CN117736606B

CN117736606B - Preparation method of water-based ink containing modified polyurea

Info

Publication number: CN117736606B
Application number: CN202311744842.3A
Authority: CN
Inventors: 张斯乔; 唐丘; 宋之太; 李颂国; 宋子轩; 张晨曦; 吴帅男
Original assignee: Jiangsu Zhonglisheng Package Technology Co ltd
Current assignee: Jiangsu Zhonglisheng Package Technology Co ltd
Priority date: 2023-12-18
Filing date: 2023-12-18
Publication date: 2024-05-17
Anticipated expiration: 2043-12-18
Also published as: CN117736606A

Abstract

The invention belongs to the technical field of ink, and relates to a preparation method of water-based ink containing modified polyurea, which comprises the following steps: firstly preparing hyperbranched monomer, then fully dissolving the hyperbranched monomer, polyamine and a water scavenger by using a solvent, heating to 70-210 ℃, adding a catalyst, preserving heat for 4-15 hours, and removing most of the solvent to obtain hyperbranched polymer containing rich carboxyl and hydroxyl; and then preparing a water-based polyurea prepolymer, finally adding the hyperbranched polymer and the pigment into the water-based polyurea prepolymer after fully dissolving, cooling to room temperature, adding a defoaming agent and a leveling agent, and performing reduced pressure rotary evaporation to obtain the water-based polyurea prepolymer. The modified aqueous polyurea prepared by the invention has the advantages that the internal crosslinking network of a system is obviously increased, the coating performance of pigment is also improved, the light transmittance of single-layer printing ink is weakened, the color overlapping rate of different color phase printing inks is generally higher, the specific color overlapping effect is generated by selecting different color sequence arrangements during printing, the imitation difficulty of a printing product is increased, and the storage adaptability of the printing ink is greatly improved.

Description

Preparation method of water-based ink containing modified polyurea

Technical Field

The invention belongs to the technical field of ink, and relates to water-based ink, in particular to a preparation method of water-based ink containing modified polyurea.

Background

The aqueous ink is mostly applied to the fields of gravure printing and flexographic printing, and is partially applied to the field of screen printing, and in recent years, the application to the field of inkjet printing has been studied. The printing stock is mainly paper (self-adhesive, white board, jin Kazhi, coated paper, etc.), cardboard (corrugated board, etc.), and plastics.

Preferably, the aqueous ink is used in the field of flexographic printing. Flexography originated in the united states originally, and was named because of its plate material being a relatively soft polymer compound, and was a green, environmentally friendly and pollution-free aqueous ink. Flexography is used for printing corrugated board, the technology and process are relatively mature, and the printing effect is almost comparable to offset printing. Almost 100% of U.S. cartons are flexography, western europe is 85%, japan is 93%, and China currently has only about 50%. Flexography is applied to flexible packaging, and is widely applied in European and American countries (75% in North America and 57% in Europe), and is relatively rarely applied in the asia-Tai region (only about 10%). Flexography is applied to the aspect of labels, mainly uses low-and-medium-grade products as main materials, and has less application in high-grade products. In addition, the billing printing can be accomplished by flexographic printing using aqueous ink. Currently, low scratch and high abrasion resistance aqueous color inks for flexography have been developed by changing the ink formulation. Research shows that the dispersion process of the ink comprises the process parameters of pre-dispersion rotating speed, pre-dispersion time, the proportion of zirconia beads and the ink, grinding time and the like, and has great influence on the dispersibility of the water-based flexo ink.

Secondly, the application of the water-based ink in the intaglio printing field. The intaglio printing utilizes the depth or opening area of the concave net holes to represent the image tone level, and is widely applied to the fields of plastic package printing, paper package printing, securities, thermal transfer printing, publishing printing, decorative paper and the like. The water-based ink is limited in large-scale application in the plastic gravure printing field due to the drying speed, the ink adhesion force and the like. Therefore, solving the contradiction between gravure speed, gravure quality and gravure drying speed has become one of the most critical factors for the wide application of aqueous inks in the field of plastic gravure. Adding some auxiliary agents such as thickening agents, thinning resin types, addition amounts of auxiliary solvents, auxiliary agents, adjusting pH values and viscosity of an ink system into the ink can have important influence on the drying performance of the water-based ink; the abrasion resistance of the ink can be effectively improved by the aid of the abrasion resistance auxiliary agent (polyethylene wax), the base material wetting agent, the isopropanol, the leveling agent and the aqueous wax emulsion. The water-based ink with good performance can be prepared by continuously improving the formula of the water-based ink, and can be used for gravure printing of thermal sublimation water-based ink, water-based plastic gravure ink, silver ink, metal ink and the like.

Again, the use of aqueous inks in the field of screen printing. The screen printing is to print ink on the surface of a printing stock through meshes in a leaking way, and is widely applied to printing in aspects of package decoration, advertisements, poster signs and the like. Screen printing is basically not affected by printing stock, and can be performed on the surfaces of paper, plastic, metal, glass, fabric and other materials; screen printing can be performed either on flat object surfaces or on curved surfaces (e.g., bottles, cans, etc.). Sweden, germany and the united states are the most successful countries in the world where aqueous inks are used in the field of screen printing. At present, water-based gold ink with gold stamping effect for paper screen printing and conductive ink adopting a screen printing mode have been developed, and water-based ink capable of applying screen printing on cards such as magnetic cards, bank cards, credit cards and the like has also been developed successfully.

Finally, the use of aqueous inks in the field of inkjet printing. Ink jet printing is one of digital printing, the technology is mature, and ink drops ejected from nozzles of an ink jet printer splash on a printing stock to form images and texts after an external electric field is applied. Therefore, the quality of ink is an important factor affecting the quality of inkjet prints, and the application of aqueous inks to the field of inkjet printing is also one of the hot spots of current research. The ink-jet recording aqueous ink was applied by the Nippon Brother Industrial Co., ltd. In 2002, and Deutsche Dai Sida textile and dye company have invented an aqueous printing ink for ink-jet printing on textile fiber materials.

The water-based ink is natural and wind-free in the printing application field, but various problems are needed to be solved.

Disclosure of Invention

Aiming at the defects that the friction resistance of the water-based ink prepared under the prior art is poor after the water-based ink is applied to printing, and the pigment is exposed to fade after the ink layer is damaged, the water-based polyurea molecular structure is modified by the hyperbranched polymer containing rich carboxyl and hydroxyl, the prepared copolymer has higher crosslinking degree, the coating performance of the pigment is better, and the effect is excellent in the aspect of the ink color folding rate.

Technical proposal

A preparation method of water-based ink containing modified polyurea comprises the following steps:

(1) Preparation of hyperbranched monomers: fully dissolving the polyhydroxy compound by using a solvent, heating to 50-112 ℃, preferably 74 ℃, adding hexamethylenetetramine or acetic acid, and then preserving heat for 1-17 hours, preferably hexamethylenetetramine and preserving heat for 3 hours; regulating the temperature of the system to 80-210 ℃, preferably 172 ℃, adding tertiary butyl diphenyl chlorosilane (TBDPSCl) and a catalyst, and then preserving the heat for 1-9 hours, preferably 4 hours; regulating the temperature of the system to 30-94 ℃, preferably 58 ℃, adding dimethyl phthalate (DMP), then preserving heat for 20-100 min, preferably 30min, adding sodium chlorite (NaClO ₂) and sodium dihydrogen phosphate (NaH ₂PO₄), and preserving heat for 1-7 h, preferably 2h; regulating the temperature of the system to 55-98 ℃, preferably 73 ℃, adding a reducing agent, then preserving the heat for 30-95 min, preferably 62min, and removing most of the solvent to obtain hyperbranched monomers; wherein the polyhydric hydroxyl compound is phloroglucinol, 1,2, 3-phloroglucinol, 1, 3-benzenediol, 1, 4-benzenediol, 2, 6-naphthalenediol, 2, 7-dihydroxynaphthalene, 1,3, 5-cyclohexanetriol, 1, 2-phenylenediamine, 1, 4-phenylenediamine, 1, 8-diaminonaphthalene, 1, 3-diaminopyrene, 1,3, 5-triaminobenzene, 2, 7-diaminonaphthalene, or the like, preferably phloroglucinol; the solvent is dioxane, benzene, toluene, pyridine, 2,4, 6-trimethylpyridine, tetrahydrofuran, dichloromethane, N-dimethylformamide, trifluoroacetic acid or the like, preferably dioxane; the catalyst is 4-Dimethylaminopyridine (DMAP), N-diisopropylethylamine, triethylamine, diisopropylethylamine, silver nitrate or the like, preferably 4-dimethylaminopyridine; the reducing agent is tetrabutylammonium oxide (TBAF), HCl/methanol solution with mass fraction of 5%, naOH/ethanol solution with mass fraction of 6.5%, KOH/methanol solution with mass fraction of 7.1%, etc., preferably tetrabutylammonium oxide; the reaction material proportion of the polyhydroxy compound, the solvent, the hexamethylenetetramine or the acetic acid, the tert-butyl diphenyl chlorosilane, the catalyst, the dimethyl phthalate, the sodium chlorite, the sodium dihydrogen phosphate and the reducing agent is 0.1 mol:50-250 mL:0.02-0.16 mol:0.12-0.25 mol:10-90 mg:0.14-5.44 mol:0.1-10 mg:0.2-10 mg:10-22 g, preferably 0.1mol:188mL:0.07mol:0.15mol:83mg:2.51mol:0.8mg:0.6mg:13g;

