A nano-modified homogenized ink and a method of making the same

Abstract

This invention discloses a nano-modified homogenized ink and its preparation method, belonging to the field of ink preparation technology. The nano-modified homogenized ink comprises the following components by weight: 4-12 parts modified nano-silica, 1.2-5.3 parts organic dispersant, 1.5-2.2 parts nano-titanium dioxide, 51-73 parts distilled water, 2-5 parts nano-calcium carbonate, 1.1-2.4 parts viscosity modifier, 0.8-1.6 parts pH adjuster, and 2.2-5.4 parts mica powder. The ink prepared by the above method exhibits excellent dispersibility, antioxidant properties, and moisture-repellent hydrophobicity.

Description

Technical Field

[0001] This invention belongs to the field of ink preparation technology, specifically relating to a nano-modified homogenized ink and its preparation method. Background Technology

[0002] In the field of traditional inks, poor dispersibility has always been a key challenge restricting performance improvement and application expansion. Due to limitations in the manufacturing process, the pigments or functional particles in ordinary inks are often large in size and unevenly distributed. These large particles have strong van der Waals forces, making them prone to aggregation and clumping. During storage, this aggregation further intensifies, leading to significant sedimentation and stratification, severely affecting stability and shortening shelf life. In the printing process, large particle clumps in poorly dispersible inks can easily clog printheads, causing printing interruptions, increasing equipment maintenance costs and production time losses. Furthermore, uneven particle distribution can cause defects such as color differences and streaks in printed patterns, reducing the quality and precision of printed products.

[0003] Patent CN115558337B discloses a luminescent nanoparticle ink, a luminescent nanoparticle color filter prepared therefrom, and a display device. The luminescent nanoparticle ink of this application includes luminescent nanoparticles, an olefinic silane compound, and an initiator; wherein the surface of the luminescent nanoparticles is modified with organic ligands from the surfactant compound. The presence of organic ligands from the surfactant compound in the luminescent nanoparticles promotes their dissolution in the olefinic silane compound, which then participates in the polymerization reaction. This results in better adhesion of the luminescent nanoparticle color filter to the substrate and superior optical performance. Although the luminescent nanoparticle ink disclosed in the above patent achieves a certain degree of dissolution in the olefinic silane compound through the organic ligands from the surfactant compound modified on the surface of the luminescent nanoparticles, and the resulting color filter exhibits good adhesion and optical performance, its dispersion performance still has certain shortcomings in practical applications. Under long-term storage or complex environmental conditions, the luminescent nanoparticles may still exhibit slight aggregation, leading to a decrease in ink uniformity and consequently affecting the consistency and stability of the display effect of the final prepared color filter and display device. Summary of the Invention

[0004] The purpose of this invention is to provide a nano-modified homogenized ink and its preparation method, which solves the technical problem of poor dispersion performance of inks in the prior art.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a nano-modified homogenized ink, composed of the following components by weight: 4-12 parts modified nano silica, 1.2-5.3 parts organic dispersant, 1.5-2.2 parts nano titanium dioxide, 51-73 parts distilled water, 2-5 parts nano calcium carbonate, 1.1-2.4 parts viscosity modifier, 0.8-1.6 parts pH adjuster, and 2.2-5.4 parts mica powder.

[0007] Preferably, the method for preparing the modified nano-silica includes the following steps:

[0008] Q1: Add 1,2,4-triazole and potassium carbonate to a container containing acetonitrile, stir, add 2-bromoacetophenone, react at room temperature, extract, and rotary evaporate to obtain intermediate 1;

[0009] Q2: Add intermediate 1 and potassium carbonate to a container containing methanol, stir and mix, then add distilled water containing dissolved hydroxylamine hydrochloride dropwise, and then heat to reflux to react. After the reaction is complete, extract, rotary evaporate, and recrystallize to obtain intermediate 2.

[0010] Q3: Add nano-silica and potassium carbonate to a container containing N,N-dimethylformamide, stir and mix, then add 1,12-dibromododecane dropwise. After reacting at room temperature, pour into ice water, collect the solid and add it to a mixed solution of petroleum ether and ethyl acetate. Stir, filter, and obtain intermediate 3.

[0011] Q4: Add intermediate 2 and potassium carbonate to a container containing N,N-dimethylformamide, stir and mix, then add intermediate 3, react at room temperature, add to ice water, filter, dry and purify to obtain modified nano silica.

