Art coating Yayanite emulsion with long construction time as well as preparation method and application of artistic coating Yayanite emulsion

Abstract

The invention discloses an acrylic emulsion for artistic coating Yayanite with long construction time as well as a preparation method and application of the acrylic emulsion. The emulsion is prepared from the following monomer components in percentage by weight through an emulsion polymerization method and then steam stripping: a) 15-70% of ester monomers; b) 14%-25% of a moisturizing functional monomer; c) 0.5%-5% of an unsaturated hydrophilic monomer; d) 0.2%-5% of a reactive silane coupling agent; e) 10 to 50% of styrene; wherein the total mass of the components a), b), c), d) and e) is 100%. A large number of F-H hydrogen bond structures are added into the emulsion, and moisture in the coating is locked through high-density F-H hydrogen bonds, so that the opening time of the coating is greatly prolonged, the Yayanite coating has more time for rubbing textures, and the constructability of the coating is greatly improved.

Description

Technical Field

[0001] The present invention relates to an acrylic emulsion, and particularly to an art paint jasper emulsion with a long construction time, its preparation method and application. Background Art

[0002] Art paints have emerged as interior paint decorations in recent years. Interior paints are an important part of interior design and decoration. With the improvement of people's living standards, there has been an increasing artistic pursuit of interior decoration styles, and people hope to add more artistic elements. Therefore, art paints have gradually emerged with various post-processing forms such as rubbing textures and polishing, which pose high requirements for jasper paints mainly composed of hard aggregates.

[0003] Since art paints mostly use emulsions with a high glass transition temperature to ensure their high hardness characteristics, emulsions with a high glass transition temperature often have problems such as quick drying and short open time, which cause great trouble to the construction time of jasper paints that require rubbing textures. The traditional post-added small molecule humectants often have a small improvement amplitude, and a large amount of addition will affect the hardness of the paint.

[0004] Patent CN 115232557A introduces a long-construction-time jasper paint prepared by using a highly thixotropic system compounded with modified urea and HK-10 cellulose, which effectively improves the workability, but the modified urea has a high cost and is extremely prone to amine odor in a high pH system.

[0005] Patent CN213449234 U introduces an operation of increasing the scraping smoothness by using a non-woven fabric layer, but this method still has the problem of increasing the construction process. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides an art paint jasper emulsion with a long construction time, its preparation method and application.

[0007] According to one aspect of the present invention, first, an art paint jasper emulsion with a long construction time is provided. A functional monomer containing a large number of fluoroalcohol structures is added to this emulsion. The monomer structure has a large number of F atoms. The F atoms on the monomer can form a large number of high-strength F-H hydrogen bonds with the water in the paint. These hydrogen bonds can effectively lock the water in the paint and improve the open time of the paint. Compared with the traditional post-added small molecule humectants, this system has a higher viscosity and moisture retention.

[0008] According to another aspect of the present invention, an application of an art paint jasper emulsion with a long construction time in paint is also provided.

[0009] To achieve the above object, the technical solutions adopted by the present invention are as follows:

[0010] An art coating elegant crystal stone emulsion with a long construction time is obtained by stripping after being prepared by emulsion polymerization from monomer components with the following weight ratios:

[0011] a) 15 - 70%, preferably 44 - 53% of ester monomers;

[0012] b) 14 - 25%, preferably 10 - 15% of functional monomers;

[0013] c) 0.5 - 5%, preferably 1 - 5% of unsaturated hydrophilic monomers;

[0014] d) 0.2 - 5%, preferably 0.5 - 2% of reactive silane coupling agents;

[0015] e) 10 - 50%, preferably 10 - 30% of styrene;

[0016] Wherein, the total mass of components a), b), c), d), and e) is 100%.

[0017] In the present invention, the component a) is selected from acrylic alkyl esters, allyl esters, vinyl acetate, and their methyl-substituted products with 1 - 16 carbon atoms, preferably selected from acrylic alkyl esters, vinyl acetate, and their methyl-substituted products with 1 - 8 carbon atoms, more preferably selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, methyl 2-methylacrylate, isopentyl methacrylate, heptyl methacrylate;

[0018] The structural formula of the functional monomer of component b) is as shown in Formula I:

[0019]

[0020] In the present invention, the component c) is selected from unsaturated monomers containing hydrophilic groups, and the hydrophilic groups are selected from carboxyl, hydroxyl, amide, sulfonic acid group, phosphate ester group, urea group, sulfonate group, sulfate group, phosphate group; preferably, the component c) is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamide, methacrylamide, isooctyl acrylate, ethyl ethylene urea, vinyl alkoxy phosphate, sodium 2-acrylamido-2-methylpropanesulfonate.