(2) Hyperbranched self-assembly: fully dissolving hyperbranched monomer, polyamine and a water scavenger by using a solvent, heating to 70-210 ℃, preferably 117 ℃, adding a catalyst, preserving heat for 4-15 hours, preferably 10 hours, and removing most of the solvent to obtain a hyperbranched polymer containing rich carboxyl and hydroxyl; wherein the polyamine is 1, 2-phenylenediamine, p-phenylenediamine, 1, 3-diaminopyrene, 1,3, 5-triaminobenzene, 2, 7-diaminonaphthalene, 3-aminobenzylamine, 4-aminobenzylamine, 1, 3-propanediamine or 2-methyl-1, 3-propanediamine, etc., preferably 2-methyl-1, 3-propanediamine; the water scavenger may be a pyridine derivative such as picolinamide, 2,4, 6-tris (pyridin-4-yl) pyridine, 3-hydroxypyridine, sulfapyridine, or 4-pyridylpyridine chloride hydrochloride, etc., or a benzotriazole derivative such as 5-methyl-1H-benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, or 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, etc., preferably 5-methyl-1H-benzotriazole; the solvent is dioxane, methyl tertiary butyl ether, acetone, methylene dichloride or N, N-dimethylformamide and the like, preferably acetone; the catalyst is 4-Dimethylaminopyridine (DMAP), sulfuric acid, hydrochloric acid, thionyl chloride, acetyl chloride, p-toluenesulfonic acid, triethylamine or ferric trichloride and the like, preferably hydrochloric acid; the proportion of the reaction materials of the hyperbranched monomer, the polyamine, the solvent, the catalyst and the water scavenger is 10 g:0.1-12.6 mmol:20-150 mL:12-40 mg:0.1-0.5 g, preferably 10g:0.4mmol:75mL:16mg:0.3g;

(3) Preparation of aqueous polyurea prepolymer: fully dissolving polyisocyanate, polyamine and a chain extender by using a solvent, heating to 88-169 ℃, preferably 154 ℃, adding a catalyst, and preserving heat for 2-17 hours, preferably 9 hours; regulating the temperature of the system to 55-120 ℃, preferably 76 ℃, and preserving heat for 15-85 min, preferably 71min after adding a neutralizing agent; cooling to room temperature, increasing stirring speed, and adding deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion; wherein the polyisocyanate is dimethylbiphenyl diisocyanate, 4 '-methylenebis (phenyl isocyanate), p-phenylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dodecylbenzene-2, 4-diisocyanate or 4,4', 4 "" -triphenylmethane triisocyanate, etc., preferably dimethylbiphenyl diisocyanate; the polyamine is polytetrahydrofuran di-p-aminobenzoate, polyether amine PEA2000, polyether amine PEA3000, polyether amine T-5000, polyether amine T-403 or polyether amine ED900, etc., preferably polyether amine PEA2000; the chain extender may be carboxylate, such as dimethylolpropionic acid (DMPA), dimethylolbutyric acid, tartaric acid, carboxyl group-containing half-ester diol, N-dihydroxymonomaleamic acid or diaminobenzoic acid, etc., and may also be ethylenediamine-based ethanesulfonic acid, 1, 2-diamino- β -propanesulfonic acid or 1, 3-diamino- β -propanesulfonic acid, etc., preferably dimethylolpropionic acid; the solvent is dioxane, N-dimethylformamide, acetone, isopropyl acetate, dimethyl sulfoxide, tetrahydrofuran, methyl ethyl ketone, benzene, toluene or xylene, etc., preferably acetone; the catalyst is dibutyl tin dilaurate, N-Dimethylcyclohexylamine (DMCHA), dimethylbenzylamine, pentamethyl diethylenetriamine, dimorpholinodiethyl ether, 1, 4-dimethylpiperazine, potassium acetate or dibutyltin di (dodecyl sulfide), etc., preferably N, N-dimethylcyclohexylamine; the neutralizing agent is Triethylamine (TEA), ammonia water, naOH or triethanolamine, and the like, preferably triethylamine; the reaction material ratio of the polyisocyanate, the polyamine, the chain extender, the solvent, the catalyst, the neutralizer and the deionized water is 1.0 mol:0.5-1.3 mol:0.1-30 mmol:5-30 mL:5-15 mg:0.23-0.95 mol:140-330 mL, preferably 1.0mol:1.1mol:26mmol:9mL:10mg:0.85mol:290mL;

(4) Preparation of hyperbranched polymer modified aqueous polyurea and aqueous ink: fully dissolving the hyperbranched polymer and pigment prepared in the step (2) by using a small amount of solvent, heating to 50-140 ℃, and preserving heat for 30-110 min, preferably 89 ℃ for 72min; regulating the temperature of the system to 110-260 ℃, preferably 185 ℃, adding the aqueous polyurea prepolymer emulsion prepared in the step (3), and preserving heat for 3-18 hours, preferably 12 hours; cooling to room temperature, adding a defoaming agent and a leveling agent, and performing reduced pressure rotary evaporation to obtain water-based ink; wherein the pigment is azo condensation, quinacridone, benzimidazolone, isoindolinone, pyrrolopyrrolidone or carbazole pyrazine, and the like, preferably pyrrolopyrrolidone; the solvent is toluene, N-dimethylformamide, acetone, acetonitrile, dioxane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, diethyl ether, isopropyl ether, methylene chloride, chloroform or the like, preferably N, N-dimethylformamide; the defoamer is a high-carbon alcohol defoamer, a P-type defoamer, a GPE-type defoamer, a GPES-type defoamer or a polyether modified silicon defoamer, and the like, and is preferably a GPE-type defoamer; the leveling agent is fluorine modified acrylic acid, alkyl acrylate, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane or the like, and is preferably polymethylphenylsiloxane; the proportion of the reaction materials of the hyperbranched polymer, the aqueous polyurea prepolymer emulsion, the pigment, the solvent, the defoamer and the leveling agent is 0.5g to 75 g to 112g, 3.2 g to 9.7g to 5ml to 9ml to 2mg to 10mg to 2mg to 6mg; preferably 0.5g:83g:4.1g:6mL:5mg:4mg.

The solid content of the water-based ink containing the modified polyurea prepared by the method is 50.5+/-0.05%.

Experimental method

(1) Infrared spectroscopy testing

The infrared spectrum of the sample was measured using an infrared spectrometer (model Nicoiet 8700, company THERMOVG, usa). Firstly, taking a proper amount of KBr as a reference, putting the KBr into an agate mortar, grinding into superfine powder, pressing the powder into a transparent sheet by a mold, forming a background image by infrared scanning, uniformly mixing a trace of sample to be tested with the KBr superfine powder, forming a test image by infrared scanning, and finally subtracting a KBr background value to obtain an infrared spectrum curve of the sample to be tested;

(2) Overprint rate testing

Red, yellow, cyan and black four-color inks are prepared according to the process route of the embodiment 1, a four-color offset press (PZ 4650 type, shanghai Guanghai Hua printing machine Co., ltd.) is adopted to print the two types of inks on the surface of white coated paper (ration 155.5g/m ²) in sequence, the printing speed is 5500 print/h, the printing pressure is 0.2MPa, and a spectrodensimeter (X-Rite 530 type, alice, america) is adopted to detect the optical density of the printed inks under the condition of a D65 light source and a 10-degree view field; the calculation formula of the overprint rate is as follows:

f_D＝(D₁₊₂-D₁)/D₂×100％

Wherein, D ₁ is the optical density of the first color ink, D ₂ is the optical density of the second color ink, and D ₁₊₂ is the optical density of the second color ink superimposed on the first color ink;

(3) Abrasion resistance test

Printing ink on the surface of double-sided white paper (ration 35.5g/m ²) uniformly by adopting a gravure ink color spreading instrument (TST-A845 type, dongguan Test detection instrument Co., ltd.), controlling the inking amount to be 0.9+/-0.001 g/m ², and maintaining at 105 ℃ for 1min to finish surface drying and curing to obtain printing paper for later use;

Cutting the printing paper into 5cm 13cm specification, fixing the printing paper on an ink friction instrument (2000 type Sutherland company, U.S.), taking A4 printing paper as a transfer medium, setting 4 pounds pressure intensity and 85 revolutions per minute, taking a smooth surface of common A4 printing paper as a supporting material for carrying out ink transfer, and observing the fading condition of the printing paper to evaluate the wear resistance of the ink;

The comparative ink was commercially available and the same test was chosen to have a hue similar to the example ink.

Advantageous effects

The present invention uses hyperbranched polymer containing rich carboxyl and hydroxyl groups to provide crosslinking sites to prepare modified aqueous polyurea, so that the internal crosslinking network of the system is obviously increased, the coating performance of the pigment is also improved, the coating of the ink is further cured after printing, the light transmittance of single-layer ink is weakened, the color stacking rate of inks with different colors is generally higher, the characteristic is that specific color stacking effect is generated when different color sequences are selected during printing, the imitation difficulty of printed products is increased, and meanwhile, the friction resistance of the printed ink layer is better than that of the conventional ink on the market due to the fact that the coating performance of high polymer components in the ink system to the pigment is stronger; in addition, the hyperbranched polymer is used as a modifier, so that the viscosity, weather resistance and the like of the final ink can be greatly improved in terms of physical properties, and great help is provided for the storage adaptability of the ink.

