Preparation method of wear-resistant and scratch-resistant water-based ink

Abstract

The invention relates to the field of ink, in particular to a preparation method of wear-resistant and scratch-resistant water-based ink. The water-based ink is prepared from the following components in parts by weight: 30 to 50 parts of self-crosslinking modified acrylic emulsion, 5 to 15 parts of modified calcium hexaboride, 5 to 20 parts of toner, 0.8 to 1.6 parts of dispersing agent, 0.5 to 2 parts of wetting leveling agent, 0.1 to 0.5 part of defoaming agent, 0.5 to 2 parts of pH regulator and 10 to 30 parts of deionized water. Through the synergistic effect of the self-crosslinking modified acrylic emulsion and the surface functionalization modified calcium hexaboride, the defect that hardness and toughness of traditional water-based ink are difficult to consider at the same time is overcome. The obtained ink film has extremely high hardness and adhesive force, also has excellent wear resistance which is far better than that of traditional water-based ink, and can meet the requirements of high-end electronic product shells, durable labels, credit cards and other application scenes with extremely harsh requirements for surface durability.

Description

Technical Field

[0001] This invention relates to the field of inks, and more specifically to a method for preparing abrasion-resistant and scratch-resistant water-based ink. Background Technology

[0002] With the rapid development of the consumer goods, electronic product casings, labels, cards, and high-end packaging printing market, higher requirements are being placed on the physical durability of printed surfaces. Water-based inks are widely used in these fields due to their environmentally friendly properties, but the mechanical strength of their ink films, especially their abrasion resistance and scratch resistance, often fails to meet the needs of high-end applications.

[0003] The abrasion and scratch resistance of ink films mainly depends on their hardness, toughness, density, and adhesion to the substrate surface. In the existing technology, there are many limitations to the means of improving the abrasion resistance of water-based inks: (1) Although the hardness of the ink film can be improved by using hard and brittle high glass transition temperature resins or high amounts of crosslinking agents, it often leads to increased brittleness and decreased flexibility of the film layer. When subjected to bending or impact, it is easy to crack or peel off, that is, it is difficult to achieve both toughness and hardness; (2) Adding inorganic nanoparticles, such as nano silica and nano alumina, to enhance the ink film by utilizing their high hardness. However, nanoparticles have a large specific surface area and are very easy to agglomerate. They are difficult to disperse stably in water-based systems, which not only affects storage stability but may also clog the screen or printhead during printing. Furthermore, the agglomerates themselves will become stress concentration points, reducing the overall performance of the ink film.

[0004] In summary, existing technologies either sacrifice other key properties of the ink film (such as adhesion and flexibility) in exchange for abrasion resistance, or suffer from deficiencies in dispersion stability, process compatibility, or cost. Developing a method for preparing abrasion-resistant and scratch-resistant water-based inks that can synergistically improve the hardness and toughness of the ink film, with stable processing and suitable for industrial production, has significant practical implications and application value. Summary of the Invention

[0005] In view of the problems existing in the prior art, the purpose of this invention is to provide a method for preparing abrasion-resistant and scratch-resistant water-based ink.

[0006] The objective of this invention is achieved through the following technical solution: In a first aspect, the present invention provides a water-based ink that is wear-resistant and scratch-resistant, comprising, by weight parts: 30-50 parts of self-crosslinking modified acrylic emulsion, 5-15 parts of modified calcium hexaboride, 5-20 parts of colorant, 0.8-1.6 parts of dispersant, 0.5-2 parts of wetting and leveling agent, 0.1-0.5 parts of defoamer, 0.5-2 parts of pH adjuster, and 10-30 parts of deionized water.

[0007] Preferably, the pigment is at least one of rutile titanium dioxide R-706, phthalocyanine blue BGS, carbon black N330, and permanent yellow HR.

[0008] Preferably, the dispersant is at least one of BYK-190, TEGO-755W, and EFKA-4580.

[0009] Preferably, the wetting and leveling agent is at least one of BYK-346, TEGO-270, and BD-109.