[0021] In the present invention, the component d) is selected from silane coupling agents containing vinyl or epoxy functional groups, preferably one or more of vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane.

[0022] In the present invention, the preparation process of component b) represented by formula I does not impose any restrictive effect on its function in the present invention. Those skilled in the art can simply synthesize component b) represented by formula I according to, for example, the following synthesis process:

[0023]

[0024] In the steps of the above synthesis process, the molar ratio of maleic anhydride to hexafluoroethyl alcohol is 1:1; further, the reaction temperature is 15 - 25 °C, and the reaction time is 0.5 h - 2 h.

[0025] In a preferred embodiment of the present invention, the raw materials for preparing the long-construction-time artistic coating Yajingshi emulsion optionally further include an emulsifier, an initiator, a neutralizing agent, a post-treatment agent, a pH regulator, and water.

[0026] In a preferred embodiment of the present invention, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium styrene sulfonate, sodium dodecyl benzene sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate, and alkyl alcohol ether phosphate, preferably sodium dodecyl sulfate and / or sodium dodecyl benzene sulfonate;

[0027] Preferably, the dosage of the emulsifier is 1 - 5%, preferably 1 - 2%, of the total mass of components a) - e);

[0028] The initiator is selected from one or more of sodium persulfate, potassium persulfate, and ammonium persulfate, preferably sodium persulfate and / or potassium persulfate;

[0029] Preferably, the total dosage of the initiator is 0.2 - 0.6%, preferably 0.2 - 0.4%, of the total mass of components a) - e);

[0030] The neutralizing agent is selected from one or more of sodium bicarbonate, diethylenetriamine, diethanolamine, and ethanolamine, preferably sodium bicarbonate;

[0031] Preferably, the dosage of the neutralizing agent is 0.1 - 4%, preferably 0.1 - 0.3%, of the total mass of monomer components a) - e);

[0032] The post-treatment agent includes an oxidizing agent and / or a reducing agent. The oxidizing agent is selected from one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate, preferably tert-butyl hydroperoxide and / or hydrogen peroxide; the reducing agent is selected from one or more of sodium bisulfite, sodium metabisulfite, and vitamin C, preferably sodium bisulfite and / or sodium metabisulfite;

[0033] Preferably, the total dosage of the post-treatment agent is 0.15 - 0.6%, preferably 0.2 - 0.4%, of the total mass of components a) - e);

[0034] The pH regulator is selected from one or more of diethylenetriamine, diethanolamine, and ethanolamine, preferably diethylenetriamine and / or ethanolamine;

[0035] Preferably, the end point of the addition amount of the pH regulator is to adjust the pH of the system to 7-9;

[0036] Preferably, the total amount of water used is 1-1.5 times, preferably 1-1.3 times, the total mass of components a)-e).

[0037] In another aspect of the present invention, there is provided a method for preparing the art paint elegant stone emulsion with a long construction time as described above, comprising the following steps:

[0038] 1) Mix components a), b), c), d), e) with water and part of the emulsifier evenly to prepare a pre-emulsion;

[0039] 2) Divide the initiator into two parts, dissolve them with water respectively to obtain the dropping initiator and the bottom-of-the-kettle initiator;

[0040] 3) Mix the neutralizer, the remaining emulsifier and water, add them into the reaction kettle, stir well, heat up to 80-90 °C; add part of the pre-emulsion, and after stirring evenly, add all the bottom-of-the-kettle initiator, react for 10-20 min to prepare a seed emulsion;

[0041] 4) Control the temperature in the reaction kettle to 80-90 °C, continue to add the remaining pre-emulsion and all the dropping initiator to the seed emulsion, the feeding time is 2-4 h, and keep warm for 20-60 min;

[0042] 5) Cool the reaction kettle to 70-80 °C, gradually add the post-treatment agent to the reaction kettle, the feeding time is 2-4 h, and then keep warm for 30-60 min;

[0043] 6) Cool down to below 45 °C, add the pH regulator to adjust the pH of the system to 7-9, carry out steam stripping and filtration to discharge the material.

