Bi-component ceramic tile repairing glue for ceramic tile hollowing and warping micropore glue injection repairing and preparation method thereof

Abstract

The invention provides a bi-component ceramic tile repair adhesive for ceramic tile hollowing and warping micropore glue injection repair and a preparation method thereof. The bi-component ceramic tile repair adhesive comprises a component A and a component B, wherein in terms of 100 parts by weight, the component A comprises the following raw materials: 79-86 parts of composite epoxy resin, 12-18 parts of a reactive diluent and 2-3 parts of a silane coupling agent; the component B comprises the following raw materials in 100 parts by weight: 47-52 parts of a compound amine curing agent, 1.5-2.5 parts of an active diluent, 5-7 parts of epoxy resin, 5-8 parts of benzyl alcohol and the balance of active calcium carbonate. By optimizing the formula, the bi-component repairing adhesive is appropriate in viscosity, good in fluidity and long in operable time, the elongation at break of the bi-component repairing adhesive is further improved, and meanwhile the bi-component repairing adhesive is low in surface tension and has excellent bonding strength, high temperature resistance and water immersion resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of building materials, and particularly relates to a two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection and a preparation method thereof. Background Art

[0002] With the acceleration of urbanization and the rapid development of the construction industry, ceramic tiles, as a common building decoration material, are being used more and more widely. However, it is difficult to generate a good mechanical anchoring force when paving with cement mortar or cement-based tile adhesives. Problems such as hollowing, warping, and falling off often occur during use, seriously affecting the beauty and safety of the building. Traditional tile repair methods have many shortcomings, such as low bond strength, poor flexibility, and insufficient weather resistance, which make it difficult to meet the high requirements of modern buildings for tile repair. Therefore, the introduction of repair adhesives based on epoxy resin systems can overcome the above shortcomings and thus improve the overall performance of tile repair adhesives.

[0003] In recent years, with the continuous advancement of materials science, two-component tile repair adhesives have gradually become an effective means of solving problems such as tile hollowing and warping due to their excellent performance. Two-component tile repair adhesives are typically composed of component A and component B. Component A primarily provides adhesion and flexibility, while component B provides curing and strength. This two-component structure allows the repair adhesive to better adapt to the characteristics of the tile and substrate during application, thereby improving the repair effect.

[0004] Chinese patent CN 114262588 B discloses a tile hollowing glue, its raw material composition, preparation method and application. The raw material composition of the tile hollowing glue includes: rosin resin and / or modified rosin resin, modified styrene-acrylic resin, adhesion enhancer, shrinkage reducer, defoamer, preservative, surfactant, plastic expansion agent, PVA glue, starch ether, nano-calcium carbonate, propylene glycol and water. The tile hollowing glue prepared by this invention is based on acrylic emulsion, which results in relatively low bonding strength.

[0005] Therefore, there is an urgent need for a two-component tile repair adhesive for repairing hollow tiles, warping and microporous glue injection, so that the bonding strength of the tile repair adhesive is good. Summary of the Invention

[0006] In response to existing technical problems, the present invention aims to provide a two-component tile repair adhesive for microporous adhesive injection repair of hollowed, warped tiles, and a preparation method thereof. By optimizing the formulation, the present invention achieves optimal viscosity, good fluidity, and a long workable time for the two-component repair adhesive, further improving its elongation at break. Furthermore, the two-component repair adhesive exhibits low surface tension, excellent bonding strength, high-temperature resistance, and water resistance.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On the one hand, the present invention provides a two-component tile repair adhesive for repairing hollow, warped and microporous tiles by glue injection. The two-component tile repair adhesive includes a component A and a component B. Component A comprises the following raw materials, based on 100 parts by weight: 79-86 parts of a composite epoxy resin, 12-18 parts of a reactive diluent, and 2-3 parts of a silane coupling agent. Component B comprises the following raw materials, based on 100 parts by weight: 47-52 parts of a composite amine curing agent, 1.5-2.5 parts of a reactive diluent, 5-7 parts of an epoxy resin, 5-8 parts of benzyl alcohol, and the balance is activated calcium carbonate.

