Low viscosity high color fastness water-based pigment and preparation method thereof

Abstract

This invention discloses a low-viscosity, high-color-fastness waterborne pigment and its preparation method, relating to the field of waterborne pigment technology. The low-viscosity, high-color-fastness waterborne pigment prepared by this invention comprises an organic color pigment, a modifier, and a waterborne medium. The waterborne medium includes water, additives, polyvinyl butyral, and a binder / crosslinker. The modifier includes a vinyl polyacrylate binder and glycerol polyoxyethylene ether. The binder / crosslinker is prepared by reacting poly(carbonate-ether) polyol, isophorone diisocyanate, and oleoyl glycolamine, followed by catalytic blocking with methylacetamide oxime. The binder / crosslinker can form a three-dimensional network structure in the waterborne medium, significantly improving the color fastness of the waterborne pigment, and the resulting coating film exhibits excellent rubbing fastness. The vinyl polyacrylate binder is prepared by copolymerizing vinyl resin and polyacrylate, improving water resistance while maintaining a low viscosity of the waterborne pigment, thus ensuring color fastness.

Description

Technical Field

[0001] This invention relates to the field of water-based pigment technology, specifically to a low-viscosity, high-color-fastness water-based pigment and its preparation method. Background Technology

[0002] Low-viscosity, high-color-fastness water-based pigments are advanced coloring materials that combine excellent processing performance with long-lasting color stability. Through specific formulation techniques and meticulous pigment processing, they achieve a balance between low viscosity and high color fastness, making them widely applicable in fields requiring high fluidity and durability. The core advantage of low-viscosity, high-color-fastness water-based pigments lies in their superior physicochemical properties. Their low viscosity ensures good fluidity and dispersibility, making them easy to mix and allowing for smooth spraying, printing, or coating without excessive dilution.

[0003] However, in order to balance low viscosity and high color fastness, the design of water-based pigment formulations becomes extremely complex, and the selection of wetting and dispersing agents and other additives is very demanding, which leads to pigment flocculation, affecting not only stability but also potentially causing appearance defects such as floating color or mottling in the coating film. Therefore, this invention studies and prepares a low-viscosity, high-color-fastness water-based pigment to solve this problem. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a low viscosity, high color fastness water-based pigment and its preparation method.

[0005] The present invention proposes a technical solution to solve the above-mentioned technical problems as follows: a low-viscosity, high-color-fastness water-based pigment, comprising the following raw material components in parts by weight: 10-20 parts of organic color pigment, 6-10 parts of modifier, and 60-80 parts of water-based medium; wherein the modifier comprises vinyl polyacrylate binder and glycerol polyoxyethylene ether; and wherein the water-based medium comprises water, crosslinking agent, polyvinyl butyral, and adhesive crosslinking agent.

[0006] Preferably, the vinyl polyacrylate adhesive is obtained by copolymerizing a polymerized vinyl resin with a polyacrylate; the polymerized vinyl resin is obtained by polymerizing styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane, and vinylbenzoyloxybenzene; the fluorinated vinyl benzoate is obtained by reacting 4-(2,4-difluorophenyl)phenol with 4-vinylbenzoyl chloride; and the vinylbenzoyloxybenzene is obtained by reacting 4-vinylbenzoyl chloride with phloroglucinol.

[0007] Preferably, the adhesive crosslinking agent is prepared by reacting poly(carbonate-ether) polyol, isophorone diisocyanate and oleoyl glycolamine, and then catalytically blocking it with methylacetamide oxime.

[0008] Preferably, the crosslinking agent is trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate].

