Ammonia-free ceramic tile back coating interface agent emulsion with high initial adhesion and high bonding strength

Abstract

The invention relates to the technical field of emulsion synthesis, and provides an ammonia-free ceramic tile back coating interface agent emulsion with high initial adhesion and high bonding strength. Comprising the following raw materials in parts by weight: 65 to 75 parts of styrene, 370 to 390 parts of n-butyl acrylate, 25 to 35 parts of 2-ethylhexyl acrylate, 7 to 8.5 parts of acrylic acid, 14 to 17 parts of hydroxyethyl methylacrylate, 2.5 to 4 parts of a coupling agent, 2.5 to 4 parts of hydroxyethyl acrylate, 0.5 to 0.7 part of a phosphate monomer, 2.1 to 2.4 parts of an initiator, 2.6 to 3.5 parts of an emulsifier A, 2.8 to 3.5 parts of an emulsifier B, 6 to 7.3 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 to 1 part of a defoaming agent and 0.5 to 5 parts of a bactericide. 0.5 part of dodecanol ester and 440 parts of water; the emulsifier A contains EO number, and the emulsifier B does not contain EO number. According to the technical scheme, the problems of low initial adhesion, low bonding strength and high ammonia content of the ceramic tile back coating interface agent emulsion in the prior art are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of emulsion synthesis, and specifically, to a high-initial-tack and high-bonding-strength ammonia-free tile back-coating interface agent emulsion. Background Art

[0002] In the field of modern architectural decoration, as a beautiful, durable and easy-to-clean decorative material, tiles are widely used in the interior and exterior wall decoration of various buildings and floor laying projects. Tile products are gradually developing towards lower water absorption rate and larger size, and ceramic thin tiles, vitrified tiles, marbles, and large slab rocks are widely used. Traditional cement mortar materials will produce dry shrinkage cracks during the hardening process, and have low bonding performance, which is easy to cause tile hollowing and falling off, and cannot meet the paving requirements. For interior wall or floor tiles with side length > 600mm, using C2 type tile adhesive for paving has a high overall paving cost.

[0003] As a new type of tile adhesive material, tile back glue is a product of polymer emulsion material. Because it has a high bonding strength, and the flexible back glue layer as a transition layer can greatly reduce the stress between the rigid mortar layer and the tile layer, it can effectively solve the common problems of hollowing and falling off of floor tiles with low water absorption rate.

[0004] However, for the products currently used for tile back-coating interface agents on the market, the products with high initial tack have low bonding strength, which is easy to cause tile falling off, and the products with high bonding strength have low initial tack, resulting in problems such as poor initial adhesion and hollowing. Moreover, the ammonia content of most products is above 800mg / Kg. When tiles are pasted, ammonia substances volatilize, causing harm to construction workers and the environment. Therefore, it is very necessary to develop a high-initial-tack and high-bonding-strength ammonia-free tile back-coating interface agent emulsion. Summary of the Invention

[0005] The present invention provides a high-initial-tack and high-bonding-strength ammonia-free tile back-coating interface agent emulsion, which solves the problems of low initial tack, low bonding strength, and high ammonia content of the tile back-coating interface agent emulsion in the related art.

[0006] The technical solution of the present invention is as follows: The present invention provides a high-initial-tack and high-bonding-strength ammonia-free tile back-coating interfacial agent emulsion, which comprises the following raw materials in parts by weight: 65-75 parts of styrene, 370-390 parts of n-butyl acrylate, 25-35 parts of 2-ethylhexyl acrylate, 7-8.5 parts of acrylic acid, 14-17 parts of hydroxyethyl methacrylate, 2.5-4 parts of coupling agent, 2.5-4 parts of hydroxyethyl acrylate, 0.5-0.7 part of phosphate monomer, 2.1-2.4 parts of initiator, 2.6-3.5 parts of emulsifier A, 2.8-3.5 parts of emulsifier B, 6-7.3 parts of dodecyl diphenyl ether disulfonate, 0.1-1 part of defoamer, 0.5-5 parts of bactericide, 0.5 part of dodecyl alcohol ester, and 440 parts of water; the emulsifier A contains an EO number, and the emulsifier B does not contain an EO number.

[0007] As a further technical solution, the emulsifier A is Kao Emulsifier LATEMUL PD-105 from Japan, and the emulsifier B is Solvay SIPOMER COPS-1.

