Acrylic emulsion, preparation method thereof and application of acrylic emulsion in soft porcelain ink-absorbing coating

Abstract

The invention discloses an acrylic emulsion, which is prepared from the following ingredients in parts by weight: 1000 to 1350 parts of water, 300 to 500 parts of methyl methacrylate, 200 to 400 parts of 2-ethylhexyl acrylate, 100 to 300 parts of styrene, 100 to 300 parts of butyl acrylate, 10 to 45 parts of cross-linking monomers, 10 to 25 parts of anionic emulsifiers, 1 to 5 parts of nonionic emulsifiers, 10 to 15 parts of acrylic acid, 5 to 15 parts of methacrylic acid, 2 to 6 parts of initiators and 0.5 to 3 parts of buffering agents. The invention also discloses a preparation method of the acrylic emulsion and application of the acrylic emulsion in a soft porcelain ink-absorbing coating. The acrylic emulsion disclosed by the invention is applied to an ink-absorbing coating of the soft porcelain, so that ink printed on the surface can be dried quickly, and a formed printed pattern layer is good in adhesive force, bright in texture and good in water resistance and weather resistance.

Description

Technical Field

[0001] This invention relates to the field of chemical materials technology, specifically to an acrylic emulsion, its preparation method, and its application in soft ceramic ink-absorbing coatings. Background Technology

[0002] "Flexible ceramic tile" (industry term: modified inorganic powder composite building cladding sheet) has the advantages of being environmentally friendly and energy-saving, thin and lightweight. It can withstand the deformation of different substrates, is not easy to crack or fall off, is safe and reliable, and has good flexibility, changing the cold and hard texture of traditional ceramic tiles. Flexible ceramic tile uses 3D printing technology to give it rich textures and colors. However, when printing dark and complex textures on a flexible ceramic tile substrate, problems such as slow ink drying speed, poor ink fixation, unclear texture, poor paint film adhesion, and easy swelling upon contact with water occur. To solve these problems and meet the diversity of product textures, an ink-absorbing coating needs to be added to the flexible ceramic tile substrate. The ink-absorbing coating is composed of acrylic emulsion, inorganic powder, and additives. Among them, acrylic acid serves as the film-forming substance and the carrier of the powder, exhibiting excellent powder encapsulation and water resistance.

[0003] In existing ink-absorbing coatings for flexible ceramics, the performance of acrylic emulsions cannot meet the needs of 3D printing in the flexible ceramics industry. Therefore, it is necessary to develop an acrylic emulsion with good water resistance, good weather resistance, good adhesion, fast ink absorption and drying speed, and bright texture for ink-absorbing coatings. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects of the prior art and provide an acrylic emulsion that, when applied to the ink-absorbing coating of soft ceramic, can make the ink printed on the surface dry quickly, and the resulting printed pattern layer has good adhesion, bright texture, and excellent water resistance and weather resistance.

[0005] To achieve the above objectives, the present invention provides the following technical solution: An acrylic emulsion, comprising, by weight: 1000-1350 parts water, 300-500 parts methyl methacrylate, 200-400 parts isooctyl acrylate, 100-300 parts styrene, 100-300 parts butyl acrylate, 10-45 parts crosslinking monomer, 10-25 parts anionic emulsifier, 1-5 parts nonionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, 2-6 parts initiator, and 0.5-3 parts buffer.

[0006] Furthermore, the acrylic emulsion of the present invention also includes 0.5-3 parts of oxidant, 0.5-3 parts of reducing agent, 10-15 parts of pH neutralizer, 0.1-1 parts of defoamer, and 2-10 parts of bactericide.

[0007] Furthermore, the acrylic emulsion of the present invention comprises a core layer preemulsion and a shell layer preemulsion. The core layer preemulsion comprises 300-400 parts water, 200-300 parts methyl methacrylate, 150-300 parts isooctyl acrylate, 100-150 parts styrene, 140-280 parts butyl acrylate, 12.5-43 parts crosslinking monomer, 6-12 parts anionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, and 2-3 parts initiator. The crosslinking monomer is selected from a mixture of acrylamide, vinyltrimethoxysilane, and ethylene glycol dimethacrylate. The shell layer preemulsion comprises 300-400 parts water, 100-200 parts methyl methacrylate, 50-100 parts isooctyl acrylate, 1.5-4 parts anionic emulsifier, 2-5 parts methacrylic acid, and 0.4-0.8 parts initiator.

[0008] Furthermore, the core-shell ratio of the acrylic emulsion of the present invention is 8:2.