[0009] Preferably, the preparation method of the low-viscosity, high-color-fastness water-based pigment includes the following specific steps: S1. Under a nitrogen atmosphere, poly(carbonate-ether) polyol, isophorone diisocyanate and acetone are mixed in a mass ratio of 20:4~5:10~20, heated to 75~85℃, and dibutyltin dilaurate catalyst (0.001~0.002 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for 2~3 hours, cooled to 60~70℃, and oleoyl glycolamine (0.08~0.12 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for another 1~2 hours, heated to 75~85℃, and methylacetamide oxime (0.08~0.12 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for another 3~4 hours, cooled to room temperature, washed 3~5 times with deionized water, dried with anhydrous sodium sulfate, filtered and rotary evaporated, precipitated with petroleum ether and dried to obtain the adhesive crosslinking agent. S2. Under a nitrogen atmosphere, tetrahydrofuran, styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene are mixed in a mass ratio of 4~6:3~4:2:0.5~1.5:0.5~1. The mixture is heated to 70~80℃, and a tetrahydrofuran solution of benzoyl peroxide initiator with a mass fraction of 30~40% is added dropwise at a rate of 1~3 ml / min at 0.2~0.4 times the mass of styrene. The reaction is continued for 3~4 h, then heated to 90~110℃ and the reaction is continued for 2~4 h. The mixture is cooled to room temperature, precipitated with petroleum ether, filtered and washed 3~5 times with petroleum ether, and dried under vacuum at 50~70℃ to obtain a polymerized vinyl resin. S3. Under a nitrogen atmosphere, polymerized vinyl resin, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, initiator lauroyl peroxide, and deionized water are mixed in a mass ratio of 6:3.6~3.8:1.9~1.95:4.5:0.1:40~50. The mixture is heated to 55~57℃ and kept at that temperature for 2~3 hours. The temperature is then raised to 60~62℃ and stirred at 200~400 rpm for 50~70 minutes. The temperature is then raised to 65~68℃ and stirred for another 50~70 minutes. The temperature is then raised to 70~72℃ and stirred for another 50~70 minutes. The temperature is then raised to 75~77℃ and stirred for another 50~70 minutes. Finally, the mixture is dried in a forced convection oven at 80~82℃ to obtain a vinyl polyacrylate adhesive. S4. Mix vinyl polyacrylate adhesive and glycerol polyoxyethylene ether at a mass ratio of 0.04~0.08:1, heat to 80~90℃, stir evenly to obtain a modifier; mix water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral and adhesive crosslinking agent to obtain an aqueous medium; S5. By weight, mix the organic pigment, crosslinking agent and aqueous medium in a planetary ball mill and grind them with zirconia beads at a speed of 4000~5000 rpm for 3~6 hours to obtain a low viscosity and high color fastness aqueous pigment.

[0010] Preferably, in step S1 above, the preparation method of poly(carbonate-ether) polyol is as follows: under a nitrogen atmosphere, 1,4-butanediol, polytetrahydrofurandiol and the catalyst tetrabutyl titanate are mixed in a mass ratio of 3:5~5.1:0.001, heated to 88~92°C, and dimethyl carbonate of 1.6~1.8 times the mass of 1,4-butanediol is added. After the reaction is kept at this temperature for 50~70 min, the temperature is raised to 180~190°C and the reaction is continued for 1~2 h. The pressure is reduced to -0.07~-0.09 MPa and the polycondensation reaction is continued for 4~6 h. The product is then cooled and discharged to obtain poly(carbonate-ether) polyol.

[0011] Preferably, in step S2 above, the preparation method of fluorinated vinyl benzoate is as follows: under a nitrogen atmosphere, 4-(2,4-difluorophenyl)phenol, anhydrous dichloromethane, triethylamine (an acid-binding agent), and 4-dimethylaminopyridine are mixed in a molar ratio of 1:50~80:1.3~1.5:0.06, transferred to an ice bath at 0~5℃, and 4-vinylbenzoyl chloride (1.1~1.2 times the molar amount of 4-(2,4-difluorophenyl)phenol) is added dropwise at a rate of 1~3 ml / min. The mixture is heated to room temperature and reacted for 8~12 h. The mixture is washed successively with dilute hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography to obtain fluorinated vinyl benzoate.

[0012] Preferably, in step S2 above, the preparation method of phenylvinyl oligosiloxysilane is as follows: dichloromethane, phenyltrimethoxysilane and methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 40~50:15:6~6.1, heated to 40~42℃, and potassium hydroxide solution with a mass fraction of 3~4% (0.3~0.32 times the mass of phenyltrimethoxysilane) is added dropwise at a rate of 1~3 ml / min. The mixture is refluxed for 72 h, the pH is adjusted to 6.8~7.2 with acetic acid, the mixture is separated and washed 3~5 times with deionized water, and then rotary evaporated to obtain phenylvinyl oligosiloxysilane.

[0013] Preferably, in step S2 above, the method for preparing vinylbenzoyloxybenzene is as follows: under a nitrogen atmosphere, phloroglucinol and dichloromethane are mixed at a mass ratio of 1:10~15, placed in an ice bath at 0~5℃, and 1.3~1.5 times the mass of phloroglucinol triethylamine and 1.1~1.3 times the mass of phloroglucinol 4-vinylbenzoyl chloride are added dropwise at a rate of 1~3 ml / min. The reaction is maintained at this temperature for 1~2 h, then the temperature is raised to room temperature, and the reaction is continued for 6~12 h. The mixture is washed successively with hydrochloric acid and deionized water, dried with anhydrous sodium sulfate, filtered, distilled under reduced pressure, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 1:1 to obtain vinylbenzoyloxybenzene.