Drawings

FIG. 1 is an infrared spectrum of the hyperbranched polymer prepared in example 1;

FIG. 2 shows the abrasion resistance effect of the ink prepared in example 1 and the comparative ink, wherein (a) represents the comparative ink and (b) represents the ink of example 1.

Detailed Description

The invention will now be described in detail with reference to specific examples which will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.

Example 1

Fully dissolving 0.1mol of phloroglucinol with 188mL of dioxane, adjusting to 74 ℃, adding 0.07mol of hexamethylenetetramine, and preserving heat for 3 hours; regulating the temperature of the system to 172 ℃, adding 0.15mol of tert-butyl diphenyl chlorosilane and 83mg of 4-dimethylaminopyridine, and preserving the heat for 4 hours; regulating the temperature of the system to 58 ℃, adding 2.51mol of dimethyl phthalate, preserving heat for 30min, adding 0.8mg of sodium chlorite and 0.6mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 73 ℃, adding 13g of tetrabutylammonium oxide, preserving the heat for 62min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 0.4mmol of 2-methyl-1, 3-propylene diamine and 0.3g of 5-methyl-1H-benzotriazole are fully dissolved by 75mL of acetone, then the temperature is adjusted to 117 ℃, 16mg of hydrochloric acid is added, the temperature is kept for 10 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of dimethylbiphenyl diisocyanate, 1.1mol of polyether amine PEA2000 and 26mmol of dimethylolpropionic acid are fully dissolved by 9mL of acetone, the temperature is adjusted to 154 ℃,10 mg of N, N-dimethylcyclohexylamine is added, and the temperature is kept for 9 hours; regulating the temperature of the system to 76 ℃, adding 0.85mol of triethylamine, and preserving heat for 71min; regulating the system to room temperature, improving the stirring rate, and adding 290mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

Fully dissolving 0.5g of the hyperbranched polymer and 4.1g of pyrrolopyrrole diketone pigment with 6mL of N, N-dimethylformamide, adjusting to 89 ℃, and preserving heat for 72min; regulating the temperature of the system to 185 ℃, adding 83g of the aqueous polyurea prepolymer emulsion, and preserving heat for 12 hours; and regulating the temperature of the system to room temperature, adding 5mg of GPE type defoamer and 4mg of polymethylphenylsiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

The synthetic route is as follows:

example 2

0.1mol of phloroglucinol is fully dissolved by 50mL of dioxane, the temperature is adjusted to 50 ℃, and 0.02mol of hexamethylenetetramine is added and then the temperature is kept for 1h; regulating the temperature of the system to 80 ℃, adding 0.12mol of tert-butyl diphenyl chlorosilane and 10mg of 4-dimethylaminopyridine, and then preserving heat for 1h; regulating the temperature of the system to 30 ℃, adding 0.14mol of dimethyl phthalate, preserving heat for 20min, adding 0.1mg of sodium chlorite and 0.2mg of sodium dihydrogen phosphate, and preserving heat for 1h; regulating the temperature of the system to 55 ℃, adding 10g of tetrabutylammonium oxide, preserving the heat for 30min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 0.1mmol of 2-methyl-1, 3-propylene diamine and 0.1g of 5-methyl-1H-benzotriazole are fully dissolved by 20mL of acetone, then the temperature is regulated to 70 ℃,12 mg of hydrochloric acid is added, the temperature is kept for 4 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of dimethylbiphenyl diisocyanate, 0.5mol of polyether amine PEA2000 and 0.1mmol of dimethylolpropionic acid are fully dissolved by 5mL of acetone, the temperature is adjusted to 88 ℃, and 5mg of N, N-dimethylcyclohexylamine is added and then the mixture is kept for 2 hours; regulating the temperature of the system to 55 ℃, adding 0.23mol of triethylamine, and preserving the heat for 15min; regulating the system to room temperature, improving the stirring rate, and adding 140mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

Fully dissolving 0.5g of the hyperbranched polymer and 3.2g of the pyrrolopyrrole diketone pigment with 5mL of toluene, adjusting the temperature to 50 ℃ and preserving the temperature for 30min; regulating the temperature of the system to 110 ℃, adding 75g of the aqueous polyurea prepolymer emulsion, and preserving heat for 3 hours; and (3) regulating the temperature of the system to room temperature, adding 2mg of GPE type defoamer and 2mg of polymethylphenylsiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 3

0.1mol of phloroglucinol is fully dissolved by 250mL of dioxane, the temperature is adjusted to 112 ℃, and the mixture is kept for 14h after 0.16mol of hexamethylenetetramine is added; regulating the temperature of the system to 210 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 90mg of 4-dimethylaminopyridine, and preserving heat for 9 hours; regulating the temperature of the system to 94 ℃, adding 5.44mol of dimethyl phthalate, preserving heat for 100min, adding 10mg of sodium chlorite and 10mg of sodium dihydrogen phosphate, and preserving heat for 7h; regulating the temperature of the system to 98 ℃, adding 22g of tetrabutylammonium oxide, preserving heat for 95min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 12.6mmol of 2-methyl-1, 3-propylene diamine and 0.5g of 5-methyl-1H-benzotriazole are fully dissolved by 150mL of acetone, then the temperature is adjusted to 210 ℃, 40mg of hydrochloric acid is added, the temperature is kept for 15 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of dimethylbiphenyl diisocyanate, 1.3mol of polyether amine PEA2000 and 30mmol of dimethylolpropionic acid are fully dissolved by 30mL of acetone, adjusted to 169 ℃, 15mg of N, N-dimethylcyclohexylamine is added, and the mixture is kept for 17 hours; regulating the temperature of the system to 120 ℃, adding 0.95mol of triethylamine, and preserving the heat for 85min; regulating the system to room temperature, improving the stirring rate, and adding 330mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 9.7g of the pyrrolopyrrole diketone pigment are fully dissolved by 9mL of N, N-dimethylformamide, and then the temperature is adjusted to 140 ℃ and is kept for 110min; regulating the temperature of the system to 260 ℃, adding 112g of the aqueous polyurea prepolymer emulsion, and preserving heat for 18h; and (3) regulating the temperature of the system to room temperature, adding 10mg of GPE type defoamer and 6mg of polymethylphenylsiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 4

Fully dissolving 0.1mol of phloroglucinol with 52mL of benzene, adjusting the temperature to 51 ℃, adding 0.03mol of hexamethylenetetramine, and preserving the heat for 2 hours; regulating the temperature of the system to 82 ℃, adding 0.13mol of tert-butyl diphenyl chlorosilane and 11mg of N, N-diisopropylethylamine, and then preserving the heat for 2 hours; regulating the temperature of the system to 31 ℃, adding 0.15mol of dimethyl phthalate, preserving heat for 21min, adding 0.2mg of sodium chlorite and 0.3mg of sodium dihydrogen phosphate, and preserving heat for 3h; regulating the temperature of the system to 56 ℃, adding 11g of 5% HCl/methanol solution, preserving the heat for 31min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer and 0.2mmol of 1, 2-phenylenediamine are fully dissolved by 21mL of dioxane, then the temperature is adjusted to 71 ℃, 13mg of 4-dimethylaminopyridine is added, the heat is preserved for 5 hours, and most of the solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of 4,4' -methylenebis (phenyl isocyanate), 0.6mol of polytetrahydrofuran di-p-aminobenzoate and 0.2mmol of dimethylolbutyric acid are fully dissolved by 6mL of dioxane, adjusted to 89 ℃, and incubated for 3 hours after adding 6mg of dibutyltin dilaurate; regulating the temperature of the system to 56 ℃, adding 0.24mol of ammonia water, and preserving heat for 16min; regulating the system to room temperature, improving the stirring rate, and adding 142mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 3.3g of azo condensation pigment are fully dissolved by 7mL of toluene, and then the temperature is adjusted to 51 ℃ and the temperature is kept for 32min; regulating the temperature of the system to 112 ℃, adding 76g of the aqueous polyurea prepolymer emulsion, and preserving heat for 4 hours; and (3) after regulating the temperature of the system to room temperature, adding 3mg of high-carbon alcohol defoamer and 3mg of fluorine modified acrylic acid, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 5

0.1mol of 1,2, 3-benzene-triphenol is fully dissolved by 55mL of toluene and then is regulated to 54 ℃, and after 0.04mol of hexamethylenetetramine is added, the temperature is kept for 4 hours; regulating the temperature of the system to 83 ℃, adding 0.14mol of tert-butyl diphenyl chlorosilane and 12mg of N, N-diisopropylethylamine, and then preserving the heat for 3 hours; regulating the temperature of the system to 35 ℃, adding 0.17mol of dimethyl phthalate, preserving heat for 22min, adding 0.3mg of sodium chlorite and 0.4mg of sodium dihydrogen phosphate, and preserving heat for 3h; regulating the temperature of the system to 57 ℃, adding 14g of 6.5% NaOH/ethanol solution, preserving the heat for 34min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 0.3mmol of p-phenylenediamine and 0.4g of 2,4, 6-tris (pyridine-4-yl) pyridine are fully dissolved by 29mL of methyl tertiary butyl ether, then the temperature is adjusted to 74 ℃, 14mg of sulfuric acid is added, the temperature is kept for 4 to 15 hours, preferably 10 hours, and most of the solvent is removed to obtain the hyperbranched polymer rich in carboxyl and hydroxyl;