[0009] Furthermore, the crosslinking monomer is any one or a mixture of two or more of the following: dodecyl methacrylate, ethylene glycol dimethacrylate, acrylamide, a mixture of methacrylate derivatives, N-hydroxymethylacrylamide, glycidyl methacrylate vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and ethylene glycol dimethacrylate; the anionic emulsifier is any one or a mixture of two or more of the following: sodium dodecyl sulfate, sodium allyloxypropyl sulfonate, sodium alkyl polyoxyethylene ether sulfate, sodium alkyl sulfonyl ethoxy ether lauryl salt, or SR-10; the nonionic emulsifier is an alkyl polyoxyethylene ether; the initiator is any one of potassium persulfate, ammonium persulfate, or sodium persulfate; the buffer is sodium bicarbonate; the oxidant is any one of tert-butyl hydroperoxide or tert-butyl peroxide; the reducing agent is any one of organic sulfite or sodium bisulfite; the pH neutralizer is ammonia; the defoamer is a mixture of organic polyether dispersions; and the bactericide is a broad-spectrum bactericide.

[0010] Furthermore, the acrylic emulsion of the present invention comprises, by weight: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 7 parts dodecyl methacrylate, 4.5 parts ammonium persulfate, 1 part glycidyl methacrylate, 3 parts vinyltrimethoxysilane, 1.5 parts oxidant, 1 part buffer, 1.2 parts reducing agent, 11 parts pH neutralizer, 0.4 parts defoamer, and 3 parts bactericide.

[0011] The present invention also provides a method for preparing the above-mentioned acrylic emulsion, which includes the following steps: Preparation of core layer preemulsion: Take a portion of water, add anionic emulsifier, styrene, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, isooctyl acrylate, crosslinking monomer and initiator, stir and mix well, and set aside. Preparation of shell pre-emulsion: Take a portion of water, add anionic emulsifier, methyl methacrylate, isooctyl acrylate, anionic emulsifier, methacrylic acid, and initiator, stir and mix well, and set aside. Preparation of pre-initiator solution: Add the remaining initiator to water, stir and mix evenly, and set aside; Preparation of oxidant solution: Add oxidant to water, stir and mix evenly, and set aside; Preparation of reducing agent solution: Add reducing agent to water, stir and mix evenly, and set aside; Crosslinking reaction steps: Add water, the remaining anionic emulsifier, nonionic emulsifier, and buffer to the reactor, start stirring, heat up, add 3%-6% by weight of the core layer pre-emulsion all at once, then add the pre-initiator emulsion all at once, keep warm, and start adding the remaining core layer pre-emulsion dropwise for the reaction. After the dropwise addition is complete, keep warm; then start adding the shell layer pre-emulsion dropwise, and keep warm after the dropwise addition reaction. Post-crosslinking step: After the heat preservation is completed, the temperature is lowered to 65-70℃, and oxidant solution and reducing agent emulsion are added dropwise over a time of 20-40 minutes. After the addition is completed, the temperature is maintained for 10-20 minutes. Post-processing steps: Cool down to below 45℃, add pH neutralizer to adjust pH to 7-9, then add defoamer and bactericide, then discharge, filter, and package to obtain the product.

[0012] In the preparation method of the acrylic emulsion, in the crosslinking reaction step, after heating to 80-85℃, the core layer pre-emulsion is added and kept at this temperature for 10-20 minutes; the core layer pre-emulsion is added dropwise over a period of 2.5-3 hours at a reaction temperature of 80-85℃, and then kept at this temperature for 0.5-1 hour; the shell layer pre-emulsion is added dropwise over a period of 0.5-1 hour at a reaction temperature of 80-85℃; and after the shell layer pre-emulsion is added, the mixture is kept at 80-88℃ for 1-1.5 hours.

[0013] The present invention also provides the application of the acrylic emulsion in ink-absorbing coatings for flexible ceramics.

[0014] Furthermore, the ink-absorbing coating comprises, by weight: 15-20 parts of the acrylic emulsion, 0.5-1 parts of thickener, 0.2-0.5 parts of dispersant, 0.2-0.5 parts of defoamer, 0.1-0.3 parts of antifreeze, 30-40 parts of pigment, and 10-20 parts of nano-silica.

[0015] Compared with the prior art, the beneficial effects of the present invention are: The acrylic emulsion of this invention employs a seed emulsion polymerization method, which does not generate new latex particles during polymerization. This effectively controls the diameter and distribution of latex particles, resulting in a more fluid emulsion. The use of a combination of anionic and nonionic emulsifiers reduces the gelation rate during polymerization and enhances the stability of the emulsion.

[0016] The acrylic emulsion of this invention uses methyl methacrylate as the main hard monomer, combined with styrene, butyl acrylate, and isooctyl acrylate in appropriate proportions and by selecting suitable crosslinking monomers. The resulting acrylic emulsion solves the problems encountered in the 3D printing process of the soft ceramics industry, such as slow ink drying speed, insufficient color vibrancy, and poor ink fixation. At the same time, it meets the requirements for yellowing resistance when applied to soft ceramics products.