[0014] Preferably, in step S4 above, the mass ratio of water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral, and adhesive crosslinking agent is 4~6:1~2:1:2~4.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The low-viscosity, high-color-fastness waterborne pigment prepared by this invention includes organic color pigment, modifier, and waterborne medium. The waterborne medium includes water, additives, polyvinyl butyral, and adhesive crosslinking agent. The modifier includes vinyl polyacrylate adhesive and glycerol polyoxyethylene ether. The adhesive crosslinking agent is prepared by reacting poly(carbonate-ether) polyol, isophorone diisocyanate and oleoyl glycolamine, and then catalytically blocking it with methylacetamide oxime. The adhesive crosslinking agent can form a three-dimensional network structure in aqueous media, reduce viscosity, significantly improve the color fastness of water-based pigments, and the resulting coating film has excellent rubbing fastness. Vinyl polyacrylate adhesives are produced by copolymerizing vinyl resins with polyacrylates. The vinyl resins are produced by polymerizing styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane, and vinylbenzoyloxybenzene. The fluorinated vinyl benzoate is produced by reacting 4-(2,4-difluorophenyl)phenol with 4-vinylbenzoyl chloride. The vinylbenzoyloxybenzene is produced by reacting 4-vinylbenzoyl chloride with phloroglucinol. By using active vinyl groups as polymerization sites, low surface energy fluorine atom silicon-oxygen bonds are introduced into the polyacrylate network, which improves water resistance while maintaining low viscosity of water-based pigments, thus ensuring color fastness. Detailed Implementation

[0016] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0017] To more clearly illustrate the method provided by the present invention, the following examples will be used to describe in detail the various test methods for the low viscosity, high color fastness water-based pigments prepared in the examples and comparative examples: Viscosity: The low viscosity and high color fastness water-based pigments prepared in the examples and comparative examples were tested for viscosity in accordance with GB / T 1723.

[0018] Color fastness to rubbing: The low viscosity, high color fastness water-based pigments prepared in the examples and comparative examples were tested for color fading in accordance with GB / T3920.

[0019] Water fastness: The low viscosity, high color fastness water-based pigments prepared in the examples and comparative examples were tested for color change grade in accordance with GB / T 5713.

[0020] Example 1 In this embodiment, the component mass parts of the low viscosity, high color fastness water-based pigment are: 10 parts organic color pigment: 15-6 parts phthalocyanine blue pigment blue, 15-6 parts modifier, and 60 parts water-based medium.