[0012] The synthesis reaction formula for modified nano-silica in the above process is as follows:

[0013] The mass spectrometry analysis results of intermediate 1 were: m / z: 187.07 (100.0%), 188.08 (11.0%), 188.07 (1.1%); the mass spectrometry analysis results of intermediate 2 were: m / z: 202.09 (100.0%), 203.09 (11.0%), 203.08 (1.5%).

[0014] Preferably, in Q1, the ratio of 1,2,4-triazole, potassium carbonate, acetonitrile, and 2-bromoacetophenone is (1.88-2.36) g : (9.89-11.12) g : (90-110) mL : (4.58-5.52) g, stirred for 10-20 min, reacted at room temperature for 10-12 h, and extracted with ethyl acetate; in Q2, the ratio of intermediate 1, potassium carbonate, methanol, hydroxylamine hydrochloride, and distilled water is (3.21-4.82) g : (8.56-9.33) g : (90-110) mL : (1.66-2.04) g : (25-35) mL, heated to 80-90℃ and refluxed for 8-10 h, extracted with ethyl acetate, and recrystallized in methanol.

[0015] Preferably, in Q3, the ratio of nano-silica, potassium carbonate, N,N-dimethylformamide, 1,12-dibromododecane and the mixed solution is (4.34-5.66) g : (5.04-5.72) g : (92-105) mL : (11.78-13.42) g : (220-260) mL, the stirring time is 10-20 min, the reaction is carried out at room temperature for 20-30 h, and the volume ratio of petroleum ether to ethyl acetate is 1:3.

[0016] Preferably, in Q4, the ratio of intermediate 2, potassium carbonate, N,N-dimethylformamide and intermediate 3 is (0.61-0.78) g : (0.45-0.66) g : (20-30) mL : (0.88-1.21) g, and the mixture is stirred for 10-20 min and reacted at room temperature for 10-12 h.

[0017] Preferably, the method for preparing the organic dispersant includes the following steps:

[0018] S1: Add hexamethylenebisacrylamide to an aqueous methanol solution, stir and mix, then add 1-amino-2-propanol, heat and react under a nitrogen atmosphere. After the reaction is complete, concentrate by rotary evaporation, precipitate, dissolve, repeat the dissolution-precipitation process, and dry to obtain viscous liquid a.

[0019] S2: Add viscous liquid a and 6-caprolactone to a container, heat and stir under nitrogen atmosphere, then add stannous octoate, cool after reaction, dissolve, precipitate, repeat dissolution-precipitation, dry to obtain organic dispersant.

[0020] In the above process, hexamethylenebisacrylamide and 1-amino-2-propanol are used as raw materials to obtain viscous liquid a through an addition reaction. Then, the side chain hydroxyl groups and secondary amine groups contained in viscous liquid a are used to perform ring-opening polymerization with 6-caprolactone to obtain an organic dispersant.

[0021] Preferably, in S1, the ratio of hexamethylenebisacrylamide, methanol aqueous solution, and 1-amino-2-propanol is (1.43-1.65) g : (22.4-28.7) mL : (0.55-0.68) g, the volume fraction of the methanol aqueous solution is 33 wt%, the reaction is carried out at 45-55℃ for 4-6 days, precipitated in acetone, dissolved in deionized water, and the dissolution-precipitation process is repeated 3-5 times.

[0022] Preferably, in S2, the ratio of viscous liquid a, 6-caprolactone, and stannous octoate is (1.34-1.82) g : (5.25-6.33) g : (0.066-0.081) g. The mixture is heated to 125-135℃, reacted for 4-6 hours, cooled, dissolved in chloroform, and precipitated with anhydrous diethyl ether. The dissolution-precipitation process is repeated 3-5 times.

[0023] Preferably, the method for preparing a nano-modified homogenized ink includes the following steps:

[0024] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0025] Step 2: Grind the mixed slurry, then homogenize it, and then slowly add a viscosity modifier. After stirring and mixing, add a pH adjuster to adjust the pH, filter, defoam, and mature to obtain nano-modified homogenized ink.

[0026] Preferably, in step two, zirconium oxide is used as the grinding medium during the grinding process, and grinding is carried out at 1500-3000 rpm for 1-3 hours until the fineness is <100nm, and the pH is adjusted to 7.5-8.