[0017] The acrylic emulsion of this invention is polymerized using a core-shell process, with a soft core and a hard shell, resulting in a lower film-forming temperature. When spraying ink-absorbing coatings, no film-forming aids are needed to form a film, greatly improving production efficiency while significantly reducing VOC emissions, making it environmentally friendly. The invention also designs a suitable monomer ratio for the core and shell, solving the problem of hot stickiness and cold brittleness of traditional acrylic emulsions. This allows the ink-absorbing coating to maintain good flexibility even under large temperature differences, thus not affecting the overall flexibility of the flexible ceramic product. The core-shell design utilizes unique hydrophilic and hydrophobic properties. The shell layer incorporates small amounts of methacrylic acid and silane coupling agents to reduce the crosslinking strength of the polymerization, preventing the emulsion film from becoming too dense and reducing the ink absorption capacity of the ink-absorbing coating. Meanwhile, the core layer features long-chain crosslinked monomers and silane coupling agents, forming a three-dimensional network structure that allows for secondary ink adsorption. The resulting ink-absorbing coating has a special microporous structure, exhibiting strong ink absorption capacity. Even when printing dark-toned patterns, it can effectively represent depth and exhibit excellent ink retention, resisting fading and drying quickly without affecting subsequent production processes, thus achieving cost reduction and efficiency improvement.

[0018] This invention designs a suitable latex particle diameter, with the emulsion serving as a carrier for the powder. During the film-forming process, the large number of micropores in the powder itself will not be blocked due to the excessively small particle size of the latex particles. This allows the ink to penetrate into the internal structure of the powder during printing, thereby improving the ink absorption and ink retention properties of the ink-absorbing coating. The introduction of a silane coupling agent enables the ink-absorbing coating to have excellent adhesion to the soft ceramic substrate, preventing the product from delaminating or peeling under sunlight and rain. Detailed Implementation

[0019] This embodiment provides an acrylic emulsion comprising, by weight: 1000-1350 parts water, 300-500 parts methyl methacrylate, 200-400 parts isooctyl acrylate, 100-300 parts styrene, 100-300 parts butyl acrylate, 10-45 parts crosslinking monomer, 10-25 parts anionic emulsifier, 1-5 parts nonionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, 2-6 parts initiator, and 0.5-3 parts buffer.

[0020] Furthermore, the acrylic emulsion of this embodiment also includes 0.5-3 parts of oxidant, 0.5-3 parts of reducing agent, 10-15 parts of pH neutralizer, 0.1-1 parts of defoamer, and 2-10 parts of bactericide.

[0021] Furthermore, the acrylic emulsion of this embodiment includes a core layer preemulsion and a shell layer preemulsion. The core layer preemulsion includes 300-400 parts water, 200-300 parts methyl methacrylate, 150-300 parts isooctyl acrylate, 100-150 parts styrene, 140-280 parts butyl acrylate, 12.5-43 parts crosslinking monomer, 6-12 parts anionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, and 2-3 parts initiator. The crosslinking monomer is a mixture of acrylamide, vinyltrimethoxysilane, and ethylene glycol dimethacrylate. The shell layer preemulsion includes 300-400 parts water, 100-200 parts methyl methacrylate, 50-100 parts isooctyl acrylate, 1.5-4 parts anionic emulsifier, 2-5 parts methacrylic acid, and 0.4-0.8 parts initiator.

[0022] Furthermore, the core-shell ratio of the acrylic emulsion in this embodiment is 8:2; the shell pre-emulsion may also optionally contain 0.5-5 parts of crosslinking monomer.

[0023] Furthermore, the crosslinking monomer is any one or a mixture of two or more of the following: dodecyl methacrylate, ethylene glycol dimethacrylate, acrylamide, a mixture of methacrylate derivatives, N-hydroxymethylacrylamide, glycidyl methacrylate vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and ethylene glycol dimethacrylate; the anionic emulsifier is any one or a mixture of two or more of the following: sodium dodecyl sulfate, sodium allyloxypropyl sulfonate, sodium alkyl polyoxyethylene ether sulfate, sodium alkyl sulfonyl ethoxy ether lauryl salt, or SR-10; the nonionic emulsifier is an alkyl polyoxyethylene ether; the initiator is any one of potassium persulfate, ammonium persulfate, or sodium persulfate; the buffer is sodium bicarbonate; the oxidant is any one of tert-butyl hydroperoxide or tert-butyl peroxide; the reducing agent is any one of organic sulfite or sodium bisulfite; the pH neutralizer is ammonia; the defoamer is a mixture of organic polyether dispersions; and the bactericide is a broad-spectrum bactericide.

[0024] Furthermore, the acrylic emulsion of this embodiment comprises, by weight: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 7 parts dodecyl methacrylate, 4.5 parts ammonium persulfate, 1 part glycidyl methacrylate, 3 parts vinyltrimethoxysilane, 1.5 parts oxidant, 1 part buffer, 1.2 parts reducing agent, 11 parts pH neutralizer, 0.4 parts defoamer, and 3 parts bactericide.