[0009] Preferably, the mass ratio of component A to component B is 1:(0.9-1.1).

[0010] The reaction mechanism and effects of the present invention are as follows:

[0011] 1. The present invention introduces an epoxy resin-based repair adhesive to overcome the problem of poor bonding strength. However, epoxy resin-based repair adhesives still suffer from high viscosity and poor fluidity, resulting in poor elongation at break. Therefore, the present invention's component A uses a combination of bisphenol A epoxy resin and bisphenol F epoxy resin in a specific mass ratio. Bisphenol A epoxy resin has good mechanical properties, but high viscosity. If only bisphenol A epoxy resin is used, the fluidity of the tile repair adhesive will be poor. Bisphenol F epoxy resin has lower viscosity and, after curing, better solvent resistance than bisphenol A epoxy resin. The combination of these two epoxy resins can synergistically improve the mechanical properties and operability of the final product.

[0012] 2. The present invention prepares a novel alicyclic amine curing agent. On the one hand, the amino group on the alicyclic amine curing agent reacts with the epoxy group to improve the bonding strength. In addition, the applicant controls the mass ratio between the complex amine curing agents to produce a synergistic effect between the alicyclic amine curing agent and the polyetheramine curing agent. This not only achieves a perfect balance between the hardness and flexibility of the adhesive, but also significantly improves the curing speed of the epoxy resin, achieving rapid curing even at lower temperatures, thereby expanding the curing temperature range of the epoxy resin, accelerating the curing process, and making the application of the epoxy resin more flexible and extensive.

[0013] On the other hand, the applicant's introduction of dynamic disulfide bonds into the molecular structure of the alicyclic amine curing agent may also impart self-healing properties to the adhesive system. Compared with traditional static cross-linking structures, the dynamic cross-linking network can better disperse external forces. When external forces act on the repair adhesive, the dynamic disulfide bonds can undergo dynamic changes, allowing the molecular chains to slide and rearrange to a certain extent, thereby absorbing more energy, improving the repair adhesive's ability to resist deformation and damage, and enhancing its toughness and impact resistance. At the same time, the functional groups contained in the molecular structure of the synthesized alicyclic amine curing agent can form a more stable cross-linking network with the epoxy resin, thereby improving the chemical and temperature resistance of the cured product, making it more stable in chemical environments, and improving the performance of epoxy resin-based repair adhesives in high-temperature environments.

[0014] 3. Calcium carbonate's high specific surface area and surface-active groups increase its contact area with organic polymers, forming physical entanglements and chemical bonds, thereby enhancing the reinforcement of tile repair adhesives. However, calcium carbonate is prone to poor dispersibility. The present invention pre-treats calcium carbonate and modifies it with stearic acid to improve its dispersibility in organic media, ensuring its uniform distribution within the tile repair adhesive, thereby enhancing its overall performance.

[0015] 4. The tile repair adhesive of the present invention has a low surface tension. When used to repair hollow tiles, the low surface tension facilitates better spreading of the adhesive in the tiny pores and hollow areas between the tile and the substrate, improving its permeability and wettability.

[0016] On the one hand, both components A and B contain active diluents (glycidyl ethers), which have low surface tension and can reduce the surface tension of the entire repair adhesive system. At the same time, component A contains a silane coupling agent composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane, which contains groups (such as amino and epoxy groups) that can bind to inorganic and organic materials. This can reduce the interfacial tension between the organic phase (organic components such as epoxy resin) and the inorganic phase (activated calcium carbonate, ceramic tiles, etc.), thereby forming a bridge at the organic-inorganic interface, making the bond between the organic and inorganic phases tighter and improving wettability.