[0010] Preferably, the defoamer is at least one of BYK-024, TEGO-810, and WT-082.

[0011] Preferably, the pH adjuster is at least one of AMP-95, triethylamine, and ammonia.

[0012] Preferably, the self-crosslinking modified acrylic emulsion comprises, by weight parts: 20-30 parts methyl methacrylate (MMA), 10-20 parts butyl acrylate (BA), 2-8 parts modified acrylamide (FAM), 1-2 parts emulsifier, 0.2-0.7 parts initiator, 0.05-0.15 parts chain transfer agent, 0.5-2 parts crosslinking agent, and 45-65 parts deionized water.

[0013] Preferably, the emulsifier is a mixture of emulsifier DNS-86 and emulsifier OP-10, with a weight ratio of 2:1.

[0014] Preferably, the initiator is ammonium persulfate (APS), the chain transfer agent is dodecyl mercaptan, and the crosslinking agent is adipic dihydrazide (ADH).

[0015] Preferably, the preparation method of the self-crosslinking modified acrylic emulsion includes: (1) Mix the emulsifier and deionized water, stir thoroughly, add methyl methacrylate (MMA), butyl acrylate (BA), and modified acrylamide (FAM), and add chain transfer agent at the same time. Stir at 200-400 r / min for half an hour to obtain a pre-emulsion. (2) Weigh 1 / 5 of the pre-emulsion and heat it to 75-85℃ under nitrogen protection. Then add 1 / 3 of the initiator and stir the reaction for half an hour to obtain the seed emulsion. (3) Add the remaining pre-emulsion and the remaining initiator to the seed emulsion separately. The addition time is controlled at 2-3 hours. After the addition is completed, continue to keep the reaction at 75-85℃ for 1 hour to obtain a mixed reaction emulsion. (4) Cool the mixed reaction emulsion to room temperature, filter it through a 200-mesh filter, add the crosslinking agent, continue stirring for half an hour, and then adjust the pH to 7.5-8.5 to obtain the self-crosslinking modified acrylic emulsion.

[0016] Preferably, the method for preparing the modified acrylamide (FAM) includes: Weigh 4-trifluoromethyl-6-aminopyrimidine and add it to tetrahydrofuran. Place the mixture in an ice-water bath, add triethylamine as an acid-binding agent, stir until homogeneous, and then gradually add methacryloyl chloride dropwise. The addition should be completed within half an hour. Remove the ice-water bath and stir at room temperature for 2-6 hours. After the reaction is complete, centrifuge and collect the supernatant. Pour the supernatant into 3-5 times its volume of dichloromethane and allow it to stand and age at 4°C for 2 hours. After complete recrystallization, collect the precipitate, wash it three times with dichloromethane, and dry it under vacuum to obtain modified acrylamide (FAM).

[0017] Preferably, the ratio of 4-trifluoromethyl-6-aminopyrimidine, methacryloxychloride, acid-binding agent and tetrahydrofuran is 10g:(9.6-10.8)g:(7.5-8.7)g:(100-200)mL.

[0018] Preferably, the acid-binding agent is triethylamine or pyridine.

[0019] Preferably, the preparation method of the modified calcium hexaboride includes: S1. Weigh out nano-sized calcium hexaboride powder and aminosilane coupling agent and mix them in a mixed solution of ethanol and water. Sonicate until homogeneous, and reflux and stir in a water bath at 70-80℃ for 3-5 hours. After the reaction is complete, centrifuge to collect the precipitate, wash it three times with alcohol, and dry it to obtain amino-modified calcium hexaboride. S2. Weigh out the aminated calcium hexaboride and disperse it in anhydrous ethanol. After stirring thoroughly, add methacryloyl chloride and a binding agent. Reflux and stir in a water bath at 70-80℃ for 4-8 hours. After the reaction is complete, remove the solvent under reduced pressure, wash three times with alcohol, and dry to obtain modified calcium hexaboride.