[0025] This embodiment also provides a method for preparing the above-mentioned acrylic emulsion, which includes the following steps: Preparation of core layer preemulsion: Take a portion of water, add anionic emulsifier, styrene, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, isooctyl acrylate, crosslinking monomer and initiator, stir and mix well, and set aside. Preparation of shell pre-emulsion: Take a portion of water, add anionic emulsifier, methyl methacrylate, isooctyl acrylate, anionic emulsifier, methacrylic acid, and initiator, stir and mix well, and set aside. Preparation of pre-initiator solution: Add the remaining initiator to water, stir and mix evenly, and set aside; Preparation of oxidant solution: Add oxidant to water, stir and mix evenly, and set aside; Preparation of reducing agent solution: Add reducing agent to water, stir and mix evenly, and set aside; Crosslinking reaction steps: Add water, the remaining anionic emulsifier, nonionic emulsifier, and buffer to the reactor, start stirring, heat up, add 3%-6% by weight of the core layer pre-emulsion all at once, then add the pre-initiator emulsion all at once, keep warm, and start adding the remaining core layer pre-emulsion dropwise for the reaction. After the dropwise addition is complete, keep warm; then start adding the shell layer pre-emulsion dropwise, and keep warm after the dropwise addition reaction. Post-crosslinking step: After the heat preservation is completed, the temperature is lowered to 65-70℃, and oxidant solution and reducing agent emulsion are added dropwise over a time of 20-40 minutes. After the addition is completed, the temperature is maintained for 10-20 minutes. Post-processing steps: Cool down to below 45℃, add pH neutralizer to adjust pH to 7-9, then add defoamer and bactericide, then discharge, filter, and package to obtain the product.

[0026] In the preparation method of the acrylic emulsion, in the crosslinking reaction step, after heating to 80-85℃, the core layer pre-emulsion is added and kept at this temperature for 10-20 minutes; the core layer pre-emulsion is added dropwise over a period of 2.5-3 hours at a reaction temperature of 80-85℃, and then kept at this temperature for 0.5-1 hour; the shell layer pre-emulsion is added dropwise over a period of 0.5-1 hour at a reaction temperature of 80-85℃; and after the shell layer pre-emulsion is added, the mixture is kept at 80-88℃ for 1-1.5 hours.

[0027] This embodiment also provides the application of the acrylic emulsion in the ink-absorbing coating of flexible ceramic.

[0028] Furthermore, the ink-absorbing coating comprises, by weight: 15-20 parts of the acrylic emulsion, 0.5-1 parts of thickener, 0.2-0.5 parts of dispersant, 0.2-0.5 parts of defoamer, 0.1-0.3 parts of antifreeze, 30-40 parts of pigment, and 10-20 parts of nano-silica.