[0044] In a preferred embodiment of the present invention, the amount of the emulsifier used in step 1) accounts for 90-99.5% of the total mass of all the emulsifiers;

[0045] Preferably, the amount of water used in step 1) accounts for 25-35% of the total mass of all the water.

[0046] In a preferred embodiment of the present invention, the amount of the initiator used to prepare the dropping initiator in step 2) accounts for 25-50% of the total mass of the initiator, and the amount of the initiator used to prepare the bottom-of-the-kettle initiator accounts for 50-75% of the total mass of the initiator;

[0047] Preferably, the amount of water used to prepare the dropping initiator in step 2) accounts for 1-6% of its total mass, and the amount of water used to prepare the bottom initiator in the kettle accounts for 1-6% of its total mass;

[0048] Preferably, the amount of the pre-emulsion used to prepare the seed emulsion in step 3) is 1-8% of its total mass.

[0049] In a preferred embodiment of the present invention, the stripping temperature in step 6) is 55-85 °C, and the pressure is controlled at -75 Kpa to -95 Kpa.

[0050] The acrylate emulsion prepared by the present invention has a solid content of 41-45%, a pH of 7-9, and an emulsion particle size of 69-80 nm.

[0051] Based on another aspect of the present invention, there is also provided an application of the high-efficiency formaldehyde-absorbing and long-construction-time art paint Yajingshi emulsion as described above or the high-efficiency formaldehyde-absorbing and long-construction-time art paint Yajingshi emulsion prepared by the method as described above in coatings.

[0052] The present invention has the following beneficial effects:

[0053] The component shown in formula I contains a hexafluoroethyl fluorohydrin structure at the same time. This structure can generate a large number of hydrogen bonds with water in the coating, greatly improving the water-locking ability of the coating and enhancing the workability of the coating. At the same time, the existence of hydrogen bonds can also improve the film-forming ability of the coating. The acrylate emulsion of the present invention has excellent workability, low-temperature film-forming property, and good environmental protection performance, and is especially suitable for the field of architectural interior wall Yajingshi art coatings, and the construction is simple. Specific Embodiments

[0054] The following further illustrates the present invention through specific examples. The examples described in the present invention are only for the illustration of the present invention and do not limit the scope of the present invention.

[0055] The raw materials used in the following examples are shown in Table 1. Other raw materials, if not otherwise specified, are ordinary commercially available raw materials:

[0056] Table 1, Raw Material Information

[0057]

[0058]

[0059] The following treatment processes are adopted in each of the following examples:

[0060] Stripping: The emulsion is placed in a buffer kettle and preheated to 55°C, and then passed into a stripping tower for stripping (stripping temperature 55°C, pressure controlled at -75Kpa to -95Kpa); the emulsion is fed at the top of the tower, and the air and steam are fed at the bottom of the tower. The two are in countercurrent contact and mixed at high speed in a short time. The steam and air carry VOC components and separate from the emulsion through the vacuum tail gas pipeline, and the emulsion is discharged from the bottom. During the stripping process, the relative flow rates of air, steam and emulsion are 1:0.5:10.

[0061] Construction performance test method: scrape and rub the wall. Wait for 2 minutes after applying, use the crystal head to rub the texture, and calculate the time until the texture can no longer be rubbed out.

[0062] Hardness: 25℃, 50% humidity, curing for 1 day, 3 days, hand touch hardness test:

[0063] Water resistance of paint film: According to JG / T 24-2000 synthetic resin sand-walled architectural coatings

[0064] Paint film drying time: According to JG / T 24-2000 synthetic resin sand-walled architectural coatings.

[0065] [Preparation Example]

[0066] The functional monomer, denoted as Q, was prepared according to the following method:

[0067]

[0068] In the steps of the above-mentioned synthesis process, the molar ratio of maleic anhydride to hexafluoroethyl alcohol is 1:1, the reaction temperature is 25° C., and the reaction time is 2 h.

