Special emulsion for changing the color of tiles, preparation method and application thereof

Abstract

The present invention relates to the technical field of tile emulsions, and in particular to a special emulsion for changing the color of tiles, a preparation method and an application thereof. Wherein, the special emulsion for changing the color of tiles, by mass, comprises raw materials for preparing the following: 28 to 32 parts of methyl methacrylate, 6 to 8 parts of butyl acrylate, 4 to 6 parts of isooctyl acrylate, 0.8 to 1.2 parts of methacrylic acid, 1.4 to 1.8 parts of diacetone acrylamide, 0.7 to 0.9 parts of oxalic acid dihydrazide, 1.8 to 2.2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.8 to 1.2 parts of emulsifier, 0.1 to 0.2 parts of initiator, 50 to 65 parts of deionized water, and the total amount of raw materials for preparing the same is 100 parts. The coating prepared by the special emulsion for changing the color of tiles of the present invention has the advantages of high hardness, good tile adhesion and good water resistance, and can be well used in the coating on the surface of tiles.

Description

Technical Field

[0001] The invention relates to the technical field of tile emulsions, and in particular to a special emulsion for changing the color of tiles, a preparation method and application thereof. Background Art

[0002] As tiles are used for a longer time, they will gradually age and break. In this case, consumers can choose to renovate and re-tile. However, this method will not only incur a large expense, but also take a long time. In addition, young people today like new things. After using tiles at home for a period of time, they will feel visual fatigue and want to replace them with another type of tiles.

[0003] In order to reduce the need to re-lay tiles, a tile coating is now available on the market, which can be made into various effects and colors that consumers want, thereby changing the surface effect of the tile.

[0004] Considering the actual application scenarios, tile coatings must have the following characteristics: (1) good tile adhesion to prevent falling off, (2) excellent aging resistance to prevent discoloration or yellowing after outdoor ultraviolet exposure, (3) a hardness of at least H to give it good anti-scratch ability, (4) excellent water resistance to prevent it from falling off and changing color at least under certain conditions of immersion in water for a certain period of time, and (5) good color development performance to enable it to achieve the colorful effects that consumers want.

[0005] However, the tile color-changing coatings currently available on the market made of single-component acrylic resins are difficult to fully meet the requirements of hardness, tile adhesion, water resistance and other related performances. In terms of hardness, the pencil hardness of single-component acrylic resins is generally only 2B-HB, and the tile adhesion test is only level 3-4. The hardness will drop significantly after the water resistance test, and it will also bubble or even fall off after long-term water resistance.

[0006] It can be seen that the existing technology still needs to be improved and enhanced. Summary of the invention

[0007] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a special emulsion for changing the color of tiles, a preparation method and application thereof, aiming to improve the comprehensive performance of the special emulsion for changing the color of tiles.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] The first aspect of the present invention provides a special emulsion for changing the color of ceramic tiles. The raw materials for its preparation include, by weight: 28 to 32 parts of methyl methacrylate, 6 to 8 parts of butyl acrylate, 4 to 6 parts of isooctyl acrylate, 0.8 to 1.2 parts of methacrylic acid, 1.4 to 1.8 parts of diacetone acrylamide, 0.7 to 0.9 parts of oxalic acid dihydrazide, 1.8 to 2.2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.8 to 1.2 parts of emulsifier, 0.1 to 0.2 parts of initiator, and 50 to 65 parts of deionized water.

[0010] The special emulsion for changing the color of tiles, wherein the emulsifier includes allyl fatty alcohol polyoxyethylene ether ammonium sulfate and fatty alcohol polyoxyethylene ether.

[0011] The special emulsion for changing the color of tiles, wherein the initiator includes one or both of ammonium persulfate and potassium persulfate.

[0012] The second aspect of the present invention provides a method for preparing an emulsion, which is used to prepare the special emulsion for changing the color of tiles as described above, comprising the following steps:

[0013] S001. Prepare the raw materials according to the formula of the special emulsion for changing the color of tiles, add 35 to 42 parts of deionized water and 0.2 to 0.4 parts of emulsifier to the reactor, heat to 80 to 85 ° C, and stir evenly;

[0014] S002. Preparation of pre-emulsion: add 8 to 12 parts of deionized water, and all of methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, diacetone acrylamide and the remaining emulsifier, and mix well;

[0015] S003. Preparation of initiator solution: Dissolve all the initiator in the remaining deionized water;

[0016] S004. The pre-emulsion and the initiator solution are simultaneously added dropwise to the reactor, and the mixture is kept warm after the addition;

[0017] S005. After the heat preservation is completed, the temperature is lowered, and then the pH is adjusted to 7-9, and then oxalic acid dihydrazide is added, and stirred for 14-16 minutes, and then γ-(2,3-epoxypropoxy)propyltrimethoxysilane is added, and stirred for 9-11 minutes to obtain the acrylic emulsion specially used for changing the color of tiles.

