Water-based acrylic marker ink and preparation method thereof

Abstract

This application discloses a water-based acrylic marker ink and its preparation method, relating to the technical field of ink production. The water-based acrylic marker ink comprises the following components by weight: 100-150 parts of a water-based acrylic emulsion, 10-20 parts of a pigment, 5-8 parts of a surfactant, 0.1-0.4 parts of a preservative, 0.2-0.8 parts of a pH regulator, and 10-20 parts of deionized water. The use of the water-based acrylic emulsion can effectively improve the stability of the water-based acrylic marker ink, ensuring the long-term stability of the marker ink.

Description

Technical Field

[0001] The present application relates to the technical field of ink production, and in particular to a water-based acrylic marker ink and a preparation method thereof. Background Art

[0002] Water-based acrylic marker inks are widely used in painting, design, and other fields, gaining market favor due to their environmental and safety characteristics. With growing environmental awareness, traditional oil-based inks are gradually being replaced, with water-based inks becoming the mainstream choice. However, water-based inks still face challenges during use, such as weather resistance and insufficient adhesion, which limit their application in high-end markets. To improve the performance of water-based inks, several methods are commonly used in existing technologies to enhance their quality: first, by adding various additives, such as thickeners and wetting agents, to enhance the ink's stability and fluidity; second, by optimizing the polymer emulsion formulation, for example, by adjusting the ratio of acrylic emulsion to polyurethane emulsion to achieve better film-forming properties and adhesion; and third, by introducing nanomaterials, such as silica or carbon nanotubes, to enhance the ink's abrasion resistance and weather resistance. While these methods can improve the performance of water-based inks to some extent, they do not address the poor stability of water-based inks over long-term use. Summary of the Invention

[0003] The purpose of this application is to provide a water-based acrylic marker ink and a preparation method thereof to solve the accumulation problem of water-based acrylic ink.

[0004] This application provides a water-based acrylic marker ink, which adopts the following technical solution:

[0005] A water-based acrylic marker ink comprises the following components by weight: 100-150 parts of a water-based acrylic emulsion, 10-20 parts of a pigment, 5-8 parts of a surfactant, 0.1-0.4 parts of a preservative, 0.2-0.8 parts of a pH regulator, and 10-20 parts of deionized water.

[0006] By adopting the above technical solution, the use of water-based acrylic emulsion can effectively improve the stability of water-based acrylic marker ink and ensure the stability of marker ink during long-term use.

[0007] Optionally, the preparation method of the water-based acrylic emulsion comprises the following steps:

[0008] S001, adding acrylic acid and bisphenol A to deionized water, dispersing them evenly, adding a chain transfer agent, raising the temperature to the reaction temperature, keeping stirring, and then adding an initiator dropwise to obtain a composite polyacrylic acid solution;

[0009] S002, mixing the composite polyacrylic acid solution prepared in step S001 and the platinum nanoparticle gel, stirring evenly, adding thiol, heating and refluxing to react, and after the reaction is completed, obtaining a water-based acrylic emulsion.

[0010] By employing the above technical solution, a composite polyacrylic acid solution is prepared and then added with a platinum nanoparticle gel, resulting in a structure that exhibits both excellent support and dispersion properties. Due to their small size and high specific surface area, platinum nanoparticles possess high surface energy, making them more likely to form a stable suspension in water. By using a hydrophobic alcohol to connect the platinum nanoparticles and the water-based acrylic emulsion, the system maintains dispersion properties in an ink environment while maintaining long-term stability thanks to the combined action of the platinum nanoparticles and modified acrylic acid.

[0011] Optionally, the thiol is selected from one of 1,2-ethanedithiol, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 2-mercaptoethanol and dimercaptosuccinic acid.

[0012] By adopting the above technical solution, a thiol with two thiol groups is selected, which can form a stable coordination bond with platinum nanoparticles, enhance the stability of the emulsion, reduce particle agglomeration, and improve the storage stability of the ink and the smoothness during use.

[0013] Optionally, in step S001, the mass ratio of acrylic acid, bisphenol A, chain transfer agent, initiator and deionized water is between 1: (0.1-0.3): (0.005-0.009): (0.003-0.006): (1.5-2.5).

[0014] By adopting the above technical solution, acrylic acid and bisphenol A are used as the products of the polymerization reaction. The dosage ratio needs to be controlled during the reaction process to avoid excessive residual reaction raw materials and reduce the performance of the composite polyacrylic acid solution. The use of chain transfer agents and initiators can increase the polymerization degree of the polymer and ensure the performance of the composite polyacrylic acid solution.