[0029] Example 1 An acrylic emulsion comprises, by weight, the following components: 1140 parts water, 14 parts sodium lauryl sulfonate salt, 2 parts anionic emulsifier SR-10, 1 part sodium allyl hydroxypropyl sulfonate, 2 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 100 parts styrene, 150 parts butyl acrylate, 420 parts methyl methacrylate, 300 parts isooctyl acrylate, 15 parts acrylic acid, 5 parts methacrylic acid, 10 parts acrylamide, 2 parts vinyltrimethoxysilane, 0.5 parts ethylene glycol dimethacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 12 parts ammonia, 0.4 parts organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0030] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 6 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 1 part anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 100 parts styrene, 150 parts butyl acrylate, 300 parts methacrylic acid, 230 parts isooctyl acrylate, 15 parts acrylic acid, 5 parts methacrylic acid, 10 parts acrylamide, 2 parts vinyltrimethoxysilane, 0.5 parts ethylene glycol dimethacrylate and 2.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain the core layer pre-emulsion for later use. ② At room temperature, add 120 parts water and 2 parts sodium lauryl sulfonate salt to a beaker, start the stirrer to disperse and dissolve, then add 120 parts methyl methacrylate, 70 parts isooctyl acrylate and 0.5 parts ammonium persulfate in sequence, stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 6 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 1 part allyl oxyhydroxypropyl sulfonate sodium salt, 2 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 12 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0031] Example 2 An acrylic emulsion comprises, by weight, the following components: 1140 parts water, 12 parts sodium lauryl sulfonate salt, 2 parts anionic emulsifier SR-10, 1 part sodium allyl hydroxypropyl sulfonate, 2 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 100 parts styrene, 150 parts butyl acrylate, 420 parts methyl methacrylate, 300 parts isooctyl acrylate, 15 parts acrylic acid, 5 parts methacrylic acid, 10 parts acrylamide, 2 parts vinyltrimethoxysilane, 0.5 parts ethylene glycol dimethacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 12 parts ammonia, 0.4 parts organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0032] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 6 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 1 part anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 100 parts styrene, 150 parts butyl acrylate, 300 parts methacrylic acid, 230 parts isooctyl acrylate, 15 parts acrylic acid, 5 parts methacrylic acid, 10 parts acrylamide, 2 parts vinyltrimethoxysilane, 0.5 parts ethylene glycol dimethacrylate and 2.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain the core layer pre-emulsion for later use. ② At room temperature, add 120 parts water and 2 parts sodium lauryl sulfonate salt to a beaker, start the stirrer to disperse and dissolve, then add 120 parts methyl methacrylate, 70 parts isooctyl acrylate and 0.5 parts ammonium persulfate in sequence, stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 1 part allyl oxyhydroxypropyl sulfonate sodium salt, 2 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 12 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0033] Example 3 An acrylic emulsion comprises, by weight, the following components: 1140 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 150 parts styrene, 245 parts butyl acrylate, 360 parts methyl methacrylate, 215 parts isooctyl acrylate, 12 parts acrylic acid, 7 parts methacrylic acid, 10 parts acrylamide, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 11 parts ammonia, 0.4 parts organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0034] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker, start the stirrer to disperse and dissolve, then add 150 parts styrene, 245 parts butyl acrylate, 235 parts methacrylic acid, 150 parts isooctyl acrylate, 12 parts acrylic acid, 7 parts methacrylic acid, 10 parts acrylamide, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate and 2.5 parts ammonium persulfate in sequence, stir for 15-20 minutes to obtain the core layer pre-emulsion, and set aside for later use; ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0035] Example 4 An acrylic emulsion comprises, by weight, the following components: 1125 parts water, 13 parts sodium lauryl sulfonate, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate, 11 parts ammonia, 0.4 parts an organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0036] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker, start the stirrer to disperse and dissolve, then add 130 parts styrene, 245 parts butyl acrylate, 255 parts methacrylic acid, 150 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate and 2.5 parts ammonium persulfate in sequence, stir for 15-20 minutes to obtain the core layer pre-emulsion, and set aside for later use; ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0037] Example 5 An acrylic emulsion comprises, by weight, the following components: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 5 parts dodecyl methacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 11 parts ammonia, 0.4 parts an organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0038] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker, start the stirrer to disperse and dissolve, then add 130 parts styrene, 245 parts butyl acrylate, 255 parts methacrylic acid, 150 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 5 parts dodecyl methacrylate and 2.5 parts ammonium persulfate, stir for 15-20 minutes to obtain the core layer pre-emulsion, and set aside for later use; ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0039] Example 6 An acrylic emulsion comprises, by weight, the following components: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 7 parts dodecyl methacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 11 parts ammonia, 0.4 parts an organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0040] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 130 parts styrene, 245 parts butyl acrylate, 255 parts methacrylic acid, 150 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 3 parts vinyltrimethoxysilane, 1 part ethylene glycol dimethacrylate, 7 parts dodecyl methacrylate and 2.5 parts ammonium persulfate. Stir for 15-20 minutes to obtain the core layer pre-emulsion for later use. ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0041] Example 7 An acrylic emulsion comprises, by weight, the following components: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 4 parts vinyltrimethoxysilane, 1 part glycidyl methacrylate, 7 parts dodecyl methacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 11 parts ammonia, 0.4 parts an organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0042] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 130 parts styrene, 245 parts butyl acrylate, 255 parts methacrylic acid, 150 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 3 parts vinyltrimethoxysilane, 1 part glycidyl methacrylate, 7 parts dodecyl methacrylate and 2.5 parts ammonium persulfate. Stir for 15-20 minutes to obtain the core layer pre-emulsion for later use. ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, 3 parts methacrylic acid, 1 part vinyltrimethoxysilane, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0043] Example 8 An acrylic emulsion comprises, by weight, the following components: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts anionic emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 1 part buffer, 4.5 parts ammonium persulfate, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts a mixture of methacrylate derivatives, 4 parts vinyltrimethoxysilane, 1 part glycidyl methacrylate, 10 parts dodecyl methacrylate, 1.5 parts tert-butyl hydroperoxide, 1.2 parts sodium organic sulfinate salt, 11 parts ammonia, 0.4 parts an organic polyether dispersion mixture, and 3 parts bactericide MIT-10.

[0044] The preparation method of the acrylic emulsion is as follows: ① At room temperature, add 340 parts deionized water, 7 parts alkyl sulfonyl ethoxy ether sodium lauryl salt and 2 parts anionic emulsifier SR-10 to a beaker, start the stirrer to disperse and dissolve, then add 130 parts styrene, 245 parts butyl acrylate, 255 parts methacrylic acid, 150 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 3 parts vinyltrimethoxysilane, 1 part glycidyl methacrylate, 10 parts dodecyl methacrylate and 2.5 parts ammonium persulfate, stir for 15-20 minutes to obtain the core layer pre-emulsion, and set aside for later use; ② At room temperature, add 120 parts water, 2 parts sodium lauryl sulfonyl ethoxy ether, and 0.5 parts anionic emulsifier SR-10 to a beaker. After dispersing and dissolving with a stirrer, add 125 parts methyl methacrylate, 65 parts isooctyl acrylate, 3 parts methacrylic acid, 1 part vinyltrimethoxysilane, and 0.5 parts ammonium persulfate in sequence. Stir for 15-20 minutes to obtain a shell pre-emulsion for later use. ③ Mix 1.5 parts ammonium persulfate and 20 parts water thoroughly to prepare a pre-initiator solution for later use; ④ Add 600 parts water, 4 parts alkyl sulfonyl ethoxy ether sodium lauryl salt, 2 parts allyl oxyhydroxypropyl sulfonate sodium salt, 3 parts alkyl polyoxyethylene ether, and 1 part sodium bicarbonate to a reaction vessel. Start stirring and heat to 80-85℃. Add 5% by weight of the core layer pre-emulsion in one go, followed by the addition of the pre-initiator solution in one go. After holding at this temperature for 20 minutes, start adding the remaining core layer pre-emulsion dropwise over 2.5 hours at a reaction temperature of 80-85℃. After the dropwise addition is complete, hold at this temperature for 0.5-1 hour. Then start adding the shell layer pre-emulsion dropwise over 0.5 hours at a reaction temperature of 80-85℃. After the pre-emulsion is completely added, hold at 80-88℃ for 1-1.5 hours. ⑤ Mix 1.5 parts of tert-butyl hydrogen peroxide and 30 parts of water until homogeneous to prepare an oxidizing agent solution; mix 1.2 parts of organic sodium sulfite salt and 30 parts of water until homogeneous to prepare a reducing agent solution. ⑥ After the heat preservation is completed, cool down to 65-70℃, and at the same time add oxidant solution and reducing agent emulsion dropwise. The dropwise addition time is 20-40 minutes. After the dropwise addition is completed, keep warm for 10-20 minutes. ⑦ Cool down to below 45℃, add 11 parts ammonia water to adjust the pH to 7-9, then add 0.4 parts organic polyether dispersion mixture and 3 parts bactericide MIT-10, then discharge, filter, and package to obtain the product.

