A modified organic black dye and a method for preparing the same
By chemically bonding organic black dyes with polymer microspheres, spherical modified dyes were prepared, solving the problems of irregular dye morphology and uneven dyeing in existing technologies. This achieved dye flowability and particle size uniformity, expanding the application range.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHENZHEN KINGFOCUS BIOMDICAL ENG CO LTD
- Filing Date
- 2026-04-01
- Publication Date
- 2026-06-30
AI Technical Summary
Existing organic black dyes suffer from problems such as unstable color development, insufficient color expression, uneven dyeing effect, and narrow application range due to the limitations of the conjugated system of molecular structure. In addition, they have irregular particle morphology, poor flowability, and difficulty in controlling particle size.
Organic black dyes are chemically bonded to polymer microspheres, and spherical modified organic black dyes are prepared by soap-free emulsion polymerization, which improves the dye morphology and enhances the dispersion uniformity.
The prepared spherical dye improves the dye's flowability and dispersion uniformity, with uniform particle size, making it suitable for applications with strict particle size requirements. It also exhibits excellent light reflection performance and color stability.
Smart Images
Figure CN122302595A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of dye modification technology, specifically to a modified organic black dye and its preparation method, and more particularly to a method for forming spherical dyes by chemically bonding organic black dyes with polymer microspheres. Background Technology
[0002] Single organic black dyes, limited by their conjugated molecular structure, not only suffer from unstable color development but also exhibit shortcomings in practical applications due to their simple structure, such as insufficient color expression, uneven dyeing effects, and a narrow range of applications. Therefore, it is necessary to modify existing black dyes to improve their overall performance.
[0003] On the other hand, in fields such as laser printing, cosmetics, and liquid crystal displays, the particle morphology, particle size uniformity, dispersion stability, and compatibility with the substrate of dyes have a significant impact on the final application results. In existing technologies, dyes are mostly irregular in shape, have poor flowability, uneven color development, and are difficult to precisely control in particle size. Therefore, there is an urgent need to provide a modification method that can improve dye morphology, enhance dyeing uniformity, and expand the range of applications. Summary of the Invention
[0004] This invention provides a modified organic black dye and its preparation method to solve the problems of poor dyeing effect and narrow application range of organic black dyes in the prior art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a modified organic black dye includes the following steps: (1) The organic black dye and the linker are chemically modified to obtain a modified black dye; (2) Polymer microspheres were prepared by soap-free emulsion polymerization; (3) The modified black dye obtained in step (1) is chemically bonded with the polymer microspheres obtained in step (2) to obtain spherical modified organic black dye.
[0006] Furthermore, the linker is selected from chlorohexanoic acid, bromohexanoic acid, and iodohexanoic acid, preferably 6-bromohexanoic acid.
[0007] Further, step (1) includes: reacting the linker with N-hydroxysuccinimide in the presence of a condensing agent to obtain an active ester; and then reacting the organic black dye with the active ester to obtain a modified black dye.
[0008] Preferably, the condensing agent is N,N'-dicyclohexylcarbodiimide.
[0009] Preferably, the organic black dye is Disperse Black 3, Disperse Black 6, or Disperse Black 7, with Disperse Black 3 being the most preferred.
[0010] The structure of Dispersed Black 3 is as follows (1): (1).
[0011] The structure of the dispersed black 6 is as follows (2): (2).
[0012] The structure of Dispersed Black 7 is as follows (3): (3).
[0013] Preferably, the reaction between the organic black dye and the reactive ester specifically involves reacting the organic black dye and the reactive ester in acetone at 4-8°C for 6-10 hours.
[0014] Further, step (2) includes: adding sodium chloride and aminostyrene monomer to deionized water, ultrasonically dispersing them, adding an initiator dropwise under nitrogen protection, and obtaining polymer microspheres through soap-free emulsion polymerization.
[0015] Preferably, the initiator is potassium persulfate or sodium persulfate, with potassium persulfate being more preferred.
[0016] Further, in step (3), the polymer microsphere dispersion is mixed with the modified black dye solution, the pH is adjusted to 8-11, and after the reaction, the mixture is separated, washed, and dried to obtain the modified organic black dye. Preferably, the pH is 9.
[0017] The polymer microsphere dispersion is an aqueous solution of polymer microspheres with a mass content of 8-12%; the modified black dye solution is an acetone solution of modified black dye with a mass content of 1-2%.