[0015] Optionally, in step S002, the mass ratio of the composite polyacrylic acid solution, platinum nanoparticle gel and thiol is between 1: (0.5-0.7): (0.002-0.006).

[0016] By adopting the above technical solution and controlling the amount of composite polyacrylic acid solution, platinum nanoparticle gel and thiol, the prepared water-based acrylic emulsion can have better stability and avoid the influence of excessive raw materials on product performance.

[0017] Optionally, the chain transfer agent is selected from one of dodecyl mercaptan, trichloroethylene and tetrachloromethane, and the initiator is selected from one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.

[0018] By adopting the above technical solution and selecting specific initiators and chain transfer agents, the polymerization reaction rate and product molecular weight distribution can be effectively controlled, thereby improving the performance stability of the composite polyacrylic acid solution and the overall performance of the ink.

[0019] Optionally, the pH regulator is selected from one or more of triethanolamine, dimethylamine, triethylamine and sodium bicarbonate.

[0020] By adopting the above technical solution, the pH regulator can optimize the performance of the ink, ensure its stability and writing smoothness under different environmental conditions, and improve its adhesion and drying performance on different materials.

[0021] Optionally, the pigment is selected from one of titanium dioxide, iron oxide, ultramarine blue, phthalocyanine and carbon black.

[0022] By adopting the above technical solution, different types of pigments can make the ink present different colors and maintain the long-term stability of the ink color.

[0023] Optionally, the surfactant is selected from one of sodium benzoate, sodium salicylate, p-aminobenzoic acid, niacinamide, acetamide, cyclohexanone, ethanol, and NN-dimethylformamide.

[0024] By adopting the above technical solution, the surfactant can increase the solubility of different substances in the solvent, thereby improving the mixing degree of various components in the ink.

[0025] In a second aspect, the present application provides a water-based acrylic marker ink, which adopts the following technical solution:

[0026] A water-based acrylic marker ink is used to prepare the water-based acrylic marker ink as described above, comprising the following steps:

[0027] A pigment, a preservative, and a portion of a surfactant are added to deionized water, stirred and dispersed uniformly to obtain a first solution; the remaining portion of the surfactant is added to a water-based acrylic emulsion, stirred and dispersed uniformly to obtain a second solution; the first solution, the second solution, and a pH regulator are mixed and stirred for 1-3 hours to obtain a water-based acrylic marker ink.

[0028] By adopting the above technical solution, the pigment is dispersed in part of the deionized water by using a surfactant, and the remaining deionized water is used to disperse the water-based acrylic emulsion, so that the pigment and the water-based acrylic emulsion are easier to mix, thereby improving the processing efficiency.

[0029] In summary, this application includes at least one of the following beneficial technical effects:

[0030] 1. Prepare a composite polyacrylic acid solution and add platinum nanoparticle gel to form a gel with both excellent support and dispersion properties. Due to their small size and high specific surface area, platinum nanoparticles have high surface energy, which makes them more likely to form a stable suspension system in water. By using a hydrophobic alcohol to connect the platinum nanoparticles and the water-based acrylic emulsion, the dispersion properties can be maintained in the ink environment, and the combined action of the platinum nanoparticles and modified acrylic acid can maintain long-term stability.

[0031] 2. The use of thiols with two sulfhydryl groups can form stable coordination bonds with platinum nanoparticles, enhance the stability of the emulsion, reduce particle agglomeration, and improve the storage stability of the ink and the smoothness during use. DETAILED DESCRIPTION

[0032] The present application is further described in detail below with reference to the following embodiments and comparative examples.

[0033] In the following examples and comparative examples, the thiol used is selected from 1,2-ethanedithiol, the chain extender is selected from 1,4-butanediol, the chain transfer agent is selected from trichloroethylene, the initiator is selected from benzoyl peroxide, the reducing agent is selected from sodium borohydride, the pigment is selected from carbon black, the surfactant is selected from sodium benzoate, the preservative is selected from phenol, and the pH regulator is selected from triethanolamine.

[0034] Example 1:

[0035] A method for preparing water-based acrylic marker ink comprises the following steps:

[0036] S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 200 g of deionized water, stir and disperse them evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 0.5 g of benzoyl peroxide, keep stirring, and react for 3 hours to obtain a composite polyacrylic acid solution.