1.0mol of terephthalyl diisocyanate, 0.7mol of polyether amine PEA3000 and 0.9mmol of tartaric acid are fully dissolved by 8mL of isopropyl acetate, the temperature is adjusted to 89 ℃, and 8mg of dimethylbenzylamine is added and then the mixture is kept for 4 hours; regulating the temperature of the system to 60 ℃, adding 0.34mol of NaOH, and preserving heat for 17min; regulating the system to room temperature, improving the stirring rate, and adding 160mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 3.9g of quinacridone pigment are fully dissolved by 8mL of acetone, and then the temperature is adjusted to 57 ℃ and kept for 41min; regulating the temperature of the system to 121 ℃, adding 81g of the aqueous polyurea prepolymer emulsion, and preserving heat for 5 hours; and (3) regulating the temperature of the system to room temperature, adding 4mg of GPES type defoamer and 5mg of alkyl acrylate, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 6

after 0.1mol of 1, 3-benzenediol is fully dissolved by 59mL of pyridine, the temperature is adjusted to 53 ℃, and after 0.06mol of hexamethylenetetramine is added, the temperature is kept for 6 hours; regulating the temperature of the system to 97 ℃, adding 0.19mol of tert-butyl diphenyl chlorosilane and 16mg of triethylamine, and preserving the heat for 5 hours; regulating the temperature of the system to 48 ℃, adding 0.19mol of dimethyl phthalate, preserving heat for 34min, adding 1.1mg of sodium chlorite and 0.7mg of sodium dihydrogen phosphate, and preserving heat for 4h; regulating the temperature of the system to 58 ℃, adding 16g of 7.1% KOH/methanol solution, preserving the temperature for 33 minutes, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 0.9mmol of 1, 3-diaminopyrene and 0.4g of 3-hydroxypyridine are fully dissolved by 29mL of dichloromethane, then the temperature is adjusted to 92 ℃, 18mg of thionyl chloride is added, the temperature is kept for 7h, and most of solvent is removed to obtain hyperbranched polymer containing rich terminal carboxyl groups and hydroxyl groups;

1.0mol of 1, 6-hexamethylene diisocyanate, 0.7mol of polyetheramine T-5000 and 0.6mmol of carboxyl half-ester diol are fully dissolved by 10mL of isopropyl acetate, the temperature is adjusted to 93 ℃, and 11mg of dimethylbenzylamine is added and then the temperature is kept for 4 hours; regulating the temperature of the system to 63 ℃, adding 0.32mol of triethanolamine, and preserving the heat for 25min; regulating the system to room temperature, improving the stirring rate, and adding 166mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

fully dissolving 0.5g of the hyperbranched polymer and 3.5g of benzimidazolone pigment with 8mL of acetonitrile, adjusting to 67 ℃, and preserving heat for 36min; regulating the temperature of the system to 122 ℃, adding 79g of the aqueous polyurea prepolymer emulsion, and preserving heat for 15h; and (3) regulating the temperature of the system to room temperature, adding 6mg of GPES type defoamer and 5mg of polyether polyester modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 7

0.1mol of 1, 4-benzenediol is fully dissolved by 103mL of 2,4, 6-trimethylpyridine, the temperature is adjusted to 63 ℃, and the mixture is kept for 10 hours after 0.09mol of hexamethylenetetramine is added; regulating the temperature of the system to 95 ℃, adding 0.19mol of tert-butyl diphenyl chlorosilane and 13mg of diisopropylethylamine, and then preserving the heat for 6 hours; regulating the temperature of the system to 44 ℃, adding 1.83mol of dimethyl phthalate, preserving heat for 39min, adding 1.2mg of sodium chlorite and 0.9mg of sodium dihydrogen phosphate, and preserving heat for 6h continuously; regulating the temperature of the system to 63 ℃, adding 17g of 7.1% KOH/methanol solution, preserving the heat for 52min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 2.8mmol of 1,3, 5-triaminobenzene and 0.5g of sulfapyridine are fully dissolved by 35mL of N, N-dimethylformamide, the temperature is adjusted to 90 ℃,20 mg of acetyl chloride is added, the temperature is kept for 11 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of 1, 6-hexamethylene diisocyanate, 0.9mol of polyetheramine T-403 and 5.7mmol of N, N-dihydroxymonomaleamic acid were fully dissolved in 12mL of methyl ethyl ketone, the temperature was adjusted to 95℃and the mixture was incubated for 8 hours after 14mg of dimethylbenzylamine was added; regulating the temperature of the system to 63 ℃, adding 0.54mol of triethylamine, and preserving the heat for 28min; regulating the system to room temperature, improving the stirring rate, and adding 166mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

Fully dissolving 0.5g of the hyperbranched polymer and 4.2g of carbazole pyrazine pigment with 7mL of diethyl ether, regulating the temperature to 73 ℃ and preserving the heat for 45min; regulating the temperature of the system to 134 ℃, adding 82g of the aqueous polyurea prepolymer emulsion, and preserving heat for 15h; and (3) regulating the temperature of the system to room temperature, adding 9mg of polyether modified silicon defoamer and 5mg of alkyl modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 8

After 0.1mol of 2, 7-dihydroxynaphthalene is fully dissolved by 177mL of trifluoroacetic acid, the temperature is adjusted to 64 ℃, and after 0.11mol of hexamethylenetetramine is added, the temperature is kept for 16 hours; regulating the temperature of the system to 135 ℃, adding 0.20mol of tert-butyl diphenyl chlorosilane and 24mg of silver nitrate, and preserving the heat for 3 hours; regulating the temperature of the system to 54 ℃, adding 3.31mol of dimethyl phthalate, preserving heat for 35min, adding 1.4mg of sodium chlorite and 1.7mg of sodium dihydrogen phosphate, and preserving heat for 5h; regulating the temperature of the system to 68 ℃, adding 14g of tetrabutylammonium oxide, preserving the heat for 70min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 3.9mmol of 1, 3-propylene diamine and 0.1g of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole are fully dissolved by 82mL of N, N-dimethylformamide, then the temperature is adjusted to 118 ℃, 17mg of ferric trichloride is added, the temperature is kept for 14 hours, and most of solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxy groups;

1.0mol of 4, 4' -triphenylmethane triisocyanate, 1.2mol of polyetheramine ED900 and 5.9mmol of 1, 3-diamino-beta-propane sulfonic acid are fully dissolved by 17mL of benzene, then the temperature is adjusted to 166 ℃, and 13mg of potassium acetate is added and then the mixture is kept for 16 hours; regulating the temperature of the system to 103 ℃, adding 0.91mol of triethanolamine, and preserving heat for 81min; regulating the system to room temperature, improving the stirring rate, and adding 210mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 4.6g of isoindolinone pigment are fully dissolved by 9mL of chloroform, and then the temperature is adjusted to 78 ℃ and the temperature is kept for 39min; regulating the temperature of the system to 223 ℃, adding 109g of the aqueous polyurea prepolymer emulsion, and preserving heat for 13h; and (3) regulating the temperature of the system to room temperature, adding 9mg of polyether modified silicon defoamer and 6mg of polyether polyester modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 9

after 0.1mol of 2, 7-diaminonaphthalene is fully dissolved by 138mL of trifluoroacetic acid, the temperature is adjusted to 111 ℃, and after 0.06mol of hexamethylenetetramine is added, the temperature is kept for 5 hours; regulating the temperature of the system to 208 ℃, adding 0.23mol of tert-butyl diphenyl chlorosilane and 77mg of diisopropylethylamine, and then preserving the heat for 7 hours; regulating the temperature of the system to 62 ℃, adding 2.62mol of dimethyl phthalate, preserving heat for 26min, adding 9mg of sodium chlorite and 8mg of sodium dihydrogen phosphate, and preserving heat for 3h; regulating the temperature of the system to 56 ℃, adding 20g of 6.5% NaOH/ethanol solution, preserving the heat for 70min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 0.9mmol of 1, 3-propylene diamine and 0.4g of pyridine amide are fully dissolved by 108mL of N, N-dimethylformamide, the temperature is adjusted to 201 ℃, 39mg of p-toluenesulfonic acid is added, the heat is preserved for 13 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich carboxyl and hydroxyl ends;

1.0mol of dodecylbenzene-2, 4-diisocyanate, 0.9mol of polyetheramine T-403 and 0.3mmol of diaminobenzoic acid are fully dissolved in 28mL of xylene, the temperature is adjusted to 155 ℃, and 8mg of dibutyltin dilaurate is added and the mixture is kept for 14 hours; regulating the temperature of the system to 57 ℃, adding 0.95mol of triethanolamine, and preserving heat for 82min; adjusting the system to room temperature, improving the stirring rate, and adding 270mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 9.3g of isoindolinone pigment are fully dissolved by 8mL of acetone, and then the temperature is adjusted to 77 ℃ and kept for 31min; regulating the temperature of the system to 206 ℃, adding 98g of the aqueous polyurea prepolymer emulsion, and preserving heat for 17 hours; and (3) after regulating the temperature of the system to room temperature, adding 3mg of high-carbon alcohol defoamer and 3mg of fluorine modified acrylic acid, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 10