[0018] The method for preparing the emulsion, wherein in S004, the dripping time of the pre-emulsion and the initiator solution is controlled within 220 to 260 minutes.

[0019] The method for preparing the emulsion, wherein, in S004, when the pre-emulsion and the initiator solution are added dropwise, the temperature in the reactor is controlled at 80-85°C.

[0020] The method for preparing the emulsion, wherein, in S004, the heat preservation time is 60 to 70 minutes.

[0021] The method for preparing the emulsion, wherein, in S005, after the insulation is completed, the temperature in the reactor is lowered to below 40° C., and then the pH is adjusted.

[0022] A third aspect of the present invention provides a tile color-changing coating, the raw materials for preparing the tile color-changing emulsion include the above-mentioned special emulsion.

[0023] Beneficial effects: The first aspect of the present invention provides a special emulsion for changing the color of ceramic tiles. The special emulsion for changing the color of ceramic tiles adopts methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, diacetone acrylamide, oxalic acid dihydrazide, γ-(2,3-epoxypropoxy)propyltrimethoxysilane and the like as raw materials for preparation. The different characteristics of different raw materials improve the performance of the special emulsion for changing the color of ceramic tiles as a whole, and improves multiple properties such as hardness during application, tile adhesion and water resistance.

[0024] The second aspect of the present invention provides a method for preparing an emulsion, which has high controllability, low energy consumption, and can prepare a special emulsion for changing the color of tiles with stable quality on a large scale. DETAILED DESCRIPTION

[0025] The present invention provides a special emulsion for changing the color of ceramic tiles, a preparation method and application thereof. In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail by the following examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0026] The first aspect of the present invention provides a special emulsion for changing the color of ceramic tiles. The raw materials for its preparation include, by weight: 28 to 32 parts of methyl methacrylate, 6 to 8 parts of butyl acrylate, 4 to 6 parts of isooctyl acrylate, 0.8 to 1.2 parts of methacrylic acid, 1.4 to 1.8 parts of diacetone acrylamide, 0.7 to 0.9 parts of oxalic acid dihydrazide, 1.8 to 2.2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.8 to 1.2 parts of emulsifier, 0.1 to 0.2 parts of initiator, and 50 to 65 parts of deionized water.

[0027] In the present invention, methyl methacrylate, butyl acrylate and isooctyl acrylate are used as the main monomers, so that the coating has excellent weather resistance and basic water resistance after application. γ-(2,3-epoxypropoxy)propyltrimethoxysilane is used as an adhesion promoter, so that the coating can achieve ideal dry and wet adhesion to tiles. Acrylamide and methacrylic acid are used to adjust the synthetic stability of the emulsion, improve the output rate, as well as the ionic stability and storage stability of the finished emulsion. The room temperature self-crosslinking monomers diacetone acrylamide and oxalic acid dihydrazide can allow the coating dry film to slowly crosslink under room temperature curing conditions to increase the crosslinking density, so that the hardness and water resistance can reach a higher level. In addition, even if the special acrylic emulsion for tile color change of the present invention only uses reactive emulsifiers and non-ionic emulsifiers, it can also provide sufficient stability and water resistance.

[0028] Preferably, the emulsifier includes allyl fatty alcohol polyoxyethylene ether ammonium sulfate and fatty alcohol polyoxyethylene ether.

[0029] Preferably, the initiator includes one or both of ammonium persulfate and potassium persulfate.