[0037] S102. Add 20.72 g of chloroplatinic acid hexahydrate to 200 g of deionized water, stir until dissolved, heat to 65° C., dropwise add 6.06 g of 1 g / ml sodium borohydride solution, react for 5 h, and let stand at room temperature for 6 h to obtain a platinum nanoparticle gel.

[0038] S103, 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102 were mixed and stirred evenly. The mixture was heated to 105° C. in a reflux device, 0.2 g of 1,2-ethanedithiol was added dropwise, and the mixture was refluxed for 3.5 hours. The pH value of the reaction product was adjusted to 6-8 to obtain a water-based acrylic emulsion.

[0039] S104. Take 15 g of deionized water, add 3 g of sodium benzoate, 15 g of carbon black and 0.3 g of phenol, stir and disperse evenly to obtain a first solution; take 125 g of the water-based acrylic emulsion prepared in step S103, add 3 g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5 g of triethanolamine, and stir for 2 hours to obtain a water-based acrylic marker ink.

[0040] Example 2

[0041] A method for preparing water-based acrylic marker ink comprises the following steps:

[0042] S101. Add 10 g of bisphenol A and 100 g of acrylic acid to 150 g of deionized water, stir and disperse them evenly, then add 0.5 g of trichloroethylene, raise the temperature to 70°C, dropwise add 0.3 g of benzoyl peroxide, keep stirring, and react for 2 h to obtain a composite polyacrylic acid solution.

[0043] S102. Add 5.18 g of chloroplatinic acid hexahydrate to 200 g of deionized water, stir until dissolved, heat to 50° C., dropwise add 1.52 g of 1 g / ml sodium borohydride solution, react for 3 h, and let stand at room temperature for 4 h to obtain a platinum nanoparticle gel.

[0044] S103, 50 g of the composite polyacrylic acid solution prepared in step S101 and 25 g of the platinum nanoparticle gel prepared in step S102 are mixed and stirred evenly. Then, the temperature is raised to 80° C. in a reflux device, 0.1 g of 1,2-ethanedithiol is added dropwise, and the mixture is refluxed for 2 h. After the pH value of the reaction product is adjusted to 6-8, a water-based acrylic emulsion is obtained.

[0045] S104. Take 15 g of deionized water, add 3 g of sodium benzoate, 15 g of carbon black and 0.3 g of phenol, stir and disperse evenly to obtain a first solution; take 125 g of the water-based acrylic emulsion prepared in step S103, add 3 g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5 g of triethanolamine, and stir for 2 hours to obtain a water-based acrylic marker ink.

[0046] Example 3

[0047] A method for preparing water-based acrylic marker ink comprises the following steps:

[0048] S101. Add 30 g of bisphenol A and 100 g of acrylic acid to 250 g of deionized water, stir and disperse them evenly, then add 0.9 g of trichloroethylene, raise the temperature to 90° C., dropwise add 0.6 g of benzoyl peroxide, keep stirring, and react for 4 hours to obtain a composite polyacrylic acid solution.

[0049] S102. Add 41.44 g of chloroplatinic acid hexahydrate to 200 g of deionized water, stir until dissolved, heat to 80° C., dropwise add 12.12 g of 1 g / ml sodium borohydride solution, react for 8 h, and let stand at room temperature for 8 h to obtain a platinum nanoparticle gel.

[0050] S103, 50 g of the composite polyacrylic acid solution prepared in step S101 and 35 g of the platinum nanoparticle gel prepared in step S102 are mixed and stirred evenly. Then, the temperature is raised to 130° C. in a reflux device, 0.3 g of 1,2-ethanedithiol is added dropwise, and the mixture is refluxed for 5 h. After the pH value of the reaction product is adjusted to 6-8, a water-based acrylic emulsion is obtained.

[0051] S104. Take 15 g of deionized water, add 3 g of sodium benzoate, 15 g of carbon black and 0.3 g of phenol, stir and disperse evenly to obtain a first solution; take 125 g of the water-based acrylic emulsion prepared in step S103, add 3 g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5 g of triethanolamine, and stir for 2 hours to obtain a water-based acrylic marker ink.

[0052] Example 4:

[0053] A method for preparing water-based acrylic marker ink comprises the following steps:

[0054] S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 300 g of deionized water, stir and disperse them evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 3.0 g of benzoyl peroxide, keep stirring, and react for 3 hours to obtain a composite polyacrylic acid solution.

