An environment-friendly coating adhesive for stone blocks and its preparation method

Abstract

The present invention provides an environment-friendly stone block coating adhesive and a preparation method thereof. The environment-friendly stone block coating adhesive comprises component A and component B. Component A includes vinyl ester resin, a hardening agent and a wetting and penetrating agent; component B includes an initiator. By weight, the vinyl ester resin includes 17.5 - 27.5 parts of aliphatic long-chain epoxy vinyl ester resin, 25 - 35 parts of phenolic epoxy vinyl ester resin and 40 - 50 parts of an environment-friendly reactive diluent. The environment-friendly reactive diluent is composed of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate. The present invention selects specific vinyl ester resins to ensure the low viscosity, excellent water resistance, heat resistance and chemical corrosion resistance of the stone block coating adhesive, while endowing the adhesive film with high mechanical strength, improving the storage stability of the product, reducing the harm to the human body and the environment, and enabling the colloid to have good adhesion, impact toughness and anti-aging performance.

Description

Technical Field

[0001] The present invention relates to the technical field of stone production, and particularly relates to an environment-friendly coating adhesive for stone blocks and a preparation method thereof. Background Art

[0002] A stone block refers to a cuboid rough blank of a certain specification cut during the mining of stones. The stone blocks need to be transported over a long distance to reach the stone processing factory. After entering the processing factory, they are cut into plates of a certain thickness by a special slicing machine set and sent to subsequent processes for further processing. Some stone structures are relatively loose, with cracks of varying depths inside, and are prone to fragmentation during the transportation process and the slicing and plate-making process, resulting in losses and increased costs. Therefore, reinforcement measures are usually taken for stone blocks, such as wrapping them with a coating adhesive on the surface of the stone blocks.

[0003] Currently, the commonly used coating adhesives for stone blocks mainly include unsaturated polyester resin adhesives and epoxy resin adhesives. However, these two coating adhesives have the following defects: 1. The epoxy resin adhesive has a very slow curing speed at low temperatures, which affects the construction progress. Moreover, in a humid environment, its bonding performance will also be greatly affected; at the same time, the construction process is relatively complex. 2. The conventional unsaturated polyester resin adhesive uses styrene as the active diluent. Styrene has a low boiling point (145°C), is volatile, causing environmental pollution. And the unsaturated polyester resin adhesive has too fast a curing speed, a short construction time, is not convenient for operation, and is not water-resistant, and is prone to falling off in a humid environment; black lines will appear on the cut surface of the stone, affecting the appearance. In addition, although the brushing process of the unsaturated polyester resin adhesive for wrapping stone blocks is simple, its permeability is not good, and the internal defects of the stone blocks cannot be repaired; and the adhesion is insufficient, brittle, and prone to falling off and cracking during the cutting process.

[0004] In recent years, polyurethane-based coating adhesives for stone blocks have emerged on the market, such as the polyurethane-based coating adhesive for stone blocks disclosed in Chinese Patent Document CN105885764B. Although this polyurethane-based coating adhesive for stone blocks can be cured well during construction at low temperatures and on wet stone blocks, the post-curing time is still relatively long, affecting the subsequent construction progress; and the production process is complex, and the raw materials used are highly toxic. Summary of the Invention

[0005] Aiming at the deficiencies of the existing technology, the present invention provides an environment-friendly coating adhesive for stone blocks and a preparation method thereof.

[0006] The present invention provides an environment-friendly coating adhesive for stone blocks, including component A and component B. Component A includes vinyl ester resin, a hardening agent, and a wetting and penetrating agent; component B includes an initiator.

[0007] Among them, by weight parts, the vinyl ester resin includes 17.5 - 27.5 parts of aliphatic long-chain epoxy vinyl ester resin, 25 - 35 parts of phenolic epoxy vinyl ester resin, and 40 - 50 parts of environment-friendly reactive diluent; the environment-friendly reactive diluent is composed of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate.

