High-stability water-based propylene ink and preparation method thereof

Abstract

The invention relates to the technical field of water-based propylene ink, and discloses high-stability water-based propylene ink and a preparation method thereof.The high-stability water-based propylene ink is prepared from, by mass, 30-35 parts of pigment, 10-15 parts of modified dispersing agent, 2-5 parts of modified nano chromic oxide, 1-2 parts of resin, 0.5-1 part of anti-settling agent and 40-50 parts of solvent. Acrylic resin formed by modified cellulose, acrylic acid and itaconic acid serves as a dispersing agent of the water-based propylene ink, the motion resistance of pigment sinking can be increased, the pigment sinking phenomenon is further prevented, and the stability of the water-based propylene ink is remarkably improved; the side chain of the acrylic resin can be adsorbed into the cavity structure of carboxymethyl-beta-cyclodextrin in the modified cellulose, so that the stability of the acrylic resin in the water-based propylene ink can be further enhanced, and the effect of preventing the pigment from settling can be better exerted; tannic acid in the modified nano chromic oxide contains a large number of hydrophobic benzene rings, so that the water resistance of the water-based propylene ink can be enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of water-based acrylic inks, and specifically to a highly stable water-based acrylic ink and a preparation method thereof. Background Art

[0002] Acrylic ink refers to a type of ink with acrylic resin as the core component. Due to its excellent performance characteristics, such as rich colors, easy to use, environmentally friendly and durable, etc., acrylic ink is widely welcomed by painting enthusiasts and artists; acrylic resin plays an important role throughout the process from ink storage to use. During the storage stage, it needs to have the function of effectively preventing pigment particles from precipitating or separating, ensuring that the ink can flow smoothly during writing or printing, with uniform color. During the writing process, it needs to endow the ink with excellent rheology and film-forming properties, making the handwriting clear, smooth, with high covering power. After writing, it also needs to exhibit excellent adhesion, water resistance, gloss, weather resistance, chemical resistance and quick drying property, while maintaining environmental friendliness.

[0003] As a dispersant for water-based acrylic ink, water-based acrylic resin has the advantages of light color, strong adhesion, excellent weather resistance, high transparency, etc., and has become the preferred matrix resin for water-based ink. However, water-based acrylic resin has poor heat resistance, which affects the stability and application range of water-based acrylic ink; by adding inorganic materials, the heat resistance, wear resistance and corrosion resistance of water-based acrylic ink can be improved, but the dispersibility of inorganic materials in water-based acrylic ink is poor, and they are prone to agglomeration and precipitation, affecting the stability of water-based acrylic ink. Summary of the Invention

[0004] The present invention provides a highly stable water-based acrylic ink and a preparation method thereof, which solve the problems of poor heat resistance of water-based acrylic resin and poor dispersibility of inorganic materials in water-based acrylic ink.

[0005] The technical solution of the present invention:

[0006] A highly stable water-based acrylic ink, comprising the following raw materials in parts by mass: 30 - 35 parts of pigment, 10 - 15 parts of modified dispersant, 2 - 5 parts of modified nano-chromium oxide, 1 - 2 parts of resin, 0.5 - 1 part of anti-settling agent, and 40 - 50 parts of solvent;

[0007] The modified dispersant is obtained by mixing and reacting composite modified cellulose, acrylic acid, itaconic acid, sodium hypophosphite and deionized water;

[0008] The composite modified cellulose is obtained by reacting carboxymethyl-β-cyclodextrin, 1-carboxy-ortho-carborane and hydroxypropyl methylcellulose, and then reacting with glycidyl methacrylate;

[0009] The modified nano-chromium oxide is obtained by modifying nano-chromium oxide with polydopamine and then mixing it with tannic acid.

[0010] A preparation method of a highly stable water-based acrylic ink, comprising the following preparation steps:

[0011] S1. Mix the pigment, modified dispersant, modified nano-chromium oxide, resin, anti-settling agent and solvent, and stir at a rate of 1800 - 2000 r / min for 30 - 40 min to obtain a mixture;

[0012] S2. Ultrasonically disperse the mixture at a frequency of 20 - 45 kHz and a power of 200 - 500 W for 15 - 30 min, and then grind it at a rotation speed of 500 - 800 rpm for 6 - 10 h to obtain the water-based acrylic ink.

[0013] Further, the pigment is titanium dioxide or carbon black.

[0014] Further, the resin is acrylic resin.

[0015] Further, the anti-settling agent is polyamide wax.

[0016] Further, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether according to the mass ratio of (20 - 22):(30 - 35):(2 - 3).

