Stone block coating adhesive and preparation method thereof

Abstract

The present invention provides a stone block coating adhesive and a preparation method thereof. The stone block coating adhesive comprises a component A and a component B. Component A comprises a vinyl ester resin, a hardener, and a wetting and penetrating agent; component B comprises an initiator; and the hardener comprises carnauba wax, polyethylene wax, and montan wax in a mass ratio of 10-40:20-40:20-50, with the mass of the hardener accounting for 1-8% of the mass of the vinyl ester resin. By selecting the vinyl ester resin and adding a specific hardener, the present invention can avoid black lines on the cut surface of the stone during construction, and can also impart greater hardness and mechanical strength to the adhesive film, ensuring the brightness of the stone and making the stone block easier to cut and shape.

Description

Technical Field

[0001] The present invention relates to the technical field of stone production, in particular to a stone block coating adhesive and a preparation method thereof. Background Art

[0002] Stone blocks refer to rough, rectangular blocks of specific specifications cut from stone during mining. Stone blocks are transported long distances to reach stone processing plants. Once there, they are cut into slabs of a specific thickness using specialized slicing machines and sent for further processing. Some stone blocks have a loose structure and internal cracks of varying depths, making them susceptible to breakage during transportation and slicing, resulting in loss and increased costs. Therefore, stone blocks are often reinforced, such as wrapping them with adhesive.

[0003] Currently, the two most commonly used adhesives for coating stone blocks are unsaturated polyester resin adhesive and epoxy resin adhesive. However, these two adhesives have the following drawbacks: 1. Epoxy resin adhesive cures very slowly at low temperatures, impacting construction progress. Furthermore, its bonding properties are significantly affected in humid conditions, and the construction process is relatively complex. 2. Conventional unsaturated polyester resin adhesive cures too quickly, resulting in a short construction time and inconvenient handling. Furthermore, it is not water-resistant and easily falls off in humid conditions, creating black lines on the cut surface of the stone, affecting its aesthetics. Furthermore, while unsaturated polyester resin adhesive offers a simple coating process for coating stone blocks, it suffers from poor permeability, making internal defects in the stone blocks impossible to repair. Furthermore, it lacks adhesion and is highly brittle, making it prone to falling off and cracking during cutting.

[0004] In recent years, polyurethane-based stone block coating adhesives have become available on the market, such as the one disclosed in Chinese patent document CN105885764B. While this polyurethane-based stone block coating adhesive cures well at low temperatures and on damp stone blocks, it still suffers from a relatively long post-curing time, hindering subsequent construction progress. Furthermore, the production process is complex, and the raw materials used are highly toxic. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a stone block coating adhesive and a preparation method thereof.

[0006] The present invention provides a stone block coating adhesive, comprising a component A and a component B, wherein the component A comprises a vinyl ester resin, a hardener and a wetting and penetrating agent; and the component B comprises an initiator;

[0007] The hardener is composed of carnauba wax, polyethylene wax and montan wax in a mass ratio of 10-40:20-40:20-50, and the mass of the hardener is 1-8% of the mass of the vinyl ester resin.

[0008] The present invention uses carnauba wax, polyethylene wax and montan wax as a hardener. The composition forms a covering layer on the surface of the colloid that isolates oxygen in the air, preventing the inhibition of resin by oxygen on the colloid surface and avoiding black lines on the cut surface of the stone during construction. Moreover, the different types of hardener compositions give the film greater hardness, ensuring the brightness of the stone, and making the stone blocks easier to cut and shape.

[0009] According to the stone block coating adhesive provided by the present invention, the wetting and penetrating agent comprises pentylphenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate in 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.

[0010] The wetting and penetrating agent selected in the present invention gives the colloid excellent wettability, allowing the colloid to better penetrate into the stone, repair stone defects, and increase the yield rate; experiments also unexpectedly found that it can significantly enhance the adhesion of the colloid to the stone and the impact toughness of the colloid.

[0011] According to the stone block coating adhesive provided by the present invention, the vinyl ester resin comprises, by weight, 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 styrene.

[0012] The present invention combines a long-chain aliphatic epoxy vinyl ester resin and a phenolic epoxy vinyl ester resin in a specific ratio to ensure low viscosity and excellent water, heat, and chemical resistance for the stone block coating adhesive, while also imparting high mechanical strength to the adhesive film. Styrene, a reactive diluent, regulates resin viscosity, participates in crosslinking and curing, and imparts improved resin properties.