[0008] As a further technical solution, the coupling agent is a silane coupling agent, and the phosphate monomer is Solvay SIPOMER PAM-200.

[0009] As a further technical solution, the silane coupling agent is silane coupling agent A-151.

[0010] As a further technical solution, the defoamer is defoamer NXZ, and the bactericide is bactericide BIT20.

[0011] As a further technical solution, the initiator is sodium persulfate.

[0012] The present invention also provides a preparation method for the high-initial-tack and high-bonding-strength ammonia-free tile back-coating interfacial agent emulsion, which comprises the following steps: S1. Prepare materials according to the raw materials in the above parts by weight. S2. Divide the emulsifier B, water, and acrylic acid into two parts respectively to obtain the first emulsifier B and the second emulsifier B, the first water and the second water, the first acrylic acid and the second acrylic acid; configure the initiator into an initiator aqueous solution and then divide it into two parts to obtain the first initiator solution and the second initiator solution. S3. Add the dodecyl diphenyl ether disulfonate, emulsifier A, and the first emulsifier B into the first water and mix them, then add styrene, n-butyl acrylate, the first acrylic acid, and hydroxyethyl methacrylate for emulsification to obtain a pre-emulsion. S4. After adding the second emulsifier B to the second water and heating it to 80 - 85°C, first add a part of the pre-emulsion and mix it with the first initiator aqueous solution, then dropwise add the remaining pre-emulsion and the second initiator aqueous solution. During the dropping process, mix the coupling agent, 2-ethylhexyl acrylate, phosphate monomer, 2-hydroxyethyl acrylate, dodecyl alcohol ester, and the second acrylic acid into the remaining pre-emulsion, stir evenly, continue to dropwise add. After the dropping is completed, keep the temperature, cool down to 40 - 65°C, adjust the pH to alkaline, add an antifoaming agent and a bactericide, and filter to obtain the tile back coating interface agent emulsion; The part of the pre-emulsion accounts for 4% - 5% of the total mass of the pre-emulsion, preferably 4.5%.

[0013] As a further technical solution, the mass ratio of the first acrylic acid to the second acrylic acid is 6 - 7.5:1.

[0014] As a further technical solution, the mass ratio of the first emulsifier B to the second emulsifier B is 2 - 2.5:1.

[0015] As a further technical solution, the mass ratio of the first water to the second water is 34:54 - 37:51.

[0016] As a further technical solution, the mass ratio of the first initiator to the second initiator is 1.3 - 1.6:0.8.

[0017] As a further technical solution, the concentrations of the first initiator solution and the second initiator solution are both 10wt%.

[0018] As a further technical solution, the adjustment of the pH to alkaline is specifically: adjust the pH to 7.5 - 8.

[0019] As a further technical solution, the solution used for adjusting the pH is a sodium carbonate solution with a mass concentration of 15%.

[0020] The working principle and beneficial effects of the present invention are: In the present invention, during the polymerization process, emulsifier A and emulsifier B are used in combination. Emulsifier A containing EO number has the characteristics of both anionic and non-ionic emulsifiers, with the charge of an anionic emulsifier and the hydration layer of a non-ionic emulsifier. Hydrophilic monomers are not easily incorporated into the interior of latex particles and are more distributed on the surface of latex particles, making phase separation prone to occur, resulting in poor emulsification effect. More aqueous oligomers are formed by hydrophilic monomers, and the water resistance deteriorates. Emulsifier B does not contain EO number and is closer to anionic. Hydrophilic monomers are easily incorporated into the interior of latex particles, with less external distribution, and the latex particles become finer. It can be used as a polymerization stabilizer, having the effects of low-foam emulsion, reducing the dosage of surfactants, improving the emulsion stability and water resistance, but the particle stability and freeze-thaw stability are reduced, and the adhesion is reduced, leading to a decrease in bonding strength. In the present invention, emulsifier A and emulsifier B are added simultaneously and used in combination to exert their synergistic effects, further improving the initial adhesion strength and bonding strength of the tile back coating interface agent emulsion. Moreover, the emulsion product synthesized in the present invention does not contain APEO, and there is no formaldehyde, ammonia, or other pollution emissions. The product has good stability. In terms of key properties, it solves the problem that existing tile back adhesives cannot simultaneously achieve high initial tackiness and high bonding strength, and has the advantages of ammonia-free environmental protection and low water absorption. The final product has excellent performance and is green and environmentally friendly. Detailed implementation mode

[0021] The following will describe clearly and completely the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts fall within the scope of the present invention.