[0017] Further, the modified dispersant is specifically prepared by the following steps:

[0018] A1. Add hydroxypropyl methylcellulose to an aqueous sodium hydroxide solution, stir evenly, add carboxymethyl-β-cyclodextrin and 1-carboxy-ortho-carborane, stir at 900 - 1100 r / min for 10 - 20 min, then stir and react at 120 - 130 °C for 1 - 2 h, cool to room temperature, filter, wash, and dry to obtain modified cellulose;

[0019] A2. Add the modified cellulose and glycidyl methacrylate to N,N-dimethylformamide, stir evenly, add a catalyst and an inhibitor, heat up to 100 - 120 °C, stir and react for 20 - 30 min, add ethyl acetate, and collect the light yellow liquid to obtain composite modified cellulose;

[0020] A3. Add acrylic acid, itaconic acid, composite modified cellulose, sodium hypophosphite and ammonium persulfate to deionized water, stir evenly, introduce nitrogen, stir and react at 70 - 80 °C for 30 - 40 min, then cool to room temperature, and add an aqueous sodium hydroxide solution to adjust the pH to 7 - 8 to obtain the modified dispersant.

[0021] Further, in the above A1 reaction process, in an aqueous sodium hydroxide solution, the hydroxyl groups in hydroxypropyl methylcellulose can react with the carboxyl groups of carboxymethyl-β-cyclodextrin, and the carboxyl groups contained in 1-carboxy-ortho-carborane can also react with the hydroxyl groups in hydroxypropyl methylcellulose, so that 1-carboxy-ortho-carborane and carboxymethyl-β-cyclodextrin are grafted onto hydroxypropyl methylcellulose to obtain modified cellulose.

[0022] Further, in the above A2 reaction process, in an organic solvent N,N-dimethylformamide, a catalyst and an inhibitor are added, so that the carboxyl groups and hydroxyl groups contained in the modified cellulose can undergo a ring-opening reaction with the epoxy groups in glycidyl methacrylate, so that glycidyl methacrylate is grafted onto the modified cellulose to obtain composite modified cellulose.

[0023] Further, in the above A3 reaction process, ammonium persulfate is used as an initiator, so that the double bonds of glycidyl methacrylate in the modified cellulose can copolymerize with the double bonds in acrylic acid and itaconic acid, and the modified cellulose molecular chain contains hydroxyl groups generated by ring-opening, which can form hydrogen bonds with the carboxyl groups in acrylic acid and itaconic acid. The cross-linked network structure of acrylic resin formed is used as a dispersant for water-based acrylic ink to obtain a modified dispersant.

[0024] Further, in step A1, the dosage ratio of the hydroxypropyl methylcellulose, aqueous sodium hydroxide solution, carboxymethyl-β-cyclodextrin and 1-carboxy-ortho-carborane is (1-3) g:(45-55) mL:(0.4-0.6) g:(0.5-0.7) g.

[0025] Further, in step A2, the dosage ratio of the modified cellulose, glycidyl methacrylate, N,N-dimethylformamide, catalyst and inhibitor is (2-3) g:(5-6) g:(45-55) mL:(1-2) g:(1.1-1.3) g.

[0026] Further, in step A3, the dosage ratio of the acrylic acid, itaconic acid, composite modified cellulose, sodium hypophosphite, ammonium persulfate and deionized water is (7-8) g:(6-7) g:(5-6) g:(2-3) g:(0.4-0.6) g:(30-40) mL.

[0027] Further, the catalyst is TBAT (tetra-n-butylammonium difluorotriphenylsilicate).

[0028] Further, the inhibitor is 2,6-di-tert-butyl-p-cresol.

[0029] Further, the modified nano chromium oxide is specifically prepared by the following steps:

[0030] B1. Add nano-chromium oxide to Tris-HCl buffer solution, stir evenly, add dopamine, stir and react for 3-4 h, filter, wash, and dry to obtain polydopamine-modified nano-chromium oxide;

[0031] B2. Add polydopamine-modified nano-chromium oxide and tannic acid to deionized water, stir at 200-300 r / min for 20-30 min, let stand, filter, wash, and dry to obtain modified nano-chromium oxide.

[0032] Furthermore, during the reaction process of B1, in Tris-HCl buffer solution, dopamine can self-polymerize on the surface of nano-chromium oxide to form polydopamine, forming polydopamine-modified nano-chromium oxide, enabling nano-chromium oxide to carry a large number of phenolic hydroxyl groups, which is beneficial to the adhesion of tannic acid on the surface of nano-chromium oxide and enhancing the water resistance of the acrylic resin dispersant.

[0033] Furthermore, during the reaction process of B2, polydopamine-modified nano-chromium oxide has excellent adhesion and contains a large number of phenolic hydroxyl groups, which can adhere to tannic acid molecules on the surface of polydopamine-modified nano-chromium oxide, enabling tannic acid to wrap nano-chromium oxide to obtain modified nano-chromium oxide.

[0034] Furthermore, in step B1, the dosage ratio of the nano-chromium oxide, Tris-HCl buffer solution, and dopamine is (1-2) g : (35-45) mL : (0.4-0.6) g.

[0035] Furthermore, in step B2, the dosage ratio of the polydopamine-modified nano-chromium oxide, tannic acid, and deionized water is (6-8) g : (3-4) g : (50-60) mL.

[0036] Furthermore, the particle size of the nano-chromium oxide is 45-55 nm.