[0018] The present invention also provides a modified organic black dye prepared by the above method, wherein the dye is spherical particles with a particle size of 1-10 μm.
[0019] The present invention also provides the application of the modified organic black dye in laser printing toner, cosmetics, liquid crystal displays or medical testing.
[0020] The preparation method of this invention combines organic black dye with polymer microspheres through chemical bonds to form spherical dyes, thereby improving the dye morphology and enhancing its flowability and dispersion uniformity. Furthermore, the polymer microspheres prepared using soap-free emulsion polymerization technology in this invention exhibit controllable particle size and good monodispersity, resulting in uniform final dye particle size, making them suitable for applications with strict particle size requirements.
[0021] The spherical black dye prepared by this invention has excellent light reflection properties, spreadability and skin compatibility in cosmetics; in laser printing toner, it can achieve uniform inkjet printing, fine texture and stable and long-lasting color.
[0022] The preparation method of the present invention has mild reaction conditions, simple post-processing, and the obtained product has high purity, making it suitable for industrial production. Attached Figure Description
[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0024] Figure 1 This is a transmission electron microscope (TEM) image of the modified organic black dye of Example 1 of the present invention.
[0025] Figure 2 The images show the dyeing effect on gauze using the modified organic black dye of Example 1 compared to existing iron oxide dyes, sulfur black dyes, and carbon black dyes. Detailed Implementation
[0026] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0027] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.
[0028] Example 1 The preparation method of the modified organic black dye in this embodiment includes the following steps: (1) Preparation of NHS-bromohexanoate Dissolve 0.4 g of 6-bromohexanoic acid in 20 mL of ethylene glycol dimethyl ether and 2 mL of dimethylformamide, then add 0.23 g of N-hydroxysuccinimide (NHS). Dissolve 0.61 g of N,N'-dicyclohexylcarbodiimide (DCC) in 5 mL of ethylene glycol dimethyl ether and then add it to the above mixture. React at 6 °C for 16 h. The reaction formula is as follows: .
[0029] After the reaction, the precipitate N,N'-dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation at 55 °C. The concentrate was dissolved in dichloromethane and transferred to a separatory funnel, then washed three times with 1 mol / L NaOH / NaHCO3 solution and four times with pure water. 20 g of magnesium sulfate was added to the dichloromethane phase and stirred for 30 min. After filtration, the filtrate was removed by rotary evaporation at 55 °C to obtain an oily substance. The oily substance was dispersed in petroleum ether, precipitating a powdery solid. The precipitate was centrifuged (8000 r / min, 2 min), and dried under vacuum for 24 h to obtain NHS-bromohexanoate.
[0030] (2) Preparation of modified Disperse Black 3 Dissolve 0.6 g of Dispersible Black 3 in acetone, sonicate for 10 min, add 0.65 g of NHS-bromohexanoate, and react at 6°C for 8 h. The reaction formula is as follows: .
[0031] The reaction solution was rotary evaporated at 30°C until no acetone was detected. Pure water was added to precipitate the solid, which was then centrifuged, washed, and vacuum dried to obtain modified disperse black 3.
[0032] (3) Preparation of polymer microspheres Take 0.03 g of sodium chloride and 5 g of aminostyrene monomer, add them to deionized water, and ultrasonically disperse until homogeneous. After purging with nitrogen to remove oxygen, slowly add 1 mL of potassium persulfate aqueous solution (0.001 g / mL). After the addition is complete, sonicate under a nitrogen atmosphere for 30 min, then heat to 70℃ and polymerize at a constant temperature under a nitrogen atmosphere for 10 h to generate polymer microspheres. The reaction formula is as follows: .
[0033] After the reaction was completed, the obtained polymer microspheres were repeatedly centrifuged and washed 5 times with deionized water, and then redispersed in deionized water to prepare a 10% (w / w) polymer microsphere aqueous solution.
[0034] (4) Preparation of modified organic black dyes Take 7 mL of the above-mentioned 10% (w / w) polymer microsphere aqueous solution, sonicate for 30 min, and then add 50 mL of a 1.5% (w / w) modified dispersion black 3-acetone solution dropwise while stirring. Adjust the pH to 9 with 1 mol / L NaOH and react at room temperature for 10 h to generate a modified organic black dye. The reaction formula is as follows: .