[0045] Performance testing: (1) The appearance, particle size, solid content and TG (glass transition temperature) of the acrylic emulsions prepared in Examples 1-8 were tested, and the results are shown in Table 1 below.

[0046] Table 1 Performance indicators of acrylic emulsions in Examples 1 to 8 Testing items Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Appearance Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Milky white with a bluish tint Particle size / nm 95.3 118.5 121.2 122.4 120.7 123.1 119.7 120.5 Solid content / % 46.8 47.1 47 47.3 47.2 46.9 47.2 47.3 TG / ℃ 20 20.2 21.5 22.1 23.1 22.1 23.2 23.4 .

[0047] (2) The acrylic emulsions prepared in Examples 1-8 were applied to the ink-absorbing coating of soft ceramics for application performance testing.

[0048] 1) The acrylic emulsions obtained in Examples 1-8 are formulated into ink-absorbing coatings according to the formulas in Table 2 below.

[0049] Table 2 Ink Absorbent Coating Formulation Components Quality percentage (%) water 33.6 Thickener 0.5 dispersant 0.4 Defoamer 0.3 gelling agent 0.2 Pigments and fillers 35 Nano silica 15 lotion 15 .

[0050] 2) Spray the prepared ink-absorbing coating onto the flexible ceramic substrate, place it in an oven set at 100℃ and dry for 15 minutes, then remove it and cure at room temperature for 48 hours to form an ink-absorbing coating on the surface of the flexible ceramic substrate. Then perform 3D printing and test the drying speed, clarity, and yellowing resistance, water resistance, and washability of the coating.

[0051] The yellowing resistance test was conducted according to the requirements of standard GB / T-23983-2009 "Determination of Yellowing Resistance of Wood Coatings". A UVA (340) lamp was used as the light source, and the test panel was placed under test conditions that met the requirements of a test panel temperature of (60±3)℃ and an irradiance of 0.68W / m². 2 After 168 hours of continuous light exposure, the color change was measured using a colorimeter. The unit of color change value is ΔE*. The smaller the measured value, the better the resistance to yellowing. The scrub resistance test is conducted according to the requirements of standard GB / T-9266-2009 "Determination of scrub resistance of building coatings". If the coating of at least one of the two test panels is not damaged to the point of exposing the substrate after being scrubbed a specified number of times, it is considered to pass. The water resistance test was conducted according to the standard GB / T-1733-1993 "Test Method for Water Resistance of Paint Films". After soaking the test panels for 48 hours, they were removed and blotted dry with filter paper. The panels were then checked for any signs of loss of gloss, discoloration, blistering, wrinkling, peeling, flaking, rusting, or other defects. The ink retention test was conducted after printing and drying, followed by 48 hours of curing. The substrate surface was then rubbed back and forth 10 times with a disposable paper towel to check for ink fading.

[0052] Additionally, using an existing acrylic emulsion as a comparison sample, the performance parameters of this acrylic emulsion are: milky white with a bluish tint in appearance, particle size of 123.7 nm, solid content of 47%, and TG temperature of 25.3℃.

