Nano-modified homogenized ink and preparation method thereof

Abstract

The invention discloses nano-modified homogenized ink and a preparation method thereof, and belongs to the technical field of ink preparation. The nano-modified homogenized ink is prepared from the following components in parts by weight: 4 to 12 parts of modified nano silicon dioxide, 1.2 to 5.3 parts of an organic dispersing agent, 1.5 to 2.2 parts of nano titanium dioxide, 51 to 73 parts of distilled water, 2 to 5 parts of nano calcium carbonate, 1.1 to 2.4 parts of a viscosity modifier, 0.8 to 1.6 parts of a pH (Potential of Hydrogen) regulator and 2.2 to 5.4 parts of mica powder. The ink prepared by the method has excellent dispersity, oxidation resistance, moisture resistance and hydrophobicity.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ink preparation, and particularly relates to a nano-modified homogenized ink and a preparation method thereof. BACKGROUND

[0002] In the field of traditional ink, poor dispersibility has always been a key problem restricting the performance improvement and application expansion. The pigments or functional particles in ordinary ink are often large in size and unevenly distributed due to the preparation process. Strong van der Waals forces exist between these large particles, which are prone to aggregation and form clumps. During storage, the aggregation phenomenon will further intensify, resulting in obvious sedimentation and stratification of the ink, which seriously affects the stability of the ink and shortens the shelf life of the ink. In the printing process, large particle clumps in ink with poor dispersibility can easily block the nozzle, causing printing interruption, increasing equipment maintenance costs and production time loss, and uneven particle distribution can cause color difference, stripes and other defects in the printed pattern, reducing the quality and fineness of the printed product.

[0003] Patent CN115558337B discloses a luminescent nanoparticle ink, a luminescent nanoparticle color film prepared therefrom, and a display device. The luminescent nanoparticle ink comprises luminescent nanoparticles, an enoic acid silane compound, and an initiator. The surface of the luminescent nanoparticles is modified with an organic ligand from a surface active compound. The presence of the organic ligand from the surface active compound in the luminescent nanoparticles facilitates the dissolution of the luminescent nanoparticles in the enoic acid silane compound. The enoic acid silane compound participates in the polymerization reaction, and the formed luminescent nanoparticle color film has better adhesion to the substrate and superior optical performance. Although the luminescent nanoparticle ink disclosed in the above patent realizes the dissolution in the enoic acid silane compound to some extent by means of the organic ligand from the surface active compound modified on the surface of the luminescent nanoparticles, and the formed color film has good adhesion and optical performance, the dispersibility of the ink still has certain defects in actual application. Under long-term storage or complex environmental conditions, the luminescent nanoparticles still exhibit slight aggregation, which leads to a decrease in the uniformity of the ink and further affects the consistency and stability of the display effect of the color film and the display device prepared therefrom. SUMMARY

[0004] The present application aims to provide a nano-modified homogenized ink and a preparation method thereof, which solve the technical problem of poor dispersibility of the ink in the prior art.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The application provides a nano-modified homogenized ink, which is composed of the following components in parts by weight: 4-12 parts of modified nano-silicon dioxide, 1.2-5.3 parts of an organic dispersant, 1.5-2.2 parts of nano-titanium dioxide, 51-73 parts of distilled water, 2-5 parts of nano-calcium carbonate, 1.1-2.4 parts of a viscosity regulator, 0.8-1.6 parts of a pH regulator and 2.2-5.4 parts of mica powder.

[0007] As preferred, the preparation method of the modified nano-silicon dioxide comprises the following steps:

[0008] Q1: 1,2,4-triazole and potassium carbonate are added to a container containing acetonitrile, 2-bromoacetophenone is added after stirring, and after reaction at room temperature, extraction, rotary evaporation, intermediate 1 is obtained;

[0009] Q2: intermediate 1 and potassium carbonate are added to a container containing methanol, and after stirring and mixing, distilled water containing hydroxylamine hydrochloride is added dropwise, followed by heating and refluxing, after the reaction is completed, extraction, rotary evaporation, recrystallization, intermediate 2 is obtained;

[0010] Q3: nano-silicon dioxide and potassium carbonate are added to a container containing N,N-dimethylformamide, and after stirring and mixing, 1,12-dibromododecane is added dropwise, after reaction at room temperature, pour into ice water, collect the solid and add to a mixed solution of petroleum ether and ethyl acetate, stir, filter, and obtain intermediate 3;

[0011] Q4: intermediate 2 and potassium carbonate are added to a container containing N,N-dimethylformamide, and after stirring and mixing, intermediate 3 is added, after reaction at room temperature, add to ice water, filter, dry, purify, and obtain modified nano-silicon dioxide.