[0035] After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with pure water, filtered, washed five times with water, and dried under vacuum to obtain the modified organic black dye.
[0036] The transmission electron microscope (TEM) image of the modified organic black dye in this embodiment is as follows: Figure 1 As shown.
[0037] The modified organic black dye of this embodiment, along with existing iron oxide dyes, sulfur black dyes, and carbon black dyes, were diluted to a mass concentration of 0.5% and then used for gauze dyeing. The gauze dyeing effect was as follows: Figure 2 As shown, a is the gauze dyed with the modified organic black dye in this embodiment, b is the gauze dyed with iron oxide dye, c is the gauze dyed with sulfur black dye, and d is the gauze dyed with carbon black dye.
[0038] Example 2 The preparation method of the modified organic black dye in this embodiment includes the following steps: (1) Preparation of NHS-bromohexanoate Dissolve 0.4 g of 6-bromohexanoic acid in 20 mL of ethylene glycol dimethyl ether and 2 mL of dimethylformamide, then add 0.23 g of N-hydroxysuccinimide (NHS). Dissolve 0.61 g of N,N'-dicyclohexylcarbodiimide (DCC) in 5 mL of ethylene glycol dimethyl ether and then add it to the above mixture. React at 8°C for 15 h.
[0039] After the reaction, the precipitate N,N'-dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation at 55 °C. The concentrate was dissolved in dichloromethane and transferred to a separatory funnel, then washed three times with 1 mol / L NaOH / NaHCO3 solution and four times with pure water. 20 g of magnesium sulfate was added to the dichloromethane phase and stirred for 30 min. After filtration, the filtrate was removed by rotary evaporation at 55 °C to obtain an oily substance. The oily substance was dispersed in petroleum ether, precipitating a powdery solid. The precipitate was centrifuged (8000 r / min, 2 min), and dried under vacuum for 24 h to obtain NHS-bromohexanoate.
[0040] (2) Preparation of modified Disperse Black 3 Dissolve 0.6g of Disperse Black 3 in acetone, sonicate for 10 min, add 0.65g of NHS-bromohexanoate, and react at 4℃ for 10 h.
[0041] The reaction solution was rotary evaporated at 30°C until no acetone was detected. Pure water was added to precipitate the solid, which was then centrifuged, washed, and vacuum dried to obtain modified disperse black 3.
[0042] (3) Preparation of polymer microspheres Take 0.03g of sodium chloride and 5g of aminostyrene monomer, add them to deionized water and ultrasonically disperse until homogeneous. After purging with nitrogen to remove oxygen, slowly add 1mL of potassium persulfate aqueous solution (0.001g / mL). After the addition is complete, sonicate under nitrogen atmosphere for 30 min, raise the temperature to 70℃ and polymerize at a constant temperature under nitrogen atmosphere for 10 h to generate polymer microspheres.
[0043] After the reaction was completed, the obtained polymer microspheres were repeatedly centrifuged and washed 5 times with deionized water, and then redispersed in deionized water to prepare an 8% (w / w) polymer microsphere aqueous solution.
[0044] (4) Preparation of modified organic black dyes Take 7 mL of the above-mentioned 8% (w / w) polymer microsphere aqueous solution, sonicate for 30 min, and add 50 mL of 1% (w / w) modified dispersible black 3-acetone solution while stirring. Adjust the pH to 8 with 1 mol / L NaOH and react at room temperature for 10 h to generate modified organic black dye.
[0045] After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with pure water, filtered, washed five times with water, and dried under vacuum to obtain the modified organic black dye.
[0046] Example 3 The preparation method of the modified organic black dye in this embodiment includes the following steps: (1) Preparation of NHS-bromohexanoate Dissolve 0.4 g of 6-bromohexanoic acid in 20 mL of ethylene glycol dimethyl ether and 2 mL of dimethylformamide, then add 0.23 g of N-hydroxysuccinimide (NHS). Dissolve 0.61 g of N,N'-dicyclohexylcarbodiimide (DCC) in 5 mL of ethylene glycol dimethyl ether and then add it to the above mixture. React at 4 °C for 20 h.