[0022] In the following examples and comparative examples: Emulsifier A: The model is Kao Emulsifier LATEMUL PD-105 from Japan; Emulsifier B: The model is Solvay SIPOMER COPS-1; Phosphate monomer: The model is Solvay SIPOMER PAM-200; Emulsifier 2A1 is sodium dodecyl diphenyl ether disulfonate.

[0023] Example 1 A preparation method of a high-initial-tack and high-bonding-strength ammonia-free tile back coating interface agent emulsion, comprising the following steps: S1. Add 3.5 parts of emulsifier A, 2 parts of emulsifier B, and 6 parts of emulsifier 2A1 to 185 parts of water. After stirring for 15 minutes, add 75 parts of styrene, 370 parts of n-butyl acrylate, 6 parts of acrylic acid, and 17 parts of 2-hydroxyethyl methacrylate, and stir for 20 minutes to obtain a pre-emulsion after emulsification; S2. Add 1 part of emulsifier B to 255 parts of water, heat up to 83°C, add the pre-emulsion obtained in step S1 (the addition amount is 4.5% of the mass of the pre-emulsion) and an aqueous sodium persulfate solution (1.3 parts of sodium persulfate, with a mass concentration of 10%). When the temperature stabilizes at 83°C again, continue to dropwise add the remaining pre-emulsion and an aqueous sodium persulfate solution (0.8 part of sodium persulfate, with a mass concentration of 10%). The dropping time is 210 min. When it is dropped for 170 min, add 4 parts of silane coupling agent A-151, 35 parts of 2-ethylhexyl acrylate, 0.7 part of phosphate functional monomer SIPOMER PAM-200, 3.5 parts of hydroxyethyl acrylate, 0.5 part of dodecyl alcohol ester and 1 part of acrylic acid to the remaining pre-emulsion, stir evenly, continue to dropwise add. After the dropping is completed, keep warm for 30 min. First cool down to 65°C, then cool down to 40°C, adjust the pH to 7.5 with a sodium carbonate solution with a mass concentration of 15%, add 0.1 part of defoaming agent NXZ and 0.5 part of fungicide BIT20, and filter to obtain the tile back-coating interface agent emulsion.

[0024] Example 2 A preparation method of a high initial adhesion and high bonding strength ammonia-free tile back-coating interface agent emulsion, comprising the following steps: S1. Add 3 parts of emulsifier A, 2.5 parts of emulsifier B and 7 parts of emulsifier 2A1 to 180 parts of water, stir for 15 min, then add 70 parts of styrene, 380 parts of n-butyl acrylate, 7 parts of acrylic acid and 15 parts of 2-hydroxyethyl methacrylate, and stir for 20 min to obtain a pre-emulsion after emulsification; S2. Add 1 part of emulsifier B to 260 parts of water, heat up to 83°C, add the pre-emulsion obtained in step S1 (the addition amount is 4.5% of the mass of the pre-emulsion) and an aqueous sodium persulfate solution (1.5 parts of sodium persulfate, with a mass concentration of 10%). After the addition, when the temperature stabilizes at 83°C again, continue to dropwise add the remaining pre-emulsion and an aqueous sodium persulfate solution (0.8 part of sodium persulfate, with a mass concentration of 10%). The dropping time is 210 min. When it is dropped for 170 min, add 3 parts of silane coupling agent A-151, 30 parts of 2-ethylhexyl acrylate, 0.6 part of phosphate functional monomer SIPOMER PAM-200, 3 parts of hydroxyethyl acrylate, 0.5 part of dodecyl alcohol ester and 1 part of acrylic acid to the remaining pre-emulsion, stir evenly, continue to dropwise add. After the dropping is completed, keep warm for 30 min. First cool down to 65°C, then cool down to 40°C, adjust the pH to 7.8 with a sodium carbonate solution with a mass concentration of 15%, add 0.5 part of defoaming agent NXZ and 3 parts of fungicide BIT20, and filter to obtain the tile back-coating interface agent emulsion.