[0012] In the above process, the synthesis reaction formula of the modified nano-silicon dioxide is as follows:

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

[0014] As preferred, in the 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, stirring for 10-20 min, reacting at room temperature for 10-12 h, and extracting with ethyl acetate; in the 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, heating to 80-90°C to reflux for 8-10 h, and extracting with ethyl acetate, and recrystallizing in methanol.

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

[0016] As preferred, in the Q4, the ratio of the amounts 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, stirring for 10-20 min, and reacting at room temperature for 10-12 h.

[0017] As preferred, the preparation method of the organic dispersant comprises the following steps:

[0018] S1: hexamethylene bisacrylamide is added to a methanol aqueous solution, after stirring and mixing, 1-amino-2-propanol is added, and heating reaction is carried out under a nitrogen atmosphere, after the reaction is completed, rotary evaporation is carried out for concentration, precipitation is carried out, dissolution is carried out, dissolution-precipitation is repeated, and drying is carried out, to obtain viscous liquid a;

[0019] S2: viscous liquid a and 6-hexalactone are added to a container, and heating stirring reaction is carried out under a nitrogen atmosphere, then stannous octoate is added, after the reaction, cooling is carried out, dissolution is carried out, precipitation is carried out, dissolution-precipitation is repeated, and drying is carried out, to obtain the organic dispersant.

[0020] In the above process, hexamethylene bisacrylamide and 1-amino-2-propanol are used as raw materials, and through addition reaction, viscous liquid a is obtained, then the side chain hydroxyl and secondary amine group contained in viscous liquid a are ring-opening polymerized with 6-hexalactone, to obtain the organic dispersant.

[0021] As preferred, in the S1, the amount ratio of hexamethylene bisacrylamide, 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 methanol aqueous solution is 33 vol%, heated to 45-55℃ for 4-6d, added into acetone for precipitation, dissolved with deionized water, repeated dissolution-precipitation for 3-5 times.

[0022] As preferred, in the S2, the amount ratio of viscous liquid a, 6-hexalactone and stannous octoate is (1.34-1.82) g:(5.25-6.33) g:(0.066-0.081) g, heated to 125-135℃, reacted for 4-6h, then cooled, dissolved with chloroform, precipitated with anhydrous ether, repeated dissolution-precipitation for 3-5 times.

[0023] As preferred, the preparation method of the nano-modified homogenized ink comprises the following steps:

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

[0025] Step two: grind the mixed slurry, then perform homogenization treatment, then slowly add the viscosity regulator, stir and mix, then add the pH regulator to adjust the pH, filter, defoam, and mature, to obtain the nano-modified homogenized ink.

[0026] As preferred, in the step two, zirconium oxide is used as the grinding medium during the grinding process, and the grinding is performed at 1500-3000rpm for 1-3h 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 solutions, the present application has the following advantages:

[0028] 1. The present application first uses 1,2,4-triazole, 2-bromoacetophenone, hydroxylamine hydrochloride, nano-silica and 1,12-dibromododecane as raw materials to prepare modified nano-silica, then uses hexamethylene bisacrylamide, 1-amino-2-propanol and 6-hexalactone as raw materials to prepare an organic dispersant, and finally adds the prepared modified nano-silica and organic dispersant into the ink, so that the ink has excellent dispersibility, wear resistance, oxidation resistance and moisture resistance.

[0029] 2. The modified nano-silica prepared by the method is added to the ink, so that the dispersibility, wear resistance, oxidation resistance and moisture resistance of the ink are effectively improved, the long-chain alkyl and triazole groups on the surface of the modified nano-silica can be fully stretched in the solvent to form an organic molecular layer around the particles, when the modified particles are close to each other, the organic molecular layer is physically overlapped and compressed to generate strong repulsive force, so that the further close and agglomeration of the particles are effectively prevented, the dispersibility of the ink is improved, the flexible long-chain grafted on the modified nano-silica can significantly improve the wear resistance through the dual mechanisms of physical enhancement and energy dissipation, meanwhile, the triazole structure contained in the structure of the modified nano-silica can capture free radicals generated under the action of heat or light to interrupt the chain reaction causing aging, so that the oxidation resistance is improved, and the long-chain alkyl with low surface energy grafted on the modified nano-silica can effectively improve the moisture resistance of the ink.