After 0.1mol of 1, 8-diaminonaphthalene was sufficiently dissolved in 52mL of methylene chloride, the temperature was adjusted to 77℃and after 0.14mol of hexamethylenetetramine was added, the mixture was kept at the temperature for 13 hours; regulating the temperature of the system to 182 ℃, adding 0.20mol of tert-butyl diphenyl chlorosilane and 90mg of triethylamine, and preserving the heat for 5 hours; regulating the temperature of the system to 31 ℃, adding 3.44mol of dimethyl phthalate, preserving heat for 61min, adding 7.8mg of sodium chlorite and 1.1mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 63 ℃, adding 22g of 7.1% KOH/methanol solution, preserving the temperature for 63min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 2.6mmol of 1, 3-propylene diamine and 0.5g of 4-pyridylpyridine chloride hydrochloride are fully dissolved by 144mL of N, N-dimethylformamide, then the temperature is adjusted to 97 ℃, 19mg of p-toluenesulfonic acid is added, the heat is preserved for 5 hours, and most of the solvent is removed to obtain the hyperbranched polymer rich in carboxyl and hydroxyl;

1.0mol of isophorone diisocyanate, 0.8mol of polyetheramine PEA3000 and 21mmol of diaminobenzoic acid are fully dissolved by 26mL of isopropyl acetate, the temperature is adjusted to 155 ℃, and 9mg of pentamethyldiethylene triamine is added and then the mixture is kept for 12 hours; regulating the temperature of the system to 70 ℃, adding 0.95mol of NaOH, and preserving the heat for 26min; adjusting the system to room temperature, improving the stirring rate, and adding 190mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 8.7g of benzimidazolone pigment are fully dissolved by 8mL of chloroform, and then the temperature is adjusted to 52 ℃ and kept for 31min; regulating the temperature of the system to 133 ℃, adding 110g of the aqueous polyurea prepolymer emulsion, and preserving heat for 16 hours; and (3) regulating the temperature of the system to room temperature, adding 4mg of polyether modified silicon defoamer and 5mg of alkyl modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 11

After 0.1mol of 1,2, 3-phloroglucinol was fully dissolved in 136mL of pyridine, the temperature was adjusted to 52℃and the mixture was kept at the temperature for 3 hours after 0.15mol of acetic acid was added; regulating the temperature of the system to 81 ℃, adding 0.19mol of tert-butyl diphenyl chlorosilane and 11mg of N, N-diisopropylethylamine, and then preserving the heat for 3 hours; regulating the temperature of the system to 38 ℃, adding 2.44mol of dimethyl phthalate, preserving heat for 23min, adding 9.9mg of sodium chlorite and 10mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 83 ℃, adding 22g of 7.1% KOH/methanol solution, preserving the temperature for 62min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 2.5mmol of 1, 3-propylene diamine and 0.5g of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole are fully dissolved by 140mL of dioxane, then the temperature is adjusted to 112 ℃, 40mg of acetyl chloride is added, the temperature is kept for 13 hours, and most of solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxy groups;

1.0mol of dodecylbenzene-2, 4-diisocyanate, 0.9mol of polytetrahydrofuran di-p-aminobenzoate and 24mmol of dimethylolpropionic acid are fully dissolved by 18mL of dimethyl sulfoxide, the temperature is adjusted to 89 ℃, and 11mg of 1, 4-dimethylpiperazine is added and then the temperature is kept for 13 hours; regulating the temperature of the system to 59 ℃, adding 0.90mol of NaOH, and preserving heat for 80min; regulating the system to room temperature, improving the stirring rate, and adding 207mL deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 8.4g of isoindolinone pigment are fully dissolved by 6mL of diethyl ether, and then the temperature is adjusted to 53 ℃ and kept for 106min; regulating the temperature of the system to 172 ℃, adding 99g of the aqueous polyurea prepolymer emulsion, and preserving heat for 13h; and (3) regulating the temperature of the system to room temperature, adding 9mg of high-carbon alcohol defoamer and 3mg of alkyl acrylate, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 12

after 0.1mol of 1, 3-diaminopyrene is fully dissolved by 155mL of dioxane, the temperature is adjusted to 70 ℃, and after 0.16mol of acetic acid is added, the temperature is kept for 10 hours; regulating the temperature of the system to 102 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 88mg of diisopropylethylamine, and then preserving heat for 5 hours; regulating the temperature of the system to 87 ℃, adding 3.44mol of dimethyl phthalate, preserving heat for 70min, adding 7.1mg of sodium chlorite and 10mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 55 ℃, adding 10g of tetrabutylammonium oxide, preserving heat for 63min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 10.6mmol of 1, 3-propylene diamine and 0.4g of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole are fully dissolved by 80mL of dioxane, then the temperature is adjusted to 137 ℃,20 mg of p-toluenesulfonic acid is added, the temperature is kept for 9 hours, and most of solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxy groups;

1.0mol of dodecylbenzene-2, 4-diisocyanate, 0.7mol of polyetheramine ED900 and 25.1mmol of diaminobenzoic acid are fully dissolved by 28mL of dioxane, the temperature is adjusted to 144 ℃, 15mg of 1, 4-dimethylpiperazine is added, and the temperature is kept for 14 hours; regulating the temperature of the system to 110 ℃, adding 0.94mol of ammonia water, and preserving heat for 65min; regulating the system to room temperature, improving the stirring rate, and adding 320mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 9.2g of benzimidazolone pigment are fully dissolved by 9mL of chloroform, and then the temperature is adjusted to 120 ℃ and the temperature is kept for 100min; regulating the temperature of the system to 137 ℃, adding 79g of the aqueous polyurea prepolymer emulsion, and preserving heat for 10 hours; 3mg of high-carbon alcohol defoamer and 6mg of fluorine modified acrylic acid are added after the temperature of the system is regulated to room temperature, and the mixture is decompressed and distilled until the solid content is within the range of 50.5+/-0.05%, so that the ink is obtained.

Example 13

0.1mol of 1, 3-diaminopyrene is fully dissolved in 120mL of 2,4, 6-trimethylpyridine, the temperature is adjusted to 64 ℃, and the mixture is kept for 8 hours after 0.15mol of acetic acid is added; regulating the temperature of the system to 133 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 81mg of silver nitrate, and then preserving heat for 2 hours; regulating the temperature of the system to 38 ℃, adding 2.44mol of dimethyl phthalate, preserving heat for 90min, adding 3.7mg of sodium chlorite and 3.9mg of sodium dihydrogen phosphate, and preserving heat for 3h; regulating the temperature of the system to 90 ℃, adding 20g of 5% HCl/methanol solution, preserving heat for 31min, and removing most of solvent to obtain hyperbranched monomer;

10g of the hyperbranched monomer, 10.1mmol of 1, 3-propylene diamine and 0.5g of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole are fully dissolved by 100mL of dioxane, then the temperature is adjusted to 116 ℃,20 mg of sulfuric acid is added, the temperature is kept for 9 hours, and most of solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxyl groups;

1.0mol of 4, 4' -triphenylmethane triisocyanate, 0.9mol of polytetrahydrofuran di-p-aminobenzoate and 27.2mmol of dimethylolpropionic acid are fully dissolved by 20mL of dioxane, the temperature is adjusted to 124 ℃, and 13mg of dimorpholinodiethyl ether is added and the temperature is kept for 10 hours; regulating the temperature of the system to 78 ℃, adding 0.91mol of triethanolamine, and preserving heat for 82min; regulating the system to room temperature, improving the stirring rate, and adding 301mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 9.2g of isoindolinone pigment are fully dissolved by 7mL of isopropyl ether, and then the temperature is adjusted to 120 ℃ and kept for 101min; regulating the temperature of the system to 223 ℃, adding 111g of the aqueous polyurea prepolymer emulsion, and preserving heat for 15h; and (3) regulating the temperature of the system to room temperature, adding 10mg of GPES type defoamer and 6mg of alkyl modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 14

After 0.1mol of 1, 8-diaminonaphthalene was sufficiently dissolved in 100mL of methylene chloride, the temperature was adjusted to 69℃and after 0.10mol of acetic acid was added, the mixture was kept for 2 hours; regulating the temperature of the system to 102 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 80mg of diisopropylethylamine, and then preserving the heat for 4 hours; regulating the temperature of the system to 78 ℃, adding 2.43mol of dimethyl phthalate, preserving heat for 75min, adding 9mg of sodium chlorite and 10mg of sodium dihydrogen phosphate, and preserving heat for 3h; regulating the temperature of the system to 61 ℃, adding 20g of 6.5% NaOH/ethanol solution, preserving heat for 65min, and removing most of solvent to obtain hyperbranched monomer;

10g of the hyperbranched monomer, 11.6mmol of 1, 3-propylene diamine and 0.4g of 4-pyridylpyridine chloride hydrochloride are fully dissolved by 120mL of N, N-dimethylformamide, the temperature is adjusted to 116 ℃, 30mg of thionyl chloride is added, the heat is preserved for 13h, and most of the solvent is removed to obtain the hyperbranched polymer rich in carboxyl and hydroxyl;

1.0mol of dimethylbiphenyl diisocyanate, 0.7mol of polyether amine ED900 and 22.5mmol of diaminobenzoic acid are fully dissolved by 13mL of methyl ethyl ketone, the temperature is adjusted to 134 ℃, and 6mg of potassium acetate is added and the mixture is kept for 10 hours; regulating the temperature of the system to 105 ℃, adding 0.33mol of triethylamine, and preserving heat for 22min; regulating the system to room temperature, improving the stirring rate, and adding 150mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

Fully dissolving 0.5g of the hyperbranched polymer and 4.7g of carbazole pyrazine pigment with 8mL of toluene, adjusting to 52 ℃, and preserving heat for 77min; regulating the temperature of the system to 130 ℃, adding 82g of the aqueous polyurea prepolymer emulsion, and preserving heat for 11h; 3mg of high-carbon alcohol defoamer and 5mg of polymethylphenylsiloxane are added after the temperature of the system is regulated to room temperature, and the mixture is decompressed and distilled until the solid content is within the range of 50.5+/-0.05%, so that the printing ink is obtained.

