network structure can also, to a certain extent, avoid the decline of the mechanical properties of the surface adhesive caused by the "agglomeration" formed by adding too much single fiber. After the two are compounded, the hardness, impact toughness and flexural modulus of elasticity and other properties of the cured colloid of the present invention can be further improved, which is significantly better than the effect of only adding a single fiber for reinforcement under the same total filler addition amount.

[0018] Further, the waterborne photocurable epoxy vinyl ester resin selected in the present invention has secondary hydroxyl groups on the side chain that interact with the hydroxyl groups on the fiber surface, improving the wettability and adhesion properties to the fiber material, thereby enhancing the mechanical strength.

[0019] Considering comprehensive properties such as curing speed, adhesion strength, air permeability, yellowing resistance, and brightness, in a preferred embodiment of the present invention, by weight, the epoxy vinyl type waterborne photocurable stone decorative surface glue comprises the following components: 100 parts of waterborne photocurable resin, 5 - 20 parts of polishing and hardening agent, 1 - 8 parts of waterborne photoinitiator, 0.5 - 3 parts of waterborne light stabilizer, 0.1 - 1 part of waterborne leveling agent, 0.1 - 1 part of waterborne defoaming agent, and 10 - 20 parts of reinforcing material.

[0020] According to the epoxy vinyl type waterborne photocurable stone decorative surface glue provided by the present invention, the waterborne photocurable epoxy vinyl ester resin comprises 50 - 90% of waterborne photocurable epoxy vinyl ester resin prepolymer and the balance of water, and the waterborne photocurable epoxy vinyl ester resin prepolymer is one or more of waterborne bisphenol A epoxy vinyl ester resin and waterborne phenolic epoxy type vinyl ester resin.

[0021] According to the epoxy vinyl type waterborne photocurable stone decorative surface glue provided by the present invention, the waterborne photoinitiator is a mixture of a waterborne acetophenone derivative photoinitiator and an organophosphorus compound photoinitiator with a mass ratio of (0.5 - 2):1.

[0022] Further, the waterborne acetophenone derivative photoinitiator is one or more of 2 - hydroxy - 4'-(2 - hydroxyethoxy)-2 - methylpropiophenone (IRGACURE 2959), 2 - hydroxy - 2 - methyl - 1 - phenyl - 1 - propanone (DAROCUR 1173), and 1 - hydroxycyclohexyl phenyl ketone (IRGACURE 184); the organophosphorus compound photoinitiator is one or more of ethyl 2,4,6 - trimethylbenzoyl phenylphosphinate (IRGACURE TPO - L) and 45% aqueous solution of bis(2,4,6 - trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819DW).

[0023] In some embodiments of the present invention, the waterborne photoinitiator is DAROCUR 1173 and IRGACURE TPO - L, and their mass ratio is 1:1.

[0024] According to the epoxy vinyl type waterborne photocurable stone decorative surface glue provided by the present invention, the waterborne light stabilizer is one or more of TINUVIN 1130, TINUVIN 477DW, TINUVIN 5050, TINUVIN 5060, and TINUVIN 5151.

[0025] The above-mentioned waterborne light stabilizers are all products of BASF. Experiments have found that adding the above-mentioned waterborne light stabilizers to the epoxy vinyl-based waterborne photocurable stone decorative surface glue of the present invention can produce a synergistic effect with the waterborne photoinitiator, making the colloid resistant to ultraviolet light, maintaining stable color, and effectively improving the yellowing resistance of the colloid.

[0026] According to the epoxy vinyl-based waterborne photocurable stone decorative surface glue provided by the present invention, the waterborne leveling agent is one or more of acrylate leveling agents and polyether silicone leveling agents.

[0027] According to the epoxy vinyl-based waterborne photocurable stone decorative surface glue provided by the present invention, the waterborne defoamer is one or more of mineral oil-based defoamers, polyether-modified polysiloxane defoamers, and hydrophobic polyether defoamers.

[0028] In a preferred embodiment of the present invention, the epoxy vinyl-based waterborne photocurable stone decorative surface glue comprises the following components in parts by weight: 30 parts of waterborne bisphenol A epoxy vinyl ester resin, 50 parts of waterborne phenolic epoxy vinyl ester resin, 20 parts of water, 14 parts of polishing and hardening agent, 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2 parts of ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, 1.5 parts of TINUVIN 477DW, 1.5 parts of TINUVIN 5050, 0.6 part of acrylate leveling agent, 0.6 part of polyether-modified polysiloxane defoamer, 4 parts of aluminum borate whiskers, 4 parts of alumina whiskers, and 8 parts of poly(diallyl diglycol carbonate) fiber.