[0030] 3. The organic dispersant prepared by the method is added to the ink, so that the dispersibility of the ink is effectively improved, and the organic dispersant is strongly adsorbed on the surface of the nano-particles through hydrogen bond, coordination bond and dipole-dipole interaction to realize strong anchoring, so that the excellent dispersibility and long-term storage stability of the nano-particles are realized. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be described clearly and completely below, obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0032] Embodiment 1: The present embodiment discloses a preparation method of modified nano-silica, comprising the following steps:

[0033] Q1: 2.07g of 1,2,4-triazole and 10.52g of potassium carbonate are added to a container containing 100mL of acetonitrile, after stirring for 20min, 5.05g of 2-bromoacetophenone is added, and after reaction at room temperature for 12h, extraction is performed with ethyl acetate, and rotary evaporation is performed to obtain intermediate 1;

[0034] Q2: 4.02g of intermediate 1 and 8.94g of potassium carbonate are added to a container containing 100mL of methanol, after stirring and mixing, 30mL of distilled water dissolving 1.85g of hydroxylamine hydrochloride is added dropwise, and then heated to 85℃ to reflux for 10h, after the reaction is completed, extraction is performed with ethyl acetate, rotary evaporation is performed, and recrystallization is performed in methanol to obtain intermediate 2;

[0035] Q3: 4.95 g of nano-silica and 5.38 g of potassium carbonate were added to a container containing 98 mL of N,N-dimethylformamide, stirred and mixed for 15 min, then 12.62 g of 1,12-dibromododecane was added dropwise, reacted at room temperature for 24 h, poured into ice water, the solid was collected and added to a mixed solution of 240 mL of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate was 1:3, stirred, filtered, and intermediate 3 was obtained;

[0036] Q4: 0.68 g of intermediate 2 and 0.51 g of potassium carbonate were added to a container containing 25 mL of N,N-dimethylformamide, stirred and mixed for 20 min, then 1.02 g of intermediate 3 was added, reacted at room temperature for 12 h, added to ice water, filtered, dried, and purified to obtain modified nano-silica.

[0037] The embodiment discloses a preparation method of an organic dispersant, comprising the following steps:

[0038] S1: 1.54 g of hexamethylene bisacrylamide was added to a 25.5 mL volume fraction of 33% methanol aqueous solution, stirred and mixed, then 0.61 g of 1-amino-2-propanol was added, heated to 50°C under a nitrogen atmosphere and reacted for 6 d, after the reaction was completed, concentrated by rotary evaporation, precipitated in acetone, dissolved in deionized water, and repeated dissolution-precipitation three times, and dried to obtain viscous liquid a;

[0039] S2: 1.53 g of viscous liquid a and 5.84 g of 6-hexanolactone were added to a container, stirred and reacted at 130°C under a nitrogen atmosphere, then 0.073 g of stannous octoate was added, reacted for 6 h, cooled, dissolved in chloroform, precipitated in anhydrous ether, repeated dissolution-precipitation three times, and dried to obtain the organic dispersant.

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

[0041] The embodiment discloses a preparation method of a nano-modified homogenized ink, comprising the following steps:

[0042] Step one: the organic dispersant was added to the distilled water, stirred and mixed, then the modified nano-silica, nano-titanium dioxide, nano-calcium carbonate and mica powder were sequentially added, stirred and mixed, and a mixed slurry was obtained;

[0043] Step two: the mixed slurry is ground with zirconium oxide as grinding medium at 2000 rpm for 2 h until the fineness is <100 nm, and then is subjected to homogenization treatment, followed by slow addition of nanocellulose, stirring and mixing, addition of sodium hydroxide to adjust pH to 7.5, filtration, defoaming, maturation, to obtain the nanomodified homogenized ink.