[0020] Preferably, the calcium hexaboride has a particle size of 80-100 nm, and the ratio of nano calcium hexaboride, aminosilane coupling agent (KH-550), ethanol and water is 10 g:(11.2-13.6) g:(160-180) mL:(20-40) mL.

[0021] Preferably, the ratio of aminated calcium hexaboride, methacryloyl chloride, acid binder and anhydrous ethanol is 10g:(7.4-9.4)g:(3.7-4.8)g:(100-200)mL.

[0022] Secondly, the present invention provides a method for preparing abrasion-resistant and scratch-resistant water-based ink, comprising the following steps: Step 1: Mix the self-crosslinking modified acrylic emulsion and deionized water, and stir evenly at a speed of 400-500 r / min. Then add the modified calcium hexaboride powder and stir evenly at a speed of 700-900 r / min. Step 2: Add color powder, dispersant, wetting and leveling agent and defoamer in sequence, stir evenly at a speed of 400-500 r / min, then add pH adjuster to adjust the pH of the ink system, filter with a 200 mesh sieve to obtain abrasion-resistant and scratch-resistant water-based ink.

[0023] The beneficial effects of this invention are as follows: 1. This invention solves the problem of traditional water-based inks' inability to balance hardness and toughness through the synergistic effect of self-crosslinking modified acrylic emulsion and surface-functionalized calcium hexaboride. The resulting ink film not only possesses extremely high hardness and adhesion but also excellent abrasion resistance, far exceeding that of traditional water-based inks. This meets the extremely demanding surface durability requirements of applications such as high-end electronic product casings, durable labels, and credit cards.

[0024] 2. This invention produces a monomer-modified acrylamide (FAM) that contains a pyrimidine ring, a trifluoromethyl group, and an amide group. The pyrimidine ring is a rigid planar structure, which improves the rigidity modulus and glass transition temperature of the polymer chain; while the trifluoromethyl group is a strongly hydrophobic group, which enhances the water resistance of the ink film. Furthermore, the combination of these three groups allows the ink film to form a dense three-dimensional covalent cross-linked network after curing, constructing a tough resin matrix that combines rigidity, hydrophobicity, and high cross-linking density.

[0025] 3. Calcium hexaboride itself is a ceramic material with extremely high hardness and good lubricity. This invention modifies its surface with methacrylamide, which on the one hand improves the compatibility and dispersion stability of calcium hexaboride nanoparticles in acrylic emulsion systems, preventing agglomeration; on the other hand, the grafted methacrylamide groups can directly participate in the self-crosslinking polymerization reaction of the emulsion, thereby forming strong covalent bonds with the emulsion, resulting in extremely strong interfacial bonding. This strengthens the performance of the ink film, further improving scratch resistance and mechanical strength. Detailed Implementation

[0026] The technical solution of the present invention is illustrated below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining the scope of the present invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the present invention.

[0027] To better understand the above technical solutions, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the invention to those skilled in the art.

[0028] The present invention will be further described below with reference to the following embodiments.

[0029] Example 1 A water-based ink that is abrasion-resistant and scratch-resistant, comprising, by weight parts: 40 parts of self-crosslinking modified acrylic emulsion, 10 parts of modified calcium hexaboride, 12 parts of color powder, 1.2 parts of dispersant, 1.3 parts of wetting and leveling agent, 0.3 parts of defoamer, 1.4 parts of pH adjuster, and 20 parts of deionized water.

[0030] The colorant is Phthalocyanine Blue BGS. The dispersant is BYK-190. The wetting and leveling agent is BYK-346. The defoamer is BYK-024. The pH adjuster is AMP-95.