[0013] According to the 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.

[0014] According to the 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.

[0015] The present invention combines the two different types of defoaming agents, effectively avoiding physical defects generated after the stone block coating glue is cured.

[0016] According to the stone block coating adhesive provided by the present invention, the accelerator is a 10% cobalt isooctanoate-styrene solution, and the mass of the accelerator is 0.1-0.6% of the mass of the vinyl ester resin. The 10% cobalt isooctanoate-styrene solution is a mass fraction, that is, 10 parts of cobalt isooctanoate is diluted with 90 parts of styrene.

[0017] According to the stone block coating adhesive provided by the present invention, the polymerization inhibitor is one or more of hydroquinone, 2,5-di-tert-butylhydroquinone, methylhydroquinone, p-benzoquinone, and 4-tert-butylcatechol, and the mass of the polymerization inhibitor is 0.01-0.08% of the mass of the vinyl ester resin.

[0018] The present invention reasonably mixes the accelerator and the polymerization inhibitor within this range, so that the obtained stone block coating adhesive has a suitable operating time.

[0019] According to the stone block coating adhesive provided by the present invention, in the component B, the initiator is methyl ethyl ketone peroxide, and the conditioning agent is dibutyl phthalate, and the mass ratio of the two is 1:1.

[0020] According to the stone block coating adhesive provided by the present invention, the mass ratio of the component A to the component B is 100:1-5.

[0021] In a preferred embodiment of the present invention, Component A comprises, by weight: 100 parts vinyl ester resin, 1-8 parts hardener, 2-12 parts wetting and penetrating agent, 0.1-0.5 parts defoamer, 0.01-0.08 parts polymerization inhibitor, and 0.1-0.6 parts accelerator. The vinyl ester resin comprises 17.5-27.5 parts aliphatic long-chain epoxy vinyl ester resin, 25-35 parts phenolic epoxy vinyl ester resin, and 40-50 parts styrene. The hardener comprises carnauba wax, polyethylene wax, and montan wax in a mass ratio of 10-40:20-40:20-50. The wetting and penetrating agent comprises amylphenyl ether, 3,3,5-trimethylcyclohexanone, and propylene glycol diacetate in a mass ratio of 35-60:15-35:10-30. Component B comprises, by weight: 50 parts methyl ethyl ketone peroxide and 50 parts dibutyl phthalate.

[0022] Under the above conditions, after the A and B components are mixed in a mass ratio of 100:1-5, the viscosity of the obtained stone block coating glue at 25°C is 0.1-0.3 Pa.s, so that the glue can more easily penetrate into the interior of the stone.

[0023] The present invention also provides a method for preparing the stone block coating adhesive, comprising: mixing the raw materials of the A component and the B component to obtain the A component and the B component respectively, and mixing them in proportion before construction.

[0024] According to the preparation method provided by the present invention, the steps of preparing the A component include: mixing the vinyl ester resin, the polymerization inhibitor, the accelerator and the hardener, heating to 80-85°C, controlling the speed at 500-1000 rpm, and stirring for 10-15 minutes; then adding the remaining materials, controlling the speed at 1300-1500 rpm, stirring for 20-25 minutes, and then ultrasonically oscillating for 20-30 minutes.

[0025] Further preferably, in the step of mixing the vinyl ester resin, polymerization inhibitor, accelerator and hardener, the amount of styrene used accounts for 40-60% of the total amount of styrene. This avoids heating all the styrene to 80-85°C and then cooling it down, which wastes energy; and the remaining styrene can be used to assist in cooling.

[0026] The present invention provides a stone block coating adhesive and a preparation method thereof. By selecting vinyl ester resin and adding a specific hardener, black lines on the cut surface of the stone can be avoided during construction. The adhesive film can also be given greater hardness and mechanical strength, thereby ensuring the brightness of the stone and making the stone block easier to cut and shape.