[0027] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0028] 1. This invention first prepares modified nano-silica using 1,2,4-triazole, 2-bromoacetophenone, hydroxylamine hydrochloride, nano-silica, and 1,12-dibromododecane as raw materials. Subsequently, an organic dispersant is prepared using hexamethylenebisacrylamide, 1-amino-2-propanol, and 6-caprolactone as raw materials. Finally, the prepared modified nano-silica and organic dispersant are added to the ink to give it excellent dispersibility, abrasion resistance, antioxidant properties, and moisture-repellent properties.

[0029] 2. This invention adds the prepared modified nano-silica to ink, which can effectively improve its dispersibility, abrasion resistance, oxidation resistance, and moisture and hydrophobic properties. The long-chain alkyl and triazole groups on the surface of the modified nano-silica can fully extend in the solvent and form an organic molecular layer around the particles. When these modified particles approach each other, the organic molecular layer will physically overlap and compress, generating a strong repulsive force, effectively preventing the particles from approaching and agglomerating further, thus improving the dispersibility of the ink. The flexible long chains grafted onto the modified nano-silica can significantly improve its abrasion resistance through a dual mechanism of physical reinforcement and energy dissipation. At the same time, the triazole structure contained in the modified nano-silica structure can capture free radicals generated under heat or light, interrupt the chain reaction that leads to aging, and improve its oxidation resistance. The grafted low surface energy long-chain alkyl groups can effectively improve the moisture and hydrophobic properties of the ink.

[0030] 3. The present invention adds the prepared organic dispersant to the ink, which can effectively improve its dispersibility. The organic dispersant is strongly adsorbed on the surface of nanoparticles through hydrogen bonds, coordination bonds, and dipole-dipole interactions to achieve strong anchoring, thereby achieving excellent dispersibility and long-term storage stability of nanoparticles. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Example 1: This example discloses a method for preparing modified nano-silica, including the following steps:

[0033] Q1: Add 2.07g of 1,2,4-triazole and 10.52g of potassium carbonate to a container containing 100mL of acetonitrile, stir for 20min, then add 5.05g of 2-bromoacetophenone, react at room temperature for 12h, extract with ethyl acetate, and rotary evaporate to obtain intermediate 1;

[0034] Q2: Add 4.02g of intermediate 1 and 8.94g of potassium carbonate to a container containing 100mL of methanol, stir and mix, then add 30mL of distilled water containing 1.85g of hydroxylamine hydrochloride, and then heat to 85℃ and reflux for 10h. After the reaction is complete, extract with ethyl acetate, rotary evaporate, and recrystallize in methanol to obtain intermediate 2.

[0035] Q3: Add 4.95g of nano-silica and 5.38g of potassium carbonate to a container containing 98mL of N,N-dimethylformamide. After stirring and mixing for 15min, add 12.62g of 1,12-dibromododecane dropwise. After reacting at room temperature for 24h, pour the mixture into ice water. Collect the solid and add it to a mixed solution of 240mL of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 1:3). Stir and filter to obtain intermediate 3.

[0036] Q4: Add 0.68g of intermediate 2 and 0.51g of potassium carbonate to a container containing 25mL of N,N-dimethylformamide. After stirring and mixing for 20min, add 1.02g of intermediate 3. After reacting at room temperature for 12h, add to ice water, filter, dry, and purify to obtain modified nano-silica.

[0037] This embodiment discloses a method for preparing an organic dispersant, including the following steps:

[0038] S1: 1.54 g of hexamethylenebisacrylamide was added to 25.5 mL of 33 vol% methanol aqueous solution. After stirring and mixing, 0.61 g of 1-amino-2-propanol was added. The mixture was heated to 50 °C under a nitrogen atmosphere and reacted for 6 days. After the reaction was completed, the mixture was concentrated by rotary evaporation and added to acetone for precipitation. The precipitate was dissolved in deionized water. The dissolution-precipitation process was repeated 3 times. After drying, a viscous liquid a was obtained.

[0039] S2: Add 1.53g of viscous liquid a and 5.84g of 6-caprolactone to a container, heat to 130℃ under nitrogen atmosphere and stir to react, then add 0.073g of stannous octoate, react for 6 hours and then cool, dissolve with chloroform, precipitate with anhydrous diethyl ether, repeat the dissolution-precipitation process 3 times, dry to obtain organic dispersant.