[0021] The method for preparing low-viscosity, high-color-fastness water-based pigments in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,4-butanediol, polytetrahydrofurandiol, and tetrabutyl titanate catalyst were mixed in a mass ratio of 3:5:0.001, heated to 88°C, and dimethyl carbonate (1.6 times the mass of 1,4-butanediol) was added. After reacting at this temperature for 50 min, the temperature was raised to 180°C and the reaction was continued for 1 h. The pressure was then reduced to -0.07 MPa, and the polycondensation reaction was continued for 4 h. The mixture was then cooled and discharged to obtain poly(carbonate-ether) polyol. Under a nitrogen atmosphere, poly(carbonate-ether) polyol, isophorone diisocyanate, and acetone were mixed in a mass ratio of 20:4. Mix 10 parts together, heat to 75°C, add 0.001 times the mass of poly(carbonate-ether) polyol and dibutyltin dilaurate catalyst, react for 2 hours, cool to 60°C, add 0.08 times the mass of poly(carbonate-ether) polyol and oleoyl glycolamine, continue to react for 1 hour, heat to 75°C, add 0.08 times the mass of poly(carbonate-ether) polyol and methylacetamide oxime, continue to react for 3 hours, cool to room temperature, wash 3 times with deionized water, dry with anhydrous sodium sulfate, filter and rotary evaporate, precipitate with petroleum ether and dry to obtain the adhesive crosslinking agent; S2. Under a nitrogen atmosphere, 4-(2,4-difluorophenyl)phenol, anhydrous dichloromethane, triethylamine (an acid-binding agent), and 4-dimethylaminopyridine were mixed in a molar ratio of 1:50:1.3:0.06. The mixture was transferred to an ice bath at 0°C, and 4-vinylbenzoyl chloride (1.1 times the molar amount of 4-(2,4-difluorophenyl)phenol) was added dropwise at a rate of 1 ml / min. The mixture was heated to room temperature and reacted for 8 h. The mixture was washed successively with dilute hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography. Fluorinated vinyl benzoate was prepared by oxidizing dichloromethane, phenyltrimethoxysilane, and methacryloxypropyltrimethoxysilane in a mass ratio of 40:15:6. The mixture was heated to 40°C, and a 3% potassium hydroxide solution (0.3 times the mass of phenyltrimethoxysilane) was added dropwise at a rate of 1 ml / min. The mixture was refluxed for 72 h, and the pH was adjusted to 6.8 with acetic acid. The mixture was separated, washed three times with deionized water, and rotary evaporated to obtain phenylvinyl oligomeric silsesquioxane. Phloroglucinol was then reacted with... Dichloromethane was mixed in a 1:10 mass ratio and placed in an ice bath at 0°C. Triethylamine (1.3 times the mass of phloroglucinol) and 4-vinylbenzoyl chloride (1.1 times the mass of phloroglucinol) were added dropwise at a rate of 1 ml / min. The mixture was kept at this temperature for 1 h, then heated to room temperature and reacted for another 6 h. The mixture was washed successively with hydrochloric acid and deionized water, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure. The resulting product was then subjected to column chromatography with petroleum ether and ethyl acetate in a 1:1 volume ratio to obtain vinylbenzoyloxybenzene. Tetrahydrofuran, styrene, and fluorine-containing compounds were then added under a nitrogen atmosphere. Vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene were mixed in a mass ratio of 4:3:2:0.5:0.5, heated to 70°C, and a tetrahydrofuran solution of benzoyl peroxide initiator with a mass fraction of 30% was added dropwise at a rate of 1 ml / min at 0.2 times the mass of styrene. The reaction was continued for 3 h, heated to 90°C, and the reaction was continued for 2 h. The mixture was cooled to room temperature, precipitated with petroleum ether, filtered and washed three times with petroleum ether, and dried under vacuum at 50°C to obtain the polymerized vinyl resin. S3. Under a nitrogen atmosphere, polymerized vinyl resin, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, initiator lauroyl peroxide, and deionized water were mixed in a mass ratio of 6:3.6:1.9:4.5:0.1:40. The mixture was heated to 55°C and kept at that temperature for 2 hours. The temperature was then increased to 60°C and stirred at 200 rpm for 50 minutes. The temperature was then increased to 65°C and stirred for another 50 minutes. The temperature was then increased to 70°C and stirred for another 50 minutes. Finally, the mixture was dried in a forced convection oven at 80°C to obtain a vinyl polyacrylate adhesive. S4. Mix vinyl polyacrylate adhesive and glycerol polyoxyethylene ether at a mass ratio of 0.04:1, heat to 80°C, and stir evenly to obtain a modifier; mix water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral and adhesive crosslinking agent at a mass ratio of 4:1:1:2 to obtain an aqueous medium; S5. By weight, the organic pigment, crosslinking agent and aqueous medium are mixed and placed in a planetary ball mill and ground with zirconia beads at a speed of 4000 rpm for 3 hours to obtain a low viscosity and high color fastness aqueous pigment.

[0022] Example 2 In this embodiment, the component mass parts of the low viscosity, high color fastness water-based pigment are: 15 parts organic color pigment: 23 parts dioxazine pigment violet, 8 parts modifier and 70 parts water-based medium.

