Water-based propylene mark pen ink and preparation method thereof

Abstract

The invention discloses water-based propylene mark pen ink and a preparation method thereof, and relates to the technical field of ink manufacturing, the water-based propylene mark pen ink comprises the following substances 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 part of a preservative, 0.2-0.8 part of a pH regulator, and 10-20 parts of deionized water. By using the water-based acrylic emulsion, the stability of the water-based propylene mark pen ink can be effectively improved, and the long-term use stability of the mark pen ink is guaranteed.

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 ink is widely used in painting, design and other fields, and is favored by the market for its environmental protection and safety. With the improvement of social awareness of environmental protection, traditional oil-based inks are gradually replaced, and water-based inks have become the mainstream choice. However, water-based inks still face some challenges during use, such as insufficient weather resistance and adhesion, which limit their application in the high-end market. In order to improve the performance of water-based inks, the following methods are usually adopted in the prior art to improve their quality: first, by adding different types of additives, such as thickeners, wetting agents, etc., to enhance the stability and fluidity of the ink; second, optimize the formula of the polymer emulsion, such as adjusting the ratio of acrylic emulsion to polyurethane emulsion, so that it has better film-forming properties and adhesion; third, introduce nanomaterials, such as silica or carbon nanotubes, to improve the wear resistance and weather resistance of the ink. Although these methods can improve the performance of water-based inks to a certain extent, the problem of poor stability of water-based inks has not been improved during long-term use. Summary of the invention

[0003] The purpose of the present 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] The present application provides a water-based acrylic marker ink, which adopts the following technical solution: A water-based acrylic marker ink comprises the following components by weight: 100-150 parts of water-based acrylic emulsion, 10-20 parts of pigment, 5-8 parts of surfactant, 0.1-0.4 parts of preservative, 0.2-0.8 parts of pH regulator and 10-20 parts of deionized water.

[0005] 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.

[0006] Optionally, 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, raising the temperature to the reaction temperature, keeping stirring, and then dropping an initiator 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 for reaction, and after the reaction is completed, obtaining a water-based acrylic emulsion.

[0007] By adopting the above technical solution, a composite polyacrylic acid solution is prepared and a platinum nanoparticle gel is added to form a gel having both better support performance and better dispersion performance. Since platinum nanoparticles have a higher surface energy due to their small size and high specific surface area, it is easier for them to form a stable suspension system in water. By using hydrophobic alcohol to connect platinum nanoparticles and water-based acrylic emulsion, in the ink environment, it is possible to maintain dispersion performance while maintaining long-term stability under the joint action of platinum nanoparticles and modified acrylic acid.

[0008] Optionally, the thiol is selected from one of 1,2-ethanedithiol, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 2-mercaptoethanol and dimercaptosuccinic acid.

[0009] 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.

[0010] Optionally, in step S001, the mass ratio of the 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).

[0011] By adopting the above technical scheme, acrylic acid and bisphenol A are used as products of the polymerization reaction, and 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.

[0012] Optionally, in step S002, the mass ratio of the composite polyacrylic acid solution, the platinum nanoparticle gel and the thiol is between 1:(0.5-0.7):(0.002-0.006).

[0013] By adopting the above technical solution and controlling the dosage of the 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.

[0014] 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 azobisisoheptanenitrile.

[0015] 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.

[0016] Optionally, the pH regulator is selected from one or more of triethanolamine, dimethylamine, triethylamine and sodium bicarbonate.

[0017] By adopting the above technical solution, the pH adjuster 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.

[0018] Optionally, the pigment is selected from one of titanium dioxide, iron oxide, ultramarine blue, phthalocyanine and carbon black.

[0019] 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.

[0020] Optionally, the surfactant is selected from one of sodium benzoate, sodium salicylate, p-aminobenzoic acid, niacinamide, acetamide, cyclohexanone, ethanol, and NN-dimethylformamide.

[0021] 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.

[0022] In a second aspect, the present application provides a water-based acrylic marker ink, which adopts the following technical solution: A water-based acrylic marker ink, used to prepare the water-based acrylic marker ink as described above, comprises the following steps: Add pigment, preservative and part of surfactant to deionized water, stir and disperse evenly to obtain a first solution; add the remaining part of surfactant to water-based acrylic emulsion, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and the pH regulator, and stir for 1-3 hours to obtain water-based acrylic marker ink.

[0023] By adopting the above technical solution, the pigment is dispersed in part of the deionized water 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 and the processing efficiency is improved.

[0024] In summary, the present application includes at least one of the following beneficial technical effects: 1. Prepare a composite polyacrylic acid solution and add platinum nanoparticle gel to form a gel with both good support performance and good dispersion performance. Since platinum nanoparticles have a high surface energy due to their small size and high specific surface area, it is easier for them to form a stable suspension system in water. By using hydrophobic alcohol to connect platinum nanoparticles and water-based acrylic emulsion, in the ink environment, it can maintain dispersion performance while maintaining long-term stability under the joint action of platinum nanoparticles and modified acrylic acid; 2. The use of thiols with two thiol 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

[0025] The present application is further described in detail below in conjunction with embodiments and comparative examples.