[0044] Example 2: This example discloses a preparation method of modified nanosilica, comprising the following steps:

[0045] Q1: 1.88 g of 1,2,4-triazole and 9.89 g of potassium carbonate are added to a container containing 90 mL of acetonitrile, stirred for 20 min, then 4.58 g of 2-bromoacetophenone is added, reacted at room temperature for 12 h, then extracted with ethyl acetate, rotary evaporation, to obtain intermediate 1;

[0046] Q2: 3.21 g of intermediate 1 and 8.56 g of potassium carbonate are added to a container containing 90 mL of methanol, stirred and mixed, then 25 mL of distilled water dissolving 1.66 g of hydroxylamine hydrochloride is added dropwise, then heated to 85°C to reflux for 10 h, after the reaction is completed, extracted with ethyl acetate, rotary evaporation, recrystallized in methanol, to obtain intermediate 2;

[0047] Q3: 4.34 g of nanosilica and 5.04 g of potassium carbonate are added to a container containing 92 mL of N,N-dimethylformamide, stirred and mixed for 15 min, then 11.78 g of 1,12-dibromododecane is added dropwise, reacted at room temperature for 24 h, then poured into ice water, the solid is collected and added to a mixed solution of 220 mL of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate is 1:3, stirred, filtered, to obtain intermediate 3;

[0048] Q4: 0.61 g of intermediate 2 and 0.45 g of potassium carbonate are added to a container containing 20 mL of N,N-dimethylformamide, stirred and mixed for 20 min, then 1.21 g of intermediate 3 is added, reacted at room temperature for 12 h, then added to ice water, filtered, dried, purified, to obtain modified nanosilica.

[0049] This example discloses a preparation method of an organic dispersant, comprising the following steps:

[0050] S1: 1.43 g of hexamethylene bisacrylamide is added to 22.4 mL of methanol aqueous solution with a volume fraction of 33 vt%, stirred and mixed, then 0.55 g of 1-amino-2-propanol is added, heated to 50°C under nitrogen atmosphere for 6 d, after the reaction is completed, concentrated by rotary evaporation, precipitated in acetone, dissolved with deionized water, repeated dissolution-precipitation for 3 times, dried, to obtain viscous liquid a;

[0051] S2: 1.34 g of viscous liquid a and 5.25 g of 6-caprolactone were added to a container, the reaction was stirred under nitrogen at 130°C, then 0.066 g of stannous octoate was added, the reaction was allowed to proceed for 6 h, then it was cooled, dissolved in chloroform and precipitated in dry ether, the dissolution-precipitation was repeated three times, and the organic dispersant was obtained by drying.

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

[0053] The example discloses a preparation method of a nano-modified homogenized ink, which comprises the following steps:

[0054] Step one: the organic dispersant was added to the distilled water, and after stirring and mixing, the modified nano-silicon dioxide, nano-titanium dioxide, nano-calcium carbonate and mica powder were sequentially added, and after stirring and mixing, a mixed slurry was obtained;

[0055] Step two: the mixed slurry was ground, zirconium oxide was used as a grinding medium during the grinding process, and the grinding was carried out at 2000 rpm for 2 h until the fineness was less than 100 nm, then the homogenization treatment was carried out, then the xanthan gum was slowly added, after stirring and mixing, the triethanolamine was added to adjust the pH value to 7.5, and then the nano-modified homogenized ink was obtained after filtration, defoaming and aging.

[0056] Example 3: The example discloses a preparation method of modified nano-silicon dioxide, which comprises the following steps:

[0057] Q1: 2.36 g of 1,2,4-triazole and 11.12 g of potassium carbonate were added to a container containing 110 mL of acetonitrile, stirred for 20 min, then 5.52 g of 2-bromoacetophenone was added, and the reaction was carried out at room temperature for 12 h, then extracted with ethyl acetate, and rotary evaporated to obtain an intermediate 1;

[0058] Q2: 4.82 g of the intermediate 1 and 9.33 g of potassium carbonate were added to a container containing 110 mL of methanol, stirred and mixed, then 35 mL of distilled water containing 2.04 g of hydroxylamine hydrochloride was added dropwise, then heated to 85°C and refluxed for 10 h, after the reaction was completed, extracted with ethyl acetate, rotary evaporated, and recrystallized in methanol to obtain an intermediate 2;

[0059] Q3: 5.66 g of nano-silica and 5.72 g of potassium carbonate were added to a container containing 105 mL of N,N-dimethylformamide, stirred and mixed for 15 min, then 13.42 g of 1,12-dibromododecane was added dropwise, reacted at room temperature for 24 h, poured into ice water, the solid was collected and added to a mixed solution of 260 mL of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate was 1:3, stirred, filtered, and intermediate 3 was obtained;

[0060] Q4: 0.78 g of intermediate 2 and 0.66 g of potassium carbonate were added to a container containing 30 mL of N,N-dimethylformamide, stirred and mixed for 20 min, then 0.88 g of intermediate 3 was added, reacted at room temperature for 12 h, added to ice water, filtered, dried, and purified to obtain modified nano-silica.