[0069] [Example 1]

[0070] Prepare the acrylic emulsion as follows:

[0071] 1) components a), b), c), d), e) and 433 g of water, 9 g of emulsifier SDS, and 9 g of emulsifier SSS were mixed uniformly to prepare a pre-emulsion;

[0072] 2) 1 g of initiator APS was fully mixed with 38 g of water to obtain a dropwise initiator; 2 g of initiator APS was fully mixed with 21 g of water to obtain a bottom initiator;

[0073] 3) 2g of sodium bicarbonate, 0.19g of emulsifier SDS and 831g of water were mixed and added to the reactor, stirred thoroughly, and heated to 85°C; 50g of pre-emulsion was added, and after stirring evenly, all the initiators at the bottom of the reactor were added, and the mixture was reacted for 10 minutes to obtain a seed emulsion;

[0074] 4) Control the temperature in the reaction kettle at 85 °C, and continue to add the remaining pre-emulsion and all of the dropping initiator to the seed emulsion simultaneously. The total dropping time is 4 h, and then keep it warm for 20 min;

[0075] 5) Cool down the reaction kettle to 75 °C, gradually add the post-treatment agent (2 g of t-BHP and 40 g of 5% aqueous sodium bisulfite solution) to the reaction kettle. The feeding time is 2 h, and then keep it warm for 30 min;

[0076] 6) Cool down to below 45 °C, add the pH regulator diethylenetriamine to adjust the pH of the system to 8, carry out steam stripping, filter through a 100-mesh filter, and discharge the material.

[0077] Among them, the types and dosages of the raw materials are shown in Table 2.

[0078]

Example 2-7

[0079] Prepare acrylic emulsions respectively according to the method basically the same as that in Example 1, with the only difference being that the raw material selection and dosage in Table 2 are different; meanwhile, ensure that in step 3), the addition amount of the pre-emulsion accounts for 5% of its total mass.

[0080]

Comparative Example 1

[0081] Prepare acrylic emulsion according to the method basically the same as that in Example 1, with the only difference being that component b is not added.

[0082]

Comparative Example 2

[0083] Prepare acrylic emulsion according to the method basically the same as that in Example 1, with the only difference being that component b is replaced with maleic acid of the same mass:

[0084]

Comparative Example 3

[0085] Prepare acrylic emulsion according to the method basically the same as that in Example 1, with the only difference being that component b is replaced with small molecule hexafluoroethylene alcohol of the same mass.

[0086] Prepare coatings according to the formulations in Table 3 with the acrylic emulsions prepared in each example, and conduct tests on film properties such as application time, water resistance, gloss, etc. The results are shown in Table 4. Prepare coatings according to the formulations in Table 3 with the acrylic emulsions prepared in each comparative example, and conduct tests on film properties such as application time, water resistance, gloss, etc. The results are shown in Table 5.

[0087] As shown in Tables 4-5, by preparing coatings with the emulsions in the examples of the present invention, the performance test results all meet the requirements for interior wall coatings in "GB / T 9756-2018 Synthetic Resin Interior Wall Coatings", and the film-forming property and freeze-thaw stability are both significantly improved.

[0088] From the above test results, it can be seen that the emulsion formulation provided by the present invention has a synergistic enhancement effect on the low-temperature film-forming property, workability, and freeze-thaw stability of the coating, and has a low VOC content and a relatively low emulsion odor; by introducing a fluoroalcohol functional monomer, the workability of the emulsion has been significantly improved.

[0089] Table 2. Selection and dosage of raw materials in Examples 1-7 (unit: g)

[0090]

[0091]

[0092] Table 3. Coating formulation

[0093]

[0094]

[0095] Table 4. Test results of the properties of the coatings obtained from the emulsions in the examples

[0096]

[0097] Table 5. Test results of the properties of the coatings obtained from the emulsions in the comparative examples

[0098]

Claims

1. An art coating emulsion of Yajingshi with a long construction time, characterized in that, the raw materials of the emulsion comprise the following components: a) 15 - 70%, preferably 44 - 53% of ester monomers; b) 14 - 25%, preferably 10 - 15% of moisturizing functional monomers; c) 0.5 - 5%, preferably 1 - 5% of unsaturated hydrophilic monomers; d) 0.2 - 5%, preferably 0.5 - 2% of reactive silane coupling agents; e) 10 - 50%, preferably 20 - 30% of styrene; wherein, the structure of component b) is as follows: wherein, the total mass of components a), b), c), d), e), f) is 100%.

2. The emulsion according to claim 1, characterized in that, component a) is selected from acrylic alkyl esters, allyl esters, vinyl acetate and their methyl substitutes with 1 - 16 carbon atoms, preferably selected from acrylic alkyl esters, vinyl acetate and their methyl substitutes with 1 - 8 carbon atoms, more preferably selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2 - ethylhexyl acrylate, isooctyl acrylate, methyl 2 - methylacrylate, isopentyl methacrylate, heptyl methacrylate.