[0030] The second aspect of the present invention provides a method for preparing an emulsion, which is used to prepare the special emulsion for changing the color of tiles as described above, comprising the following steps:

[0031] S001. Prepare the raw materials according to the formula of the special emulsion for changing the color of tiles, add 35 to 42 parts of deionized water and 0.2 to 0.4 parts of emulsifier to the reactor, heat to 80 to 85 ° C, and stir evenly;

[0032] S002. Preparation of pre-emulsion: add 8 to 12 parts of deionized water, and all of methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, diacetone acrylamide and the remaining emulsifier, and mix well;

[0033] S003. Preparation of initiator solution: Dissolve all the initiator in the remaining deionized water;

[0034] S004. The pre-emulsion and the initiator solution are simultaneously added dropwise to the reactor, and the mixture is kept warm after the addition;

[0035] S005. After the heat preservation is completed, the temperature is lowered, and then the pH is adjusted to 7-9, and then oxalic acid dihydrazide is added, and stirred for 14-16 minutes, and then γ-(2,3-epoxypropoxy)propyltrimethoxysilane is added, and stirred for 9-11 minutes to obtain the acrylic emulsion specially used for changing the color of tiles.

[0036] Preferably, in S004, the dripping time of the pre-emulsion and the initiator solution is controlled within 220 to 260 minutes.

[0037] Preferably, in S004, when the pre-emulsion and the initiator solution are added dropwise, the temperature in the reactor is controlled at 80-85°C.

[0038] Preferably, in S004, the insulation time is 60 to 70 minutes.

[0039] Preferably, in S005, after the insulation is completed, the temperature in the reactor is lowered to below 40° C., and then the pH is adjusted.

[0040] A third aspect of the present invention provides a tile color-changing coating, the raw materials for preparing the tile color-changing emulsion include the above-mentioned special emulsion.

[0041] The present invention is further described below with reference to specific examples.

[0042] Example 1

[0043] A special emulsion for changing the color of ceramic tiles, the preparation method of which comprises the following steps, calculated by weight:

[0044] S001. Prepare the raw materials according to the formula of the special emulsion for tile color change, add 36.45 parts of deionized water, 0.3 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate to the reactor, heat to 83 ° C, and stir evenly;

[0045] S002. Preparation of pre-emulsion: 10 parts of deionized water, 30 parts of methyl methacrylate, 7 parts of butyl acrylate, 5 parts of isooctyl acrylate, 1 part of methacrylic acid, 1.6 parts of diacetone acrylamide, 0.3 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate and 0.4 parts of fatty alcohol polyoxyethylene ether were added and mixed evenly;

[0046] S003. Preparation of initiator solution: 0.15 parts of initiator were dissolved in 5 parts of deionized water;

[0047] S004. When the reactor temperature reaches 83 ° C, the pre-emulsion and the initiator solution are added dropwise to the reactor at the same time, the addition time is controlled at 240min, the reactor temperature is maintained at 83-85 ° C during the addition, and the insulation is carried out after the addition, the insulation time is 60min, and the insulation temperature is 83-85 ° C;

[0048] S005. After the heat preservation is completed, start cooling in a water bath to below 40°C, then adjust the pH to 7-9, add 0.8 parts of oxalic acid dihydrazide, stir for 15 minutes, add 2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, stir for 10 minutes, and obtain the acrylic emulsion specially used for changing the color of ceramic tiles.

[0049] Example 2

[0050] A special emulsion for changing the color of ceramic tiles, the preparation method of which comprises the following steps, calculated by weight:

[0051] S001. Prepare the raw materials according to the formula of the special emulsion for tile color change, add 37.05 parts of deionized water, 0.3 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate to the reactor, heat to 83 ° C, and stir evenly;

[0052] S002. Preparation of pre-emulsion: 10 parts of deionized water, 30 parts of methyl methacrylate, 7 parts of butyl acrylate, 5 parts of isooctyl acrylate, 1 part of methacrylic acid, 1.2 parts of diacetone acrylamide, 0.5 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate and 0.2 parts of fatty alcohol polyoxyethylene ether were added and mixed evenly;

[0053] S003. Preparation of initiator solution: 0.15 parts of initiator were dissolved in 5 parts of deionized water;

[0054] S004. When the reactor temperature reaches 83 ° C, the pre-emulsion and the initiator solution are added dropwise to the reactor at the same time, the addition time is controlled at 240min, the reactor temperature is maintained at 83-85 ° C during the addition, and the insulation is carried out after the addition, the insulation time is 60min, and the insulation temperature is 83-85 ° C;

[0055] S005. After the heat preservation is completed, start cooling in a water bath to below 40°C, then adjust the pH to 7-9, add 0.6 parts of oxalic acid dihydrazide, stir for 15 minutes, add 2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, stir for 10 minutes, and obtain the acrylic emulsion specially used for changing the color of ceramic tiles.