[0037] The present invention has the following beneficial effects:

[0038] (1) In the technical solution of the present invention, 1-carboxy-o-carborane and carboxymethyl-β-cyclodextrin are grafted onto hydroxypropyl methylcellulose to obtain modified cellulose. On the one hand, carboxymethyl-β-cyclodextrin grafted onto hydroxypropyl methylcellulose endows the cellulose with a cavity structure, weakens the hydrogen bond interaction between cellulose molecules, and under the action of gravity in the water-based acrylic ink, makes the cellulose molecules move relatively, thereby improving the fluidity of the water-based acrylic ink and adjusting the viscosity of the ink to avoid sedimentation of the ink and enhance the stability of the water-based ink. On the other hand, carboxylated o-carborane contains a stable cage structure and has high thermal stability. Therefore, grafting 1-carboxy-o-carborane onto hydroxypropyl methylcellulose and adding it to the acrylic resin network can improve the heat resistance of the acrylic resin, avoiding the poor heat resistance of the water-based acrylic resin and affecting the stability and application range of the water-based acrylic ink.

[0039] (2) In the technical solution of the present invention, glycidyl methacrylate is grafted onto the modified cellulose, endowing the modified cellulose with a double bond for copolymerization with acrylic acid and itaconic acid, which is beneficial for the modified cellulose to be grafted in the acrylic dispersant and enhance the heat resistance of the acrylic resin, thereby enhancing the stability of the water-based acrylic ink; the modified cellulose, acrylic acid, and itaconic acid undergo a copolymerization reaction, and the modified cellulose molecular chain contains hydroxyl groups generated by ring opening, which can combine with the carboxyl groups in acrylic acid and itaconic acid through hydrogen bonds. The acrylic resin with a cross-linked network structure formed serves as a dispersant for the water-based acrylic ink, which can increase the movement resistance when the pigment titanium dioxide sinks, thereby preventing the pigment from sedimenting, significantly increasing the stability of the water-based acrylic ink, and the side chain of the acrylic resin can be adsorbed into the cavity structure of carboxymethyl-β-cyclodextrin in the modified cellulose, further enhancing the stability of the acrylic resin in the water-based acrylic ink and better playing the role of preventing pigment sedimentation.

[0040] (3) In the technical solution of the present invention, polydopamine-modified nano-chromium oxide has excellent adhesion and contains a large number of phenolic hydroxyl groups, which can adhere to tannic acid molecules on the surface of polydopamine-modified nano-chromium oxide, enabling tannic acid to wrap nano-chromium oxide to obtain modified nano-chromium oxide. On the one hand, tannic acid is coated on the surface of nano-chromium oxide through polydopamine, avoiding the aggregation and easy sedimentation of nano-chromium oxide in the water-based acrylic ink and affecting the stability of the water-based acrylic ink. On the other hand, the tannic acid on the surface of the modified nano-chromium oxide contains rich pyrogallol groups, which can combine with the carboxyl groups on the polyacrylic acid molecular chain in the modified dispersant through strong hydrogen bonds, enabling the modified nano-chromium oxide to be dispersed in the water-based acrylic ink, improving the stability of the water-based acrylic ink, and the hydrophobic benzene ring of the pyrogallol group in tannic acid has excellent water resistance, thereby enhancing the water resistance of the water-based acrylic ink. In addition, nano-chromium oxide itself has good wear resistance and heat resistance, and high infrared light reflectivity, reducing heat energy, which is beneficial for increasing the heat resistance temperature and weather resistance of the water-based ink. Detailed implementation mode

[0041] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0042] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0043] Among them, the resin is acrylic resin, Hubei Tuobang Chemical Co., Ltd.

[0044] The pigment is carbon black, CAS: 1333-86-4, Shanghai Kayin Chemical Co., Ltd.

[0045] The anti-settling agent is polyamide wax.

[0046] The catalyst is TBAT (tetra-n-butylammonium difluorotriphenyl silicate).

[0047] The inhibitor is 2,6-di-tert-butyl-p-cresol.

[0048] Nanometer chromium oxide, CAS: 1333-82-0, particle size is 50nm, Yunyan New Materials (Shanghai) Co., Ltd.

[0049] Example 1

[0050] A high-stability water-based acrylic ink, comprising the following raw materials in parts by mass: 30 parts of carbon black, 10 parts of modified dispersant, 2 parts of modified nanometer chromium oxide, 1 part of acrylic resin, 0.5 part of polyamide wax, and 40 parts of solvent;

[0051] A preparation method of a high-stability water-based acrylic ink, comprising the following preparation steps:

[0052] S1. Mix carbon black, modified dispersant, modified nanometer chromium oxide, acrylic resin, polyamide wax and solvent, and stir at a rate of 1800 r / min for 30 min to obtain a mixture;

[0053] Among them, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether in a mass ratio of 20:30:2;

[0054] S2. Ultrasonically disperse the mixture at a frequency of 20 kHz and a power of 200 W for 15 min, and then grind it at a rotation speed of 500 rpm for 6 h to obtain the water-based acrylic ink.