[0017] On the other hand, the amino groups in the molecular structure of alicyclic amine curing agents also have structural characteristics that can reduce surface tension. Furthermore, during the preparation of activated calcium carbonate, the calcium carbonate is treated with sodium hydroxide and stearic acid. The organic coating on the surface can reduce the interfacial tension between the calcium carbonate and organic components such as epoxy resin, allowing the activated calcium carbonate to be better dispersed in the repair adhesive system, thereby improving the overall wetting of the repair adhesive on the tile surface.

[0018] In some embodiments, the composite epoxy resin in component A is a combination of bisphenol A epoxy resin and bisphenol F epoxy resin.

[0019] Preferably, the mass ratio of the bisphenol A epoxy resin to the bisphenol F epoxy resin is 10:(0.5-1.5).

[0020] In some embodiments, the reactive diluent is any one or more of n-butyl glycidyl ether, benzyl glycidyl ether, and allyl glycidyl ether.

[0021] In some embodiments, the silane coupling agent in component A is γ-aminopropyltriethoxysilane and / or γ-glycidoxypropyltrimethoxysilane.

[0022] Preferably, the silane coupling agent in component A is a combination of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0023] Further preferably, the mass ratio of the γ-aminopropyltriethoxysilane to the γ-glycidyloxypropyltrimethoxysilane is 1:1.

[0024] In some embodiments, the method for preparing activated calcium carbonate comprises the following steps:

[0025] Mix calcium carbonate and water, heat to 60-80°C, stir, add sodium hydroxide and stearic acid, mix and shake to obtain activated calcium carbonate.

[0026] Preferably, the mass ratio of calcium carbonate to stearic acid is 1:0.2.

[0027] In some embodiments, the complex amine curing agent in component B is a combination of a polyetheramine curing agent and an alicyclic amine curing agent.

[0028] Preferably, the mass ratio of the complex amine curing agent in component B is 1:(1.7-2.1) between the polyetheramine curing agent and the alicyclic amine curing agent.

[0029] More preferably, the polyetheramine curing agent is amino-terminated polyether.

[0030] In some embodiments, the method for preparing the alicyclic amine curing agent comprises the following steps:

[0031] Q1. Add ethylenediamine and 4,4'-dicyclohexanone to a reactor, stir, and heat to 40-50°C. Add an aqueous solution of n-valeraldehyde, continue stirring, and heat to 80-95°C. Keep the temperature for 2-5 hours, then distill under reduced pressure to obtain the reactant.

[0032] Q2. The reactants obtained in step Q1, 3-[(2-aminoethyl)dithio]propionic acid and p-toluenesulfonic acid are added to a reactor, stirred and heated to 70-90°C, reacted at a constant temperature for 3-5h, and distilled under reduced pressure and purified to obtain an alicyclic amine curing agent.

[0033] In some embodiments, the molar ratio of ethylenediamine, cyclohexanone and n-valeraldehyde in step Q1 is (2-2.3):1:(2-2.4).

[0034] In some embodiments, the mass ratio of the reactant to 3-[(2-aminoethyl)dithio]propionic acid in step Q2 is 1:(0.8-0.9).

[0035] Another aspect of the present invention provides a method for preparing a two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection, comprising the following steps:

[0036] S1. The composite epoxy resin, reactive diluent, and silane coupling agent are mixed and stirred for 1-2h to obtain component A;

[0037] S2. Mix the complex amine curing agent and benzyl alcohol and stir evenly, then heat to 70-90°C, add the reactive diluent and epoxy resin, stir and react for 2-3 hours, and then add activated calcium carbonate and stir for 1-2 hours to obtain component B.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. The present invention optimizes the formula to make the two-component tile repair adhesive have appropriate viscosity, good fluidity, and long operating time, further improving the elongation at break of the two-component repair adhesive. At the same time, the two-component repair adhesive of the present invention has low surface tension and excellent bonding strength, high temperature resistance and water immersion resistance.