[0031] The preparation method of the modified calcium hexaboride includes: S1. Weigh 10g of 80-100nm calcium hexaboride powder and 12.4g of aminosilane coupling agent (KH-550) and mix them in a mixed solution of 170mL ethanol and 30mL water. Sonicate until homogeneous, and reflux and stir for 4h in a water bath at 75℃. After the reaction is complete, centrifuge to collect the precipitate, wash it three times with alcohol, and dry it to obtain amino-modified calcium hexaboride. S2. Weigh 10g of aminated calcium hexaboride and disperse it in 150mL of anhydrous ethanol. After stirring thoroughly, add 8.4g of methacryloyl chloride and 4.2g of acid-binding agent pyridine. Reflux and stir for 6h in a water bath at 75℃. After the reaction is complete, remove the solvent under reduced pressure, wash three times with alcohol, and dry to obtain modified calcium hexaboride.

[0032] The components of the self-crosslinking modified acrylic emulsion, calculated by weight, include: 25 parts methyl methacrylate (MMA), 15 parts butyl acrylate (BA), 5 parts modified acrylamide (FAM), 1.5 parts emulsifier, 0.5 parts initiator, 0.1 parts chain transfer agent, 0.8 parts crosslinking agent, and 55 parts deionized water.

[0033] The emulsifier is a mixture of emulsifier DNS-86 and emulsifier OP-10, with a weight ratio of DNS-86 to OP-10 of 2:1. The initiator is ammonium persulfate (APS), the chain transfer agent is dodecyl mercaptan, and the crosslinking agent is adipic dihydrazide (ADH).

[0034] The preparation method of the self-crosslinking modified acrylic emulsion includes: (1) Weigh 10g of 4-trifluoromethyl-6-aminopyrimidine and add it to 150mL of tetrahydrofuran. Place it in an ice-water bath, add 8.1g of acid-binding agent pyridine, stir evenly, and then gradually add 10.2g of methacryloyl chloride. The addition is completed within half an hour. Remove the ice-water bath and stir at room temperature for 4h. After the reaction is completed, centrifuge and collect the supernatant. Pour it into 4 times the volume of dichloromethane and let it stand in a refrigerator at 4℃ for 2h. After recrystallization is complete, collect the precipitate, wash it three times with cold dichloromethane, and dry it under vacuum to obtain modified acrylamide (FAM). (2) Mix the emulsifier and deionized water, stir thoroughly, add methyl methacrylate (MMA), butyl acrylate (BA), and modified acrylamide (FAM), and add chain transfer agent at the same time. Stir at 300 r / min for half an hour to obtain a pre-emulsion. (3) Weigh 1 / 5 of the pre-emulsion, heat it to 80°C under nitrogen protection, add 1 / 3 of the initiator, stir the reaction for half an hour to obtain the seed emulsion; (4) Add the remaining pre-emulsion and the remaining initiator dropwise to the seed emulsion. The dropwise addition time is controlled at 2h. After the dropwise addition is completed, continue to keep the reaction at 80℃ for 1h to obtain a mixed reaction emulsion. (5) Cool the mixed reaction emulsion to room temperature, filter it through a 200-mesh filter, add the crosslinking agent, continue stirring for half an hour, and then adjust the pH to 8 to obtain the self-crosslinking modified acrylic emulsion.

[0035] The preparation method of the above-mentioned abrasion-resistant and scratch-resistant water-based ink includes the following steps: Step 1: Mix the self-crosslinking modified acrylic emulsion and deionized water, stir at 400 r / min until homogeneous, then add modified calcium hexaboride powder and stir at 800 r / min until homogeneous. Step 2: Add color powder, dispersant, wetting and leveling agent and defoamer in sequence, stir evenly at 500 r / min, then add pH adjuster to adjust the pH of ink system, filter with 200 mesh sieve to obtain abrasion-resistant and scratch-resistant water-based ink.

[0036] Example 2 A water-based ink that is abrasion-resistant and scratch-resistant, comprising, by weight parts: 30 parts of self-crosslinking modified acrylic emulsion, 5 parts of modified calcium hexaboride, 5 parts of color powder, 0.8 parts of dispersant, 0.5 parts of wetting and leveling agent, 0.1 parts of defoamer, 0.5 parts of pH adjuster, and 10 parts of deionized water.