[0055] The modified dispersant is specifically prepared by the following steps:

[0056] A1. Add 1 g of hydroxypropyl methylcellulose to 45 mL of an aqueous sodium hydroxide solution with a mass fraction of 5%, stir evenly, add 0.4 g of carboxymethyl-β-cyclodextrin and 0.5 g of 1-carboxy-ortho-carborane, stir at 900 r / min for 10 min, then stir and react at 120 °C for 1 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0057] A2. Add 2 g of modified cellulose and 5 g of glycidyl methacrylate to 45 mL of N,N-dimethylformamide, stir evenly, add 1 g of TBAT and 1.1 g of 2,6-di-tert-butyl-p-cresol, heat to 100 °C, stir and react for 20 min, add 30 mL of ethyl acetate, collect the light yellow liquid to obtain composite modified cellulose;

[0058] A3. Add 7 g of acrylic acid, 6 g of itaconic acid, 5 g of composite modified cellulose, 2 g of sodium hypophosphite, and 0.4 g of ammonium persulfate to 30 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 70 °C for 30 min, then cool to room temperature, and adjust the pH to 7 with an aqueous sodium hydroxide solution with a mass fraction of 40% to obtain a modified dispersant.

[0059] The modified nano chromium oxide is specifically prepared by the following steps:

[0060] B1. Add 1 g of nano chromium oxide to 35 mL of Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.4 g of dopamine, stir and react for 3 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain polydopamine-modified nano chromium oxide;

[0061] B2. Add 6 g of polydopamine-modified nano chromium oxide and 3 g of tannic acid to 50 mL of deionized water, stir at 200 r / min for 20 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain modified nano chromium oxide.

[0062] Example 2

[0063] A highly stable water-based acrylic ink comprises the following raw materials in parts by mass: 33 parts of carbon black, 13 parts of modified dispersant, 3 parts of modified nano chromium oxide, 1.5 parts of acrylic resin, 0.8 part of polyamide wax, and 45 parts of solvent;

[0064] A preparation method of a highly stable water-based acrylic ink comprises the following preparation steps:

[0065] S1. Mix carbon black, a modified dispersant, modified nano-chromium oxide, acrylic resin, polyamide wax, and a solvent, and stir at a rate of 1900 r / min for 35 min to obtain a mixture;

[0066] Among them, the solvent is obtained by mixing deionized water, diethylene glycol, and diethylene glycol monobutyl ether according to a mass ratio of 21:33:2.5;

[0067] S2. Ultrasonically disperse the mixture at a frequency of 35 kHz and a power of 300 W for 22 min, and then grind it at a rotation speed of 650 rpm for 8 h to obtain water-based acrylic ink.

[0068] The modified dispersant is specifically prepared by the following steps:

[0069] A1. Add 2 g of hydroxypropyl methylcellulose to 50 mL of a 5% sodium hydroxide aqueous solution, stir evenly, add 0.5 g of carboxymethyl-β-cyclodextrin and 0.6 g of 1-carboxy-ortho-carborane, stir at 1000 r / min for 15 min, then stir and react at 125 °C for 1.5 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0070] A2. Add 2.5 g of modified cellulose and 5.5 g of glycidyl methacrylate to 50 mL of N,N-dimethylformamide, stir evenly, add 1.5 g of TBAT and 1.2 g of 2,6-di-tert-butyl-p-cresol, heat to 110 °C, stir and react for 25 min, add 30 mL of ethyl acetate, and collect the light yellow liquid to obtain composite modified cellulose;

[0071] A3. Add 7.5 g of acrylic acid, 6.5 g of itaconic acid, 5.5 g of composite modified cellulose, 2.5 g of sodium hypophosphite, and 0.5 g of ammonium persulfate to 35 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 75 °C for 35 min, then cool to room temperature, and add a 40% sodium hydroxide aqueous solution to adjust the pH to 7.5 to obtain the modified dispersant.

[0072] The modified nano-chromium oxide is specifically prepared by the following steps:

[0073] B1. Add 1.5 g of nano-chromium oxide to 40 mL of a Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.5 g of dopamine, stir and react for 3.5 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain polydopamine-modified nano-chromium oxide;

[0074] B2. Add 7 g of polydopamine-modified nano-chromium oxide and 3.5 g of tannic acid to 55 mL of deionized water, stir at 250 r / min for 25 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain modified nano-chromium oxide.

[0075] Example 3

[0076] A highly stable water-based acrylic ink, comprising the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of modified nano-chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0077] A preparation method of a highly stable water-based acrylic ink, comprising the following preparation steps:

[0078] S1. Mix carbon black, modified dispersant, modified nano-chromium oxide, acrylic resin, polyamide wax and solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0079] Among them, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether according to a mass ratio of 22:35:3;

[0080] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind at a rotation speed of 800 rpm for 10 h to obtain the water-based acrylic ink.