[0040] 2. The two-component tile repair adhesive of the present invention uses a millimeter-level drill bit to drill holes in the tiles, and a special grouting machine is used to inject the tile repair adhesive. The gaps are then blocked with toothpicks, and the holes are filled with color repair paste after the surface is dry. This method has low maintenance costs and high efficiency. The tiles can be restored to use after curing for about 2 hours, while achieving good repairability and durability.

[0041] 3. The alicyclic amine curing agent and polyether curing agent prepared by the present invention will produce a synergistic reaction, and the introduction of dynamic disulfide bonds on the alicyclic amine curing agent may also give the adhesive system self-healing characteristics; in addition, the stable cross-linked network formed by the curing agent improves the chemical resistance and temperature resistance of the cured product.

[0042] 4. The present invention uses the combined action of the active diluent, the silane coupling agent, the activated calcium carbonate and the alicyclic amine curing agent to ensure that the tile repair adhesive has low surface tension and good wettability. DETAILED DESCRIPTION

[0043] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention, not to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0044] According to the ratios of the raw materials and the preparation methods specified in the following examples and comparative examples, two-component tile repair adhesives were prepared.

[0045] In order to facilitate those skilled in the art to implement the present invention, some raw material manufacturers of the embodiments and comparative examples are described as follows:

[0046] Calcium carbonate: 1500 mesh;

[0047] Bisphenol A epoxy resin: purchased from Nanya Electronic Materials (Kunshan) Co., Ltd., model: epoxy resin E51, epoxy equivalent weight: 184-190 g / mol;

[0048] Bisphenol F epoxy resin: purchased from Shenzhen Longdi Chemical Co., Ltd., model: epoxy resin NPEF-170, epoxy equivalent weight 160-180 g / mol;

[0049] Polyetheramine: amino-terminated polyether ZM-1207, purchased from Zibo Zhengda Polyurethane Co., Ltd.;

[0050] Unless otherwise specified, other raw materials can be purchased from the market.

[0051] Preparation Example 1

[0052] The preparation method of alicyclic amine curing agent-1 comprises the following steps:

[0053] Q1. 1.1 mol of n-valeraldehyde was dispersed in distilled water to obtain a 35 wt% aqueous solution of n-valeraldehyde. 1.1 mol of ethylenediamine and 0.5 mol of cyclohexanone were added to a reactor, stirred, and heated to 45°C. The prepared aqueous solution of n-valeraldehyde was then added in two portions at half-hour intervals. The mixture was stirred and heated to 85°C. The reaction was maintained at this temperature for 3.5 hours, and then distilled under reduced pressure at 100°C to obtain the reactant.

[0054] Q2. 100 g of the reactant obtained in step Q1, 85 g of 3-[(2-aminoethyl)disulfide]propionic acid and 7 g of p-toluenesulfonic acid were added to a reactor, stirred and heated to 80 ° C. The reaction was kept at this temperature for 4 h, and the mixture was distilled under reduced pressure at 100 ° C., purified, and cooled to room temperature to obtain alicyclic amine curing agent-1.

[0055] Preparation Example 2

[0056] The preparation method of alicyclic amine curing agent-2 is the same as that of Preparation Example 1, except that 0.55 mol of ethylenediamine is added in step Q1.

[0057] Preparation Example 3

[0058] The preparation method of alicyclic amine curing agent-3 is the same as that of Preparation Example 1, except that 60 g of 3-[(2-aminoethyl)dithio]propionic acid is added in step Q3.

[0059] Preparation Example 4

[0060] The preparation method of activated calcium carbonate comprises the following steps:

[0061] Mix 10 g of calcium carbonate and 100 mL of water, heat to 70° C. and stir for 1 h, add 0.05 g of sodium hydroxide and 2 g of stearic acid, mix and shake for 30 min to obtain activated calcium carbonate.