[0056] Example 3

[0057] A special emulsion for changing the color of ceramic tiles, the preparation method of which comprises the following steps, calculated by weight:

[0058] S001. Prepare the raw materials according to the formula of the special emulsion for tile color change, add 50 parts of deionized water and 0.3 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate to the reactor, heat to 83 ° C, and stir evenly;

[0059] S002. Preparation of pre-emulsion: 10 parts of deionized water, 30 parts of methyl methacrylate, 7 parts of butyl acrylate, 5 parts of isooctyl acrylate, 1 part of methacrylic acid, 1.2 parts of diacetone acrylamide, 0.5 parts of allyl fatty alcohol polyoxyethylene ether ammonium sulfate and 0.2 parts of fatty alcohol polyoxyethylene ether were added and mixed evenly;

[0060] S003. Preparation of initiator solution: 0.15 parts of initiator were dissolved in 5 parts of deionized water;

[0061] S004. When the reactor temperature reaches 83 ° C, the pre-emulsion and the initiator solution are added dropwise to the reactor at the same time, the addition time is controlled at 240min, the reactor temperature is maintained at 83-85 ° C during the addition, and the insulation is carried out after the addition, the insulation time is 60min, and the insulation temperature is 83-85 ° C;

[0062] S005. After the heat preservation is completed, start cooling in a water bath to below 40°C, then adjust the pH to 7-9, add 0.6 parts of oxalic acid dihydrazide, stir for 15 minutes, add 2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, stir for 10 minutes, and obtain the acrylic emulsion specially used for changing the color of ceramic tiles.

[0063] Comparative Example 1

[0064] An acrylic emulsion, the preparation method of which is different from that of Example 1 in that styrene is used to completely replace methyl methacrylate.

[0065] Comparative Example 2

[0066] An acrylic emulsion, the preparation method of which is different from that of Example 1 in that γ-(2,3-epoxypropoxy)propyltrimethoxysilane is not added, and the same amount of deionized water is used for supplementation.

[0067] Comparative Example 3

[0068] An acrylic emulsion, the preparation method of which is different from that of Example 1 in that diacetone acrylamide and oxalic acid dihydrazide are not added, and the same amount of deionized water is used to supplement.

[0069] Comparative Example 4

[0070] An acrylic emulsion, the preparation method of which is different from that of Example 1 in that all propyl fatty alcohol polyoxyethylene ether ammonium sulfate is replaced by fatty alcohol polyoxyethylene ether in equal amounts.

[0071] Comparative Example 5

[0072] An acrylic emulsion, the preparation method of which is different from that of Example 1 in that the reaction temperature of the reactors in S001 and S004 is reduced to 70°C.

[0073] The solid content and gel amount of the emulsions of the above embodiments and comparative examples were measured.

[0074] The emulsions of the above embodiments and comparative examples were used to prepare tile color-changing coatings, and performance tests were performed. The test contents included:

[0075] Weather resistance (GB / T 1766-2008);

[0076] 7-day self-drying hardness (GB / T 6739-2022),

[0077] Tile adhesion after 7 days of self-drying (GB / T 9286-2021);

[0078] 7 days of self-drying, 24h water resistance hardness (GB / T 6739-2022);

[0079] 7 days of self-drying and 4 hours of boiling water hardness (GB / T 6739-2022);

[0080] After drying for 7 days, the ceramic tile adhesion will be restored for 1 minute after being boiled in boiling water for 4 hours (GBxxxx). The formula of the ceramic tile color changing coating is as follows:

[0081] Raw material name Weight / g water 9.3 Bentonite 0.2 AMP-95 pH Regulator 0.3 Dispersants 1.2 SN-154 defoamer 0.1 TEGO902W defoamer 0.1 Titanium dioxide 20 Precipitated barium sulfate 8 Lotion 50 50% DPNB film-forming aid 8 C-12 film-forming aid 1.5 BYK-024 defoamer 0.1 LXE Antifungal Fungicide 0.2 104E Wetting Agent 0.2 2020 Thickener 0.5 PUR64 (80%) thickener 0.3

[0082] The corresponding test results are as follows:

[0083] Table 1

[0084]

[0085] Table 2

[0086]

[0087] From the above results, it can be seen that the special emulsion for changing the color of tiles in Examples 1-3 has a low gel rate after preparation, and the coating further prepared has good weather resistance, high hardness, good adhesion, and still maintains good hardness and adhesion after soaking in water.