3. The emulsion according to claim 1, characterized in that, component c) is selected from unsaturated monomers containing hydrophilic groups, and the hydrophilic groups are selected from carboxyl, hydroxyl, amide, sulfonic acid group, phosphate ester group, urea group, sulfonate group, sulfate group, phosphate group; component c) is preferably one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamide, methacrylamide, isooctyl acrylate, ethyl ethylene urea, vinyl alkoxy phosphate, sodium 2 - acrylamido - 2 - methylpropane sulfonate.

4. The emulsion according to claim 1, characterized in that, component d) is selected from silane coupling agents containing vinyl or epoxy functional groups, preferably one or more of vinyltrimethoxysilane, γ - methacryloyloxypropyltrimethoxysilane, γ - glycidylethoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane.

5. The emulsion according to any one of claims 1 - 4, characterized in that, the raw materials for preparing the emulsion also optionally include emulsifiers, initiators, neutralizing agents, post - treatment agents, pH regulators, water; preferably, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium p - styrenesulfonate, sodium dodecylbenzenesulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate, alkyl alcohol ether phosphate; preferably, the dosage of the emulsifier is 1 - 5% of the total mass of components a) - e); preferably, the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate; preferably, the total dosage of the initiator is 0.2 - 0.6% of the total mass of components a) - e), preferably 0.2 - 0.4%; preferably, the neutralizing agent is selected from one or more of sodium bicarbonate, diethylenetriamine, diethanolamine, ethanolamine; Preferably, the dosage of the neutralizing agent is 0.1-4% of the total mass of monomer components a)-e); Preferably, the post-treatment agent includes an oxidizing agent and a reducing agent. The oxidizing agent is selected from one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate; the reducing agent is selected from one or more of sodium bisulfite, sodium metabisulfite, and vitamin C; Preferably, the total dosage of the post-treatment agent is 0.15-0.6% of the total mass of components a)-e); Preferably, the pH regulator is selected from one or more of diethylenetriamine, diethanolamine, and ethanolamine; Preferably, the end point of the dosage of the pH regulator is to adjust the pH of the system to 7-9; Preferably, the total dosage of the water is 1-1.5 times the total mass of components a)-e).

6. A method for preparing an emulsion according to any one of claims 1-5, characterized in that, comprises the following steps: 1) Mix components a), b), c), d), e), f) and water and part of the emulsifier evenly to prepare a pre-emulsion; 2) Divide the initiator into two parts, dissolve them separately with water to obtain the dropping initiator and the bottom-of-the-kettle initiator; 3) Mix the neutralizing agent, the remaining emulsifier and water, add them into the reaction kettle, stir well and heat up; preferably heat up to 80-90 °C; Add part of the pre-emulsion, and after stirring evenly, add all the bottom-of-the-kettle initiator and react to obtain a seed emulsion; 4) Control the temperature in the reaction kettle at 80-90 °C, continue to add the remaining pre-emulsion and all the dropping initiator to the seed emulsion, and then keep warm; 5) Cool the reaction kettle to 70-80 °C, gradually add the post-treatment agent to the reaction kettle, and then keep warm; 6) Cool down to below 45 °C, add the pH regulator to adjust the pH of the system to 7-9, carry out steam stripping and filtration for discharging; preferably, the steam stripping temperature is 55-85 °C, and the pressure is controlled at -75 Kpa to -95 Kpa.

7. According to the preparation method described in claim 6, characterized in that, in step 1), the dosage of the emulsifier accounts for 90-99.5% of the total mass of all the emulsifiers.

8. According to the preparation method described in claim 6, characterized in that, in step 2), the dosage of the initiator used to prepare the dropping initiator accounts for 25-50% of its total mass, and the dosage of the initiator used to prepare the bottom-of-the-kettle initiator accounts for 50-75% of its total mass.

9. According to the preparation method described in any one of claims 6-8, characterized in that, in step 3), the dosage of the pre-emulsion used to prepare the seed emulsion is 1-8% of its total mass.

10. Application of the emulsion according to any one of claims 1-5 or the emulsion prepared by the preparation method according to any one of claims 6-9 in coatings.

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