[0053] 3) The test results are shown in Table 3 below. Table 3 Ink Absorption Coating Test Results Test Project Difference in resistance to yellowing Coating damage after 3000 washes Water resistance Print drying speed / seconds ink fixation Clarity / Darkness Example 1 1.3 One of the test panels had a leak at the bottom. Slight discoloration and bubbling 200 Severe color fading The pattern is blurry and swollen. Example 2 1.0 One of the test panels had a leak at the bottom. Slight discoloration and bubbling 182 fade Blurry pattern Example 3 0.7 One of the test panels had a leak at the bottom. Slight discoloration 178 fade Blurry pattern Example 4 0.8 No damage or leaks No abnormalities 179 fade Blurry pattern Example 5 0.7 No damage or leaks No abnormalities 140 Slight color fading Clear pattern Example 6 0.9 No damage or leaks No abnormalities 125 Colorfast Clear pattern Example 7 0.7 No damage or leaks No abnormalities 110 Colorfast Clear pattern Example 8 0.7 No damage or leaks No abnormalities 130 fade Blurry pattern Comparison Samples 1.8 One of the test panels had a leak at the bottom. Slight discoloration and wrinkling 210 Severe color fading The pattern is blurry and swollen. .

[0054] As can be seen from Table 3, the acrylic emulsion prepared in Example 6 has excellent resistance to yellowing, washing and water when used to prepare a soft ceramic ink-absorbing coating. It also has a fast printing and drying speed. In particular, when printing dark-colored patterns, the patterns are clear and have a good sense of layering, which meets the market demand for soft ceramic 3D printing.

[0055] The yellowing resistance difference of the ink-absorbing coating emulsions for flexible porcelain prepared in Examples 1 to 7 is less than 1.5, and there is almost no color change visible to the naked eye, indicating that the emulsions have excellent resistance to yellowing and do not affect the decorative properties of flexible porcelain products. Example 2, based on Example 1, increased the particle size of the emulsion. Data on printing drying speed showed that the drying speed was improved, indicating that the large-particle-size emulsion has great compatibility with pigments and fillers during the paint film drying process, reducing the airtightness of pigments and fillers, allowing ink to penetrate into the pigments and fillers, and improving the ink absorption of the coating. However, the increased particle size reduced the water resistance. Therefore, the amount of A-171 and AMA was increased in this example to improve the water resistance of the paint film. Example 4 introduces crosslinking monomer HA to replace crosslinking monomer AM. HA is a derivative of methacrylic acid and contains vinyl, hydroxyl, and amide groups, which can copolymerize with acrylate monomers. A comparison of the washability and water resistance data of Example 4 and Example 3 shows that the introduction of crosslinking monomer HA improves both properties of the emulsion. Example 5 shows that the printing drying speed was significantly improved by introducing the lipophilic functional monomer dodecyl methacrylate (LMA). This is because the present invention selects soft BA and 2-EHA as the main soft monomers, both of which are medium- and short-chain alkyl esters, while LMA is a long-chain alkyl ester. During polymerization, LMA undergoes crosslinking and graft copolymerization with A-171, GMA, etc., to form a better three-dimensional network structure. This avoids the chain segments occupying the internal space of the resin and can effectively improve the effective network space for ink absorption. Compared with ordinary acrylic emulsions, it has a better drying speed. As can be seen from the data of Examples 5 and 6, increasing the amount of LMA within a certain range is not necessarily better the more it is added. As can be seen from the data of Example 8, after increasing the amount of LMA, the printing drying speed becomes slower and the pattern becomes blurry. This is because the increased amount of long-chain LMA increases the cross-linking strength, enhances the steric hindrance, and prevents the ink from entering the resin, thereby reducing the ink absorption of the resin. Examples 6 and 7 show different core-shell hydrophilic and hydrophobic properties. A small amount of MAA and A-171 are added to the shell layer to reduce the crosslinking strength of the polymerization while ensuring the water resistance and adhesion of the emulsion. This prevents the emulsion film from becoming too dense, which would reduce the ink absorption capacity of the ink-absorbing coating.

[0056] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. An acrylic emulsion, characterized in that, By weight, it includes: 1000-1350 parts water, 300-500 parts methyl methacrylate, 200-400 parts isooctyl acrylate, 100-300 parts styrene, 100-300 parts butyl acrylate, 10-45 parts crosslinking monomer, 10-25 parts anionic emulsifier, 1-5 parts nonionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, 2-6 parts initiator, and 0.5-3 parts buffer.

2. The acrylic emulsion according to claim 1, characterized in that, It also includes 0.5-3 parts of oxidant, 0.5-3 parts of reducing agent, 10-15 parts of pH neutralizer, 0.1-1 parts of defoamer, and 2-10 parts of bactericide.

3. The acrylic emulsion according to claim 1, characterized in that: The product includes a core preemulsion and a shell preemulsion. The core preemulsion comprises 300-400 parts water, 200-300 parts methyl methacrylate, 150-300 parts isooctyl acrylate, 100-150 parts styrene, 140-280 parts butyl acrylate, 12.5-43 parts crosslinking monomer, 6-12 parts anionic emulsifier, 10-15 parts acrylic acid, 5-15 parts methacrylic acid, and 2-3 parts initiator. The crosslinking monomer is a mixture of acrylamide, vinyltrimethoxysilane, and ethylene glycol dimethacrylate. The shell preemulsion comprises 300-400 parts water, 100-200 parts methyl methacrylate, 50-100 parts isooctyl acrylate, 1.5-4 parts anionic emulsifier, 2-5 parts methacrylic acid, and 0.4-0.8 parts initiator.