[0040] This embodiment discloses a nano-modified homogenized ink, which is composed of the following components by weight: 8 parts modified nano silica, 3.3 parts organic dispersant, 1.8 parts nano titanium dioxide, 62 parts distilled water, 3.5 parts nano calcium carbonate, 1.9 parts nano cellulose, 1.2 parts sodium hydroxide and 3.8 parts mica powder.

[0041] This embodiment discloses a method for preparing a nano-modified homogenized ink, including the following steps:

[0042] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0043] Step 2: Grind the mixed slurry using zirconium oxide as the grinding medium at 2000 rpm for 2 hours until the fineness is <100 nm. Then, homogenize the mixture, slowly add nanocellulose, stir and mix, add sodium hydroxide to adjust the pH to 7.5, filter, defoam, and mature to obtain nano-modified homogenized ink.

[0044] Example 2: This example discloses a method for preparing modified nano-silica, including the following steps:

[0045] Q1: Add 1.88g of 1,2,4-triazole and 9.89g of potassium carbonate to a container containing 90mL of acetonitrile, stir for 20min, then add 4.58g of 2-bromoacetophenone, react at room temperature for 12h, extract with ethyl acetate, and rotary evaporate to obtain intermediate 1;

[0046] Q2: Add 3.21g of intermediate 1 and 8.56g of potassium carbonate to a container containing 90mL of methanol, stir and mix, then add 25mL of distilled water containing 1.66g of hydroxylamine hydrochloride, and then heat to 85℃ and reflux for 10h. After the reaction is complete, extract with ethyl acetate, rotary evaporate, and recrystallize in methanol to obtain intermediate 2.

[0047] Q3: Add 4.34g of nano-silica and 5.04g of potassium carbonate to a container containing 92mL of N,N-dimethylformamide. After stirring and mixing for 15min, add 11.78g of 1,12-dibromododecane dropwise. After reacting at room temperature for 24h, pour the mixture into ice water. Collect the solid and add it to a mixed solution of 220mL of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 1:3). Stir and filter to obtain intermediate 3.

[0048] Q4: Add 0.61g of intermediate 2 and 0.45g of potassium carbonate to a container containing 20mL of N,N-dimethylformamide, stir and mix for 20min, then add 1.21g of intermediate 3, react at room temperature for 12h, then add to ice water, filter, dry, and purify to obtain modified nano silica.

[0049] This embodiment discloses a method for preparing an organic dispersant, including the following steps:

[0050] S1: 1.43 g of hexamethylenebisacrylamide was added to 22.4 mL of 33 vol% methanol aqueous solution. After stirring and mixing, 0.55 g of 1-amino-2-propanol was added. The mixture was heated to 50 °C under a nitrogen atmosphere and reacted for 6 days. After the reaction was completed, the mixture was concentrated by rotary evaporation and added to acetone for precipitation. The precipitate was dissolved in deionized water. The dissolution-precipitation process was repeated 3 times. After drying, a viscous liquid a was obtained.

[0051] S2: Add 1.34g of viscous liquid a and 5.25g of 6-caprolactone to a container, heat to 130℃ under nitrogen atmosphere and stir to react, then add 0.066g of stannous octoate, react for 6h and then cool, dissolve with chloroform, precipitate with anhydrous diethyl ether, repeat the dissolution-precipitation process 3 times, dry to obtain organic dispersant.

[0052] This embodiment discloses a nano-modified homogenized ink, which is composed of the following components by weight: 4 parts modified nano silica, 1.2 parts organic dispersant, 1.5 parts nano titanium dioxide, 51 parts distilled water, 2 parts nano calcium carbonate, 1.1 parts xanthan gum, 0.8 parts triethanolamine and 2.2 parts mica powder.

[0053] This embodiment discloses a method for preparing a nano-modified homogenized ink, including the following steps:

[0054] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0055] Step 2: Grind the mixed slurry using zirconium oxide as the grinding medium at 2000 rpm for 2 hours until the fineness is <100 nm. Then, homogenize the mixture, slowly add xanthan gum, stir and mix, add triethanolamine to adjust the pH to 7.5, filter, defoam, and cure to obtain nano-modified homogenized ink.