[0026] 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.

[0027] Embodiment 1: A method for preparing a water-based acrylic marker ink comprises the following steps: S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 200 g of deionized water, stir and disperse evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 0.5 g of benzoyl peroxide, keep stirring, react for 3 hours, and obtain a composite polyacrylic acid solution.

[0028] 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 stand at room temperature for 6 h to obtain platinum nanoparticle gel.

[0029] S103, mixing 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102, stirring evenly, raising the temperature to 105° C. in a reflux device, adding dropwise 0.2 g of 1,2-ethanedithiol, and refluxing for 3.5 hours, adjusting the pH value of the reaction product to 6-8, and obtaining a water-based acrylic emulsion.

[0030] S104, take 15g of deionized water, add 3g of sodium benzoate, 15g of carbon black and 0.3g of phenol, stir and disperse evenly to obtain a first solution; take 125g of the water-based acrylic emulsion prepared in step S103, add 3g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5g of triethanolamine, and stir for 2h to obtain a water-based acrylic marker ink.

[0031] Example 2 A method for preparing a water-based acrylic marker ink comprises the following steps: S101. Add 10 g of bisphenol A and 100 g of acrylic acid to 150 g of deionized water, stir and disperse evenly, then add 0.5 g of trichloroethylene, raise the temperature to 70°C, dropwise add 0.3 g of benzoyl peroxide, keep stirring, react for 2 hours, and obtain a composite polyacrylic acid solution.

[0032] 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 stand at room temperature for 4 h to obtain platinum nanoparticle gel.

[0033] S103, mixing 50 g of the composite polyacrylic acid solution prepared in step S101 and 25 g of the platinum nanoparticle gel prepared in step S102, stirring evenly, raising the temperature to 80° C. in a reflux device, adding dropwise 0.1 g of 1,2-ethanedithiol, and refluxing for 2 h, adjusting the pH value of the reaction product to 6-8, and obtaining a water-based acrylic emulsion.

[0034] S104, take 15g of deionized water, add 3g of sodium benzoate, 15g of carbon black and 0.3g of phenol, stir and disperse evenly to obtain a first solution; take 125g of the water-based acrylic emulsion prepared in step S103, add 3g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5g of triethanolamine, and stir for 2h to obtain a water-based acrylic marker ink.

[0035] Example 3 A method for preparing a water-based acrylic marker ink comprises the following steps: S101. Add 30 g of bisphenol A and 100 g of acrylic acid to 250 g of deionized water, stir and disperse 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.

[0036] 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 stand at room temperature for 8 h to obtain platinum nanoparticle gel.

[0037] S103, mixing 50 g of the composite polyacrylic acid solution prepared in step S101 and 35 g of the platinum nanoparticle gel prepared in step S102, stirring evenly, raising the temperature to 130° C. in a reflux device, adding dropwise 0.3 g of 1,2-ethanedithiol, and refluxing for 5 hours, adjusting the pH value of the reaction product to 6-8, and obtaining a water-based acrylic emulsion.

[0038] S104, take 15g of deionized water, add 3g of sodium benzoate, 15g of carbon black and 0.3g of phenol, stir and disperse evenly to obtain a first solution; take 125g of the water-based acrylic emulsion prepared in step S103, add 3g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.5g of triethanolamine, and stir for 2h to obtain a water-based acrylic marker ink.

[0039] Embodiment 4: A method for preparing a water-based acrylic marker ink comprises the following steps: S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 300 g of deionized water, stir and disperse evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 3.0 g of benzoyl peroxide, keep stirring, react for 3 hours, and obtain a composite polyacrylic acid solution.

[0040] 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 stand at room temperature for 6 h to obtain platinum nanoparticle gel.

[0041] S103, mixing 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102, stirring evenly, raising the temperature to 105° C. in a reflux device, adding dropwise 0.2 g of 1,2-ethanedithiol, and refluxing for 3.5 hours, adjusting the pH value of the reaction product to 6-8, and obtaining a water-based acrylic emulsion.

[0042] S104, take 10g of deionized water, add 2.5g of sodium benzoate, 10g of carbon black and 0.1g of phenol, stir and disperse evenly to obtain a first solution; take 100g of the water-based acrylic emulsion prepared in step S103, add 2.5g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.2g of triethanolamine, and stir for 1h to obtain a water-based acrylic marker ink.

[0043] Embodiment 5: A method for preparing a water-based acrylic marker ink comprises the following steps: S101. Add 20 g of bisphenol A and 100 g of acrylic acid to 300 g of deionized water, stir and disperse evenly, then add 0.7 g of trichloroethylene, raise the temperature to 80°C, dropwise add 3.0 g of benzoyl peroxide, keep stirring, react for 3 hours, and obtain a composite polyacrylic acid solution.

[0044] 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 stand at room temperature for 6 h to obtain platinum nanoparticle gel.

[0045] S103, mixing 50 g of the composite polyacrylic acid solution prepared in step S101 and 30 g of the platinum nanoparticle gel prepared in step S102, stirring evenly, raising the temperature to 105° C. in a reflux device, adding dropwise 0.2 g of 1,2-ethanedithiol, and refluxing for 3.5 hours, adjusting the pH value of the reaction product to 6-8, and obtaining a water-based acrylic emulsion.