[0062] Example 1

[0063] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection, the two-component tile repair adhesive comprises component A and component B, the mass ratio of the two components being 1:1; wherein,

[0064] Calculated by weight in 100 parts, the component A comprises the following raw materials: 82.5 parts of composite epoxy resin, 15 parts of n-butyl glycidyl ether, and 2.5 parts of silane coupling agent; calculated by weight in 100 parts, the component B comprises the following raw materials: 50 parts of composite amine curing agent, 2 parts of n-butyl glycidyl ether, 6 parts of epoxy resin NPEF-170, 6.5 parts of benzyl alcohol, and the balance is activated calcium carbonate;

[0065] The composite epoxy resin consists of epoxy resin E51 and epoxy resin NPEF-170 in a mass ratio of 10:1;

[0066] The silane coupling agent is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:1;

[0067] The composite amine curing agent is composed of amino-terminated polyether ZD-123 and alicyclic amine curing agent-1 in a mass ratio of 1:1.9.

[0068] The preparation method of the two-component tile repair adhesive of this embodiment comprises the following steps:

[0069] S1. The composite epoxy resin, n-butyl glycidyl ether, and silane coupling agent were mixed and stirred for 1.5 h to obtain component A;

[0070] S2. Mix the complex amine curing agent and benzyl alcohol and stir them evenly, then heat to 80°C. Then add n-butyl glycidyl ether and epoxy resin NPEF-170 and stir to react for 2.5 hours. Then, add activated calcium carbonate and stir for 1.5 hours to obtain component B.

[0071] Example 2

[0072] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection, the two-component tile repair adhesive comprises component A and component B, the mass ratio of the two components being 1:1; wherein,

[0073] Calculated by weight, the A component contains the following raw materials: 79 parts of composite epoxy resin, 12 parts of n-butyl glycidyl ether, and 2 parts of silane coupling agent; calculated by weight, the B component contains the following raw materials: 47 parts of composite amine curing agent, 1.5 parts of n-butyl glycidyl ether, 5 parts of epoxy resin NPEF-170, 5 parts of benzyl alcohol, and the balance is activated calcium carbonate;

[0074] The composite epoxy resin is composed of epoxy resin E51 and epoxy resin NPEF-170 in a mass ratio of 10:0.5;

[0075] The silane coupling agent is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:1;

[0076] The composite amine curing agent is composed of amino-terminated polyether ZD-123 and alicyclic amine curing agent-1 in a mass ratio of 1:1.7.

[0077] The preparation method of the two-component tile repair adhesive of this embodiment comprises the following steps:

[0078] S1. The composite epoxy resin, n-butyl glycidyl ether, and silane coupling agent were mixed and stirred for 1 h to obtain component A;

[0079] S2. Mix the complex amine curing agent and benzyl alcohol and stir them evenly, then heat to 90°C, add n-butyl glycidyl ether and epoxy resin NPEF-170, stir and react for 2 hours, and then add activated calcium carbonate and stir for 2 hours to obtain component B.

[0080] Example 3

[0081] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection, the two-component tile repair adhesive comprises component A and component B, the mass ratio of the two components being 1:1; wherein,

[0082] Calculated in parts by weight, the component A comprises the following raw materials: 86 parts of composite epoxy resin, 18 parts of n-butyl glycidyl ether, and 3 parts of silane coupling agent; calculated in parts by weight, the component B comprises the following raw materials: 52 parts of composite amine curing agent, 2.5 parts of n-butyl glycidyl ether, 7 parts of epoxy resin NPEF-170, 8 parts of benzyl alcohol, and the balance is activated calcium carbonate;

[0083] The composite epoxy resin is composed of epoxy resin E51 and epoxy resin NPEF-170 in a mass ratio of 10:1.5;

[0084] The silane coupling agent is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:1;

[0085] The composite amine curing agent is composed of amino-terminated polyether ZD-123 and alicyclic amine curing agent-1 in a mass ratio of 1:2.1.