[0023] The method for preparing low-viscosity, high-color-fastness water-based pigments in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,4-butanediol, polytetrahydrofurandiol, and tetrabutyl titanate catalyst were mixed in a mass ratio of 3:5.05:0.001, heated to 90°C, and dimethyl carbonate (1.7 times the mass of 1,4-butanediol) was added. After reacting at this temperature for 60 min, the temperature was raised to 185°C and the reaction was continued for 1.5 h. The pressure was then reduced to -0.08 MPa, and the polycondensation reaction was continued for 5 h. The product was then cooled and discharged to obtain poly(carbonate-ether) polyol. Under a nitrogen atmosphere, poly(carbonate-ether) polyol, isophorone diisocyanate, and acetone were mixed in a mass ratio of 20:4. The mixture was prepared in a 5:15 ratio, heated to 80°C, and 0.0015 times the mass of poly(carbonate-ether) polyol was added as a catalyst, dibutyltin dilaurate. The reaction was carried out for 2.5 hours, then cooled to 65°C, and 0.1 times the mass of poly(carbonate-ether) polyol was added as oleoyl glycolamine. The reaction was continued for 1.5 hours, then heated to 80°C, and 0.1 times the mass of poly(carbonate-ether) polyol was added as methylacetamide oxime. The reaction was continued for 3.5 hours, then cooled to room temperature and washed four times with deionized water. The mixture was dried with anhydrous sodium sulfate, filtered, and rotary evaporated. The precipitate was then dried with petroleum ether to obtain the adhesive crosslinking agent. S2. Under a nitrogen atmosphere, 4-(2,4-difluorophenyl)phenol, anhydrous dichloromethane, triethylamine (an acid-binding agent), and 4-dimethylaminopyridine were mixed in a molar ratio of 1:65:1.4:0.06. The mixture was transferred to an ice bath at 3°C, and 4-vinylbenzoyl chloride (1.15 times the molar amount of 4-(2,4-difluorophenyl)phenol) was added dropwise at a rate of 2 ml / min. The mixture was then heated to room temperature and reacted for 10 h. The mixture was washed successively with dilute hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography. Fluorinated vinyl benzoate was prepared; dichloromethane, phenyltrimethoxysilane, and methacryloxypropyltrimethoxysilane were mixed in a mass ratio of 45:15:6.05, heated to 401℃, and a 3.5% potassium hydroxide solution (0.31 times the mass of phenyltrimethoxysilane) was added dropwise at a rate of 2 ml / min. The mixture was refluxed for 72 h, the pH was adjusted to 7.0 with acetic acid, the mixture was separated, washed four times with deionized water, and rotary evaporated to obtain phenylvinyl oligomeric silsesquioxane; under a nitrogen atmosphere, m-phenyltrimethoxysilane was further processed... Phenol and dichloromethane were mixed at a mass ratio of 1:13 and placed in an ice bath at 3°C. Triethylamine (1.4 times the mass of phloroglucinol) and 4-vinylbenzoyl chloride (1.2 times the mass of phloroglucinol) were added dropwise at a rate of 2 ml / min. The mixture was kept at this temperature for 1.5 h, then heated to room temperature and reacted for another 9 h. The mixture was washed successively with hydrochloric acid and deionized water, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure. The resulting product was then subjected to column chromatography with petroleum ether and ethyl acetate in a 1:1 volume ratio to obtain vinylbenzoyloxybenzene. Tetrahydrofuran, styrene, and fluorine-containing compounds were then added under a nitrogen atmosphere. Vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene were mixed in a mass ratio of 5:3.5:2:1:0.75, heated to 75°C, and a tetrahydrofuran solution of benzoyl peroxide initiator with a mass fraction of 35% was added dropwise at a rate of 2 ml / min at 0.3 times the mass of styrene. The reaction was continued for 3.5 h, heated to 100°C, and reacted for another 3 h. The mixture was cooled to room temperature, precipitated with petroleum ether, filtered and washed four times with petroleum ether, and dried under vacuum at 60°C to obtain the polymerized vinyl resin. S3. Under a nitrogen atmosphere, polymerized vinyl resin, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, initiator lauroyl peroxide, and deionized water were mixed in a mass ratio of 6:3.7:1.93:4.5:0.1:45. The mixture was heated to 56°C and kept at that temperature for 2.5 hours. The temperature was then increased to 61°C and stirred at 300 rpm for 60 minutes. The temperature was then increased to 66°C and stirred for another 60 minutes. The temperature was then increased to 71°C and stirred for another 60 minutes. Finally, the mixture was dried in a forced convection oven at 81°C to obtain a vinyl polyacrylate adhesive. S4. Mix vinyl polyacrylate adhesive and glycerol polyoxyethylene ether at a mass ratio of 0.06:1, heat to 85°C, and stir evenly to obtain a modifier; mix water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral and adhesive crosslinking agent at a mass ratio of 5:1.5:1:3 to obtain an aqueous medium; S5. By weight, the organic pigment, crosslinking agent and aqueous medium are mixed and placed in a planetary ball mill and ground with zirconia beads at a speed of 4500 rpm for 4.5 h to obtain a low viscosity and high color fastness aqueous pigment.

[0024] Example 3 In this embodiment, the component mass parts of the low viscosity, high color fastness water-based pigment are: 20 parts organic color pigment: quinacridone pigment red 122, 10 parts modifier and 80 parts water-based medium.