[0027] Furthermore, through the combination of components such as the wetting penetrant, a stone block coating adhesive was finally obtained that has a suitable operation time, can be quickly constructed even at low temperatures, has strong water resistance and chemical corrosion resistance, high bonding strength, high hardness, good toughness, good permeability and adhesion, and does not break, fall off, crack, or produce black lines during the cutting process. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The graph is a graph showing the hardness and impact toughness of the stone block coated with adhesive as a function of the amount of hardener added;

[0029] Figure 2 The graph is a graph showing the changes in the bending elastic modulus and compressive shear bond strength of the stone block coated adhesive as a function of the amount of hardener added;

[0030] Figure 3 The graph shows the variation of the penetration depth of the stone block coating adhesive with the amount of hardener added;

[0031] Figure 4 The graph shows the variation of penetration depth and adhesion of stone block coating adhesive with the amount of wetting penetrant added;

[0032] Figure 5 The graph is a graph showing the changes in the bending elastic modulus and impact toughness of the stone block coated adhesive solidified product with the addition amount of the wetting penetrant;

[0033] Figure 6 This is a graph showing the compressive shear bond strength of stone block coated adhesive cured material as a function of the amount of wetting penetrant added. DETAILED DESCRIPTION

[0034] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0035] Unless otherwise specified, the materials used in the following examples are all commercially available.

[0036] Example 1

[0037] This embodiment provides a stone block coating adhesive, including two components A and B. Component A comprises, by weight, 25 parts of aliphatic long-chain epoxy vinyl ester resin, 25 parts of phenolic epoxy vinyl ester resin, 50 parts of styrene, 0.4 parts of 10% cobalt isooctanoate-styrene solution, 0.03 parts of 2,5-di-tert-butylhydroquinone, 0.02 parts 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 parts of BYK-530 defoamer, and 0.15 parts of Airex-910 defoamer. Component B comprises, by weight, 50 parts of methyl ethyl ketone peroxide and 50 parts of dibutyl phthalate.

[0038] The preparation method of component A of the stone block coating glue is as follows: first, add aliphatic long-chain epoxy vinyl ester resin, phenolic epoxy vinyl ester resin, inhibitor, accelerator, hardener and 50% styrene into a dual planetary power mixer, heat to 83°C, control the speed at 800 rpm, and stir for 12 minutes; then add the remaining materials, control the speed at 1500 rpm, stir for 23 minutes, and then use an ultrasonic oscillator to oscillate for 20 minutes.

[0039] Weigh 100 parts by weight of component A and 3 parts by weight of component B, and mix them evenly to obtain the stone block coating adhesive.

[0040] It should be noted that the inventors tested other preparation conditions under the formula composition of Example 1 and found that the performance of the obtained stone block coating adhesive was basically similar and there was no significant difference when the parameters were used for preparation: "first, aliphatic long-chain epoxy vinyl ester resin, phenolic epoxy vinyl ester resin, polymerization inhibitor, accelerator, hardener and 40-60% styrene were added to a dual planetary power mixer, heated to 80-85°C, the speed was controlled at 500-1000 rpm, and stirred for 10-15 minutes; then the remaining materials were added, the speed was controlled at 1300-1500 rpm, stirred for 20-25 minutes, and then ultrasonically vibrated for 20-30 minutes; 100 parts by weight of component A and 1-5 parts by weight of component B were weighed and mixed evenly."

[0041] In addition, the present invention also provides 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 do not mean that the comparative examples do not necessarily fall within the scope of protection of the present invention, the same below) and Examples 2-6, the raw material composition of their component A is shown in Table 1; stone block coating adhesives with different wetting and penetrating agents from Example 1, namely, Comparative Examples 9-16 and Examples 7-11, the raw material composition of their component A is shown in Table 2, their component B compositions are the same as in Example 1, and their preparation methods are the same as in Example 1.

[0042] Table 1

[0043]

[0044] Table 2

[0045]

[0046] In addition, the present invention also provides a stone block coating adhesive as shown in Examples 12-18, and Comparative Examples 17-18, wherein the composition of component B is the same as that of Example 1, and the composition of the raw materials of component A is shown in Table 3 in parts by weight.

[0047] Table 3

[0048]

[0049]

[0050] Experimental example

[0051] In order to demonstrate the excellent effect of the stone block coating adhesive of the present invention, the stone block coating adhesives obtained in Examples 1-18 of the present invention and Comparative Examples 1-20 were respectively subjected to performance tests, including bending elastic modulus, impact toughness, compressive shear bond strength (cured for 168 hours under standard conditions), compressive shear bond strength (immersed in water for 168 hours), hardness, penetration depth, adhesion, black line condition on the cut surface, and curing time. The test results are shown in Tables 4-5. Figure 1-3 The following are the change curves corresponding to Examples 2-6 and Comparative Examples 1 and 8: Figure 4-6 The graphs are the change curves corresponding to Examples 8-11, Example 5, Comparative Example 9, and Comparative Example 16. The resin used in Comparative Example 17 is a commonly used low-viscosity unsaturated polyester resin, Comparative Example 19 is a commercially available unsaturated polyester resin adhesive, Comparative Example 20 is a commercially available epoxy resin adhesive, and Comparative Example 21 is the best embodiment of the polyurethane-based stone block wrapping adhesive disclosed in Chinese Patent Document CN105885764B.