[0056] Example 3: This example discloses a method for preparing modified nano-silica, including the following steps:

[0057] Q1: Add 2.36g of 1,2,4-triazole and 11.12g of potassium carbonate to a container containing 110mL of acetonitrile, stir for 20min, then add 5.52g of 2-bromoacetophenone, react at room temperature for 12h, extract with ethyl acetate, and rotary evaporate to obtain intermediate 1;

[0058] Q2: Add 4.82g of intermediate 1 and 9.33g of potassium carbonate to a container containing 110mL of methanol, stir and mix, then add 35mL of distilled water containing 2.04g of hydroxylamine hydrochloride, and then heat to 85℃ and reflux for 10h. After the reaction is complete, extract with ethyl acetate, rotary evaporate, and recrystallize in methanol to obtain intermediate 2.

[0059] Q3: Add 5.66g of nano-silica and 5.72g of potassium carbonate to a container containing 105mL of N,N-dimethylformamide. After stirring and mixing for 15min, add 13.42g of 1,12-dibromododecane dropwise. After reacting at room temperature for 24h, pour the mixture into ice water. Collect the solid and add it to a mixed solution of 260mL of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 1:3). Stir and filter to obtain intermediate 3.

[0060] Q4: Add 0.78g of intermediate 2 and 0.66g of potassium carbonate to a container containing 30mL of N,N-dimethylformamide. After stirring and mixing for 20min, add 0.88g of intermediate 3. After reacting at room temperature for 12h, add to ice water, filter, dry, and purify to obtain modified nano-silica.

[0061] This embodiment discloses a method for preparing an organic dispersant, including the following steps:

[0062] S1: 1.65 g of hexamethylenebisacrylamide was added to 28.7 mL of 33 vol% methanol aqueous solution. After stirring and mixing, 0.68 g of 1-amino-2-propanol was added. The mixture was heated to 50 °C under a nitrogen atmosphere and reacted for 6 days. After the reaction was completed, the mixture was concentrated by rotary evaporation and added to acetone for precipitation. The precipitate was dissolved in deionized water and the dissolution-precipitation process was repeated 3 times. After drying, a viscous liquid a was obtained.

[0063] S2: Add 1.82g of viscous liquid a and 6.33g of 6-caprolactone to a container, heat to 130℃ under nitrogen atmosphere and stir to react, then add 0.081g of stannous octoate, react for 6h and then cool, dissolve with chloroform, precipitate with anhydrous diethyl ether, repeat the dissolution-precipitation process 3 times, dry to obtain organic dispersant.

[0064] This embodiment discloses a nano-modified homogenized ink, which is composed of the following components by weight: 12 parts modified nano silica, 5.3 parts organic dispersant, 2.2 parts nano titanium dioxide, 73 parts distilled water, 5 parts nano calcium carbonate, 2.4 parts hydroxyethyl cellulose, 1.6 parts ammonia and 5.4 parts mica powder.

[0065] This embodiment discloses a method for preparing a nano-modified homogenized ink, including the following steps:

[0066] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0067] Step 2: Grind the mixed slurry using zirconium oxide as the grinding medium at 2000 rpm for 2 hours until the fineness is <100 nm. Then, homogenize the mixture and slowly add hydroxyethyl cellulose. After stirring and mixing, add ammonia to adjust the pH to 7.5, filter, defoam, and cure to obtain nano-modified homogenized ink.

[0068] Example 4: This example discloses a method for preparing modified nano-silica, including the following steps:

[0069] Q1: Add 1.96g of 1,2,4-triazole and 10.17g of potassium carbonate to a container containing 95mL of acetonitrile, stir for 20min, then add 4.78g of 2-bromoacetophenone, react at room temperature for 12h, extract with ethyl acetate, and rotary evaporate to obtain intermediate 1;

[0070] Q2: Add 3.61g of intermediate 1 and 8.87g of potassium carbonate to a container containing 105mL of methanol, stir and mix, then add 32mL of distilled water containing 1.72g of hydroxylamine hydrochloride, and then heat to 85℃ and reflux for 10h. After the reaction is complete, extract with ethyl acetate, rotary evaporate, and recrystallize in methanol to obtain intermediate 2.