[0029] In another preferred embodiment of the present invention, the epoxy vinyl-based waterborne photocurable stone decorative surface glue comprises the following components in parts by weight: 50 parts of waterborne bisphenol A epoxy vinyl ester resin, 30 parts of waterborne phenolic epoxy vinyl ester resin, 20 parts of water, 15 parts of polishing and hardening agent, 1.5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2 parts of 45% aqueous solution of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.5 part of TINUVIN 1130, 0.5 part of TINUVIN 477DW, 2 parts of TINUVIN 5050, 0.4 part of acrylate leveling agent, 0.3 part of polyether silicone leveling agent, 0.7 part of mineral oil-based defoamer, 4 parts of calcium carbonate whiskers, 6 parts of poly(diallyl diglycol carbonate) fiber, and 6 parts of styrene acrylonitrile copolymer fiber.

[0030] The present invention provides an epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration. By selecting a waterborne photocurable epoxy vinyl ester resin, the hydrolysis stability of the cured product of the epoxy vinyl ester resin is greatly improved; by selecting an emulsion formed by dispersing a paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition in an emulsifier and deionized water as a gloss enhancing and hardening agent, it can not only improve the glossiness but also significantly impart greater hardness to the colloid.

[0031] Furthermore, the present invention compositely blends whisker materials with light-transmitting fibers. The whisker materials can be tightly combined with the light-transmitting fibers and intertwined with each other to form a "whisker-light-transmitting fiber" network structure, which synergistically interacts with the other components in the colloid, enhancing the adhesive strength of the colloid. Specific Embodiments

[0032] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts shall fall within the protection scope of the present invention.

[0033] In the following embodiments, unless otherwise specified, all reagents can be obtained through commercial purchase.

[0034] Examples 1 - 23

[0035] Examples 1 - 23 respectively provide an epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration, and its composition is shown in Tables 1 - 3. The preparation method is as follows:

[0036] (1) Preparation of the gloss enhancing and hardening agent: Add the paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition and the emulsifiers span-80 and tween-80 to a high-shear dispersion emulsifier in proportion, and slowly heat up to the emulsification temperature of 80 - 100 °C while stirring; then slowly dropwise add deionized water at the same temperature in proportion and perform high-speed shear dispersion emulsification; after the dropping is completed, naturally cool to obtain the gloss enhancing and hardening agent.

[0037] (2) Weigh each raw material according to the formula. First, add the waterborne photocurable resin, gloss enhancing and hardening agent, waterborne photoinitiator composition, waterborne light stabilizer, waterborne leveling agent, and waterborne defoaming agent to a planetary stirrer, control the rotation speed at 1000 - 1500 revolutions per minute, and perform negative pressure stirring for 10 - 15 minutes; then add the remaining materials, control the rotation speed at 1000 - 1500 revolutions per minute, and perform negative pressure stirring for 10 - 15 minutes to obtain the epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration.

[0038] The present invention also provides waterborne photocurable stone decorative surface adhesives with different glossing and hardening agents from Example 1 (Comparative Examples 1-8), and waterborne photocurable stone decorative surface adhesives with different reinforcing materials from Example 1 (Comparative Examples 9-13). The compositions of each raw material are shown in Tables 3-4, and the preparation method is the same as that of Example 1.

[0039] Table 1

[0040]

[0041]

[0042] Table 2

[0043]

[0044]

[0045] Table 3

[0046]

[0047]

[0048] Table 4

[0049]

[0050]

[0051] Experimental Example

[0052] To prove the excellent effects of the epoxy vinyl-based waterborne photocurable stone decorative surface adhesive of the present invention, the epoxy vinyl-based waterborne photocurable stone decorative surface adhesives obtained in Examples 1-23 of the present invention were respectively subjected to performance tests with Comparative Examples 1-13 and each example in Chinese Patent Document CN110903799A (the results are summarized in Comparative Example 14 of the present invention), including curing time, glossiness, hardness, impact toughness, flexural modulus of elasticity, color difference value, and water vapor transmission rate. The test results are shown in Table 5.