[0081] The modified dispersant is specifically prepared by the following steps:

[0082] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of a 5% sodium hydroxide aqueous solution, stir evenly, add 0.6 g of carboxymethyl-β-cyclodextrin and 0.7 g of 1-carboxy-ortho-carborane, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0083] A2. Add 3 g of modified cellulose and 6 g of glycidyl methacrylate to 55 mL of N,N-dimethylformamide, stir evenly, add 2 g of TBAT and 1.3 g of 2,6-di-tert-butyl-p-cresol, heat up to 120 °C, stir and react for 30 min, add 30 mL of ethyl acetate, and collect the light yellow liquid to obtain composite modified cellulose;

[0084] A3. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of composite modified cellulose, 3 g of sodium hypophosphite, and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, and adjust the pH to 8 by adding a 40% sodium hydroxide aqueous solution to obtain a modified dispersant.

[0085] The modified nano chromium oxide is specifically prepared by the following steps:

[0086] B1. Add 2 g of nano chromium oxide to 45 mL of Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react for 4 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain polydopamine-modified nano chromium oxide;

[0087] B2. Add 8 g of polydopamine-modified nano chromium oxide and 4 g of tannic acid to 60 mL of deionized water, stir at 300 r / min for 30 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain modified nano chromium oxide.

[0088] Comparative Example 1

[0089] A high-stability water-based acrylic ink, comprising the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of modified nano chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0090] A preparation method of a high-stability water-based acrylic ink, comprising the following preparation steps:

[0091] S1. Mix carbon black, modified dispersant, modified nano chromium oxide, acrylic resin, polyamide wax, and solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0092] Among them, the solvent is obtained by mixing deionized water, diethylene glycol, and diethylene glycol monobutyl ether in a mass ratio of 22:35:3;

[0093] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind at a speed of 800 rpm for 10 h to obtain a water-based acrylic ink.

[0094] The modified dispersant is specifically prepared by the following steps:

[0095] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of an aqueous sodium hydroxide solution with a mass fraction of 5%, stir evenly, add 0.6 g of carboxymethyl-β-cyclodextrin, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain carboxymethyl-β-cyclodextrin grafted hydroxypropyl methylcellulose;

[0096] A2. Add 3 g of carboxymethyl-β-cyclodextrin grafted hydroxypropyl methylcellulose and 6 g of glycidyl methacrylate to 55 mL of N,N-dimethylformamide, stir evenly, add 2 g of TBAT and 1.3 g of 2,6-di-tert-butyl-p-cresol, heat to 120 °C, stir and react for 30 min, add 30 mL of ethyl acetate, collect the light yellow liquid to obtain the composite modified cellulose;

[0097] A3. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of the composite modified cellulose, 3 g of sodium hypophosphite, and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, and adjust the pH to 8 with an aqueous sodium hydroxide solution with a mass fraction of 40% to obtain the modified dispersant.

[0098] The modified nano chromium oxide is specifically prepared by the following steps:

[0099] B1. Add 2 g of nano chromium oxide to 45 mL of Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react for 4 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain polydopamine-modified nano chromium oxide;

[0100] B2. Add 8 g of polydopamine-modified nano chromium oxide and 4 g of tannic acid to 60 mL of deionized water, stir at 300 r / min for 30 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain the modified nano chromium oxide.

[0101] Comparative Example 2

[0102] A high-stability water-based acrylic ink, comprising the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of modified nano chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0103] A preparation method of a high-stability water-based acrylic ink, comprising the following preparation steps:

[0104] S1. Mix carbon black, a modified dispersant, modified nano-chromium oxide, acrylic resin, polyamide wax, and a solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0105] Among them, the solvent is obtained by mixing deionized water, diethylene glycol, and diethylene glycol monobutyl ether according to a mass ratio of 22:35:3;

[0106] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind it at a rotation speed of 800 rpm for 10 h to obtain water-based acrylic ink.

[0107] The modified dispersant is specifically prepared by the following steps:

[0108] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of a 5% sodium hydroxide aqueous solution, stir evenly, add 0.7 g of 1-carboxy-closo-carborane, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain 1-carboxy-closo-carborane grafted hydroxypropyl methylcellulose;

[0109] A2. Add 3 g of 1-carboxy-closo-carborane grafted hydroxypropyl methylcellulose and 6 g of glycidyl methacrylate to 55 mL of N,N-dimethylformamide, stir evenly, add 2 g of TBAT and 1.3 g of 2,6-di-tert-butyl-p-cresol, heat up to 120 °C, stir and react for 30 min, add 30 mL of ethyl acetate, and collect the light yellow liquid to obtain the composite modified cellulose;

[0110] A3. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of the composite modified cellulose, 3 g of sodium hypophosphite, and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, pass in nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, and add a 40% sodium hydroxide aqueous solution to adjust the pH to 8 to obtain the modified dispersant.