[0071] Q3: Add 4.72g of nano-silica and 5.18g of potassium carbonate to a container containing 96mL of N,N-dimethylformamide. After stirring and mixing for 15min, add 12.06g of 1,12-dibromododecane dropwise. After reacting at room temperature for 24h, pour the mixture into ice water. Collect the solid and add it to a mixed solution of 230mL of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 1:3). Stir and filter to obtain intermediate 3.

[0072] Q4: Add 0.63g of intermediate 2 and 0.48g of potassium carbonate to a container containing 22mL of N,N-dimethylformamide, stir and mix for 20min, then add 0.96g of intermediate 3, react at room temperature for 12h, then add to ice water, filter, dry, and purify to obtain modified nano silica.

[0073] This embodiment discloses a method for preparing an organic dispersant, including the following steps:

[0074] S1: 1.48 g of hexamethylenebisacrylamide was added to 23.6 mL of 33 vt% methanol aqueous solution. After stirring and mixing, 0.57 g of 1-amino-2-propanol was added. The mixture was heated to 50 °C for 6 days under a nitrogen atmosphere. After the reaction was completed, the mixture was concentrated by rotary evaporation and added to acetone for precipitation. The precipitate was dissolved in deionized water. The dissolution-precipitation process was repeated 3 times. After drying, a viscous liquid a was obtained.

[0075] S2: Add 1.48g of viscous liquid a and 5.57g of 6-caprolactone to a container, heat to 130℃ under nitrogen atmosphere and stir to react, then add 0.071g of stannous octoate, react for 6 hours and then cool, dissolve with chloroform, precipitate with anhydrous diethyl ether, repeat the dissolution-precipitation process 3 times, dry to obtain organic dispersant.

[0076] This embodiment discloses a nano-modified homogenized ink, which is composed of the following components by weight: 6 parts modified nano silica, 2.1 parts organic dispersant, 1.6 parts nano titanium dioxide, 58 parts distilled water, 3 parts nano calcium carbonate, 1.5 parts polyvinyl alcohol, 1 part sodium carbonate and 2.8 parts mica powder.

[0077] This embodiment discloses a method for preparing a nano-modified homogenized ink, including the following steps:

[0078] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0079] Step 2: Grind the mixed slurry using zirconium oxide as the grinding medium at 2000 rpm for 2 hours until the fineness is <100 nm. Then, homogenize the mixture, slowly add polyvinyl alcohol, stir and mix, add sodium carbonate to adjust the pH to 7.5, filter, defoam, and cure to obtain nano-modified homogenized ink.

[0080] Example 5: This example discloses a method for preparing modified nano-silica, including the following steps:

[0081] Q1: Add 2.21g of 1,2,4-triazole and 10.96g of potassium carbonate to a container containing 105mL of acetonitrile, stir for 20min, then add 5.36g of 2-bromoacetophenone, react at room temperature for 12h, extract with ethyl acetate, and rotary evaporate to obtain intermediate 1;

[0082] Q2: Add 4.43g of intermediate 1 and 9.12g of potassium carbonate to a container containing 95mL of methanol, stir and mix, then add 28mL of distilled water containing 1.98g of hydroxylamine hydrochloride, and then heat to 85℃ and reflux for 10h. After the reaction is complete, extract with ethyl acetate, rotary evaporate, and recrystallize in methanol to obtain intermediate 2.

[0083] Q3: Add 5.32g of nano-silica and 5.66g of potassium carbonate to a container containing 100mL of N,N-dimethylformamide. After stirring and mixing for 15min, add 13.12g of 1,12-dibromododecane dropwise. After reacting at room temperature for 24h, pour the mixture into ice water. Collect the solid and add it to a mixed solution of 250mL of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 1:3). Stir and filter to obtain intermediate 3.

[0084] Q4: Add 0.74g of intermediate 2 and 0.61g of potassium carbonate to a container containing 28mL of N,N-dimethylformamide. After stirring and mixing for 20min, add 1.11g of intermediate 3. After reacting at room temperature for 12h, add to ice water, filter, dry, and purify to obtain modified nano-silica.