[0061] The embodiment discloses a preparation method of an organic dispersant, comprising the following steps:

[0062] S1: 1.65 g of hexamethylene bisacrylamide was added to a 28.7 mL volume fraction of 33 vt% methanol aqueous solution, stirred and mixed, then 0.68 g of 1-amino-2-propanol was added, heated to 50℃ under nitrogen atmosphere and reacted for 6 d, after the reaction was completed, rotary evaporation was performed for concentration, added to acetone for precipitation, dissolved with deionized water, repeated dissolution-precipitation for 3 times, and dried to obtain viscous liquid a;

[0063] S2: 1.82 g of viscous liquid a and 6.33 g of 6-hexanolactone were added to a container, stirred and reacted at 130℃ under nitrogen atmosphere, then 0.081 g of stannous octoate was added, reacted for 6 h, cooled, dissolved with chloroform, precipitated with anhydrous ether, repeated dissolution-precipitation for 3 times, and dried to obtain the organic dispersant.

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

[0065] The embodiment discloses a preparation method of a nano-modified homogenized ink, comprising the following steps:

[0066] Step one: the organic dispersant was added to the distilled water, stirred and mixed, then the modified nano-silica, nano-titanium dioxide, nano-calcium carbonate and mica powder were sequentially added, stirred and mixed, and a mixed slurry was obtained;

[0067] Step two: the mixed slurry is ground with zirconium oxide as grinding medium at 2000 rpm for 2 h until the fineness is <100 nm, and then is subjected to homogenization treatment, followed by the slow addition of hydroxyethyl cellulose, stirring and mixing, the addition of ammonia water to adjust pH = 7.5, filtration, defoaming, aging, to obtain the nano-modified homogenized ink.

[0068] Example 4: This example discloses a preparation method of modified nano-silica, comprising the following steps:

[0069] Q1: 1.96 g of 1,2,4-triazole and 10.17 g of potassium carbonate are added to a container containing 95 mL of acetonitrile, stirred for 20 min, then 4.78 g of 2-bromoacetophenone is added, reacted at room temperature for 12 h, extracted with ethyl acetate, rotary evaporation, to obtain intermediate 1;

[0070] Q2: 3.61 g of intermediate 1 and 8.87 g of potassium carbonate are added to a container containing 105 mL of methanol, stirred and mixed, then 32 mL of distilled water dissolving 1.72 g of hydroxylamine hydrochloride is added dropwise, then heated to 85°C and refluxed for 10 h, after the reaction is completed, extracted with ethyl acetate, rotary evaporation, recrystallized in methanol, to obtain intermediate 2;

[0071] Q3: 4.72 g of nano-silica and 5.18 g of potassium carbonate are added to a container containing 96 mL of N,N-dimethylformamide, stirred and mixed for 15 min, then 12.06 g of 1,12-dibromododecane is added dropwise, reacted at room temperature for 24 h, poured into ice water, the solid is collected and added to a mixed solution of 230 mL of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate is 1:3, stirred, filtered, to obtain intermediate 3;

[0072] Q4: 0.63 g of intermediate 2 and 0.48 g of potassium carbonate are added to a container containing 22 mL of N,N-dimethylformamide, stirred and mixed for 20 min, then 0.96 g of intermediate 3 is added, reacted at room temperature for 12 h, added to ice water, filtered, dried, purified, to obtain modified nano-silica.