[0053] The specific methods for each test are as follows:

[0054] Curing time: After pre-treatment by drying to remove water, irradiate under a 500W ultraviolet lamp, and test the curing time under different temperature conditions;

[0055] Glossiness: After pre-treatment by drying to remove water from the sample to be tested, irradiate and cure under a 500W ultraviolet lamp, and test the glossiness by 60° specular gloss test according to GB / T 9754-2007, and compare the glossiness.

[0056] Hardness: After the sample to be tested is pretreated by drying to remove water, it is irradiated and cured under a 500W ultraviolet lamp. The Barcol hardness of the cured product is measured using a Barcol hardness tester (Beijing Times Peak Technology Co., Ltd., model HBA-1) with reference to the test method for Barcol hardness of cured products specified in GB / T 3854-2005.

[0057] Impact toughness and flexural modulus of elasticity: With reference to the test method specified in JC / T989-2016, after preparing a sample block of the cured product, it is tested using a universal tensile testing machine.

[0058] Color difference: According to the test method specified in GB / T14522-2008, after the colloidal cured product is irradiated under a UVA340nm fluorescent ultraviolet lamp in an ultraviolet light aging test chamber (model: LRHS-UVN, manufacturer: Shenyang Ultraviolet Aging Test Chamber Factory) for 70 hours, its color difference is measured using a color difference meter (brand: 3nh, model: NR110, manufacturer: Shenzhen Tianyouli Standard Light Source Co., Ltd.).

[0059] Water vapor transmission rate: According to the test method specified in GB / T30412-2013, the cured product sample to be detected is fixed in the sample chamber of a water vapor transmission rate tester (Guangzhou Xitang Electromechanical Technology Co., Ltd., W-B-61E water vapor transmission rate tester) for testing.

[0060] Table 5

[0061]

[0062]

[0063]

[0064] It can be seen from the above results that the gloss, hardness, impact toughness, and flexural modulus of elasticity of the cured products of the epoxy vinyl-based waterborne photocurable stone decorative surface adhesives in Examples 1-23 of the present invention are much higher than those of Comparative Example 14.

[0065] Among them, Comparative Example 1 is an aqueous photocurable surface adhesive for stone decoration without any polishing and hardening agent. In Comparative Example 2, only a polishing and hardening agent made of paraffin wax was added. In Comparative Example 3, only a polishing and hardening agent made of oxidized polyethylene wax was added. In Comparative Example 4, only a polishing and hardening agent made of Fischer-Tropsch wax was added. Compared with Comparative Example 1, the glossiness of the colloidal cured product increased, but the increase in hardness, impact toughness, and flexural modulus of elasticity was not obvious. In Comparative Example 8, only a polishing and hardening agent made of beeswax was added. The glossiness of the colloidal cured product was poor, and the color difference was large. The performance of beeswax was inferior to that of the paraffin wax, oxidized polyethylene wax, and Fischer-Tropsch wax preferred in the present invention. In Comparative Examples 5-7, the paraffin wax, oxidized polyethylene wax, and Fischer-Tropsch wax were mixed in pairs to make a polishing and hardening agent. Although each index was improved compared with single addition, the effect was not ideal. In Example 2, the paraffin wax, oxidized polyethylene wax, and Fischer-Tropsch wax were mixed together to make a polishing and hardening agent. Under the same addition amount, the glossiness and hardness of the colloidal cured product were significantly improved, and the impact toughness and flexural modulus of elasticity were also improved to a certain extent. It was found through experiments that by adding the polishing and hardening agent made of the paraffin wax, oxidized polyethylene wax, and Fischer-Tropsch wax composition of the present invention, while improving the glossiness, it could significantly endow the colloid with greater hardness.

[0066] Comparative Example 9 is an aqueous photocurable surface adhesive for stone decoration without any reinforcing material. In Comparative Example 10, only whisker materials were added. In Comparative Example 11, only light-transmitting fibers were added. In Comparative Example 12, only conventional light-transmitting powder was added. Compared with Comparative Example 9, when a single variety of reinforcing material was added, the hardness, impact toughness, and flexural modulus of elasticity of the colloidal cured product were improved, but the increase effect was not ideal. In Comparative Example 13, the whisker materials and light-transmitting powder were compounded as the reinforcing material. Although it could further improve the hardness, impact toughness, and flexural modulus of elasticity of the colloidal cured product, the improvement amplitude was limited. In Example 5, the whisker materials and light-transmitting fibers were compounded as the reinforcing material. The whisker materials could be closely combined with the light-transmitting fibers and intertwined with each other to form a "whisker-light-transmitting fiber" network structure. Moreover, the secondary hydroxyl groups on the side chain of the aqueous photocurable epoxy vinyl ester resin could cooperate with the hydroxyl groups on the fiber surface to improve the wettability and adhesiveness to the fiber material, thereby improving the mechanical strength.