[0008] In the present invention, the aliphatic long-chain epoxy vinyl ester resin and the phenolic epoxy vinyl ester resin are compounded in a certain proportion, which ensures the low viscosity and excellent water resistance, heat resistance, and chemical corrosion resistance of the stone block coating adhesive, and at the same time endows the adhesive film with high mechanical strength. Among them, the composition of β-hydroxyethyl methacrylate (boiling point 205°C), a monofunctional group with a relatively high boiling point, and neopentyl glycol diacrylate, a bifunctional group with good non-volatile air-drying property, is used to replace styrene, which can avoid the pollution of the environment and the harm to the human body caused by the volatile styrene, meeting the environmental protection requirements; it is found in the experiment that using this environment-friendly reactive diluent can also make the colloid have good adhesion, impact toughness, and anti-aging performance.

[0009] According to the environment-friendly stone block coating adhesive provided by the present invention, in the environment-friendly reactive diluent, the mass ratio of β-hydroxyethyl methacrylate is 10 - 30%.

[0010] The present invention studies and finds that the content of β-hydroxyethyl methacrylate should not exceed 30%, otherwise the flexural modulus of elasticity of the colloid cured product will decrease significantly.

[0011] According to the environment-friendly stone block coating adhesive provided by the present invention, the hardening agent is composed of carnauba wax, polyethylene wax, and montan wax with a mass ratio of 10 - 40:20 - 40:20 - 50, and the mass of the hardening agent is 1 - 8% of the mass of the vinyl ester resin.

[0012] In the present invention, carnauba wax, polyethylene wax, and montan wax are used to form a hardening agent. This composition forms a covering layer on the surface of the colloid to isolate oxygen in the air, preventing the inhibition of polymerization of the resin by oxygen on the surface of the colloid and avoiding the black lines on the cut surface of the stone during construction; moreover, different types of hardening agent compositions endow the adhesive film with greater hardness, ensuring the brightness of the stone, and making it easier to cut and form the stone block.

[0013] According to the environment-friendly stone block coating adhesive provided by the present invention, the wetting and penetrating agent includes amyl phenyl ether, 3,3,5-trimethylcyclohexanone, and propylene glycol diacetate with a mass ratio of 35 - 60:15 - 35:10 - 30, and the mass of the wetting and penetrating agent is 2 - 12% of the mass of the vinyl ester resin.

[0014] The wetting and penetrating agent selected in the present invention gives the colloid excellent wettability, so that the colloid can better penetrate into the stone, repair stone defects, and have a higher yield rate; it was also unexpectedly found in the experiment that it can also significantly enhance the adhesion of the colloid to the stone and the impact toughness of the colloid.

[0015] According to the environmentally friendly stone block coating adhesive provided by the present invention, the component A further comprises a defoamer, an inhibitor and an accelerator; and the component B further comprises a blending agent.

[0016] According to the environmentally friendly stone block coating adhesive provided by the present invention, the defoamer comprises BYK-530 containing organosiloxane and Airex-910 not containing organosiloxane in a mass ratio of 40-60:60-40, and the mass of the defoamer is 0.1-0.5% of the mass of the vinyl ester resin.

[0017] The present invention uses the above defoamer composition to effectively avoid physical defects caused by the environmentally friendly stone rough material coating adhesive after curing.

[0018] According to the environmentally friendly stone rough material coating adhesive provided by the present invention, the accelerator is a 10% cobalt isooctanoate solution, and the mass of the accelerator is 0.2-0.8% of the mass of the vinyl ester resin. Among them, the 10% cobalt isooctanoate solution is a mass fraction, that is, 10 parts of cobalt isooctanoate are diluted with 90 parts of diluent. In the embodiment of the present invention, a mixed solution of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate with a mass ratio of 1:4 is preferably used as the diluent.

[0019] According to the environmentally friendly stone rough material coating adhesive provided by the present invention, the inhibitor is one or more of hydroquinone, 2,5-di-tert-butylhydroquinone, methylhydroquinone, p-benzoquinone, and 4-tert-butylcatechol, and the mass of the inhibitor is 0.01-0.05% of the mass of the vinyl ester resin.

[0020] The invention reasonably mixes the accelerator and the inhibitor within the range, so that the obtained environmentally friendly stone rough material coating adhesive has a suitable operating time.

[0021] According to the environmentally friendly stone rough material coating adhesive provided by the present invention, in the B component, the initiator is methyl ethyl ketone peroxide, and the regulator is dibutyl phthalate, and the mass ratio of the two is 1:1.