[0055] S102. Add 20.72 g of chloroplatinic acid hexahydrate to 200 g of deionized water, stir until dissolved, heat to 65° C., dropwise add 6.06 g of 1 g / ml sodium borohydride solution, react for 5 h, and let stand at room temperature for 6 h to obtain a platinum nanoparticle gel.

[0056] S103, 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102 were mixed and stirred evenly. The mixture was heated to 105° C. in a reflux device, 0.2 g of 1,2-ethanedithiol was added dropwise, and the mixture was refluxed for 3.5 hours. The pH value of the reaction product was adjusted to 6-8 to obtain a water-based acrylic emulsion.

[0057] S104. Take 10 g of deionized water, add 2.5 g of sodium benzoate, 10 g of carbon black and 0.1 g of phenol, stir and disperse evenly to obtain a first solution; take 100 g of the water-based acrylic emulsion prepared in step S103, add 2.5 g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.2 g of triethanolamine, and stir for 1 hour to obtain a water-based acrylic marker ink.

[0058] Example 5:

[0059] A method for preparing water-based acrylic marker ink comprises the following steps:

[0060] S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 300 g of deionized water, stir and disperse them evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 3.0 g of benzoyl peroxide, keep stirring, and react for 3 hours to obtain a composite polyacrylic acid solution.

[0061] S102. Add 20.72 g of chloroplatinic acid hexahydrate to 200 g of deionized water, stir until dissolved, heat to 65° C., dropwise add 6.06 g of 1 g / ml sodium borohydride solution, react for 5 h, and let stand at room temperature for 6 h to obtain a platinum nanoparticle gel.

[0062] S103, 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102 were mixed and stirred evenly. The mixture was heated to 105° C. in a reflux device, 0.2 g of 1,2-ethanedithiol was added dropwise, and the mixture was refluxed for 3.5 hours. The pH value of the reaction product was adjusted to 6-8 to obtain a water-based acrylic emulsion.

[0063] S104. Take 20 g of deionized water, add 4 g of sodium benzoate, 20 g of carbon black and 0.4 g of phenol, stir and disperse evenly to obtain a first solution; take 150 g of the water-based acrylic emulsion prepared in step S103, add 4 g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.8 g of triethanolamine, and stir for 3 hours to obtain a water-based acrylic marker ink.

[0064] Comparative Example 1

[0065] Compared with Example 1, the difference is that step S102 and step S103 are not performed, and in step S104, the composite polyacrylic acid solution prepared in step S101 of equal mass is used to replace the water-based acrylic emulsion prepared in step S103.

[0066] Comparative Example 2

[0067] Compared with Example 1, the difference is that in step S101, acrylic acid of equal mass is used instead of bisphenol A.

[0068] Performance tests were performed on the water-based acrylic marker inks prepared in the examples and comparative examples.

[0069] Ink sedimentation stability test: Seal the ink and place it in a 60°C oven for 20 days. Take it out and cool it, then stir it evenly for 1 hour. Take 8 ml of ink and place it in a 10 ml centrifuge tube. Centrifuge it at a high speed of 12,000 rpm for 30 minutes. Observe the amount of sediment and divide it into three levels according to the amount of sediment. The amount of sediment is good if it is very small, poor if it is a lot, and fair if it is in between.

[0070] Adhesion Test: According to the national standard QB / T 2777-2015 for the adhesion test of water-based marker inks, five consecutive circles with a diameter of 20mm-30mm are drawn on a glass plate with a pen. After 5 minutes, the traces are covered with two layers of medical gauze and pressed with a 500g special weight (bottom diameter 50mm). The traces are rubbed back and forth five times to test whether they have been erased. The adhesion strength of the ink to the substrate is graded from 0 to 5, with grade 0 indicating excellent adhesion with no signs of detachment, grade 1 indicating 5% detachment, grade 2 indicating 15% detachment, grade 3 indicating 35% detachment, grade 4 indicating 65% detachment, and grade 5 indicating complete detachment and no adhesion.

[0071] Table 1 Performance test results of water-based acrylic marker inks prepared in Examples and Comparative Examples

[0072] Stability testing Adhesion test Stability testing Adhesion test Example 1 good Level 0 Example 5 good Level 0 Example 2 good Level 0 Comparative Example 1 Difference Level 1 Example 3 good Level 0 Comparative Example 2 Difference Level 1 Example 4 good Level 0

[0073] The properties of acrylic marker ink were investigated according to Table 1, Examples, and Comparative Examples.