Example 15

0.1mol of 1, 3-diaminopyrene is fully dissolved by 90mL of 2,4, 6-trimethylpyridine, the temperature is adjusted to 66 ℃, and the mixture is kept for 8 hours after 0.12mol of acetic acid is added; regulating the temperature of the system to 192 ℃, adding 0.14mol of tert-butyl diphenyl chlorosilane and 12mg of diisopropylethylamine, and then preserving the heat for 3 hours; regulating the temperature of the system to 78 ℃, adding 3.33mol of dimethyl phthalate, preserving heat for 50min, adding 7.8mg of sodium chlorite and 0.9mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 63 ℃, adding 14g of tetrabutylammonium oxide, preserving heat for 92min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 12.2mmol of 3-aminobenzylamine and 0.4g of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole are fully dissolved by 88mL of dioxane, then the temperature is adjusted to 202 ℃,13 mg of thionyl chloride is added, the heat is preserved for 12 hours, and most of the solvent is removed to obtain the hyperbranched polymer rich in carboxyl and hydroxy;

1.0mol of dimethylbiphenyl diisocyanate, 0.7mol of polyether amine ED900 and 5.9mmol of N, N-dihydroxymonomaleamic acid are fully dissolved by 26mL of dioxane, the temperature is adjusted to 133 ℃, and 12mg of dimorpholinyl diethyl ether is added and the temperature is kept for 12 hours; regulating the temperature of the system to 114 ℃, adding 0.87mol of triethanolamine, and preserving the heat for 22min; regulating the system to room temperature, improving the stirring rate, and adding 143mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 3.3g of isoindolinone pigment are fully dissolved by 7mL of toluene, and then the temperature is adjusted to 124 ℃ and kept for 83min; regulating the temperature of the system to 155 ℃, adding 104g of the aqueous polyurea prepolymer emulsion, and preserving heat for 9 hours; and (3) regulating the temperature of the system to room temperature, adding 7mg of GPES type defoamer and 3mg of fluorine modified acrylic acid, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 16

0.1mol of 1, 2-phenylenediamine is fully dissolved by 224mL of pyridine, the temperature is adjusted to 77 ℃, and 0.09mol of acetic acid is added for 3 hours; regulating the temperature of the system to 192 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 43mg of triethylamine, and then preserving the heat for 3 hours; regulating the temperature of the system to 59 ℃, adding 3.61mol of dimethyl phthalate, preserving heat for 70min, adding 8.8mg of sodium chlorite and 3.0mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 91 ℃, adding 14g of 7.1% KOH/methanol solution, preserving the temperature for 37min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 10.1mmol of 1,3, 5-triaminobenzene and 0.4g of sulfapyridine are fully dissolved by 22mL of dichloromethane, then the temperature is adjusted to 92 ℃, 18mg of p-toluenesulfonic acid is added, the heat is preserved for 13 hours, and most of solvent is removed to obtain hyperbranched polymer containing rich terminal carboxyl groups and hydroxyl groups;

1.0mol of dodecylbenzene-2, 4-diisocyanate, 1.0mol of polytetrahydrofuran di-p-aminobenzoate and 27.3mmol of N, N-dihydroxymonomaleamic acid are fully dissolved by 28mL of dimethyl sulfoxide, adjusted to 156 ℃, and then the mixture is heated for 10 hours after 13mg of potassium acetate is added; regulating the temperature of the system to 78 ℃, adding 0.91mol of NaOH, and preserving heat for 18min; adjusting the system to room temperature, improving the stirring rate, and adding 280mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 7.3g of isoindolinone pigment are fully dissolved by 5mL of chloroform, and then the temperature is adjusted to 58 ℃ and kept for 109 minutes; regulating the temperature of the system to 199 ℃, adding 93g of the aqueous polyurea prepolymer emulsion, and preserving heat for 10 hours; and (3) after regulating the temperature of the system to room temperature, adding 3mg of high-carbon alcohol defoamer and 3mg of polydimethylsiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 17

Fully dissolving 0.1mol of 2, 6-naphthalene diphenol with 112mL of pyridine, adjusting the temperature to 77 ℃, adding 0.14mol of acetic acid, and preserving the temperature for 15 hours; regulating the temperature of the system to 133 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 90mg of triethylamine, and preserving the heat for 4 hours; regulating the temperature of the system to 48 ℃, adding 1.44mol of dimethyl phthalate, preserving heat for 26min, adding 7.9mg of sodium chlorite and 1.2mg of sodium dihydrogen phosphate, and preserving heat for 2h continuously; regulating the temperature of the system to 56 ℃, adding 11g of 7.1% KOH/methanol solution, preserving the heat for 52min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 10.2mmol of 1, 3-propylene diamine and 0.4g of 4-pyridylpyridine chloride hydrochloride are fully dissolved by 90mL of N, N-dimethylformamide, then are adjusted to 107 ℃, 31mg of sulfuric acid is added, and then the heat preservation is carried out for 9 hours, and most of the solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxyl;

1.0mol of isophorone diisocyanate, 1.2mol of polyetheramine ED900 and 15.8mmol of N, N-dihydroxymonomaleamic acid are fully dissolved by 27mL of isopropyl acetate, the temperature is adjusted to 124 ℃, and 11mg of 1, 4-dimethylpiperazine is added and then the temperature is kept for 12 hours; regulating the temperature of the system to 108 ℃, adding 0.23mol of ammonia water, and preserving heat for 16min; regulating the system to room temperature, improving the stirring rate, and adding 230mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 4.4g of benzimidazolone pigment are fully dissolved by 7mL of toluene, and then are adjusted to 51 ℃ and kept for 110min; regulating the temperature of the system to 113 ℃, adding 110g of the aqueous polyurea prepolymer emulsion, and preserving heat for 7 hours; and (3) regulating the temperature of the system to room temperature, adding 6mg of GPES type defoamer and 5mg of alkyl modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the ink.

Example 18

0.1mol of 2, 6-naphthalene diphenol is fully dissolved by 150mL of toluene, the temperature is adjusted to 82 ℃, and the mixture is kept for 13 hours after 0.15mol of acetic acid is added; regulating the temperature of the system to 82 ℃, adding 0.20mol of tert-butyl diphenyl chlorosilane and 13mg of diisopropylethylamine, and then preserving heat for 8 hours; regulating the temperature of the system to 78 ℃, adding 0.44mol of dimethyl phthalate, preserving heat for 35min, adding 3mg of sodium chlorite and 3mg of sodium dihydrogen phosphate, and preserving heat for 5h; regulating the temperature of the system to 63 ℃, adding 22g of 7.1% KOH/methanol solution, preserving the heat for 72min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 6.6mmol of 2-methyl-1, 3-propylene diamine and 0.5g of pyridine amide are fully dissolved by 21mL of N, N-dimethylformamide, then the temperature is regulated to 98 ℃,20 mg of p-toluenesulfonic acid is added, the heat is preserved for 14h, and most of solvent is removed to obtain hyperbranched polymer rich in carboxyl and hydroxyl;

1.0mol of dimethylbiphenyl diisocyanate, 0.6mol of polyether amine ED900 and 20.7mmol of N, N-dihydroxymonomaleamic acid are fully dissolved by 18mL of isopropyl acetate, the temperature is adjusted to 104 ℃,10 mg of 1, 4-dimethylpiperazine is added, and the temperature is kept for 10 hours; regulating the temperature of the system to 58 ℃, adding 0.90mol of triethanolamine, and preserving the heat for 60min; regulating the system to room temperature, improving the stirring rate, and adding 330mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 6.0g of azo condensation pigment are fully dissolved by 9mL of acetone, and then the temperature is adjusted to 63 ℃ and kept for 55min; regulating the temperature of the system to 126 ℃, adding 112g of the aqueous polyurea prepolymer emulsion, and preserving heat for 10 hours; and (3) regulating the temperature of the system to room temperature, adding 9mg of high-carbon alcohol defoamer and 6mg of alkyl modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 19

0.1mol of 2, 7-diaminonaphthalene is fully dissolved by 150mL of tetrahydrofuran, the temperature is adjusted to 70 ℃, and 0.16mol of acetic acid is added for 15h of heat preservation; regulating the temperature of the system to 202 ℃, adding 0.25mol of tert-butyl diphenyl chlorosilane and 90mg of silver nitrate, and preserving heat for 6 hours; regulating the temperature of the system to 80 ℃, adding 5.44mol of dimethyl phthalate, preserving heat for 70min, adding 0.1mg of sodium chlorite and 0.6mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 83 ℃, adding 20g of 7.1% KOH/methanol solution, preserving the temperature for 31min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 7.3mmol of 1,3, 5-triaminobenzene and 0.4g of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole are fully dissolved by 144mL of dioxane, then the temperature is adjusted to 117 ℃, 40mg of sulfuric acid is added, the temperature is kept for 9 hours, and most of the solvent is removed to obtain the hyperbranched polymer rich in carboxyl and hydroxy;