[0037] The pigment is rutile titanium dioxide R-706. The dispersant is TEGO-755W. The wetting and leveling agent is TEGO-270. The defoamer is TEGO-810. The pH adjuster is AMP-95.

[0038] The preparation method of the modified calcium hexaboride includes: S1. Weigh 10g of calcium hexaboride powder with a particle size of 80-100nm and 11.2g of aminosilane coupling agent (KH-550) and mix them in a mixed solution of 160mL ethanol and 40mL water. Sonicate until homogeneous, and reflux and stir for 3h under 70℃ water bath conditions. After the reaction is completed, centrifuge to collect the precipitate, wash it three times with alcohol, and dry it to obtain amino-modified calcium hexaboride. S2. Weigh 10g of aminated calcium hexaboride and disperse it in 100mL of anhydrous ethanol. After stirring thoroughly, add 7.4g of methacryloyl chloride and 3.7g of acid-binding agent pyridine. Reflux and stir for 4h in a water bath at 70℃. After the reaction is complete, remove the solvent under reduced pressure, wash three times with alcohol, and dry to obtain modified calcium hexaboride.

[0039] The components of the self-crosslinking modified acrylic emulsion, calculated by weight, include: 20 parts methyl methacrylate (MMA), 10 parts butyl acrylate (BA), 2 parts modified acrylamide (FAM), 1 part emulsifier, 0.2 parts initiator, 0.05 parts chain transfer agent, 0.5 parts crosslinking agent, and 45 parts deionized water.

[0040] The emulsifier is a mixture of emulsifier DNS-86 and emulsifier OP-10, with a weight ratio of DNS-86 to OP-10 of 2:1. The initiator is ammonium persulfate (APS), the chain transfer agent is dodecyl mercaptan, and the crosslinking agent is adipic dihydrazide (ADH).

[0041] The preparation method of the self-crosslinking modified acrylic emulsion includes: (1) Weigh 10g of 4-trifluoromethyl-6-aminopyrimidine and add it to 100mL of tetrahydrofuran. Place it in an ice-water bath, add 7.5g of triethylamine as an acid-binding agent, stir evenly, and then gradually add 9.6g of methacryloyl chloride. The addition is completed within half an hour. Remove the ice-water bath and stir at room temperature for 2 hours. After the reaction is complete, centrifuge and collect the supernatant. Pour it into 3 times the volume of dichloromethane and let it stand in a refrigerator at 4℃ for 2 hours. After recrystallization is complete, collect the precipitate, wash it three times with dichloromethane, and dry it under vacuum to obtain modified acrylamide (FAM).

[0042] (2) Mix the emulsifier and deionized water, stir thoroughly, add methyl methacrylate (MMA), butyl acrylate (BA), and modified acrylamide (FAM), and add chain transfer agent at the same time. Stir at 200 r / min for half an hour to obtain a pre-emulsion. (3) Weigh 1 / 5 of the pre-emulsion, heat it to 75°C under nitrogen protection, add 1 / 3 of the initiator, stir the reaction for half an hour to obtain the seed emulsion; (4) Add the remaining pre-emulsion and the remaining initiator dropwise to the seed emulsion. The dropwise addition time is controlled at 2h. After the dropwise addition is completed, continue to keep the reaction at 75℃ for 1 hour to obtain a mixed reaction emulsion. (5) Cool the mixed reaction emulsion to room temperature, filter it through a 200-mesh filter, add the crosslinking agent, continue stirring for half an hour, and then adjust the pH to 8 to obtain the self-crosslinking modified acrylic emulsion.

[0043] The preparation method of the above-mentioned abrasion-resistant and scratch-resistant water-based ink includes the following steps: Step 1: Mix the self-crosslinking modified acrylic emulsion and deionized water, stir at 400 r / min until homogeneous, then add modified calcium hexaboride powder and stir at 700 r / min until homogeneous. Step 2: Add color powder, dispersant, wetting and leveling agent and defoamer in sequence, stir evenly at 400 r / min, then add pH adjuster to adjust the pH of the ink system, filter with a 200 mesh sieve to obtain abrasion-resistant and scratch-resistant water-based ink.