[0111] The modified nano-chromium oxide is specifically prepared by the following steps:

[0112] B1. Add 2 g of nano-chromium oxide to 45 mL of a Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react for 4 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain poly-dopamine modified nano-chromium oxide;

[0113] B2. Add 8 g of polydopamine-modified nano-chromium oxide and 4 g of tannic acid to 60 mL of deionized water, stir at 300 r / min for 30 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain modified nano-chromium oxide.

[0114] Comparative Example 3

[0115] A highly stable water-based acrylic ink, comprising the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of modified nano-chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0116] A preparation method of a highly stable water-based acrylic ink, comprising the following preparation steps:

[0117] S1. Mix carbon black, modified dispersant, modified nano-chromium oxide, acrylic resin, polyamide wax and solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0118] Among them, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether according to a mass ratio of 22:35:3;

[0119] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind at a speed of 800 rpm for 10 h to obtain a water-based acrylic ink.

[0120] The modified dispersant is specifically prepared by the following steps:

[0121] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of a 5% sodium hydroxide aqueous solution, stir evenly, add 0.6 g of carboxymethyl-β-cyclodextrin and 0.7 g of 1-carboxy-ortho-carborane, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0122] A2. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of modified cellulose, 3 g of sodium hypophosphite and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, and adjust the pH to 8 with a 40% sodium hydroxide aqueous solution to obtain a modified dispersant.

[0123] The modified nano-chromium oxide is specifically prepared by the following steps:

[0124] B1. Add 2 g of nano-chromium oxide to 45 mL of Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react for 4 h, filter, wash with deionized water three times, and dry in an oven at 70 °C for 10 min to obtain polydopamine-modified nano-chromium oxide;

[0125] B2. Add 8 g of polydopamine-modified nano-chromium oxide and 4 g of tannic acid to 60 mL of deionized water, stir at 300 r / min for 30 min, let stand, filter, wash with deionized water three times, and dry in an oven at 70 °C for 10 min to obtain modified nano-chromium oxide.

[0126] Comparative Example 4

[0127] A highly stable water-based acrylic ink, comprising the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of modified nano-chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0128] A preparation method of a highly stable water-based acrylic ink, comprising the following preparation steps:

[0129] S1. Mix carbon black, modified dispersant, modified nano-chromium oxide, acrylic resin, polyamide wax and solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0130] Among them, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether according to a mass ratio of 22:35:3;

[0131] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind at a rotation speed of 800 rpm for 10 h to obtain the water-based acrylic ink.

[0132] The modified dispersant is specifically prepared by the following steps:

[0133] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of sodium hydroxide aqueous solution with a mass fraction of 5%, stir evenly, add 0.6 g of carboxymethyl-β-cyclodextrin and 0.7 g of 1-carboxy-ortho-carborane, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water three times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0134] A2. Add 3 g of modified cellulose and 6 g of glycidyl methacrylate to 55 mL of N,N-dimethylformamide, stir evenly, add 2 g of TBAT and 1.3 g of 2,6-di-tert-butyl-p-cresol, heat up to 120 °C, stir and react for 30 min, add 30 mL of ethyl acetate, collect the light yellow liquid to obtain the composite modified cellulose;

[0135] A3. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of composite modified cellulose, 3 g of sodium hypophosphite and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, add a 40% sodium hydroxide aqueous solution to adjust the pH to 8 to obtain the modified dispersant.

[0136] The modified nano chromium oxide is specifically prepared by the following steps:

[0137] Add 8 g of nano chromium oxide and 4 g of tannic acid to 60 mL of deionized water, stir at 300 r / min for 30 min, let stand, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain the modified nano chromium oxide.

[0138] Comparative Example 5

[0139] A highly stable water-based acrylic ink comprises the following raw materials in parts by mass: 35 parts of carbon black, 15 parts of modified dispersant, 5 parts of polydopamine-modified nano chromium oxide, 2 parts of acrylic resin, 1 part of polyamide wax, and 50 parts of solvent;

[0140] A preparation method of a highly stable water-based acrylic ink comprises the following preparation steps:

[0141] S1. Mix carbon black, modified dispersant, polydopamine-modified nano chromium oxide, acrylic resin, polyamide wax and solvent, and stir at a rate of 2000 r / min for 40 min to obtain a mixture;

[0142] Among them, the solvent is obtained by mixing deionized water, diethylene glycol and diethylene glycol monobutyl ether according to a mass ratio of 22:35:3;

[0143] S2. Ultrasonically disperse the mixture at a frequency of 45 kHz and a power of 500 W for 30 min, and then grind at a rotation speed of 800 rpm for 10 h to obtain the water-based acrylic ink.