[0052] The specific methods for each performance test are as follows:

[0053] Flexural modulus, impact toughness, compressive shear bond strength (cured for 168 hours under standard conditions), and compressive shear bond strength (immersed in water for 168 hours): Refer to the test methods of JC / T 989-2016 "Non-structural Load-bearing Stone Adhesives" and prepare cured specimens for testing using a universal tensile testing machine and a pendulum impact testing machine.

[0054] Adhesion: The test was conducted using the PosiTest AT-A fully automatic digital display pull-off adhesion tester from DeFelsko, USA.

[0055] Hardness: Tested using a D-type Shore hardness tester;

[0056] Penetration depth: Separate two stone blocks into a gap of 0.6mm and fix them. Measure several gaps of 100mm long and 0.6mm wide. Dip a brush in the evenly mixed stone block coating adhesive and brush back and forth three times. After the adhesive solidifies, measure the penetration depth of the stone block coating adhesive.

[0057] Black lines on the cutting surface: Use the mixed colloid to brush the stone block, cut it after solidification, and observe whether there are black lines on the cutting surface;

[0058] Working time and curing time: refer to standard GB / T 12954-1991 General test methods for building adhesives.

[0059] Table 4

[0060]

[0061]

[0062] Table 5

[0063]

[0064]

[0065] From the above results we can see that:

[0066] Comparative Example 1 is a stone block coating adhesive without any hardener. Comparative Example 2 only adds carnauba wax. As shown in Table 4, the colloid hardness and flexural modulus are significantly increased compared with Comparative Example 1, the black line of the cut surface is improved, but the impact toughness is significantly reduced, and the compression shear bond strength and penetration depth are reduced. Comparative Example 3 only adds polyethylene wax. The colloid hardness is significantly increased, but not as high as Comparative Examples 2 and 4. The black line of the cut surface is improved, and the impact toughness is not greatly affected. However, the penetration depth and flexural modulus are significantly reduced, and the compression shear bond strength is reduced. Comparative Example 4 only adds montan wax. The colloid hardness is significantly increased, slightly inferior to Comparative Example 2. The black line of the cut surface is improved, and the flexural modulus is not greatly affected, but the penetration depth, impact toughness and compression shear bond strength are reduced. Comparative Examples 5-7 mix carnauba wax, polyethylene wax and montan wax in pairs. Although various indicators are improved compared with single addition, the effect is not ideal. In Examples 1 and 6, carnauba wax, polyethylene wax and montan wax were added together. As shown in Table 4, when the hardener was added in the same amount, except for a decrease in penetration depth, the colloid hardness, bending elastic modulus, impact toughness and compressive shear bond strength were significantly increased; 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 4 and Figure 1-3 As shown in the figure, with the gradual increase of hardener, the colloid hardness is gradually increasing, and the bending elastic modulus, impact toughness, compressive shear bond strength and adhesion are also slightly increased. When it is added to 5 parts, it reaches the best. If the hardener is continued to be added, the hardness basically does not increase, but the bending elastic modulus, impact toughness, compressive shear bond strength and adhesion will slowly decrease. After adding to 8 parts, the decrease is obvious. When the hardener is added to 1 part, the black line on the cut surface of the stone block is already very shallow and almost invisible to the naked eye. After adding to 3 parts, there is no black line on the cut surface of the stone block.