[0044] Example 3 A water-based ink that is abrasion-resistant and scratch-resistant, comprising, by weight parts: 50 parts of self-crosslinking modified acrylic emulsion, 15 parts of modified calcium hexaboride, 20 parts of color powder, 1.6 parts of dispersant, 2 parts of wetting and leveling agent, 0.5 parts of defoamer, 2 parts of pH adjuster, and 30 parts of deionized water.

[0045] The colorant is carbon black N330. The dispersant is EFKA-4580. The wetting and leveling agent is BD-109. The defoamer is WT-082. The pH adjuster is AMP-95.

[0046] The preparation method of the modified calcium hexaboride includes: S1. Weigh 10g of calcium hexaboride powder with a particle size of 80-100nm and mix it with 13.6g of aminosilane coupling agent (KH-550) in a mixed solution of 180mL: ethanol and 20mL water. Sonicate until homogeneous, and reflux and stir for 5h under 80℃ water bath conditions. After the reaction is completed, centrifuge to collect the precipitate, wash it three times with alcohol, and dry it to obtain amino-modified calcium hexaboride. S2. Weigh 10g of aminated calcium hexaboride and disperse it in 200mL of anhydrous ethanol. After stirring thoroughly, add 9.4g of methacryloyl chloride and 4.8g of acid-binding agent pyridine. Reflux and stir for 8h in a water bath at 80℃. After the reaction is complete, remove the solvent under reduced pressure, wash three times with alcohol, and dry to obtain modified calcium hexaboride.

[0047] The components of the self-crosslinking modified acrylic emulsion, calculated by weight, include: 30 parts methyl methacrylate (MMA), 20 parts butyl acrylate (BA), 8 parts modified acrylamide (FAM), 2 parts emulsifier, 0.7 parts initiator, 0.15 parts chain transfer agent, 2 parts crosslinking agent, and 45-65 parts deionized water.

[0048] The emulsifier is a mixture of emulsifier DNS-86 and emulsifier OP-10, with a weight ratio of DNS-86 to OP-10 of 2:1. The initiator is ammonium persulfate (APS), the chain transfer agent is dodecyl mercaptan, and the crosslinking agent is adipic dihydrazide (ADH).

[0049] The preparation method of the self-crosslinking modified acrylic emulsion includes: (1) Weigh 10g of 4-trifluoromethyl-6-aminopyrimidine and add it to 200mL of tetrahydrofuran. Place it in an ice-water bath, add 8.7g of triethylamine as an acid-binding agent, stir evenly, and then gradually add 10.8g of methacryloyl chloride. The addition is completed within half an hour. Remove the ice-water bath and stir at room temperature for 6 hours. After the reaction is completed, centrifuge and collect the supernatant. Pour it into 5 times the volume of dichloromethane and let it stand in a refrigerator at 4℃ for 2 hours. After recrystallization is complete, collect the precipitate, wash it three times with dichloromethane, and dry it under vacuum to obtain modified acrylamide (FAM).

[0050] (2) Mix the emulsifier and deionized water, stir thoroughly, add methyl methacrylate (MMA), butyl acrylate (BA), and modified acrylamide (FAM), and add chain transfer agent at the same time. Stir at 400 r / min for half an hour to obtain a pre-emulsion. (3) Weigh 1 / 5 of the pre-emulsion, heat it to 85°C under nitrogen protection, add 1 / 3 of the initiator, stir the reaction for half an hour to obtain the seed emulsion; (4) Add the remaining pre-emulsion and the remaining initiator dropwise to the seed emulsion. The dropwise addition time is controlled at 2-3 hours. After the dropwise addition is completed, continue to keep the reaction at 85°C for 1 hour to obtain a mixed reaction emulsion. (5) Cool the mixed reaction emulsion to room temperature, filter it through a 200-mesh filter, add the crosslinking agent, continue stirring for half an hour, and then adjust the pH to 8.5 to obtain the self-crosslinking modified acrylic emulsion.