[0086] The preparation method of the two-component tile repair adhesive of this embodiment comprises the following steps:

[0087] S1. The composite epoxy resin, n-butyl glycidyl ether, and silane coupling agent were mixed and stirred for 2 h to obtain component A;

[0088] S2. Mix the complex amine curing agent and benzyl alcohol and stir them evenly, then heat to 70°C, add n-butyl glycidyl ether and epoxy resin NPEF-170, stir and react for 3 hours, and then add activated calcium carbonate and stir for 1 hour to obtain component B.

[0089] Example 4

[0090] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of alicyclic amine curing agent-2 is used instead of alicyclic amine curing agent-1.

[0091] Example 5

[0092] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of alicyclic amine curing agent-3 is used instead of alicyclic amine curing agent-1.

[0093] Comparative Example 1

[0094] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of epoxy resin E51 is used in component A instead of composite epoxy resin.

[0095] Comparative Example 2

[0096] A two-component tile repair adhesive for repairing hollow, warped and microporous tiles by injection and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of amino-terminated polyether ZD-123 is used in component B to replace the complex amine curing agent.

[0097] Comparative Example 3

[0098] A two-component tile repair adhesive for repairing hollow, warped, and microporous tiles by injection and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of calcium carbonate is used instead of activated calcium carbonate.

[0099] Effect evaluation:

[0100] The two-component tile repair adhesives prepared in Examples 1-5 and Comparative Examples 1-3 were tested and analyzed, and the specific results are shown in Table 1.

[0101] Performance testing:

[0102] 1. Component A and component B of the two-component tile repair adhesive obtained in each embodiment and comparative example were mixed in a mass ratio of 1:1 and then the following tests were performed:

[0103] (1) Flexibility: Elongation at break is tested according to GB / T 16777-2008;

[0104] (2) Bond strength: The tensile shear bond strength was tested according to the method specified in 6.6 of the JC887-2001 standard. The substrates of the bonding specimens were tested according to the provisions of 6.1.2.2 of the standard, and the specimens were prepared according to the provisions of 6.1.3 of the standard for tensile shear bonding specimens.

[0105] (3) High temperature resistance: The tensile shear bond strength after thermal aging treatment is carried out in accordance with 6.7.3 of JC887-2001 standard;

[0106] (4) Water immersion resistance: The tensile shear bond strength after water immersion treatment shall be tested in accordance with 6.7.2 of JC887-2001 standard.

[0107] Table 1

[0108]

[0109]

[0110] From the results in Table 1, it can be seen that the two-component tile repair adhesives of Examples 1-3 have good elongation at break, and also have excellent tensile shear bonding strength, high temperature resistance, water immersion resistance, and wet adhesive strength.

[0111] In Example 4, an equal amount of alicyclic amine curing agent-2 was used to replace alicyclic amine curing agent-1, and the molar ratio of ethylenediamine, cyclohexanone and n-valeraldehyde was changed, thereby reducing the amino group. In Example 5, an equal amount of alicyclic amine curing agent-3 was used to replace alicyclic amine curing agent-1, and the mass ratio of 3-[(2-aminoethyl)disulfide]propionic acid to the reactants was changed, thereby reducing the elongation at break of the two-component tile repair adhesive and having a certain impact on its tensile shear bond strength, high temperature resistance and water immersion resistance.

[0112] In Comparative Example 1, an equal amount of epoxy resin E51 was used to replace the composite epoxy resin, resulting in excessive viscosity. In Comparative Example 2, an equal amount of amino-terminated polyether ZD-123 was used to replace the composite amine curing agent, which reduced the flexibility of the repair glue. In Comparative Example 3, an equal amount of calcium carbonate was used to replace the activated calcium carbonate, resulting in poor dispersibility. All of these factors will affect the elongation at break, tensile bonding strength, high temperature resistance, and water resistance of the two-component tile repair glue.