1.0mol of 4, 4' -triphenylmethane triisocyanate, 1.3mol of polyetheramine ED900 and 20.7mmol of N, N-dihydroxymonomaleamic acid are fully dissolved by 30mL of dimethyl sulfoxide, the temperature is adjusted to 155 ℃, and 15mg of dibutyltin dilaurate is added and the temperature is kept for 8 hours; regulating the temperature of the system to 103 ℃, adding 0.91mol of triethylamine, and preserving heat for 80min; regulating the system to room temperature, improving the stirring rate, and adding 150mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 8.9g of isoindolinone pigment are fully dissolved by 7mL of toluene, and then the temperature is adjusted to 120 ℃ and kept for 42min; regulating the temperature of the system to 175 ℃, adding 110g of the aqueous polyurea prepolymer emulsion, and preserving heat for 10 hours; and (3) regulating the temperature of the system to room temperature, adding 9mg of polyether modified silicon defoamer and 6mg of fluorine modified acrylic acid, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Example 20

0.1mol of 1, 3-benzenediol is fully dissolved by 150mL of toluene, the temperature is adjusted to 84 ℃, and 0.12mol of acetic acid is added and then the mixture is kept for 3 hours; regulating the temperature of the system to 152 ℃, adding 0.24mol of tert-butyl diphenyl chlorosilane and 77mg of 4-dimethylaminopyridine, and then preserving heat for 2 hours; regulating the temperature of the system to 31 ℃, adding 0.14mol of dimethyl phthalate, preserving heat for 33min, adding 8.5mg of sodium chlorite and 10mg of sodium dihydrogen phosphate, and preserving heat for 2h; regulating the temperature of the system to 73 ℃, adding 21g of tetrabutylammonium oxide, preserving heat for 65min, and removing most of the solvent to obtain hyperbranched monomers;

10g of the hyperbranched monomer, 2.3mmol of 2, 7-diaminonaphthalene and 0.2g of 3-hydroxypyridine are fully dissolved by 110mL of dichloromethane, then the temperature is adjusted to 118 ℃, 40mg of p-toluenesulfonic acid is added, the temperature is kept for 12 hours, and most of solvent is removed to obtain hyperbranched polymer rich in carboxyl and hydroxyl;

1.0mol of dodecylbenzene-2, 4-diisocyanate, 0.6mol of polyetheramine ED900 and 30mmol of diaminobenzoic acid are fully dissolved by 7mL of dioxane, the temperature is adjusted to 89 ℃, 15mg of 1, 4-dimethylpiperazine is added, and the temperature is kept for 3 hours; regulating the temperature of the system to 75 ℃, adding 0.95mol of triethylamine, and preserving the heat for 80min; regulating the system to room temperature, improving the stirring rate, and adding 330mL of deionized water for full dispersion to obtain aqueous polyurea prepolymer emulsion;

0.5g of the hyperbranched polymer and 9.3g of isoindolinone pigment are fully dissolved by 9mL of isopropyl ether, and then the temperature is adjusted to 60 ℃ and the temperature is kept for 40min; regulating the temperature of the system to 175 ℃, adding 111g of the aqueous polyurea prepolymer emulsion, and preserving heat for 12 hours; and (3) regulating the temperature of the system to room temperature, adding 10mg of high-carbon alcohol defoamer and 6mg of polyether polyester modified organosiloxane, and performing reduced pressure rotary evaporation until the solid content is within the range of 50.5+/-0.05%, thus obtaining the printing ink.

Experimental results and analysis

(1) The hyperbranched polymer obtained in example 1 was tested for infrared spectrum, and the results are shown in FIG. 1, and it can be seen that: the presence of a broad absorption peak at 3205cm ^-1, usually derived from the stretching vibration of O-H in the phenol structure, an absorption peak at 2972cm ^-1, derived from the stretching vibration of O-H in the carboxylic acid structure, an absorption peak at 1464cm ^-1、1101cm^-1, derived from the bending vibration of O-H in the carboxylic acid structure, and an absorption peak at 1731cm ^-1, usually derived from the c=o stretching vibration of aromatic carboxylic acid, can determine that both-OH and-COOH are contained in the molecular structure of the test sample; the absorption peaks at two positions of 2944cm ^-1、1298cm^-1 are respectively from C-H stretching vibration and bending vibration of an alkane chain part of 2-methyl-1, 3-propylene diamine, the absorption peak at 2739cm ^-1 is from C-H stretching vibration of a-CH (3 DEG) part of 2-methyl-1, 3-propylene diamine, the absorption peak at two positions of 1674cm ^-1、938cm^-1 is from in-plane bending vibration of N-H in an R-NH-R 'structure, and the absorption peak at 1247cm ^-1 is from C-N stretching vibration in an R-NH-R' structure; meanwhile, the absorption peaks at three positions 1320cm ^-1、1512cm^-1、1255cm^-1 are respectively derived from C-N stretching vibration, C=O stretching vibration and N-H stretching vibration in an amide-CO-NH-structure, so that hyperbranched self-assembly can be judged; in addition, absorption peaks at two places of 1123cm ^-1、1563cm^-1 are respectively derived from in-plane bending vibration and C-C stretching vibration of C-H in the benzene ring structure.

(2) Based on the process of example 1, four types of red, yellow, cyan and black color inks were prepared, and two types of inks were used to test the overprint rate, and the results are shown in table 1, and it can be seen that: according to the process route of the embodiment 1, the mutual overprinting rate of the four types of red, yellow, cyan and black ink is basically within the range of 85.0+/-4.0%, the overprinting rate is higher, and the inter-phase overlaying effect of each color is similar, so that the printed matters corresponding to different printing color sequences are arranged in actual printing operation, and the imitation difficulty of the printed matters is increased in a phase changing manner;

TABLE 1 results of ink overprint test

(3) The ink of example 1 and the comparative ink were applied to a double-sided glossy white paper and the color fading of the ink layer was tested, respectively, the two inks were similar in color, and the abrasion resistance test results are shown in fig. 2, as can be seen: the compared ink has obvious fading phenomenon on the surface of the support material after wear-resistant test, compared with the ink in the embodiment 1, the fading of the ink is not obvious or negligible, and the hyperbranched polymer prepared by the technical scheme is mainly due to the fact that the hyperbranched polymer contains rich carboxyl and hydroxyl ends, has the characteristic of general hyperbranched molecules, has excellent hydrophilicity, can be well dispersed in an aqueous polyurea system, provides a plurality of crosslinking sites, and can be copolymerized with the aqueous polyurea molecular chains to form a compact network structure, so that pigment molecules are more effectively wrapped, the wear resistance of an ink layer is obviously enhanced, and the fading is not obvious or negligible during wear-resistant test.

The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims

1. The preparation method of the water-based ink containing the modified polyurea is characterized by comprising the following steps of:

(1) Fully dissolving a polyhydroxy compound by using a solvent, heating to 50-112 ℃, adding hexamethylenetetramine or acetic acid, then preserving heat for 1-17 hours, regulating the temperature of a system to 80-210 ℃, adding tert-butyldiphenylchlorosilane TBDPSCl and a catalyst, then preserving heat for 1-9 hours, regulating the temperature of the system to 30-94 ℃, adding dimethyl phthalate DMP, then preserving heat for 20-100 minutes, then adding sodium chlorite NaClO ₂ and sodium dihydrogen phosphate NaH ₂PO₄, continuously preserving heat for 1-7 hours, regulating the temperature of the system to 55-98 ℃, adding a reducing agent, then preserving heat for 30-95 minutes, and removing most of the solvent to obtain hyperbranched monomers; wherein the polyhydric hydroxyl compound is phloroglucinol, 1,2, 3-phloroglucinol, 1, 3-benzenediol, 1, 4-benzenediol, 2, 6-naphthalenediol, 2, 7-dihydroxynaphthalene, 1,3, 5-cyclohexanetriol, 1, 2-phenylenediamine, 1, 4-phenylenediamine, 1, 8-diaminonaphthalene, 1, 3-diaminopyrene, 1,3, 5-triaminobenzene, or 2, 7-diaminonaphthalene; the solvent is dioxane, benzene, toluene, pyridine, 2,4, 6-trimethylpyridine, tetrahydrofuran, dichloromethane, N-dimethylformamide or trifluoroacetic acid; the catalyst is 4-dimethylaminopyridine DMAP, N-diisopropylethylamine, triethylamine, diisopropylethylamine or silver nitrate; the reducing agent is tetrabutylammonium oxide TBAF, HCl/methanol solution with the mass fraction of 5 percent, naOH/ethanol solution with the mass fraction of 6.5 percent or KOH/methanol solution with the mass fraction of 7.1 percent; the reaction material ratio of the polyhydroxy compound, the solvent, the hexamethylenetetramine or acetic acid, the tert-butyl diphenyl chlorosilane, the catalyst, the dimethyl phthalate, the sodium chlorite, the sodium dihydrogen phosphate and the reducing agent is 0.1 mol:50-250 mL:0.02-0.16 mol:0.12-0.25 mol:10-90 mg:0.14-5.44 mol:0.1-10 mg:0.2-10 mg:10-22 g;