[0051] The preparation method of the above-mentioned abrasion-resistant and scratch-resistant water-based ink includes the following steps: Step 1: Mix the self-crosslinking modified acrylic emulsion and deionized water, stir at 500 r / min until homogeneous, then add modified calcium hexaboride powder and stir at 900 r / min until homogeneous. Step 2: Add color powder, dispersant, wetting and leveling agent and defoamer in sequence, stir evenly at 500 r / min, then add pH adjuster to adjust the pH of ink system, filter with 200 mesh sieve to obtain abrasion-resistant and scratch-resistant water-based ink.

[0052] Comparative Example 1 A water-based ink differs from Example 1 in that the modified acrylamide used in the preparation of the self-crosslinking modified acrylic emulsion is replaced with conventional acrylamide; and the modified calcium hexaboride is replaced with aminated calcium hexaboride. The rest is the same as in Example 1. Specifically: Water-based inks, calculated by weight, include: 40 parts of self-crosslinking modified acrylic emulsion, 10 parts of aminated calcium hexaboride, 12 parts of colorant, 1.2 parts of dispersant, 1.3 parts of wetting and leveling agent, 0.3 parts of defoamer, 1.4 parts of pH adjuster, and 20 parts of deionized water.

[0053] The components of the self-crosslinking modified acrylic emulsion, calculated by weight, include: 25 parts methyl methacrylate (MMA), 15 parts butyl acrylate (BA), 5 parts acrylamide (AM), 1.5 parts emulsifier, 0.5 parts initiator, 0.1 parts chain transfer agent, 0.8 parts crosslinking agent, and 55 parts deionized water.

[0054] Comparative Example 2 A water-based ink differs from Example 1 in that the modified acrylamide used in the preparation of the self-crosslinking modified acrylic emulsion is replaced with conventional acrylamide. The rest is the same as in Example 1.

[0055] Comparative Example 3 A water-based ink differs from Example 1 in that the modified calcium hexaboride in the composition is replaced with aminated calcium hexaboride. The rest is the same as in Example 1.

[0056] Experimental Example The water-based inks prepared in Example 1 and Comparative Examples 1-3 were labeled and numbered. They were dried using a "room temperature surface drying + baking curing" method. Room temperature surface drying involved drying at room temperature for 20 minutes; baking curing involved baking in an oven at 80°C for 15 minutes, followed by cooling to room temperature. Performance tests were then conducted on the different water-based inks, including: Abrasion loss (ASTM D4060, Taber abrasion machine, CS-10 grinding wheel, 1000 cycles, 1000g load); Pencil hardness (GB / T 6739, the higher the grade, the better the hardness); Adhesion (GB / T 13217.7, grade 0 is the best, grade 5 is the worst); Water contact angle (ASTM D7490: assess the hydrophobicity of the ink film surface using a contact angle meter, the larger the angle, the better the hydrophobicity); Water resistance (immerse the dried ink film in deionized water for 24 hours, then observe for wrinkling, whitening, peeling, etc.).

[0057] The test results are shown in Table 1:

[0058] The test results show that Example 1, due to the synergistic effect of modified calcium hexaboride and the self-crosslinking emulsion, exhibits significantly better wear resistance, hardness, and adhesion than the comparative example. Furthermore, it also demonstrates excellent water resistance. Comparative Example 1, which simultaneously replaced modified acrylamide (FAM) and modified calcium hexaboride, showed the most significant performance decline. Comparative Examples 2 and 3, retaining only a single modified component, showed relatively better performance. Comparative Examples 2 and 3 also demonstrate that the self-crosslinking emulsion has a greater impact on overall performance.