[0022] According to the environmentally friendly stone rough material coating adhesive provided by the present invention, the mass ratio of the component A to the component B is 100:1-5.

[0023] In a preferred embodiment of the present invention, the environmentally friendly stone block coating adhesive comprises two components, A and B; wherein, component A by weight comprises: 17.5-27.5 parts of aliphatic long-chain epoxy vinyl ester resin, 25-35 parts of phenolic epoxy vinyl ester resin, 40-50 parts of environmentally friendly reactive diluent, 1-8 parts of hardening agent, 2-12 parts of wetting and penetrating agent, 0.1-0.5 parts of defoaming agent, 0.01-0.05 parts of inhibitor and 0.2-0.8 parts of accelerator, wherein the environmentally friendly reactive diluent consists of β-hydroxyethyl methacrylate accounting for 10-30% by mass and the remaining neopentyl glycol diacrylate; the hardening agent consists of carnauba wax, polyethylene wax and montan wax with a mass ratio of 10-40:20-40:20-50; the wetting and penetrating agent consists of amyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate with a mass ratio of 35-60:15-35:10-30; component B by weight comprises: 50 parts of methyl ethyl ketone peroxide and 50 parts of dibutyl phthalate.

[0024] Take 100 parts by weight of component A and 1-5 parts by weight of component B, and mix them evenly to obtain the environmentally friendly stone block coating adhesive. The mixed environmentally friendly stone block coating adhesive has a viscosity of 0.1-0.3 Pa·s at 25 °C, so that the adhesive liquid can more easily penetrate into the stone interior.

[0025] The present invention also provides a preparation method of the above-mentioned environmentally friendly stone block coating adhesive, comprising: respectively mixing the raw materials of component A and component B to obtain component A and component B, and mixing them in proportion before construction.

[0026] Further, the steps of preparing component A include: mixing vinyl ester resin, inhibitor, accelerator and hardening agent, heating to 80-85 °C, controlling the rotation speed at 500-1000 revolutions per minute, and stirring for 10-15 minutes; then adding the remaining materials, controlling the rotation speed at 1300-1500 revolutions per minute, stirring for 20-25 minutes, and then performing ultrasonic oscillation for 20-30 minutes.

[0027] Further preferably, in the step of mixing vinyl ester resin, inhibitor, accelerator and hardening agent, the dosage of the environmentally friendly reactive diluent accounts for 40-60% of the total amount of the environmentally friendly reactive diluent, which can avoid wasting energy by heating all the environmentally friendly reactive diluent to 80-85 °C and then cooling it down, and can also use the remaining styrene to assist in cooling.

[0028] An environment-friendly stone block coating adhesive provided by the present invention and its preparation method ensure the low viscosity, excellent water resistance, heat resistance and chemical corrosion resistance of the stone block coating adhesive by compounding aliphatic long-chain epoxy vinyl ester resin and phenolic epoxy vinyl ester resin in a certain proportion, and at the same time endow the adhesive film with high mechanical strength. Among them, the composition of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate is used to replace styrene, which is safe and environment-friendly, improves the storage stability, and reduces the harm to human body and environment. Moreover, the colloid has good adhesion, impact toughness and anti-aging performance.

[0029] Furthermore, through the compatibility of components such as hardening agents and wetting and penetrating agents, an environment-friendly stone block coating adhesive with an appropriate operation time, strong water resistance, chemical corrosion resistance, high bonding strength, high hardness, good toughness, good permeability and adhesion, and no breakage, no shedding, no brittle fracture and no black line generation during the cutting process is finally obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a graph showing the change of the hardness and impact toughness of the cured product of the environment-friendly stone block coating adhesive with the addition amount of the hardening agent;

[0031] Figure 2 It is a graph showing the change of the flexural elastic modulus and compressive shear bond strength of the cured product of the environment-friendly stone block coating adhesive with the addition amount of the hardening agent;

[0032] Figure 3 It is a graph showing the change of the penetration depth of the environment-friendly stone block coating adhesive with the addition amount of the hardening agent;

[0033] Figure 4 It is a graph showing the change of the penetration depth and adhesion of the environment-friendly stone block coating adhesive with the addition amount of the wetting and penetrating agent;

[0034] Figure 5 It is a graph showing the change of the flexural elastic modulus and impact toughness of the cured product of the environment-friendly stone block coating adhesive with the addition amount of the wetting and penetrating agent;

[0035] Figure 6 It is a graph showing the change of the compressive shear bond strength of the cured product of the environment-friendly stone block coating adhesive with the addition amount of the wetting and penetrating agent. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] 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.