(2) Fully dissolving hyperbranched monomer, polyamine and a water scavenger by using a solvent, heating to 70-210 ℃, adding a catalyst, preserving heat for 4-15 hours, and removing most of the solvent to obtain a hyperbranched polymer containing rich carboxyl and hydroxyl; wherein the polyamine is 1, 2-phenylenediamine, p-phenylenediamine, 1, 3-diaminopyrene, 1,3, 5-triaminobenzene, 2, 7-diaminonaphthalene, 3-aminobenzylamine, 4-aminobenzylamine, 1, 3-propanediamine or 2-methyl-1, 3-propanediamine; the water scavenger is a pyridine derivative or a benzotriazole derivative; the solvent is dioxane, methyl tertiary butyl ether, acetone, methylene dichloride or N, N-dimethylformamide; the catalyst is 4-Dimethylaminopyridine (DMAP), sulfuric acid, hydrochloric acid, thionyl chloride, acetyl chloride, p-toluenesulfonic acid, triethylamine or ferric trichloride; the proportion of the reaction materials of the hyperbranched monomer, the polyamine, the solvent, the catalyst and the water scavenger is 10 g:0.1-12.6 mmol:20-150 mL:12-40 mg:0.1-0.5 g;

(3) Fully dissolving polyisocyanate, polyamine and a chain extender by using a solvent, heating to 88-169 ℃, adding a catalyst, preserving heat for 2-17 hours, adjusting the system temperature to 55-120 ℃, adding a neutralizer, preserving heat for 15-85 minutes, cooling to room temperature, improving the stirring rate, and adding deionized water for full dispersion to obtain a water-based polyurea prepolymer emulsion; wherein the polyisocyanate is dimethylbiphenyl diisocyanate, 4 '-methylenebis (phenyl isocyanate), p-phenylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dodecylbenzene-2, 4-diisocyanate, or 4,4', 4 "" -triphenylmethane triisocyanate; the polyatomic amine is polytetrahydrofuran di-p-aminobenzoate, polyether amine PEA2000, polyether amine PEA3000, polyether amine T-5000, polyether amine T-403 or polyether amine ED900; the chain extender is dimethylolpropionic acid DMPA, dimethylolbutyric acid, tartaric acid, carboxyl-containing half-ester dihydric alcohol, N-dihydroxymonomaleamic acid or diaminobenzoic acid, or ethylenediamine-based ethanesulfonic acid, ethylenedihydroxyethanesulfonic acid, 1, 2-diamino-beta-propanesulfonic acid or 1, 3-diamino-beta-propanesulfonic acid; the solvent is dioxane, N-dimethylformamide, acetone, isopropyl acetate, dimethyl sulfoxide, tetrahydrofuran, methyl ethyl ketone, benzene, toluene or xylene; the catalyst is dibutyl tin dilaurate, N-dimethyl cyclohexylamine DMCHA, dimethylbenzylamine, pentamethyl diethylenetriamine, dimorpholinodiethyl ether, 1, 4-dimethyl piperazine, potassium acetate or dibutyl tin dilaurate; the neutralizer is triethylamine TEA, ammonia water, naOH or triethanolamine; the reaction material ratio of the polyisocyanate, the polyamine, the chain extender, the solvent, the catalyst, the neutralizer and the deionized water is 1.0 mol:0.5-1.3 mol:0.1-30 mmol:5-30 mL:5-15 mg:0.23-0.95 mol:140-330 mL;

(4) Fully dissolving the hyperbranched polymer and pigment prepared in the step (2) by using a small amount of solvent, heating to 50-140 ℃, preserving heat for 30-110 min, regulating the system temperature to 110-260 ℃, adding the aqueous polyurea prepolymer emulsion prepared in the step (3), preserving heat for 3-18 h, cooling to room temperature, adding a defoaming agent and a leveling agent, and performing reduced pressure rotary evaporation to obtain aqueous ink; wherein the pigment is azo condensation, quinacridone, benzimidazolone, isoindolinone, pyrrolopyrrole dione or carbazole pyrazine; the solvent is toluene, N-dimethylformamide, acetone, acetonitrile, dioxane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, diethyl ether, isopropyl ether, methylene chloride or chloroform; the defoaming agent is a high-carbon alcohol defoaming agent, a P-type defoaming agent, a GPE-type defoaming agent, a GPES-type defoaming agent or a polyether modified silicon defoaming agent; the leveling agent is fluorine modified acrylic acid, acrylic acid alkyl ester, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane or alkyl modified organosiloxane; the proportion of the reaction materials of the hyperbranched polymer, the aqueous polyurea prepolymer emulsion, the pigment, the solvent, the defoamer and the leveling agent is 0.5g, 75-112 g, 3.2-9.7 g, 5-9 mL, 2-10 mg and 2-6 mg.

2. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (1), fully dissolving a polyhydroxy compound by using a solvent, heating to 74 ℃, adding hexamethylenetetramine, preserving heat for 3 hours, adjusting the temperature of a system to 172 ℃, adding tert-butyl diphenyl chlorosilane TBDPSCl and a catalyst, preserving heat for 4 hours, adjusting the temperature of the system to 58 ℃, adding dimethyl phthalate DMP, preserving heat for 30 minutes, adding sodium chlorite NaClO ₂ and sodium dihydrogen phosphate NaH ₂PO₄, and preserving heat for 2 hours continuously; regulating the temperature of the system to 73 ℃, adding a reducing agent, then preserving the heat for 62min, and removing most of the solvent to obtain the hyperbranched monomer.

3. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (1), the polyhydric hydroxyl compound is phloroglucinol.

4. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (1), the solvent is dioxane.

5. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (1), the catalyst is 4-dimethylaminopyridine.

6. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (1), the reducing agent is tetrabutylammonium oxide TBAF.

7. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (1), the ratio of the reaction materials of the polyhydroxy compound, the solvent, the hexamethylenetetramine or acetic acid, the tert-butyl diphenyl chlorosilane, the catalyst, the dimethyl phthalate, the sodium chlorite, the sodium dihydrogen phosphate and the reducing agent is 0.1mol:188mL:0.07mol:0.15mol:83mg:2.51mol:0.8mg:0.6mg:13g.

8. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (2), the hyperbranched monomer, polyamine and a water scavenger are fully dissolved by a solvent, then the temperature is raised to 117 ℃, a catalyst is added, then the heat is preserved for 10 hours, and most of the solvent is removed to obtain the hyperbranched polymer containing rich carboxyl and hydroxyl.

9. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (2), the polyamine is 2-methyl-1, 3-propanediamine.

10. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (2), the pyridine derivative is picolinamide, 2,4, 6-tris (pyridin-4-yl) pyridine, 3-hydroxypyridine, sulfapyridine or 4-pyridylpyridine chloride hydrochloride.

11. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (2), the benzotriazole derivative is 5-methyl-1H-benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole or 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole.

12. The method for preparing the modified polyurea containing aqueous ink according to claim 11, wherein: in step (2), the benzotriazole derivative is 5-methyl-1H-benzotriazole.

13. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (2), the solvent is acetone.

14. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (2), the catalyst is hydrochloric acid.

15. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (2), the reaction material ratio of the hyperbranched monomer, the polyamine, the solvent, the catalyst and the water scavenger is 10g:0.4mmol:75mL:16mg:0.3g.

16. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (3), the temperature is raised to 154 ℃ after the polyisocyanate, the polyamine and the chain extender are fully dissolved by using a solvent, the temperature is kept for 9 hours after the catalyst is added, the system temperature is regulated to 76 ℃, the temperature is kept for 71 minutes after the neutralizer is added, the temperature is cooled to room temperature, the stirring speed is increased, and the deionized water is added for full dispersion, thus obtaining the aqueous polyurea prepolymer emulsion.

17. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (3), the polyisocyanate is dimethylbiphenyl diisocyanate.

18. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (3), the polyamine is polyetheramine PEA2000.

19. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (3), the chain extender is dimethylolpropionic acid.

20. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (3), the solvent is acetone.

21. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (3), the catalyst is N, N-dimethylcyclohexylamine.

22. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (3), the neutralizing agent is triethylamine.

23. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (3), the reaction material ratio of the polyisocyanate, the polyamine, the chain extender, the solvent, the catalyst, the neutralizer and the deionized water is 1.0mol:1.1mol:26mmol:9mL:10mg:0.85mol:290mL.

24. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (4), fully dissolving the hyperbranched polymer and pigment prepared in the step (2) by using a small amount of solvent, heating to 89 ℃, preserving heat for 72min, regulating the system temperature to 185 ℃, adding the aqueous polyurea prepolymer emulsion prepared in the step (3), and preserving heat for 12h; cooling to room temperature, adding a defoaming agent and a leveling agent, and performing reduced pressure rotary evaporation to obtain the water-based ink.

25. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (4), the pigment is a pyrrolopyrroldiketone.

26. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (4), the solvent is N, N-dimethylformamide.

27. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (4), the antifoaming agent is a GPE-type antifoaming agent.

28. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in step (4), the leveling agent is polymethylphenylsiloxane.

29. The method for preparing the modified polyurea containing aqueous ink according to claim 1, wherein: in the step (4), the reaction material ratio of the hyperbranched polymer, the aqueous polyurea prepolymer emulsion, the pigment, the solvent, the defoamer and the leveling agent is 0.5g:83g:4.1g:6mL:5mg:4mg.

30. The aqueous ink containing modified polyurea prepared according to any one of claims 1-29.