[0088] In the emulsion of comparative example 1, methyl methacrylate is not used, but all styrene is used. From the results, its application performance is slightly reduced, but yellowing is serious and cannot meet the application requirements.

[0089] The emulsion of Comparative Example 2 does not contain γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and its hardness, adhesion and water resistance are seriously reduced compared with those of Examples 1-3, and cannot meet the application requirements.

[0090] The emulsion of Comparative Example 3 does not contain crosslinking monomers diacetone acrylamide and oxalic acid dihydrazide. Compared with Examples 1-3, its adhesion is slightly reduced and its hardness is seriously reduced, which cannot meet the application requirements.

[0091] In the emulsion of Comparative Example 4, only nonionic emulsifier was used, and demulsification problem occurred during the reaction, and normal synthesis could not be performed.

[0092] After the reaction temperature was lowered in Comparative Example 5, the solid content was only 42.65%, which was lower than that of other groups, and the conversion rate was significantly reduced, which was not in line with actual production. It should be noted that although the solid content of Example 3 was lower than that of Comparative Example 5, the amount of deionized water used in Example 3 was the largest, and after comprehensive comparison, the conversion rate of Comparative Example 5 was still the lowest.

[0093] It is understandable that those skilled in the art can make equivalent substitutions or changes based on the technical solution and inventive concept of the present invention, and all these changes or substitutions should fall within the protection scope of the claims attached to the present invention.

Claims

1. A special emulsion for changing the color of tiles, characterized in that: The raw materials for its preparation include, by mass, 28 to 32 parts of methyl methacrylate, 6 to 8 parts of butyl acrylate, 4 to 6 parts of isooctyl acrylate, 0.8 to 1.2 parts of methacrylic acid, 1.4 to 1.8 parts of diacetone acrylamide, 0.7 to 0.9 parts of oxalic acid dihydrazide, 1.8 to 2.2 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.8 to 1.2 parts of emulsifier, 0.1 to 0.2 parts of initiator and 50 to 65 parts of deionized water.

2. The special emulsion for changing the color of tiles according to claim 1, characterized in that: The emulsifier includes allyl fatty alcohol polyoxyethylene ether ammonium sulfate and fatty alcohol polyoxyethylene ether.

3. The special emulsion for changing the color of tiles according to claim 1, characterized in that: The initiator includes one or both of ammonium persulfate and potassium persulfate.

4. A method for preparing an emulsion, characterized in that: The method for preparing the special emulsion for changing the color of ceramic tiles as claimed in any one of claims 1 to 3 comprises the following steps: S001. Prepare the raw materials according to the formula of the special emulsion for changing the color of tiles, add 35 to 42 parts of deionized water and 0.2 to 0.4 parts of emulsifier to the reactor, heat to 80 to 85 ° C, and stir evenly; S002. Preparation of pre-emulsion: add 8 to 12 parts of deionized water, and all of methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, diacetone acrylamide and the remaining emulsifier, and mix well; S003. Preparation of initiator solution: Dissolve all the initiator in the remaining deionized water; S004. The pre-emulsion and the initiator solution are simultaneously added dropwise to the reactor, and the mixture is kept warm after the addition; S005. After the heat preservation is completed, the temperature is lowered, and then the pH is adjusted to 7-9, and then oxalic acid dihydrazide is added, and stirred for 14-16 minutes, and then γ-(2,3-epoxypropoxy)propyltrimethoxysilane is added, and stirred for 9-11 minutes to obtain the acrylic emulsion specially used for changing the color of tiles.

5. The method for preparing the emulsion according to claim 4, characterized in that: In the step S004, the dropwise addition time of the pre-emulsion and the initiator solution is controlled within a range of 220 to 260 minutes.

6. The method for preparing the emulsion according to claim 4, characterized in that: In the step S004, when the pre-emulsion and the initiator solution are added dropwise, the temperature in the reactor is controlled at 80-85°C.

7. The method for preparing the emulsion according to claim 4, characterized in that: In the step S004, the heat preservation time is 60 to 70 minutes.

8. The method for preparing the emulsion according to claim 4, characterized in that: In S005, after the insulation is completed, the temperature in the reactor is lowered to below 40°C, and then the pH is adjusted.

9. A tile color-changing coating, characterized in that: The raw materials for its preparation include the special emulsion for changing the color of tiles as described in any one of claims 1 to 3.

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