[0144] The modified dispersant is specifically prepared by the following steps:

[0145] A1. Add 3 g of hydroxypropyl methylcellulose to 55 mL of an aqueous sodium hydroxide solution with a mass fraction of 5%, stir evenly, add 0.6 g of carboxymethyl-β-cyclodextrin and 0.7 g of 1-carboxy-ortho-carborane, stir at 1100 r / min for 20 min, then stir and react at 130 °C for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 10 min to obtain modified cellulose;

[0146] A2. Add 3 g of modified cellulose and 6 g of glycidyl methacrylate to 55 mL of N,N-dimethylformamide, stir evenly, add 2 g of TBAT and 1.3 g of 2,6-di-tert-butyl-p-cresol, heat up to 120 °C, stir and react for 30 min, add 30 mL of ethyl acetate, collect the light yellow liquid to obtain composite modified cellulose;

[0147] A3. Add 8 g of acrylic acid, 7 g of itaconic acid, 6 g of composite modified cellulose, 3 g of sodium hypophosphite, and 0.6 g of ammonium persulfate to 40 mL of deionized water, stir evenly, introduce nitrogen, stir and react at 80 °C for 40 min, then cool to room temperature, add an aqueous sodium hydroxide solution with a mass fraction of 40% to adjust the pH to 8 to obtain a modified dispersant.

[0148] The poly-dopamine modified nano-chromium oxide is specifically prepared by the following steps:

[0149] Add 2 g of nano-chromium oxide to 45 mL of Tris-HCl buffer solution with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react for 4 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain poly-dopamine modified nano-chromium oxide.

[0150] Now, the performance of the water-based acrylic ink prepared in Examples 1-3 and Comparative Examples 1-5 is detected.

[0151] Fineness determination: Determine the fineness of the above-prepared water-based acrylic ink according to GB / T13217.3-2008 "Test Method for Fineness of Liquid Ink", and observe the state of the above-prepared water-based acrylic ink after standing for 5 days.

[0152] Heat resistance: Determine the heat resistance of the above-prepared water-based acrylic ink by the crucible method, and take the highest temperature without color change as the heat resistance temperature of the sample.

[0153] Water resistance: Determine the water resistance of the above-prepared water-based acrylic ink at 25 °C according to GB / T1733-1993 "Method for Determining Water Resistance of Paint Films".

[0154] Weather resistance evaluation: The color difference of the prepared water-based acrylic ink was measured by the artificial daylight exposure method in the national standard GB / T 1710-2008 "Lightfastness of Similar Coloring Pigments", and the national standard GB / T 250-2008 "Grey Scale for Assessing Color Change in Colorfastness Tests of Textiles" was used to evaluate the weather resistance of the prepared water-based acrylic ink.

[0155] The test results are shown in Table 1 below.

[0156] Table 1 Performance Detection of Water-based Acrylic Inks Prepared in Examples 1-3 and Comparative Examples 1-5

[0157]

[0158]

[0159] It can be seen from the data in Table 1 that the water-based acrylic inks prepared in Examples 1-3 have high stability.

[0160] In Comparative Example 1, the modified dispersant prepared by replacing the modified cellulose with carboxymethyl-β-cyclodextrin grafted hydroxypropyl methyl cellulose was added to the water-based acrylic ink, and its heat resistance and stability decreased, which proved that 1-carboxy-o-carborane was grafted onto hydroxypropyl methyl cellulose and added to the acrylic resin network to improve the heat resistance of the acrylic resin and avoid the poor heat resistance of the water-based acrylic resin from affecting the stability and application range of the water-based acrylic ink.

[0161] In Comparative Example 2, the modified dispersant prepared by replacing the modified cellulose with 1-carboxy-o-carborane grafted hydroxypropyl methyl cellulose was added to the water-based acrylic ink, and its stability decreased, which proved that carboxymethyl-β-cyclodextrin was grafted onto hydroxypropyl methyl cellulose, endowing the cellulose with a cavity structure and weakening the hydrogen bond interaction between cellulose molecules. In the water-based acrylic ink, under the action of gravity, the cellulose molecules move relatively, thereby improving the fluidity of the water-based acrylic ink and adjusting the viscosity of the ink to avoid sedimentation of the ink and enhance the stability of the water-based ink.

[0162] In Comparative Example 3, the modified dispersant prepared by replacing the composite modified cellulose with modified cellulose was added to the water-based acrylic ink, and its heat resistance and stability decreased, which proved that glycidyl methacrylate was grafted onto the modified cellulose, endowing the modified cellulose with double bonds for copolymerization with acrylic acid and itaconic acid, which is beneficial to the grafting of the modified cellulose in the acrylic dispersant and enhancing the heat resistance of the acrylic resin, and further enhancing the stability of the water-based acrylic ink.

[0163] Comparative Example 4: The modified nano-chromium oxide prepared by replacing the polydopamine-modified nano-chromium oxide with nano-chromium oxide was added to the water-based acrylic ink. Its water resistance, weather resistance and stability demonstrated that tannic acid was coated on the surface of nano-chromium oxide through polydopamine, preventing nano-chromium oxide from aggregating and settling easily in the water-based acrylic ink, which would affect the stability of the water-based acrylic ink. Moreover, the hydrophobic benzene ring of the pyrogallol group in tannic acid has excellent water resistance, thereby enhancing the water resistance of the water-based acrylic ink.