[0085] This embodiment discloses a method for preparing an organic dispersant, including the following steps:

[0086] S1: 1.58 g of hexamethylenebisacrylamide was added to 27.1 mL of 33 vt% methanol aqueous solution. After stirring and mixing, 0.64 g of 1-amino-2-propanol was added. The mixture was heated to 50 °C under a nitrogen atmosphere and reacted for 6 days. After the reaction was completed, the mixture was concentrated by rotary evaporation and added to acetone for precipitation. The precipitate was dissolved in deionized water. The dissolution-precipitation process was repeated 3 times. After drying, a viscous liquid a was obtained.

[0087] S2: Add 1.62g of viscous liquid a and 6.02g of 6-caprolactone to a container, heat to 130℃ under nitrogen atmosphere and stir to react, then add 0.076g of stannous octoate, react for 6h and then cool, dissolve with chloroform, precipitate with anhydrous diethyl ether, repeat the dissolution-precipitation process 3 times, dry to obtain organic dispersant.

[0088] This embodiment discloses a nano-modified homogenized ink, which is composed of the following components by weight: 10 parts modified nano silica, 4.8 parts organic dispersant, 2.1 parts nano titanium dioxide, 68 parts distilled water, 4 parts nano calcium carbonate, 2.1 parts carboxymethyl cellulose, 1.4 parts triethanolamine and 4.2 parts mica powder.

[0089] This embodiment discloses a method for preparing a nano-modified homogenized ink, including the following steps:

[0090] Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry;

[0091] Step 2: Grind the mixed slurry using zirconium oxide as the grinding medium at 2000 rpm for 2 hours until the fineness is <100 nm. Then, homogenize the mixture and slowly add carboxymethyl cellulose. After stirring and mixing, add triethanolamine to adjust the pH to 7.5, filter, defoam, and cure to obtain nano-modified homogenized ink.

[0092] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not add organic dispersant during the preparation of nano-modified homogenized ink, and all other conditions remained unchanged.

[0093] Comparative Example 2: Compared with Example 1, Comparative Example 2 uses nano-silica instead of modified nano-silica in the process of preparing nano-modified homogenized ink, while other conditions remain unchanged.

[0094] Performance testing:

[0095] The homogenized inks prepared according to Examples 1-5 and Comparative Examples 1-2 were subjected to performance testing. The water resistance of the samples was tested according to GB / T18724-2024, and the abrasion resistance was tested according to GB / T 9266-2009, using an emissivity of (42±2) W / m in the wavelength range of 300-400 nm. 2 After 100 hours of xenon arc lamp irradiation, the color difference ΔE was measured, and the test results are shown in Table 1.

[0096] Table 1 Example 1 0 2.12 0.8 Example 2 0 2.21 0.9 Example 3 0 2.18 0.9 Example 4 0 2.17 1.0 Example 5 0 2.20 0.9 Comparative Example 1 1 2.22 1.2 Comparative Example 2 3 4.68 2.7

[0097] For the water resistance test results, a rating was given based on visual inspection: Grade 0 was no visible difference, Grade 1 was slight difference or <10% difference, Grade 2 was considerable difference or 10%-50% damage, Grade 3 was severe difference or 50%-90% damage, and Grade 4 was total difference >90% damage. Table 1 shows that the samples prepared according to Examples 1-5 have excellent water resistance, abrasion resistance, and oxidation resistance. Comparing Comparative Example 1 with Examples 1-5, the absence of an organic dispersant leads to a decrease in water resistance. This is because the lack of an organic dispersant may cause particle agglomeration, resulting in slight differences due to localized water molecule penetration, which meets the Grade 1 rating. The increased color difference is due to micro-agglomeration of particles caused by the lack of an organic dispersant, making localized oxidation reactions more likely. However, the triazole structure still has excellent antioxidant properties, so ΔE is only slightly higher than in Examples 1-5. Comparing Comparative Example 2 with Examples 1-5, the addition of modified nano-silica can effectively improve the water resistance, abrasion resistance, and oxidation resistance of the samples.