[0037] Unless otherwise specified, the materials used in the following examples are all commercially available.

[0038] In the following examples, the 10% cobalt octoate solution used is composed of 10 parts by mass of cobalt octoate and 90 parts of a diluent, where the diluent is a mixed solution of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate with a mass ratio of 1:4.

[0039] Example 1

[0040] This example provides an environmentally friendly stone block coating adhesive, which includes two components, A and B. Component A, by weight, includes: 25 parts of aliphatic long-chain epoxy vinyl ester resin, 25 parts of phenolic epoxy vinyl ester resin, 10 parts of β-hydroxyethyl methacrylate, 40 parts of neopentyl glycol diacrylate, 0.5 part of 10% cobalt octoate solution, 0.02 part of 2,5-di-tert-butylhydroquinone, 0.01 part of 4-tert-butylcatechol, 2 parts of carnauba wax, 2 parts of polyethylene wax, 2 parts of montan wax, 4 parts of amyl phenyl ether, 2.4 parts of 3,3,5-trimethylcyclohexanone, 1.6 parts of propylene glycol diacetate, 0.15 part of BYK-530 defoamer, and 0.15 part of Airex-910 defoamer. Component B, by weight, includes: 50 parts of methyl ethyl ketone peroxide and 50 parts of dibutyl phthalate.

[0041] The preparation method of component A of the environmentally friendly stone block coating adhesive is as follows: First, put the aliphatic long-chain epoxy vinyl ester resin, phenolic epoxy vinyl ester resin, 50% environmentally friendly active diluent (β-hydroxyethyl methacrylate and neopentyl glycol diacrylate), inhibitor, accelerator, and hardening agent into a double planetary power mixer, heat up to 83°C, control the rotation speed at 800 revolutions per minute, and stir for 12 minutes; then put in the remaining materials, control the rotation speed at 1500 revolutions per minute, stir for 23 minutes, and then ultrasonically vibrate for 20 minutes with an ultrasonic oscillator.

[0042] Weigh 100 parts by weight of component A and 3 parts by weight of component B, and mix them evenly to obtain the environmentally friendly stone block coating adhesive.

[0043] It should be noted that the inventor tested other preparation conditions under the formulation composition of Example 1 and found that when preparing according to the parameters within the range of "first put in aliphatic long-chain epoxy vinyl ester resin, phenolic epoxy vinyl ester resin, inhibitor, accelerator, hardener and 40-60% environmentally friendly reactive diluent into a double planetary power mixer, heat up to 80-85 °C, control the rotation speed at 500-1000 revolutions per minute, stir for 10-15 minutes; then put in the remaining materials, control the rotation speed at 1300-1500 revolutions per minute, stir for 20-25 minutes, and then perform ultrasonic oscillation for 20-30 minutes; weigh 100 parts by weight of Component A and 1-5 parts by weight of Component B, and mix evenly", the performance of the environmentally friendly stone block coating adhesive obtained is basically close and there is no significant difference.

[0044] In addition, the present invention also provides environmentally friendly stone block coating adhesives with different hardeners from Example 1, namely Comparative Examples 1-8 (it should be noted that the comparative examples listed in the present invention are for highlighting the preferred conditions of a certain parameter, and it does not necessarily mean that the comparative example does not fall within the protection scope of the present invention, the same below) and Examples 2-6, and the raw material composition of their Component A is shown in Table 1 below; environmentally friendly stone block coating adhesives with different wetting and penetrating agents from Example 1, namely Comparative Examples 9-16 and Examples 7-11, and the raw material composition of their Component A is shown in Table 2 below. Their Component B composition is the same as that of Example 1, and the preparation method is the same as that of Example 1.