[0073] This example discloses a preparation method of an organic dispersant, comprising the following steps:

[0074] S1: 1.48 g of hexamethylene bisacrylamide is added to 23.6 mL of methanol aqueous solution with a volume fraction of 33 vt%, stirred and mixed, then 0.57 g of 1-amino-2-propanol is added, heated to 50°C under nitrogen atmosphere for 6 d, after the reaction is completed, concentrated by rotary evaporation, precipitated in acetone, dissolved with deionized water, repeated dissolution-precipitation for 3 times, dried, to obtain viscous liquid a;

[0075] S2: 1.48 g of viscous liquid a and 5.57 g of 6-caprolactone were added to a container, the reaction was stirred under nitrogen at 130°C, then 0.071 g of stannous octoate was added, the reaction was allowed to proceed for 6 h, then it was cooled, dissolved in chloroform and precipitated in dry ether, the dissolution-precipitation was repeated three times, and the organic dispersant was obtained by drying.

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

[0077] The example discloses a preparation method of a nano-modified homogenized ink, which comprises the following steps:

[0078] Step one: the organic dispersant was added to the distilled water, and after stirring and mixing, the modified nano-silicon dioxide, nano-titanium dioxide, nano-calcium carbonate and mica powder were sequentially added, and after stirring and mixing, a mixed slurry was obtained;

[0079] Step two: the mixed slurry was ground, zirconium oxide was used as a grinding medium during the grinding process, and the grinding was carried out at 2000 rpm for 2 h until the fineness was less than 100 nm, and then the homogenization treatment was carried out, then the polyvinyl alcohol was slowly added, after stirring and mixing, the sodium carbonate was added to adjust the pH value to 7.5, and then the nano-modified homogenized ink was obtained after filtration, defoaming and aging.

[0080] Example 5: The example discloses a preparation method of modified nano-silicon dioxide, which comprises the following steps:

[0081] Q1: 2.21 g of 1,2,4-triazole and 10.96 g of potassium carbonate were added to a container containing 105 mL of acetonitrile, stirred for 20 min, then 5.36 g of 2-bromoacetophenone was added, and the reaction was carried out at room temperature for 12 h, then extracted with ethyl acetate, and rotary evaporated to obtain an intermediate 1;

[0082] Q2: 4.43 g of the intermediate 1 and 9.12 g of potassium carbonate were added to a container containing 95 mL of methanol, stirred and mixed, then 28 mL of distilled water containing 1.98 g of hydroxylamine hydrochloride was added dropwise, then heated to 85°C and refluxed for 10 h, after the reaction was completed, extracted with ethyl acetate, rotary evaporated, and recrystallized in methanol to obtain an intermediate 2;

[0083] Q3: 5.32 g of nano-silica and 5.66 g of potassium carbonate were added to a container containing 100 mL of N,N-dimethylformamide, stirred and mixed for 15 min, then 13.12 g of 1,12-dibromododecane was added dropwise, reacted at room temperature for 24 h, poured into ice water, the solid was collected and added to a mixed solution of 250 mL of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate was 1:3, stirred, filtered, and intermediate 3 was obtained;

[0084] Q4: 0.74 g of intermediate 2 and 0.61 g of potassium carbonate were added to a container containing 28 mL of N,N-dimethylformamide, stirred and mixed for 20 min, then 1.11 g of intermediate 3 was added, reacted at room temperature for 12 h, added to ice water, filtered, dried, and purified to obtain modified nano-silica.

[0085] The embodiment discloses a preparation method of an organic dispersant, comprising the following steps:

[0086] S1: 1.58 g of hexamethylene bisacrylamide was added to 27.1 mL of a methanol aqueous solution with a volume fraction of 33 vt%, stirred and mixed, then 0.64 g of 1-amino-2-propanol was added, heated to 50°C under a nitrogen atmosphere, and reacted for 6 d, after the reaction was completed, concentrated by rotary evaporation, precipitated in acetone, dissolved in deionized water, and repeated dissolution-precipitation three times, and dried to obtain viscous liquid a;

[0087] S2: 1.62 g of viscous liquid a and 6.02 g of 6-hexanolactone were added to a container, stirred and reacted at 130°C under a nitrogen atmosphere, then 0.076 g of stannous octoate was added, reacted for 6 h, cooled, dissolved in chloroform, precipitated in anhydrous ether, repeated dissolution-precipitation three times, and dried to obtain the organic dispersant.