[0059] 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. A wear and scratch resistant water-based ink, characterized by, According to the weight parts, comprising: The self-crosslinking modified acrylic emulsion 30-50 parts, the modified calcium hexaboride 5-15 parts, the toner 5-20 parts, the dispersing agent 0.8-1.6 parts, the wetting and leveling agent 0.5-2 parts, the defoaming agent 0.1-0.5 parts, the pH regulator 0.5-2 parts, and the deionized water 10-30 parts are included. According to the weight parts, the self-crosslinking modified acrylic emulsion comprises: The methyl methacrylate 20-30 parts, the butyl acrylate 10-20 parts, the modified acrylamide 2-8 parts, the emulsifier 1-2 parts, the initiator 0.2-0.7 parts, the chain transfer agent 0.05-0.15 parts, the crosslinking agent 0.5-2 parts, and the deionized water 45-65 parts are included.

2. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The toner is at least one of the rutile titanium dioxide R-706, the phthalocyanine blue BGS, the carbon black N330, and the permanent yellow HR.

3. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The dispersing agent is at least one of the BYK-190, the TEGO-755W, and the EFKA-4580; the wetting and leveling agent is at least one of the BYK-346, the TEGO-270, and the BD-109.

4. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The defoaming agent is at least one of the BYK-024, the TEGO-810, and the WT-082; the pH regulator is at least one of the AMP-95, the triethylamine, and the ammonia.

5. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The emulsifier is a mixture of the emulsifier DNS-86 and the emulsifier OP-10, and the weight ratio of the emulsifier DNS-86 to the emulsifier OP-10 is 2:1; the initiator is the ammonium persulfate, the chain transfer agent is the dodecanethiol, and the crosslinking agent is the adipic acid dihydrazide.

6. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The preparation method of the modified acrylamide comprises: The 4-trifluoromethyl-6-aminopyrimidine is weighed and added into tetrahydrofuran, placed in an ice water bath, and then the acid binding agent triethylamine is added, stirred uniformly, and then the methyl acryloyl chloride is gradually added dropwise, the ice water bath is removed, and stirring is performed at room temperature for 2-6 hours, and then the modified acrylamide is obtained after the reaction is completed.

7. A scratch and abrasion resistant water-based ink according to claim 6, wherein, The ratio of the 4-trifluoromethyl-6-aminopyrimidine, the methyl acryloyl chloride, the acid binding agent, and the tetrahydrofuran is 10g:(9.6-10.8)g:(7.5-8.7)g:(100-200)mL.

8. The abrasion and scratch resistant water-based ink according to claim 1, wherein, The preparation method of the modified calcium hexaboride comprises: S1, the nanoscale calcium hexaboride powder and the amino silane coupling agent are weighed and mixed in an ethanol and water mixed solution, ultrasonically stirred until uniform, and then reflux stirring is performed at 70-80℃ water bath for 3-5 hours, and then the aminoated calcium hexaboride is obtained after the reaction is completed; S2, the aminoated calcium hexaboride is weighed and dispersed into anhydrous ethanol, fully stirred, and then the methyl acryloyl chloride and the acid binding agent are added, and then reflux stirring is performed at 70-80℃ water bath for 4-8 hours, and then the modified calcium hexaboride is obtained after the reaction is completed.

9. A scratch and abrasion resistant water-based ink according to claim 8, wherein, The ratio of nano calcium hexaboride, amino silane coupling agent, ethanol and water in S1 is 10g:(11.2-13.6)g:(160-180)mL:(20-40)mL; the ratio of amino calcium hexaboride, methacryloyl chloride, acid binding agent and anhydrous ethanol in S2 is 10g:(7.4-9.4)g:(3.7-4.8)g:(100-200)mL.

10. A method of preparing the abrasion and scratch resistant water-based ink of claim 1, characterized by, The method comprises the following steps: Step 1, mix the self-crosslinking modified acrylic emulsion and deionized water, stir uniformly at a speed of 400-500r / min, then add the modified calcium hexaboride powder, stir uniformly at a speed of 700-900r / min; Step 2, add the toner, dispersant, wetting and leveling agent and defoaming agent in sequence, stir uniformly at a speed of 400-500r / min, then drop the pH regulator, adjust the pH of the ink system, filter with a 200-mesh screen, and obtain the wear-resistant and scratch-resistant water-based ink.

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