[0045] Table 1

[0046]

[0047]

[0048] Table 2

[0049]

[0050]

[0051] The present invention also provides stone block coating adhesives with different reactive diluents, namely Comparative Examples 17-18 and Examples 12-13, and the raw material composition of their Component A is shown in Table 3 below. Their Component B composition is the same as that of Example 1, and the preparation method is the same as that of Example 1.

[0052] Table 3

[0053]

[0054]

[0055] Experiments found that the reactive diluent β-hydroxyethyl methacrylate has good compatibility with the resin, no volatilization under conventional heating. When it is used alone to replace the reactive diluent styrene in the resin, the storage period of the obtained resin is better than that of the resin containing styrene. The resin can initially set, but does not emit smoke, is relatively soft after curing, and has a relatively low exothermic peak value. The reactive diluent neopentyl glycol diacrylate contains a saturated tertiary carbon atom structure in its molecular structure and an ester group in the carbon chain. The polyester crosslinked and cured with its participation has good stability, high toughness, and wear resistance. By compounding and using β-hydroxyethyl methacrylate and neopentyl glycol diacrylate, it is found that the adhesion and impact resistance of the colloid are outstanding, and the anti-aging performance is also very excellent. However, the content of β-hydroxyethyl methacrylate should not exceed 30%, otherwise the flexural modulus of elasticity of the colloid cured product will decrease significantly.

[0056] In addition, the present invention also provides an environmentally friendly stone block coating adhesive shown in Examples 14-20 and Comparative Examples 19-20, and the composition of component B is the same as that of Example 1, and the raw material composition of component A is shown in Table 4 by weight parts.

[0057] Table 4

[0058]

[0059]

[0060] Experimental Examples

[0061] To prove the excellent effects of the environmentally friendly stone block coating adhesive of the present invention, the environmentally friendly stone block coating adhesives obtained in Examples 1-20 of the present invention and Comparative Examples 1-23 were respectively subjected to performance tests, including flexural modulus of elasticity, impact toughness, compressive shear bond strength (cured for 168 h under standard conditions), compressive shear bond strength (immersed in water for 168 h), hardness, penetration depth, adhesion, black line condition of the cut surface, and curing time. The test results are shown in Table 5 and Table 6. Figures 1-3 It is a change curve graph corresponding to Examples 2-6 and Comparative Examples 1 and 8. Figures 4-6 It is a change curve graph corresponding to Examples 8-11, Example 5, Comparative Example 9 and Comparative Example 16. Among them, the resin used in Comparative Example 19 is a common low-viscosity unsaturated polyester resin, Comparative Example 21 is an unsaturated polyester resin adhesive on the market, Comparative Example 22 is an epoxy resin adhesive on the market, and Comparative Example 23 is the best example of the polyurethane-type stone block wrapping adhesive disclosed in Chinese Patent Document CN105885764B.

[0062] The specific methods for each performance test are as follows:

[0063] Flexural modulus of elasticity, impact toughness, compressive-shear bond strength (cured for 168 h under standard conditions), compressive-shear bond strength (immersed in water for 168 h): Refer to the test method of JC / T 989-2016 "Stone Adhesives for Non-Structural Load-Bearing". After preparing the cured sample blocks, use a universal tensile testing machine and a pendulum impact testing machine for testing;

[0064] Adhesion: Test using the PosiTest AT-A fully automatic digital display pull-off adhesion tester from DeFelsko Corporation, USA;

[0065] Hardness: Test using a Type D Shore hardness tester;

[0066] Penetration depth: Separate two thin slabs of rough stone materials by a 0.6-mm gap and fix them. Measure several gaps that are 100 mm long and 0.6 mm wide respectively. Dip a brush into the well-mixed rough stone material coating adhesive and brush back and forth 3 times. After the colloid cures, measure the penetration depth of the rough stone material coating adhesive;

[0067] Black line condition on the cutting surface: Brush the rough stone material with the mixed colloid. After curing, perform cutting and observe whether there are black lines on the cutting surface;

[0068] Pot life and curing time: Refer to the general test method for building adhesives of GB / T 12954-1991.