[0164] Comparative Example 5: The modified nano-chromium oxide was replaced with polydopamine-modified nano-chromium oxide and added to the water-based acrylic ink. Its water resistance, weather resistance and stability decreased, demonstrating that the hydrophobic benzene ring of the pyrogallol group in tannic acid has excellent water resistance, thereby enhancing the water resistance of the water-based acrylic ink. Moreover, tannic acid contains abundant pyrogallol groups, which can bind to the carboxyl groups on the polyacrylic acid molecular chain in the modified dispersant through strong hydrogen bonds, enabling the modified nano-chromium oxide to be dispersed in the water-based acrylic ink and improving the stability of the water-based acrylic ink.

[0165] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0166] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

Claims

1. A high stability water-based acrylic ink, characterized in that: The method comprises the following raw materials in parts by weight: 30-35 parts of pigment, 10-15 parts of modified dispersant, 2-5 parts of modified nano chromium oxide, 1-2 parts of resin, 0.5-1 parts of anti-settling agent, and 40-50 parts of solvent; The modified dispersant is obtained by mixing and reacting composite modified cellulose, acrylic acid, itaconic acid, sodium hypophosphite and deionized water; The composite modified cellulose is obtained by reacting carboxymethyl-β-cyclodextrin, 1-carboxy-o-carborane and hydroxypropyl methylcellulose, and then reacting with glycidyl methacrylate; The modified nano chromium oxide is obtained by modifying the nano chromium oxide with polydopamine and then mixing it with tannic acid.

2. A high stability water-based acrylic ink according to claim 1, characterized in that: The modified dispersant is specifically prepared by the following steps: A1. Add hydroxypropyl methylcellulose to an aqueous sodium hydroxide solution, stir evenly, add carboxymethyl-β-cyclodextrin and 1-carboxyl-o-carborane, stir at 900-1100 r / min for 10-20 min, stir at 120-130° C. for 1-2 h, cool to room temperature, filter, wash, and dry to obtain modified cellulose; A2. Add modified cellulose and glycidyl methacrylate to N,N-dimethylformamide, stir evenly, add catalyst and inhibitor, heat to 100-120°C, stir and react for 20-30 minutes, add ethyl acetate, collect light yellow liquid, and obtain composite modified cellulose; A3. Add acrylic acid, itaconic acid, composite modified cellulose, sodium hypophosphite and ammonium persulfate to deionized water, stir evenly, introduce nitrogen, stir and react at 70-80°C for 30-40 minutes, cool to room temperature, add sodium hydroxide aqueous solution to adjust the pH to 7-8, and obtain a modified dispersant.

3. A high stability water-based acrylic ink according to claim 2, characterized in that: In step A1, the ratio of hydroxypropyl methylcellulose, sodium hydroxide aqueous solution, carboxymethyl-β-cyclodextrin and 1-carboxy-o-carborane is (1-3) g: (45-55) mL: (0.4-0.6) g: (0.5-0.7) g.

4. A high stability water-based acrylic ink according to claim 2, characterized in that: In step A2, the amount ratio of the modified cellulose, glycidyl methacrylate, N,N-dimethylformamide, catalyst, and inhibitor is (2-3) g: (5-6) g: (45-55) mL: (1-2) g: (1.1-1.3) g.

5. A high stability water-based acrylic ink according to claim 2, characterized in that: In step A3, the usage ratio of acrylic acid, itaconic acid, composite modified cellulose, sodium hypophosphite, ammonium persulfate and deionized water is (7-8) g: (6-7) g: (5-6) g: (2-3) g: (0.4-0.6) g: (30-40) mL.

6. The high stability water-based acrylic ink according to claim 1, characterized in that: The modified nano chromium oxide is specifically prepared by the following steps: B1. Add nano-chromium oxide to Tris-HCl buffer, stir evenly, add dopamine, stir and react for 3-4 hours, filter, wash and dry to obtain polydopamine-modified nano-chromium oxide; B2. Add polydopamine-modified nano-chromium oxide and tannic acid into deionized water, stir at 200-300 r / min for 20-30 min, let stand, filter, wash and dry to obtain modified nano-chromium oxide.

7. A high stability water-based acrylic ink according to claim 6, characterized in that: In step B1, the ratio of the nano-chromium oxide, Tris-HCl buffer and dopamine is (1-2) g: (35-45) mL: (0.4-0.6) g.

8. The high stability water-based acrylic ink according to claim 6, characterized in that: In step B2, the ratio of the polydopamine-modified nano-chromium oxide, tannic acid and deionized water is (6-8) g: (3-4) g: (50-60) mL.

9. A method for preparing a high-stability water-based acrylic ink according to any one of claims 1 to 8, characterized in that: The method comprises the following preparation steps: S1. The pigment, modified dispersant, modified nano chromium oxide, resin, anti-settling agent and solvent are mixed and stirred at a rate of 1800-2000r / min for 30-40min to obtain a mixture; S2. The mixture is ultrasonically dispersed at a frequency of 20-45 kHz and a power of 200-500 W for 15-30 min, and then ground at a rotation speed of 500-800 rpm for 6-10 h to obtain a water-based acrylic ink.

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