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

[0089] The embodiment discloses a preparation method of a nano-modified homogenized ink, comprising the following steps:

[0090] Step one: the organic dispersant was added to distilled water, stirred and mixed, then the modified nano-silica, nano-titanium dioxide, nano-calcium carbonate, and mica powder were sequentially added, stirred and mixed, and a mixed slurry was obtained;

[0091] Step two: grind the mixed slurry, use zirconium oxide as grinding medium during the grinding process, grind at 2000 rpm for 2 h until fineness <100 nm, then homogenize, then slowly add carboxymethyl cellulose, stir and mix, then add triethanolamine to adjust pH=7.5, filter, degas, and mature to obtain the nano-modified homogenized ink.

[0092] Comparative Example 1: Comparative Example 1 is compared with Example 1. In the process of preparing the nano-modified homogenized ink, no organic dispersant is added, and other conditions remain unchanged.

[0093] Comparative Example 2: Comparative Example 2 is compared with Example 1. In the process of preparing the nano-modified homogenized ink, nano-silica is used instead of modified nano-silica, and other conditions remain unchanged.

[0094] Performance test:

[0095] The homogenized inks prepared according to Examples 1-5 and Comparative Examples 1-2 are subjected to performance testing. The water resistance of the samples is tested according to GB / T18724-2024, and the wear resistance of the samples is tested according to GB / T 9266-2009. The wavelength range of the radiation degree is 300-400 nm, and the irradiation time is 100 h. 2 After 100 h of xenon arc lamp irradiation, the color difference ΔE is measured, and the test results are shown in Table 1:

[0096] Table 1 Item Water resistance Mass loss rate / % △E 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 test results of water resistance, visual evaluation is used. Grade 0 is no visible difference, grade 1 is slight difference or <10% difference, grade 2 is considerable difference or 10%-50% damage, grade 3 is severe difference or 50%-90% damage, and grade 4 is total difference >90% damage. As can be seen from the test results in Table 1, the samples prepared according to Examples 1-5 have excellent water resistance, wear resistance and oxidation resistance. As can be seen from the comparison between Comparative Example 1 and Examples 1-5, the absence of an organic dispersant can lead to a decrease in water resistance, as the absence of an organic dispersant can cause particle agglomeration, and water molecules can penetrate local areas, resulting in slight differences, which meet the grade 1 rating. The increase in color difference is due to the lack of organic dispersant, which causes particle agglomeration, and local oxidation reactions are more likely to occur, but the triazole structure still has excellent antioxidant properties, so ΔE is only slightly higher than that of Examples 1-5. As can be seen from the comparison between Comparative Example 2 and Examples 1-5, the addition of modified nano-silica can effectively improve the water resistance, wear resistance and oxidation resistance of the samples.

[0098] The above merely describes preferred embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, within the technical scope disclosed by the present application, can make equivalent replacements or changes according to the technical scheme and inventive concept of the present application, which should be covered within the protection scope of the present application.

[0099] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and do not limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and their full scope and equivalents.

Claims

1. A nanomodified homogenized ink, characterized in that, The modified nano-silica is prepared by the following steps: Q1: adding 1,2,4-triazole and potassium carbonate into a container containing acetonitrile, stirring, then adding 2-bromoacetophenone, reacting at room temperature, extracting, rotary evaporation, to obtain intermediate 1; Q2: adding intermediate 1 and potassium carbonate into a container containing methanol, stirring and mixing, then adding hydroxylamine hydrochloride dissolved in distilled water dropwise, then heating and refluxing, after the reaction is completed, extracting, rotary evaporation, recrystallization, to obtain intermediate 2; Q3: adding nano-silica and potassium carbonate into a container containing N,N-dimethylformamide, stirring and mixing, then adding 1,12-dibromododecane dropwise, reacting at room temperature, then pouring into ice water, collecting the solid, adding into a mixed solution of petroleum ether and ethyl acetate, stirring, filtering, to obtain intermediate 3; Q4: adding intermediate 2 and potassium carbonate into a container containing N,N-dimethylformamide, stirring and mixing, then adding intermediate 3, reacting at room temperature, then adding into ice water, filtering, drying, purifying, to obtain the modified nano-silica.