[0069] Table 5

[0070]

[0071]

[0072] Table 6

[0073]

[0074]

[0075] From the above results, it can be seen that:

[0076] Comparative Example 1 is an environment-friendly stone block coating adhesive without any hardening agent. In Comparative Example 2, only carnauba wax was added, and the colloidal hardness and flexural modulus of elasticity were significantly increased compared with Comparative Example 1. The black lines on the cutting surface were improved, but the impact toughness decreased significantly, and the compression-shear bond strength and penetration depth decreased somewhat. In Comparative Example 3, only polyethylene wax was added, and the colloidal hardness increased significantly, but it was not as high as that in Comparative Example 2 and 4. The black lines on the cutting surface were improved, and the impact toughness was not greatly affected, but the penetration depth and flexural modulus of elasticity decreased significantly, and the compression-shear bond strength decreased somewhat. In Comparative Example 4, only montan wax was added, and the colloidal hardness increased significantly, slightly inferior to Comparative Example 2. The black lines on the cutting surface were improved, and the flexural modulus of elasticity was not greatly affected, but the penetration depth, impact toughness, and compression-shear bond strength decreased somewhat. In Comparative Examples 5-7, carnauba wax, polyethylene wax, and montan wax were mixed in pairs, and although each index was improved compared with single addition, the effect was not ideal. In Examples 1 and 6, carnauba wax, polyethylene wax, and montan wax were added together. Under the same addition amount of the hardening agent, except for the decrease in the penetration depth, the indexes of colloidal hardness, flexural modulus of elasticity, impact toughness, and compression-shear bond strength all increased significantly; and when the ratio of carnauba wax, polyethylene wax, and montan wax was 3:3:4, the data was the best. In Examples 1-6 and Comparative Example 8, carnauba wax, polyethylene wax, and montan wax were added together. As shown in Table 5 and Figures 1-3 as follows, as the hardening agent was gradually increased, the colloidal hardness gradually increased, and the flexural modulus of elasticity, impact toughness, compression-shear bond strength, and adhesion also increased slightly. When added to 5 parts, it reached the best. When the hardening agent was continuously added, the hardness basically did not increase, but the flexural modulus of elasticity, impact toughness, compression-shear bond strength, and adhesion would slowly decrease. After adding to 8 parts, the decrease was obvious; when the hardening agent was added to 1 part, the black lines on the cutting surface of the stone block were already very light and almost invisible to the naked eye. After adding to 3 parts, there were no black lines on the cutting surface of the stone block.

[0077] Comparative Example 9 is an environmentally friendly stone block coating adhesive without any wetting and penetrating agent. In Comparative Example 10, only amyl phenyl ether was added, and the penetration depth, adhesion and impact toughness of the colloid increased significantly compared with Comparative Example 9, the flexural modulus of elasticity and the compression-shear bond strength increased slightly, and the hardness decreased slightly. In Comparative Example 11, only 3,3,5-trimethylcyclohexanone was added, and the penetration depth, adhesion and impact toughness of the colloid increased significantly compared with Comparative Example 9, but were not as high as those in Comparative Example 10 and 12. The flexural modulus of elasticity increased significantly, the compression-shear bond strength increased slightly, and the hardness decreased slightly. In Comparative Example 12, only propylene glycol diacetate was added, and the penetration depth, adhesion and impact toughness of the colloid increased significantly, slightly inferior to Comparative Example 10. The flexural modulus of elasticity and the compression-shear bond strength increased slightly, and the hardness decreased slightly. In Comparative Examples 13-15, amyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were mixed in pairs, and the comprehensive indexes improved, but the effect was not ideal, and the penetration depth still needed to be further improved. In Examples 7 and 11, amyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were added together, showing that under the same addition amount of the wetting and penetrating agent, except for the hardness, the indexes of the penetration depth, adhesion, impact toughness, flexural modulus of elasticity and compression-shear bond strength of the colloid increased significantly; and when the ratio of amyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate was 5:3:2, the effect was the best. In Examples 5, 8-11 and Comparative Example 16, amyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were added together. As shown in Table 5 and Figures 4-6 as shown, with the gradual increase of the wetting and penetrating agent, the penetration depth, adhesion, impact toughness, flexural modulus of elasticity and compression-shear bond strength of the colloid also increased gradually. When added to 8 parts, the colloid adhesion, impact toughness, flexural modulus of elasticity and compression-shear bond strength reached the best. When the wetting and penetrating agent was continuously added, although the penetration depth of the colloid continued to increase, the growth rate was very slow. At the same time, the colloid adhesion, impact toughness, flexural modulus of elasticity and compression-shear bond strength would decrease significantly. After adding to 12 parts, the decrease was obvious.