[0025] The method for preparing low-viscosity, high-color-fastness water-based pigments in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,4-butanediol, polytetrahydrofurandiol, and tetrabutyl titanate catalyst were mixed in a mass ratio of 3:5.1:0.001, heated to 92°C, and dimethyl carbonate (1.8 times the mass of 1,4-butanediol) was added. After reacting at this temperature for 70 min, the temperature was raised to 190°C and the reaction continued for 2 h. The pressure was then reduced to -0.09 MPa, and the polycondensation reaction continued for 6 h. The mixture was then cooled and discharged to obtain poly(carbonate-ether) polyol. Under a nitrogen atmosphere, poly(carbonate-ether) polyol, isophorone diisocyanate, and acetone were mixed in a mass ratio of 20: Mix 5:20, heat to 85℃, add 0.002 times the mass of poly(carbonate-ether) polyol and dibutyltin dilaurate catalyst, react for 3 hours, cool to 70℃, add 0.12 times the mass of poly(carbonate-ether) polyol and oleoyl glycolamine, continue to react for 2 hours, heat to 85℃, add 0.12 times the mass of poly(carbonate-ether) polyol and methylacetamide oxime, continue to react for 4 hours, cool to room temperature, wash 5 times with deionized water, dry with anhydrous sodium sulfate, filter and rotary evaporate, precipitate with petroleum ether and dry to obtain the adhesive crosslinking agent; S2. Under a nitrogen atmosphere, 4-(2,4-difluorophenyl)phenol, anhydrous dichloromethane, triethylamine (an acid-binding agent), and 4-dimethylaminopyridine were mixed in a molar ratio of 1:80:1.5:0.06. The mixture was transferred to an ice bath at 5°C, and 4-vinylbenzoyl chloride (1.2 times the molar amount of 4-(2,4-difluorophenyl)phenol) was added dropwise at a rate of 3 ml / min. The mixture was heated to room temperature and reacted for 12 h. The mixture was washed successively with dilute hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography. Fluorinated vinyl benzoate was prepared by oxidizing dichloromethane, phenyltrimethoxysilane, and methacryloxypropyltrimethoxysilane in a mass ratio of 50:15:6.1. The mixture was heated to 42°C, and a 4% potassium hydroxide solution (0.32 times the mass of phenyltrimethoxysilane) was added dropwise at a rate of 3 ml / min. The mixture was refluxed for 72 h, and the pH was adjusted to 7.2 with acetic acid. The mixture was separated, washed five times with deionized water, and rotary evaporated to obtain phenylvinyl oligomeric silsesquioxane. Under a nitrogen atmosphere, m-phenyltrimethoxysilane was further oxidized by oxidizing dichloromethane, phenyltrimethoxysilane, and methacryloxypropyltrimethoxysilane in a mass ratio of 50:15:6.1. Phenol and dichloromethane were mixed at a mass ratio of 1:15 and placed in an ice bath at 5°C. Triethylamine (1.5 times the mass of resorcinol) and 4-vinylbenzoyl chloride (1.3 times the mass of resorcinol) were added dropwise at a rate of 3 ml / min. The mixture was kept at this temperature for 2 h, then heated to room temperature and reacted for another 12 h. The mixture was washed successively with hydrochloric acid and deionized water, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure. The resulting product was then subjected to column chromatography with petroleum ether and ethyl acetate in a 1:1 volume ratio to obtain vinylbenzoyloxybenzene. Tetrahydrofuran, styrene, and... Fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene were mixed in a mass ratio of 6:4:2:1.5:1, heated to 80°C, and a tetrahydrofuran solution of benzoyl peroxide initiator with a mass fraction of 40% was added dropwise at a rate of 3 ml / min at 0.4 times the mass of styrene. The reaction was continued for 4 h, heated to 110°C, and the reaction was continued for 4 h. The mixture was cooled to room temperature, precipitated with petroleum ether, filtered and washed 5 times with petroleum ether, and dried under vacuum at 70°C to obtain the polymerized vinyl resin. S3. Under a nitrogen atmosphere, polymerized vinyl resin, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, initiator lauroyl peroxide, and deionized water were mixed in a mass ratio of 6:3.8:1.95:4.5:0.1:50. The mixture was heated to 57°C and kept at that temperature for 3 hours. The temperature was then increased to 62°C and stirred at 400 rpm for 70 minutes. The temperature was then increased to 68°C and stirred for another 70 minutes. The temperature was then increased to 72°C and stirred for another 70 minutes. Finally, the mixture was heated to 77°C and stirred for another 70 minutes. The mixture was then dried in a forced convection oven at 82°C to obtain a vinyl polyacrylate adhesive. S4. Mix vinyl polyacrylate adhesive and glycerol polyoxyethylene ether at a mass ratio of 0.08:1, heat to 90°C, and stir evenly to obtain a modifier; mix water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral and adhesive crosslinking agent at a mass ratio of 6:2:1:4 to obtain an aqueous medium; S5. By weight, the organic pigment, crosslinking agent and aqueous medium are mixed and placed in a planetary ball mill and ground with zirconia beads at a speed of 5000 rpm for 6 hours to obtain a low viscosity and high color fastness aqueous pigment.

[0026] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between this low-viscosity, high-color-fastness water-based pigment and Example 2 is that the adhesive crosslinking agent is only poly(carbonate-ether) polyol.

[0027] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between this low-viscosity, high-color-fastness water-based pigment and Example 2 is that the polymerized vinyl resin is obtained by polymerizing styrene, fluorinated vinyl benzoate, and phenyl vinyl oligomeric silsesquioxane.

[0028] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between this low-viscosity, high-color-fastness water-based pigment and Example 2 is that the polymerized vinyl resin is obtained by polymerizing styrene, phenyl vinyl oligomeric silsesquioxane, and vinylbenzoyloxybenzene.