[0025] Example 3 A preparation method of a high initial adhesion and high bonding strength ammonia-free tile back-coating interface agent emulsion, comprising the following steps: S1. Add 2.6 parts of emulsifier A, 2 parts of emulsifier B and 7.3 parts of emulsifier 2A1 into 170 parts of water. After stirring for 15 min, add 65 parts of styrene, 390 parts of n-butyl acrylate, 7.5 parts of acrylic acid and 14 parts of 2-hydroxyethyl methacrylate, and stir for 20 min to obtain a pre-emulsion after emulsification. S2. Add 0.8 part of emulsifier B into 270 parts of water, heat up to 83 °C, add the pre-emulsion obtained in step S1 (the addition amount is 4.5% of the mass of the pre-emulsion) and an aqueous solution of sodium persulfate (1.6 parts of sodium persulfate, with a mass concentration of 10%). After the addition is completed, when the temperature stabilizes at 83 °C again, continue to dropwise add the remaining pre-emulsion and an aqueous solution of sodium persulfate (0.8 part of sodium persulfate, with a mass concentration of 10%). The dropping time is 210 min. When it is dropped for 170 min, add 2.5 parts of silane coupling agent A-151, 25 parts of 2-ethylhexyl acrylate, 0.5 part of phosphate functional monomer SIPOMER PAM-200, 2.5 parts of 2-hydroxyethyl acrylate, 0.5 part of dodecyl alcohol ester and 1 part of acrylic acid to the remaining pre-emulsion, stir evenly, continue to dropwise add, and keep the temperature for 30 min after the dropping is completed. First cool down to 65 °C, then cool down to 40 °C, adjust the pH to 8 with a sodium carbonate solution with a mass concentration of 15%, add 1 part of defoaming agent NXZ and 5 parts of fungicide BIT20, and filter to obtain the tile back coating interface agent emulsion.

[0026] Example 4 Compared with Example 2, the difference in Example 4 is that emulsifier A is replaced with an equal amount of emulsifier Rhenafac ELT 300-30EO.

[0027] Example 5 Compared with Example 2, the difference in Example 5 is that emulsifier B is replaced with an equal amount of emulsifier SVS.

[0028] Comparative Example 1 Compared with Example 2, the difference in Comparative Example 1 is that emulsifier B is replaced with an equal amount of emulsifier A.

[0029] Comparative Example 2 Compared with Example 2, the difference in Comparative Example 2 is that emulsifier A is replaced with an equal amount of emulsifier B. Since emulsifier B has no emulsifying effect and cannot emulsify the monomers, it cannot be used alone, and no test data is available.

[0030] Comparative Example 3 Compared with Example 2, the difference in Comparative Example 3 is that emulsifier A and emulsifier B are replaced with an equal amount of sodium dodecylbenzenesulfonate.

[0031] Comparative Example 4 Compared with Example 2, the difference in Comparative Example 4 is that emulsifier A and emulsifier B are replaced with an equal amount of emulsifier SR-10.

[0032] The tile back-coating interface agent emulsions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were tested according to the following test methods: 1. Initial adhesion: The test conditions were 23°C and a humidity of 50%. The test method was as follows: A1. Clean the glass plate and the film applicator, and dry them for later use. A2. Place the prepared glass plate on a horizontal tabletop, and use a 100-μm film applicator to form a uniform coating film of the back-coating adhesive. A3. Place the glass plate in A2 horizontally in an oven at 40°C and dry for 30 min. After taking it out, place it in a standard curing room and cool it to room temperature for 1 h for later use. A4. Join a blank glass with the glass plate in A3 and place it on a horizontally adjusted tabletop. Confirm the "0 point" on the coating film of the back adhesive; align the front end of the initial adhesion tester with the "0 point"; before each test, wipe the #14 steel ball clean with an alcohol cotton ball and then start the test. Each sample was tested 5 times repeatedly. A5. Measure the distance that the steel ball moves on the back adhesive, and take the average value of the 5 test results as the initial adhesion.

[0033] 2. Bonding strength: According to the test method specified in JC / T 547-2017 "Ceramic Tile Adhesives", test the conventional bonding strength, the bonding strength after immersion in water, the bonding strength after heat aging, and the bonding strength after freeze-thaw cycles of the test specimens; the temperature of immersion in water was 23°C and the immersion time was 7 d; the temperature of heat aging was 70°C and the aging time was 14 d; the conditions of freeze-thaw cycles refer to the conditions of the tensile bonding strength after freeze-thaw cycles in the standard: each freeze-thaw cycle was to take out the test piece from water, cool it to -15°C within 2 h, keep it for 2 h, then immerse it in water at a temperature of 20°C, heat it up to 15°C, and before the next freeze-thaw cycle, cure it at 15°C for 2 h, and repeat 25 cycles.