2. A nano-modified homogenized ink according to claim 1, characterized in that, The modified nano-silica is prepared by the following steps: Q1: adding 1,2,4-triazole and potassium carbonate into a container containing acetonitrile, stirring, then adding 2-bromoacetophenone, reacting at room temperature, extracting, rotary evaporation, to obtain intermediate 1; Q2: adding intermediate 1 and potassium carbonate into a container containing methanol, stirring and mixing, then adding hydroxylamine hydrochloride dissolved in distilled water dropwise, then heating and refluxing, after the reaction is completed, extracting, rotary evaporation, recrystallization, to obtain intermediate 2; Q3: adding nano-silica and potassium carbonate into a container containing N,N-dimethylformamide, stirring and mixing, then adding 1,12-dibromododecane dropwise, reacting at room temperature, then pouring into ice water, collecting the solid, adding into a mixed solution of petroleum ether and ethyl acetate, stirring, filtering, to obtain intermediate 3; Q4: adding intermediate 2 and potassium carbonate into a container containing N,N-dimethylformamide, stirring and mixing, then adding intermediate 3, reacting at room temperature, then adding into ice water, filtering, drying, purifying, to obtain the modified nano-silica. In the Q1, the amount 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; in the Q2, the amount 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. In the Q3, the amount 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. In the Q4, the amount 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. The preparation method of the organic dispersant comprises the following steps: S1: adding hexamethylene bisacrylamide into a methanol aqueous solution, stirring and mixing, then adding 1-amino-2-propanol, heating and reacting under a nitrogen atmosphere, after the reaction is completed, concentrating by rotary evaporation, precipitating, dissolving, repeating the dissolving-precipitating, drying, to obtain viscous liquid a; S2: adding viscous liquid a into a mixed solution of distilled water and ethanol, stirring, then adding sodium hydroxide, stirring, then adding sodium dodecyl sulfate, stirring, then adding sodium chloride, stirring, then adding distilled water, stirring, to obtain the organic dispersant.

3. A nano-modified homogenized ink according to claim 2, characterized in that, The preparation method of the organic dispersant comprises the following steps: S1: adding hexamethylene bisacrylamide into a methanol aqueous solution, stirring and mixing, then adding 1-amino-2-propanol, heating and reacting under a nitrogen atmosphere, after the reaction is completed, concentrating by rotary evaporation, precipitating, dissolving, repeating the dissolving-precipitating, drying, to obtain viscous liquid a; S2: adding viscous liquid a into a mixed solution of distilled water and ethanol, stirring, then adding sodium hydroxide, stirring, then adding sodium dodecyl sulfate, stirring, then adding sodium chloride, stirring, then adding distilled water, stirring, to obtain the organic dispersant.

4. The nano-modified homogenized ink of claim 2, wherein, ​ 5. The nano-modified homogenized ink of claim 2, wherein, ​ 6. The nano-modified homogenized ink of claim 1, wherein, ​ ​ S2: viscous liquid a and 6-hexalactone are added to a container, and the reaction is stirred under nitrogen atmosphere at elevated temperature, then stannous octoate is added, and after the reaction, the mixture is cooled, dissolved, precipitated, and repeated dissolution-precipitation, dried to obtain an organic dispersant.

7. A nano-modified homogenized ink according to claim 6, characterized in that, In the S1, the amount ratio of hexamethylene bisacrylamide, methanol aqueous solution and 1-amino-2-propanol is (1.43-1.65) g:(22.4-28.7) mL:(0.55-0.68) g.

8. The nano-modified homogenized ink of claim 6, wherein, In the S2, the amount ratio of viscous liquid a, 6-hexalactone and stannous octoate is (1.34-1.82) g:(5.25-6.33) g:(0.066-0.081) g.

9. A method of preparing a nano-modified homogenized ink according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: Step one: the organic dispersant is added to distilled water, and after stirring and mixing, modified nano-silica, nano-titanium dioxide, nano-calcium carbonate and mica powder are sequentially added, and after stirring and mixing, a mixed slurry is obtained; Step two: the mixed slurry is ground, and then subjected to homogenization treatment, then a viscosity regulator is slowly added, and after stirring and mixing, a pH regulator is added to adjust the pH, filtered, defoamed, aged to obtain a nano-modified homogenized ink.

10. The method for preparing a nano-modified homogenized ink according to claim 9, characterized in that, In the step two, zirconium oxide is used as a grinding medium in the grinding process, and the grinding is carried out at 1500-3000 rpm for 1-3 h until the fineness is <100 nm, and the pH is adjusted to 7.5-8.

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