[0029] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between this low-viscosity, high-color-fastness water-based pigment and Example 2 is that the polymerized vinyl resin is obtained by polymerizing styrene, fluorinated vinyl benzoate, and vinylbenzoyloxybenzene.

[0030] Comparative Example 5 The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between this low-viscosity, high-color-fastness water-based pigment and Example 2 is that the vinyl polyacrylate adhesive is prepared by copolymerization of styrene and polyacrylate.

[0031] Example of effect Table 1 below shows the performance test results of the low viscosity, high color fastness water-based pigments prepared in the examples and comparative examples: Table 1

[0032] As can be seen from the performance data comparison in Table 1, the low viscosity and high color fastness water-based pigment prepared by the present invention not only has low viscosity, but also has rubbing fastness and water fastness. A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 reveals that the adhesive crosslinking agent prepared by reacting poly(carbonate-ether) polyol, isophorone diisocyanate, and oleoyl glycolamine with methylacetamide oxime catalytic blocking can form a three-dimensional network structure in an aqueous medium, significantly improving the color fastness of water-based pigments while reducing viscosity, and the resulting coating film exhibits excellent rubbing fastness.

[0033] A comparison of the experimental data from Examples 1, 2, 3 and Comparative Examples 4 and 5 reveals that the vinyl resin obtained by polymerizing styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene, and then copolymerizing it with polyacrylate to obtain a vinyl polyacrylate adhesive, uses active vinyl groups as polymerization points to introduce low surface energy fluorine atoms and flexible siloxane bonds into the polyacrylate network, thereby improving water resistance while maintaining low viscosity of water-based pigments, thus ensuring color fastness.

[0034] Obviously, the above embodiments are merely examples to clearly illustrate the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.

Claims

1. A low-viscosity, high-color-fastness water-based pigment, characterized in that, The raw material components include the following parts by weight: 10-20 parts of organic color pigment, 6-10 parts of modifier, and 60-80 parts of aqueous medium; the modifier includes vinyl polyacrylate adhesive and glycerol polyoxyethylene ether; the aqueous medium includes water, crosslinking agent, polyvinyl butyral, and adhesive crosslinking agent.

2. The low-viscosity, high-color-fastness water-based pigment according to claim 1, characterized in that, The vinyl polyacrylate adhesive is prepared by copolymerization of a polymerized vinyl resin and a polyacrylate; the polymerized vinyl resin is prepared by polymerization of styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene; the fluorinated vinyl benzoate is prepared by reaction of 4-(2,4-difluorophenyl)phenol and 4-vinylbenzoyl chloride; the vinylbenzoyloxybenzene is prepared by reaction of 4-vinylbenzoyl chloride and phloroglucinol.

3. The low-viscosity, high-color-fastness water-based pigment according to claim 1, characterized in that, The adhesive crosslinking agent is prepared by reacting poly(carbonate-ether) polyol, isophorone diisocyanate and oleoyl glycolamine, followed by catalytic blocking with methylacetamide oxime.

4. The low-viscosity, high-color-fastness water-based pigment according to claim 1, characterized in that, The crosslinking agent is trimethylolpropane tri[3-(azacyclopropane-1-yl)propionate].

5. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 1, characterized in that, The specific steps include the following: S1. Under a nitrogen atmosphere, poly(carbonate-ether) polyol, isophorone diisocyanate and acetone are mixed in a mass ratio of 20:4~5:10~20, heated to 75~85℃, and dibutyltin dilaurate catalyst (0.001~0.002 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for 2~3 hours, cooled to 60~70℃, and oleoyl glycolamine (0.08~0.12 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for another 1~2 hours, heated to 75~85℃, and methylacetamide oxime (0.08~0.12 times the mass of poly(carbonate-ether) polyol) is added. The mixture is reacted for another 3~4 hours, cooled to room temperature, washed 3~5 times with deionized water, dried with anhydrous sodium sulfate, filtered and rotary evaporated, precipitated with petroleum ether and dried to obtain the adhesive crosslinking agent. S2. Under a nitrogen atmosphere, tetrahydrofuran, styrene, fluorinated vinyl benzoate, phenyl vinyl oligomeric silsesquioxane and vinylbenzoyloxybenzene are mixed in a mass ratio of 4~6:3~4:2:0.5~1.5:0.5~1. The mixture is heated to 70~80℃, and a tetrahydrofuran solution of benzoyl peroxide initiator with a mass fraction of 30~40% is added dropwise at a rate of 1~3 ml / min at 0.2~0.4 times the mass of styrene. The reaction is continued for 3~4 h, then heated to 90~110℃ and the reaction is continued for 2~4 h. The mixture is cooled to room temperature, precipitated with petroleum ether, filtered and washed 3~5 times with petroleum ether, and dried under vacuum at 50~70℃ to obtain a polymerized vinyl resin. S3. Under a nitrogen atmosphere, polymerized vinyl resin, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, initiator lauroyl peroxide, and deionized water are mixed in a mass ratio of 6:3.6~3.8:1.9~1.95:4.5:0.1:40~50. The mixture is heated to 55~57℃ and kept at that temperature for 2~3 hours. The temperature is then raised to 60~62℃ and stirred at 200~400 rpm for 50~70 minutes. The temperature is then raised to 65~68℃ and stirred for another 50~70 minutes. The temperature is then raised to 70~72℃ and stirred for another 50~70 minutes. The temperature is then raised to 75~77℃ and stirred for another 50~70 minutes. Finally, the mixture is dried in a forced convection oven at 80~82℃ to obtain a vinyl polyacrylate adhesive. S4. Mix vinyl polyacrylate adhesive and glycerol polyoxyethylene ether at a mass ratio of 0.04~0.08:1, heat to 80~90℃, stir evenly to obtain a modifier; mix water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral and adhesive crosslinking agent to obtain an aqueous medium; S5. By weight, mix the organic pigment, crosslinking agent and aqueous medium in a planetary ball mill and grind them with zirconia beads at a speed of 4000~5000 rpm for 3~6 hours to obtain a low viscosity and high color fastness aqueous pigment.

6. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 5, characterized in that, In step S1 above, the preparation method of poly(carbonate-ether) polyol is as follows: under a nitrogen atmosphere, 1,4-butanediol, polytetrahydrofurandiol and the catalyst tetrabutyl titanate are mixed in a mass ratio of 3:5~5.1:0.001, heated to 88~92℃, and dimethyl carbonate of 1.6~1.8 times the mass of 1,4-butanediol is added. After the reaction is kept at this temperature for 50~70 min, the temperature is raised to 180~190℃ and the reaction is continued for 1~2 h. The pressure is reduced to -0.07~-0.09 MPa and the polycondensation reaction is continued for 4~6 h. The product is then cooled and discharged to obtain poly(carbonate-ether) polyol.

7. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 5, characterized in that, In step S2 above, the preparation method of fluorinated vinyl benzoate is as follows: Under a nitrogen atmosphere, 4-(2,4-difluorophenyl)phenol, anhydrous dichloromethane, triethylamine (an acid-binding agent), and 4-dimethylaminopyridine are mixed in a molar ratio of 1:50~80:1.3~1.5:0.06, transferred to an ice bath at 0~5℃, and 4-vinylbenzoyl chloride (1.1~1.2 times the molar amount of 4-(2,4-difluorophenyl)phenol) is added dropwise at a rate of 1~3 ml / min. The mixture is heated to room temperature and reacted for 8~12 h. The mixture is washed successively with dilute hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography to obtain fluorinated vinyl benzoate.

8. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 5, characterized in that, In step S2 above, the preparation method of phenylvinyl oligosilsesquioxane is as follows: dichloromethane, phenyltrimethoxysilane and methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 40~50:15:6~6.1, heated to 40~42℃, and potassium hydroxide solution with a mass fraction of 3~4% (0.3~0.32 times the mass of phenyltrimethoxysilane) is added dropwise at a rate of 1~3 ml / min. The mixture is refluxed for 72 h, the pH is adjusted to 6.8~7.2 with acetic acid, the mixture is separated and washed 3~5 times with deionized water, and then rotary evaporated to obtain phenylvinyl oligosilsesquioxane.

9. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 5, characterized in that, In step S2 above, the method for preparing vinylbenzoyloxybenzene is as follows: Under a nitrogen atmosphere, phloroglucinol and dichloromethane are mixed at a mass ratio of 1:10~15 and placed in an ice bath at 0~5℃. Triethylamine and 4-vinylbenzoyl chloride, which are 1.3~1.5 times the mass of phloroglucinol, are added dropwise at a rate of 1~3 ml / min. The reaction is maintained at this temperature for 1~2 h, then the temperature is raised to room temperature and the reaction is continued for 6~12 h. The mixture is washed successively with hydrochloric acid and deionized water, dried with anhydrous sodium sulfate, filtered, distilled under reduced pressure, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 1:1 to obtain vinylbenzoyloxybenzene.

10. The method for preparing a low-viscosity, high-color-fastness water-based pigment according to claim 5, characterized in that, In step S4 above, the mass ratio of water, crosslinking agent trimethylolpropane tris[3-(azacyclopropane-1-yl)propionate], polyvinyl butyral, and adhesive crosslinking agent is 4~6:1~2:1:2~4.

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