[0067] Comparative Example 9 is a stone block coating adhesive without any wetting penetrant, and Comparative Example 10 only adds amylphenyl ether. As shown in the data in Table 4, the colloid penetration depth, adhesion and impact toughness are significantly increased compared with Comparative Example 9, the bending elastic modulus and compressive shear bond strength are slightly increased, and the hardness is slightly reduced; Comparative Example 11 only adds 3,3,5-trimethylcyclohexanone, and the colloid penetration depth, adhesion, and impact toughness are significantly increased compared with Comparative Example 9, but not as high as Comparative Examples 10 and 12, the bending elastic modulus is significantly increased, the compressive shear bond strength is slightly increased, and the hardness is slightly reduced; Comparative Example 12 only adds propylene glycol diacetate, and the colloid penetration depth, adhesion and impact toughness are significantly increased, which is slightly inferior to Comparative Example 10, the bending elastic modulus and compressive shear bond strength are slightly increased, and the hardness is slightly reduced. In Comparative Examples 13-15, pentyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were mixed in pairs, and the comprehensive indicators were improved, but the effect was not ideal, and the penetration depth needed to be further improved. In Examples 7 and 11, pentyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were added together. As shown in the data in Table 4, when the wetting penetrant was added in the same amount, except for the hardness, the colloid penetration depth, adhesion, impact toughness, bending elastic modulus and compressive shear bonding strength indicators were significantly increased; and when the ratio of pentyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate was 5:3:2, the data was optimal. In Example 5, Examples 8-11 and Comparative Example 16, pentyl phenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate were added together, as shown in Tables 4 and Figure 4-6 As shown in the figure, with the gradual increase of wetting penetrant, the colloid penetration depth, adhesion, impact toughness, bending elastic modulus and compressive shear bond strength are also gradually increasing. When it is added to 8 parts, the colloid adhesion, impact toughness, bending elastic modulus and compressive shear bond strength reach the best. If the wetting penetrant is continued to be added, although the colloid penetration depth continues to increase, the growth rate is very slow. At the same time, the colloid adhesion, impact toughness, bending elastic modulus and compressive shear bond strength will be significantly reduced. After adding 12 parts, the decline is obvious.

[0068] The resin used in Comparative Example 17 is a commonly used low-viscosity unsaturated polyester resin, and the resin used in Comparative Example 18 is the preferred aliphatic long-chain epoxy vinyl ester resin and phenolic epoxy vinyl ester resin of the present invention, which are compounded in a ratio of 1:1. As shown in the data in Table 4, the mechanical properties, water resistance and permeability of the stone block coating adhesive obtained in Comparative Example 18 are significantly improved.

[0069] In summary, the stone block coating adhesive provided by the present invention has a suitable operation time, can be quickly constructed even at low temperatures, has strong water resistance, high bonding strength, high hardness, good permeability and adhesion, and has no black lines on the cut surface of the stone block, meeting the requirements.

[0070] 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 it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A stone block coating adhesive, characterized in that: The method comprises component A and component B, wherein the component A comprises a vinyl ester resin, a hardener and a wetting and penetrating agent; and the component B comprises an initiator. The hardener is composed of carnauba wax, polyethylene wax and montan wax in a mass ratio of 10-40:20-40:20-50, and the mass of the hardener is 1-8% of the mass of the vinyl ester resin; The wetting and penetrating agent comprises amylphenyl ether, 3,3,5-trimethylcyclohexanone and propylene glycol diacetate in 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; In parts by weight, the vinyl ester resin comprises 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 styrene.

2. The stone block coating adhesive according to claim 1, characterized in that: The component A further comprises a defoamer, an inhibitor and an accelerator; the component B further comprises a blending agent.

3. The stone block coating adhesive according to claim 2, characterized in that: The defoaming agent comprises BYK-530 containing organosiloxane and Airex-910 not containing organosiloxane in a mass ratio of 40-60:60-40. The mass of the defoaming agent is 0.1-0.5% of the mass of the vinyl ester resin.

4. The stone block coating adhesive according to claim 3, characterized in that: The accelerator is a 10% cobalt isooctanoate-styrene solution, and the mass of the accelerator is 0.1-0.6% of the mass of the vinyl ester resin; And / or, the polymerization inhibitor is one or more of hydroquinone, 2,5-di-tert-butylhydroquinone, methylhydroquinone, p-benzoquinone, and 4-tert-butylcatechol, and the mass of the polymerization inhibitor is 0.01-0.08% of the mass of the vinyl ester resin.

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

1.

6. The stone block coating adhesive according to claim 5, characterized in that: The mass ratio of the component A to the component B is 100:1-5.

7. The method for preparing the stone block coating adhesive according to any one of claims 1 to 6, characterized in that: include: The raw materials of the component A and the component B are mixed separately to obtain the component A and the component B, and they are mixed in proportion before construction.

8. The method for preparing stone block coating adhesive according to claim 7, characterized in that: The steps of preparing the A component include: mixing a vinyl ester resin, an inhibitor, an accelerator and a hardener, heating to 80-85° C., controlling the speed at 500-1000 rpm, and stirring for 10-15 minutes; then adding the remaining materials, controlling the speed at 1300-1500 rpm, stirring for 20-25 minutes, and then ultrasonically shaking for 20-30 minutes.

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