[0046] S104, take 20g of deionized water, add 4g of sodium benzoate, 20g of carbon black and 0.4g of phenol, stir and disperse evenly to obtain a first solution; take 150g of the water-based acrylic emulsion prepared in step S103, add 4g of sodium benzoate, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and 0.8g of triethanolamine, and stir for 3h to obtain a water-based acrylic marker ink.

[0047] Comparative Example 1 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.

[0048] Comparative Example 2 Compared with Example 1, the difference is that in step S101, an equal mass of acrylic acid is used to replace bisphenol A.

[0049] The water-based acrylic marker inks prepared in the examples and comparative examples were tested for performance.

[0050] Ink sedimentation stability test: seal the ink and place it in a 60℃ oven for 20 days. Take it out and cool it, 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 12000 rpm for 30 minutes, observe the amount of sediment, and divide it into 3 levels according to the amount of sediment. The one with very little sediment is good, the one with a lot of sediment is poor, and the one in between is fair.

[0051] Adhesion test: According to the national standard QB / T 2777-2015 for the adhesion test method of water-based marker ink, use a pen to draw 5 consecutive circles with a diameter of 20mm-30mm on the glass plate. After 5 minutes, cover the traces with two layers of medical gauze, press a 500g special weight (bottom diameter is 50mm), and rub back and forth five times to test whether the traces are erased. According to the strength of the adhesion between the ink and the substrate, it is divided into 0-5 levels, 0 means excellent adhesion and no signs of shedding, 1 means 5% shedding, 2 means 15% shedding, 3 means 35% shedding, 4 means 65% shedding, and 5 means complete shedding and no adhesion.

[0052] Table 1 Performance test results of water-based acrylic marker ink prepared in Examples and Comparative Examples Stability test Adhesion test Stability test 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 According to Table 1, the performance of acrylic marker ink was investigated in Examples and Comparative Examples.

[0053] Comparing Example 1, Example 2 and Example 3, the difference is that the raw material amounts of the prepared composite polyacrylic acid solution and the platinum nanoparticle gel are different. It can be seen that within the raw material amount range of the present application, the prepared composite polyacrylic acid solution and the 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.

[0054] Comparing Example 1, Example 4 and Example 5, the difference is that the amount of raw materials used to prepare the water-based acrylic marker ink is different. 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 the raw material dosage of the present 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.

[0055] 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 to replace the water-based acrylic emulsion prepared in step S103. It can be seen that compared with Example 1, although the adhesion of Comparative Example 1 decreases less, the stability decreases more. After aging and centrifugation, more sediment is generated, indicating that after long-term use, the water-based acrylic emulsion prepared by adding platinum nanoparticle gel can help maintain the stability and dispersion of the ink.

[0056] Comparing Example 1 and Comparative Example 2, the difference is that in step S101, an equal mass of acrylic acid is used to replace bisphenol A. It can be seen that compared with Example 1, although the adhesion of Comparative Example 2 decreases less, the stability decreases more. After aging and centrifugation, more sediment is generated, indicating that the composite acrylic acid solution prepared by adding bisphenol A can effectively improve the stability of the ink and reduce the sediment of the ink after long-term use.

[0057] The embodiments of this specific implementation are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. The same components are represented by the same reference numerals. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present 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 surfactant, 0.1-0.4 parts of preservative, 0.2-0.8 parts of pH regulator and 10-20 parts of deionized water.

2. The water-based acrylic marker ink according to claim 1, characterized in that: 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, raising the temperature to the reaction temperature, keeping stirring, and then dropping an initiator 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 for reaction, and after the reaction is completed, obtaining a water-based acrylic emulsion.

3. The water-based acrylic marker ink according to claim 2, characterized in that: The thiol is selected from one of 1,2-ethanedithiol, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 2-mercaptoethanol and dimercaptosuccinic acid.

4. The water-based acrylic marker ink according to claim 2, characterized in that: In the step S001, the mass ratio of the 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).

5. The water-based acrylic marker ink according to claim 2, characterized in that: In the step S002, the mass ratio of the composite polyacrylic acid solution, the platinum nanoparticle gel and the thiol is between 1: (0.5-0.7): (0.002-0.006).

6. The water-based acrylic marker ink according to claim 2, characterized in that: 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 azobisisoheptylnitrile.

7. 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.

8. 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.

9. The water-based acrylic marker ink according to claim 1, characterized in that: The surfactant is selected from one of sodium benzoate, sodium salicylate, p-aminobenzoic acid, niacinamide, acetamide, cyclohexanone, ethanol, and NN-dimethylformamide.

10. 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 9, comprising the following steps: Add pigment, preservative and part of surfactant to deionized water, stir and disperse evenly to obtain a first solution; add the remaining part of surfactant to water-based acrylic emulsion, stir and disperse evenly to obtain a second solution; mix the first solution, the second solution and the pH regulator, and stir for 1-3 hours to obtain water-based acrylic marker ink.