[0098] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0099] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A nano-modified homogenized ink, characterized in that, It is composed of the following components by weight: 4-12 parts modified nano-silica, 1.2-5.3 parts organic dispersant, 1.5-2.2 parts nano-titanium dioxide, 51-73 parts distilled water, 2-5 parts nano-calcium carbonate, 1.1-2.4 parts viscosity modifier, 0.8-1.6 parts pH adjuster, and 2.2-5.4 parts mica powder; wherein the viscosity modifier is selected from one of nano-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol; The method for preparing the modified nano-silica includes the following steps: Q1: Add 1,2,4-triazole and potassium carbonate to a container containing acetonitrile, stir, add 2-bromoacetophenone, react at room temperature, extract, and rotary evaporate to obtain intermediate 1; Q2: Add intermediate 1 and potassium carbonate to a container containing methanol, stir and mix, then add distilled water containing dissolved hydroxylamine hydrochloride dropwise, and then heat to reflux to react. After the reaction is complete, extract, rotary evaporate, and recrystallize to obtain intermediate 2. Q3: Add nano-silica and potassium carbonate to a container containing N,N-dimethylformamide, stir and mix, then add 1,12-dibromododecane dropwise. After reacting at room temperature, pour into ice water, collect the solid and add it to a mixed solution of petroleum ether and ethyl acetate. Stir, filter, and obtain intermediate 3. Q4: Add intermediate 2 and potassium carbonate to a container containing N,N-dimethylformamide, stir and mix, then add intermediate 3, react at room temperature, add to ice water, filter, dry and purify to obtain modified nano silica; The method for preparing the organic dispersant includes the following steps: S1: Add hexamethylenebisacrylamide to an aqueous methanol solution, stir and mix, then add 1-amino-2-propanol, heat and react under a nitrogen atmosphere. After the reaction is complete, concentrate by rotary evaporation, precipitate, dissolve, repeat the dissolution-precipitation process, and dry to obtain viscous liquid a. S2: Add viscous liquid a and 6-caprolactone to a container, heat and stir under nitrogen atmosphere, then add stannous octoate, cool after reaction, dissolve, precipitate, repeat dissolution-precipitation, dry to obtain organic dispersant.

2. The nano-modified homogenized ink according to claim 1, characterized in that, In Q1, the ratio of the amounts of 1,2,4-triazole, potassium carbonate, acetonitrile, and 2-bromoacetophenone is (1.88-2.36) g : (9.89-11.12) g : (90-110) mL : (4.58-5.52) g; in Q2, the ratio of the amounts of intermediate 1, potassium carbonate, methanol, hydroxylamine hydrochloride, and distilled water is (3.21-4.82) g : (8.56-9.33) g : (90-110) mL : (1.66-2.04) g : (25-35) mL.

3. The nano-modified homogenized ink according to claim 1, characterized in that, In Q3, the ratio of the amounts of nano-silica, potassium carbonate, N,N-dimethylformamide, 1,12-dibromododecane and the mixed solution is (4.34-5.66) g : (5.04-5.72) g : (92-105) mL : (11.78-13.42) g : (220-260) mL.

4. The nano-modified homogenized ink according to claim 1, characterized in that, In Q4, the ratio of intermediate 2, potassium carbonate, N,N-dimethylformamide and intermediate 3 is (0.61-0.78) g : (0.45-0.66) g : (20-30) mL : (0.88-1.21) g.

5. The nano-modified homogenized ink according to claim 1, characterized in that, In S1, the ratio of hexamethylenebisacrylamide, methanol aqueous solution and 1-amino-2-propanol is (1.43-1.65) g : (22.4-28.7) mL : (0.55-0.68) g.

6. The nano-modified homogenized ink according to claim 1, characterized in that, In S2, the ratio of viscous liquid a, 6-caprolactone and stannous octoate is (1.34-1.82) g : (5.25-6.33) g : (0.066-0.081) g.

7. A method for preparing a nano-modified homogenized ink according to any one of claims 1-6, characterized in that, Includes the following steps: Step 1: Add the organic dispersant to distilled water, stir and mix, then add modified nano silica, nano titanium dioxide, nano calcium carbonate and mica powder in sequence, stir and mix to obtain a mixed slurry; Step 2: Grind the mixed slurry, then homogenize it, and then slowly add a viscosity modifier. After stirring and mixing, add a pH adjuster to adjust the pH, filter, defoam, and mature to obtain nano-modified homogenized ink.

8. The method for preparing a nano-modified homogenized ink according to claim 7, characterized in that, In step two, zirconium oxide is used as the grinding medium during the grinding process. Grinding is carried out at 1500-3000 rpm for 1-3 hours until the fineness is <100nm, and the pH is adjusted to 7.5-8.

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