[0078] The resin used in Comparative Example 19 is a commonly used low-viscosity unsaturated polyester resin. The resin used in Comparative Example 20 is a preferred aliphatic long-chain epoxy vinyl ester resin and a phenolic epoxy vinyl ester resin of the present invention, compounded in a ratio of 1:1. As described in the data in Table 5, the mechanical properties, water resistance and permeability of the environmentally friendly stone block coating adhesive obtained in Comparative Example 20 were significantly improved.

[0079] In summary, an environmentally friendly stone block coating adhesive provided by the embodiments of the present invention has an appropriate operation time, can be quickly constructed at low temperature, has strong water resistance, high bonding strength, high hardness, good permeability and adhesion, and there is no black line on the cut surface of the stone block, meeting the requirements.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended 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 described in the foregoing embodiments, or perform equivalent replacements for 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. A stone block coating adhesive, characterized in that, It includes Component A and Component B. Component A includes vinyl ester resin, hardening agent and wetting and penetrating agent; Component B includes initiator; the mass ratio of Component A to Component B is 100:1 - 5; Among them, by weight, the vinyl ester resin includes 17.5 - 27.5 parts of aliphatic long-chain epoxy vinyl ester resin, 25 - 35 parts of phenolic epoxy vinyl ester resin and 40 - 50 parts of reactive diluent; the reactive diluent is composed of β-hydroxyethyl methacrylate and neopentyl glycol diacrylate; in the reactive diluent, the mass proportion of β-hydroxyethyl methacrylate is 10 - 30%; The hardening agent is composed of carnauba wax, polyethylene wax and montan wax, and the mass of the hardening agent is 1 - 8% of the mass of the vinyl ester resin; The wetting and penetrating agent includes amyl phenyl ether, 3,3,5 - trimethylcyclohexanone and propylene glycol diacetate, and the mass of the wetting and penetrating agent is 2 - 12% of the mass of the vinyl ester resin.

2. The stone block coating adhesive according to claim 1, characterized in that, The hardening agent is composed of carnauba wax, polyethylene wax and montan wax with a mass ratio of 10 - 40:20 - 40:20 - 50.

3. The stone block coating adhesive according to claim 1, characterized in that, The wetting and penetrating agent includes amyl phenyl ether, 3,3,5 - trimethylcyclohexanone and propylene glycol diacetate with a mass ratio of 35 - 60:15 - 35:10 - 30.

4. The stone block coating adhesive according to claim 1, characterized in that, Component A also includes defoamer, inhibitor and accelerator; Component B also includes conditioner.

5. The stone block coating adhesive according to claim 4, characterized in that, The defoamer includes BYK - 530 containing organosiloxane and Airex - 910 without organosiloxane with a mass ratio of 40 - 60:60 - 40, and the mass of the defoamer is 0.1 - 0.5% of the mass of the vinyl ester resin.

6. The stone block coating adhesive according to claim 4, characterized in that, The accelerator is 10% cobalt octoate solution, and the mass of the accelerator is 0.2 - 0.8% of the mass of the vinyl ester resin; And / or, the inhibitor is one or more of hydroquinone, 2,5 - di - tert - butylhydroquinone, methylhydroquinone, p - benzoquinone, 4 - tert - butylcatechol, and the mass of the inhibitor is 0.01 - 0.05% of the mass of the vinyl ester resin.

7. The stone block coating adhesive according to claim 4, characterized in that, In Component B, the initiator is methyl ethyl ketone peroxide, and the conditioner is dibutyl phthalate, and the mass ratio of the two is 1:

1.

8. A preparation method of the stone block coating adhesive according to any one of claims 1-7, characterized in that, It includes: Mix the raw materials of Component A and Component B respectively to obtain Component A and Component B, and mix them in proportion before construction.

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