[0067] In summary, the epoxy vinyl type aqueous photocurable surface adhesive for stone decoration in the embodiments of the present invention has the characteristics of high glossiness, high hardness, high bonding strength, fast curing speed, good air permeability, and excellent yellowing resistance.

[0068] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration, characterized in that, By weight parts, the epoxy vinyl-based waterborne photocurable surface glue for stone decoration comprises the following components: 100 parts of waterborne photocurable epoxy vinyl ester resin, 5 - 20 parts of gloss and hardness enhancer, 1 - 6 parts of waterborne photoinitiator, 1 - 4 parts of waterborne light stabilizer, 0.1 - 1 part of waterborne leveling agent, 0.1 - 1 part of waterborne defoaming agent, and 10 - 20 parts of reinforcing material; the gloss and hardness enhancer is an emulsion formed by dispersing paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition in an emulsifier and deionized water; The mass ratio of paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax is (0.5 - 1.5):(0.5 - 1.5):1; The mass of the paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition accounts for 25 - 30% of the mass of the gloss and hardness enhancer; The epoxy vinyl-based waterborne photocurable surface glue for stone decoration further comprises a reinforcing material, and the reinforcing material includes whisker material and light-transmitting fiber. The length of the whisker material is 10 - 25 μm, and the length of the light-transmitting fiber is 10 - 25 μm; The whisker material is one or more of aluminum borate whisker, alumina whisker, calcium sulfate whisker, and calcium carbonate whisker; The light-transmitting fiber is one or more of poly(diallyl diglycol carbonate) fiber and styrene acrylonitrile copolymer fiber; 2. The epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration according to claim 1, characterized in that, The emulsifier is composed of span-80 and tween-80 with a mass ratio of (0.9 - 1.1):1; The mass of the emulsifier accounts for 8 - 10% of the mass of the gloss and hardness enhancer; 3. The epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration according to claim 2, characterized in that, The preparation method of the gloss and hardness enhancer includes: adding paraffin wax, polyethylene wax oxide, and Fischer-Tropsch wax composition and the emulsifier into a high-shear dispersion emulsifier, heating to the emulsification temperature of 80 - 100 °C, and dropping deionized water at the same temperature. The rotation speed is controlled at 1000 - 1500 revolutions per minute for shear dispersion emulsification. After dropping, it is naturally cooled to obtain the gloss and hardness enhancer.

4. The epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration according to claim 1, characterized in that, The waterborne photocurable epoxy vinyl ester resin includes 50 - 90% of waterborne photocurable epoxy vinyl ester resin prepolymer and the balance of water. The waterborne photocurable epoxy vinyl ester resin prepolymer is one or more of waterborne bisphenol A epoxy vinyl ester resin and waterborne phenolic epoxy vinyl ester resin; 5. The epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration according to claim 1, characterized in that, The waterborne photoinitiator is a mixture of a waterborne acetophenone derivative photoinitiator and an organophosphorus compound photoinitiator with a mass ratio of (0.5 - 2):1; The waterborne acetophenone derivative photoinitiator is one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexyl phenyl ketone; the organophosphorus compound photoinitiator is one or more of ethyl 2,4,6-trimethylbenzoyl phenylphosphinate and 45% aqueous solution of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; 6. The epoxy vinyl-based waterborne photocurable surface adhesive for stone decoration according to claim 1, characterized in that, The waterborne light stabilizer is one or more of TINUVIN1130, TINUVIN477DW, TINUVIN5050, TINUVIN5060, and TINUVIN5151; And / or, the aqueous leveling agent is one or more of acrylate leveling agents and polyether silicone leveling agents; And / or, the aqueous defoaming agent is one or more of mineral oil-based defoaming agents, polyether-modified polysiloxane defoaming agents, and hydrophobic polyether defoaming agents.

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