[0113] 2. Component A and component B of the two-component tile repair adhesive obtained in Examples 1-3 were mixed in a mass ratio of 1:1 and then subjected to the following tests. The specific results are shown in Table 2:

[0114] (1) Fluidity: The initial fluidity of the tile repair adhesive at 25°C and the fluidity after mixing and stirring for 10 minutes were tested according to the JC / T 985-2017 standard;

[0115] (2) Adhesion strength to wet substrate: The test was conducted in accordance with JC / T 2217-2014. The wet substrate test specimens were prepared in accordance with 7.9.2.2 of the standard.

[0116] Table 2

[0117]

[0118]

[0119] As can be seen from Table 2, the tile repair adhesives of Examples 1-3 have good bonding strength to the wet base surface and good fluidity, which is conducive to the application of tile adhesives in actual production.

[0120] The above is only a preferred embodiment of the present invention and does not limit the present application in any form. Although the present application is disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any technician familiar with this profession, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the technical content disclosed above, which are equivalent to equivalent implementation cases. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection, characterized in that: The two-component tile repair adhesive includes component A and component B. Component A comprises the following raw materials, based on 100 parts by weight: 79-86 parts of a composite epoxy resin, 12-18 parts of a reactive diluent, and 2-3 parts of a silane coupling agent. Component B comprises the following raw materials, based on 100 parts by weight: 47-52 parts of a composite amine curing agent, 1.5-2.5 parts of a reactive diluent, 5-7 parts of an epoxy resin, 5-8 parts of benzyl alcohol, and the balance being activated calcium carbonate.

2. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 1 is characterized in that: The composite epoxy resin in component A is a composition of bisphenol A epoxy resin and bisphenol F epoxy resin.

3. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 1, characterized in that: The active diluent is any one or more of n-butyl glycidyl ether, benzyl glycidyl ether and allyl glycidyl ether.

4. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 1, characterized in that: The silane coupling agent in component A is γ-aminopropyltriethoxysilane and / or γ-glycidyloxypropyltrimethoxysilane.

5. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 1, characterized in that: The preparation method of the activated calcium carbonate comprises the following steps: Mix calcium carbonate and water, heat to 60-80°C, stir, add sodium hydroxide and stearic acid, mix and shake to obtain activated calcium carbonate.

6. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 1, characterized in that: The complex amine curing agent in component B is a composition of a polyetheramine curing agent and an alicyclic amine curing agent.

7. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 6, characterized in that: The preparation method of the alicyclic amine curing agent comprises the following steps: Q1. Add ethylenediamine and 4,4'-dicyclohexanone to a reactor, stir, and heat to 40-50°C. Add an aqueous solution of n-valeraldehyde, continue stirring, and heat to 80-95°C. Keep the temperature for 2-5 hours, then distill under reduced pressure to obtain the reactant. Q2. The reactants obtained in step Q1, 3-[(2-aminoethyl)dithio]propionic acid and p-toluenesulfonic acid are added to a reactor, stirred and heated to 70-90°C, reacted at a constant temperature for 3-5h, and distilled under reduced pressure and purified to obtain an alicyclic amine curing agent.

8. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 7, characterized in that: The molar ratio of ethylenediamine, cyclohexanone and n-valeraldehyde in step Q1 is (2-2.3):1:(2-2.4).

9. The two-component tile repair adhesive for repairing hollow and warped tiles with microporous glue injection according to claim 7, characterized in that: The mass ratio of the reactant in step Q2 to 3-[(2-aminoethyl)dithio]propionic acid is 1:(0.8-0.9).

10. A method for preparing a two-component tile repair adhesive for repairing hollow and warped tiles by microporous glue injection according to any one of claims 1 to 9, characterized in that: The following steps are included: S1. The composite epoxy resin, reactive diluent, and silane coupling agent are mixed and stirred for 1-2h to obtain component A; S2. Mix the complex amine curing agent and benzyl alcohol and stir evenly, then heat to 70-90°C, add the reactive diluent and epoxy resin, stir and react for 2-3 hours, and then add activated calcium carbonate and stir for 1-2 hours to obtain component B.

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