4. The acrylic emulsion according to claim 1 or 3, characterized in that: The core-shell ratio of the acrylic emulsion is 8:

2.

5. The acrylic emulsion according to claim 2, characterized in that: The crosslinking monomer is any one or a mixture of two or more of the following: dodecyl methacrylate, ethylene glycol dimethacrylate, acrylamide, a mixture of methacrylate derivatives, N-hydroxymethylacrylamide, glycidyl methacrylate vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and ethylene glycol dimethacrylate; the anionic emulsifier is any one or a mixture of two or more of the following: sodium dodecyl sulfate, sodium allyloxyhydroxypropyl sulfonate, sodium alkyl polyoxyethylene ether sulfate, sodium alkyl sulfoethoxy ether lauryl salt, or SR-10; the nonionic emulsifier is an alkyl polyoxyethylene ether; the initiator is any one of potassium persulfate, ammonium persulfate, or sodium persulfate; the buffer is sodium bicarbonate; the oxidant is any one of tert-butyl hydroperoxide or tert-butyl peroxide; the reducing agent is any one of organic sulfite or sodium bisulfite; the pH neutralizer is ammonia; the defoamer is a mixture of organic polyether dispersions; and the bactericide is a broad-spectrum bactericide.

6. The acrylic emulsion according to claim 1, characterized in that: By weight, it includes: 1125 parts water, 13 parts sodium lauryl sulfonate salt, 2.5 parts emulsifier SR-10, 2 parts sodium allyl hydroxypropyl sulfonate, 3 parts alkyl polyoxyethylene ether, 130 parts styrene, 245 parts butyl acrylate, 380 parts methyl methacrylate, 215 parts isooctyl acrylate, 10 parts acrylic acid, 15 parts methacrylic acid, 25 parts methacrylate derivative mixture, 7 parts dodecyl methacrylate, 4.5 parts ammonium persulfate, 1 part glycidyl methacrylate, 3 parts vinyltrimethoxysilane, 1.5 parts oxidant, 1 part buffer, 1.2 parts reducing agent, 11 parts pH neutralizer, 0.4 parts defoamer, and 3 parts bactericide.

7. The method for preparing the acrylic emulsion according to any one of claims 1 to 6, characterized in that, Includes the following steps: Preparation of core layer preemulsion: Take a portion of water, add anionic emulsifier, styrene, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, isooctyl acrylate, crosslinking monomer and initiator, stir and mix well, and set aside. Preparation of shell pre-emulsion: Take a portion of water, add anionic emulsifier, methyl methacrylate, isooctyl acrylate, anionic emulsifier, methacrylic acid, and initiator, stir and mix well, and set aside. Preparation of pre-initiator solution: Add the remaining initiator to water, stir and mix evenly, and set aside; Preparation of oxidant solution: Add oxidant to water, stir and mix evenly, and set aside; Preparation of reducing agent solution: Add reducing agent to water, stir and mix evenly, and set aside; Crosslinking reaction steps: Add water, the remaining anionic emulsifier, nonionic emulsifier, and buffer to the reactor, start stirring, heat up, add 3%-6% by weight of the core layer pre-emulsion all at once, then add the pre-initiator emulsion all at once, keep warm, and start adding the remaining core layer pre-emulsion dropwise for the reaction. After the dropwise addition is complete, keep warm; then start adding the shell layer pre-emulsion dropwise, and keep warm after the dropwise addition reaction. Post-crosslinking step: After the heat preservation is completed, the temperature is lowered to 65-70℃, and oxidant solution and reducing agent emulsion are added dropwise over a time of 20-40 minutes. After the addition is completed, the temperature is maintained for 10-20 minutes. Post-processing steps: Cool down to below 45℃, add pH neutralizer to adjust pH to 7-9, then add defoamer and bactericide, then discharge, filter, and package to obtain the product.

8. The method for preparing acrylic emulsion according to claim 7, characterized in that: In the crosslinking reaction step, after heating to 80-85℃, the core layer pre-emulsion is added and kept at this temperature for 10-20 minutes; the core layer pre-emulsion is added dropwise over a period of 2.5-3 hours at a reaction temperature of 80-85℃, and then kept at this temperature for 0.5-1 hour; the shell layer pre-emulsion is added dropwise over a period of 0.5-1 hour at a reaction temperature of 80-85℃; and after the shell layer pre-emulsion is added, the mixture is kept at 80-88℃ for 1-1.5 hours.

9. The application of the acrylic emulsion according to any one of claims 1 to 6 in a flexible ceramic ink-absorbing coating.

10. The application of the acrylic emulsion according to claim 9 in the ink-absorbing coating of flexible ceramic, characterized in that, The ink-absorbing coating comprises, by weight: 15-20 parts of the acrylic emulsion, 0.5-1 parts of thickener, 0.2-0.5 parts of dispersant, 0.2-0.5 parts of defoamer, 0.1-0.3 parts of antifreeze, 30-40 parts of pigment, and 10-20 parts of nano-silica.