[0034] 3. Water absorption rate of the emulsion film: Coat the emulsion on a glass plate, weigh it after drying, wipe the surface moisture after immersion in water and then weigh it again, and calculate the water absorption rate: Water absorption rate = (mass after immersion in water - original mass) / original mass × 100%.

[0035] The commercially available emulsion in the table is XG-9166.

[0036] The test results are shown in Table 1: Table 1 Performance test results of the tile back-coating interface agent emulsions prepared in Examples 1 to 5 and Comparative Examples 1 to 4

[0037] As can be seen from Table 1, the adhesive prepared from the tile back-coating interface agent emulsion provided by the present invention has good initial adhesion and bonding strength, indicating that emulsifier A and emulsifier B play a synergistic role, which can further improve the initial adhesion strength and bonding strength of the tile back-coating interface agent emulsion.

[0038] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion, characterized in that: The invention comprises the following raw materials in parts by weight: 65-75 parts of styrene, 370-390 parts of n-butyl acrylate, 25-35 parts of 2-ethylhexyl acrylate, 7-8.5 parts of acrylic acid, 14-17 parts of hydroxyethyl methacrylate, 2.5-4 parts of coupling agent, 2.5-4 parts of hydroxyethyl acrylate, 0.5-0.7 parts of phosphate monomer, 2.1-2.4 parts of initiator, 2.6-3.5 parts of emulsifier A, 2.8-3.5 parts of emulsifier B, 6-7.3 parts of sodium dodecyl diphenyl oxide disulfonate, 0.1-1 parts of defoamer, 0.5-5 parts of bactericide, 0.5 parts of dodecyl alcohol ester and 440 parts of water; the emulsifier A contains EO, and the emulsifier B does not contain EO.

2. The high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 1, characterized in that: The model of the emulsifier A is Japanese Kao emulsifier LATEMUL PD-105, and the model of the emulsifier B is Solvay SIPOMER COPS-1.

3. The high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 1, characterized in that: The coupling agent is a silane coupling agent, and the phosphate monomer is Solvay SIPOMER PAM-200.

4. The high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 1, characterized in that: The defoamer is defoamer NXZ, and the bactericide is bactericide BIT20.

5. A method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion, which is used to prepare a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: S1, preparing the raw materials according to the weight portions; S2, dividing the emulsifier B, water, and acrylic acid into two parts, respectively obtaining a first emulsifier B and a second emulsifier B, a first water and a second water, a first acrylic acid and a second acrylic acid; configuring the initiator into an initiator water solvent and then dividing it into two parts, respectively obtaining a first initiator solution and a second initiator solution; S3, adding sodium dodecyl diphenyl ether disulfonate, emulsifier A and the first emulsifier B into the first water and mixing, and then adding styrene, n-butyl acrylate, the first acrylic acid and hydroxyethyl methacrylate for emulsification to obtain a pre-emulsion; S4, adding the second emulsifier B to the second water and heating it to 80-85°C, first adding part of the pre-emulsion and the first initiator aqueous solution and mixing, then dropping the remaining pre-emulsion and the second initiator aqueous solution, mixing the coupling agent, 2-ethylhexyl acrylate, phosphate monomer, hydroxyethyl acrylate, dodecyl alcohol ester and the second acrylic acid into the remaining pre-emulsion during the dropping process, stirring evenly, continuing to drop, and keeping warm after the dropping is completed, cooling to 40-65°C, adjusting the pH to alkaline, adding a defoamer and a bactericide, and filtering to obtain a tile back coating interface agent emulsion; The partial pre-emulsion accounts for 4% to 5% of the total mass of the pre-emulsion.

6. The method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 5, characterized in that: The mass ratio of the first acrylic acid to the second acrylic acid is 6-7.5:

1.

7. The method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 5, characterized in that: The mass ratio of the first emulsifier B to the second emulsifier B is 2-2.5:

1.

8. The method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 5, characterized in that: The mass ratio of the first water to the second water is 34:54-37:

51.

9. The method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 5, characterized in that: The mass ratio of the first initiator to the second initiator is 1.3~1.6:0.

8.

10. The method for preparing a high initial adhesion and high bonding strength ammonia-free tile back coating interface agent emulsion according to claim 5, characterized in that: The pH is adjusted to be alkaline, specifically: the pH is adjusted to 7.5-8.

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