[0074] Comparing Example 1, Example 2 and Example 3, the difference lies in the different amounts of raw materials used in the prepared composite polyacrylic acid solution and platinum nanoparticle gel. It can be seen that within the range of raw material amounts in the present application, the prepared composite polyacrylic acid solution and platinum nanoparticle gel can form ink with excellent stability and good adhesion after subsequent processing, thereby ensuring the stability of the ink during long-term use.

[0075] By comparing Example 1, Example 4, and Example 5, the difference lies in the different amounts of raw materials used in preparing the water-based acrylic marker ink. It can be seen that when the raw materials for preparing the composite polyacrylic acid solution and the platinum nanoparticle gel are the same, within the range of raw material amounts used in this application, the prepared water-based acrylic marker ink has good stability and adhesion, which further indicates that the ink can remain stable during long-term use.

[0076] Comparing Example 1 with Comparative Example 1, the difference is that the composite polyacrylic acid solution prepared in step S101 of equal mass is used instead of the water-based acrylic emulsion prepared in step S103. It can be seen that while Comparative Example 1 exhibits a smaller decrease in adhesion compared to Example 1, its stability is significantly reduced. After aging and centrifugation, a larger amount of sediment is produced, indicating that the addition of the platinum nanoparticle gel to the water-based acrylic emulsion can help maintain ink stability and dispersion after long-term use.

[0077] Comparing Example 1 and Comparative Example 2, the difference is that in step S101, an equal mass of acrylic acid is used instead of bisphenol A. It can be seen that while the adhesion of Comparative Example 2 decreases less than that of Example 1, its stability decreases significantly. After aging and centrifugation, more sediment is produced. This indicates that the composite acrylic acid solution prepared by adding bisphenol A can effectively improve the stability of the ink and reduce ink sediment after long-term use.

[0078] The examples of this specific embodiment are all preferred embodiments of this application and are not intended to limit the scope of protection of this application. Identical components are represented by the same reference numerals. Therefore, any equivalent changes made based on the structure, shape, and principle of this application should be included in the scope of protection of this application.

Claims

1. A water-based acrylic marker ink, characterized in that: The material comprises the following components by weight: 100-150 parts of water-based acrylic emulsion, 10-20 parts of pigment, 5-8 parts of sodium benzoate, 0.1-0.4 parts of preservative, 0.2-0.8 parts of pH regulator, and 10-20 parts of deionized water; The preparation method of the water-based acrylic emulsion comprises the following steps: S001, adding acrylic acid and bisphenol A to deionized water, dispersing them evenly, adding a chain transfer agent, heating to the reaction temperature, keeping stirring, and then adding an initiator dropwise to obtain a composite polyacrylic acid solution; S002, mixing the composite polyacrylic acid solution prepared in step S001 and the platinum nanoparticle gel, stirring evenly, adding thiol, heating and refluxing to react, and obtaining a water-based acrylic emulsion after the reaction is completed; Wherein, the thiol is selected from one of 1,2-ethanedithiol, 1,3-dimercaptopropane, 1,4-dimercaptobutane and dimercaptosuccinic acid; In step S001, the mass ratio of acrylic acid, bisphenol A, chain transfer agent, initiator and deionized water is 1: (0.1-0.3): (0.005-0.009): (0.003-0.006): (1.5-2.5); In step S002, the mass ratio of the composite polyacrylic acid solution, platinum nanoparticle gel and thiol is 1: (0.5-0.7): (0.002-0.006); The chain transfer agent is selected from one of dodecyl mercaptan, trichloroethylene and tetrachloromethane, and the initiator is selected from one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.

2. The water-based acrylic marker ink according to claim 1, characterized in that: The pH regulator is selected from one or more of triethanolamine, dimethylamine, triethylamine and sodium bicarbonate.

3. The water-based acrylic marker ink according to claim 1, characterized in that: The pigment is selected from one of titanium dioxide, iron oxide, ultramarine blue, phthalocyanine and carbon black.

4. A method for preparing a water-based acrylic marker ink, for preparing the water-based acrylic marker ink according to any one of claims 1 to 3, comprising the following steps: A pigment, a preservative, and a portion of sodium benzoate are added to deionized water, and the mixture is stirred and dispersed uniformly to obtain a first solution; the remaining portion of sodium benzoate is added to a water-based acrylic emulsion, and the mixture is stirred and dispersed uniformly to obtain a second solution; the first solution, the second solution, and a pH adjuster are mixed and stirred for 1-3 hours to obtain a water-based acrylic marker ink.