[0047] After the reaction, the precipitate N,N'-dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation at 55 °C. The concentrate was dissolved in dichloromethane and transferred to a separatory funnel, then washed three times with 1 mol / L NaOH / NaHCO3 solution and four times with pure water. 20 g of magnesium sulfate was added to the dichloromethane phase and stirred for 30 min. After filtration, the filtrate was removed by rotary evaporation at 55 °C to obtain an oily substance. The oily substance was dispersed in petroleum ether, precipitating a powdery solid. The precipitate was centrifuged (8000 r / min, 2 min), and dried under vacuum for 24 h to obtain NHS-bromohexanoate.
[0048] (2) Preparation of modified Disperse Black 3 Dissolve 0.6g of Disperse Black 3 in acetone, sonicate for 10 min, add 0.65g of NHS-bromohexanoate, and react at 8°C for 6 h.
[0049] The reaction solution was rotary evaporated at 30°C until no acetone was detected. Pure water was added to precipitate the solid, which was then centrifuged, washed, and vacuum dried to obtain modified disperse black 3.
[0050] (3) Preparation of polymer microspheres Take 0.03g of sodium chloride and 5g of aminostyrene monomer, add them to deionized water and ultrasonically disperse until homogeneous. After purging with nitrogen to remove oxygen, slowly add 1mL of sodium persulfate aqueous solution (0.001g / mL). After the addition is complete, sonicate under nitrogen atmosphere for 30 min, raise the temperature to 70℃ and polymerize at a constant temperature under nitrogen atmosphere for 10 h to generate polymer microspheres.
[0051] After the reaction was completed, the obtained polymer microspheres were repeatedly centrifuged and washed 5 times with deionized water, and then redispersed in deionized water to prepare a polymer microsphere aqueous solution with a mass concentration of 12%.
[0052] (4) Preparation of modified organic black dyes Take 7 mL of the above-mentioned 12% (w / w) polymer microsphere aqueous solution, sonicate for 30 min, and add 50 mL of 1.5% (w / w) modified dispersible black 3-acetone solution dropwise while stirring. Adjust the pH to 11 with 1 mol / L NaOH and react at room temperature for 10 h to generate modified organic black dye.
[0053] After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with pure water, filtered, washed five times with water, and dried under vacuum to obtain the modified organic black dye.
[0054] Example 4 The preparation method of the modified organic black dye in this embodiment includes the following steps: (1) Preparation of modified Disperse Black 6 Dissolve 0.56 g of Disperse Black 6 in acetone, sonicate for 10 min, add 0.65 g of NHS-bromohexanoate prepared according to Example 1, and react at 6 °C for 8 h.
[0055] The reaction solution was rotary evaporated at 30°C until no acetone was detected. Pure water was added to precipitate the solid, which was then centrifuged, washed, and dried under vacuum to obtain modified disperse black 6.
[0056] (2) Preparation of polymer microspheres Take 0.03g of sodium chloride and 5g of aminostyrene monomer, add them to deionized water and ultrasonically disperse until homogeneous. After purging with nitrogen to remove oxygen, slowly add 1mL of potassium persulfate aqueous solution (0.001g / mL). After the addition is complete, sonicate under nitrogen atmosphere for 30 min, raise the temperature to 70℃ and polymerize at a constant temperature under nitrogen atmosphere for 10 h to generate polymer microspheres.
[0057] After the reaction was completed, the obtained polymer microspheres were repeatedly centrifuged and washed 5 times with deionized water, and then redispersed in deionized water to prepare a 10% (w / w) polymer microsphere aqueous solution.
[0058] (3) Preparation of modified organic black dyes Take 7 mL of the above-mentioned 10% (w / w) polymer microsphere aqueous solution, sonicate for 30 min, and add 50 mL of 1.5% (w / w) modified dispersible black 6-acetone solution while stirring. Adjust the pH to 9 with 1 mol / L NaOH and react at room temperature for 10 h to generate modified organic black dye.
[0059] After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with pure water, filtered, washed five times with water, and dried under vacuum to obtain the modified organic black dye.
[0060] Example 5 The preparation method of the modified organic black dye in this embodiment includes the following steps: (1) Preparation of modified Disperse Black 7 Dissolve 0.63 g of Disperse Black 7 in acetone, sonicate for 10 min, add 0.65 g of NHS-bromohexanoate prepared according to Example 1, and react at 6°C for 8 h.
[0061] The reaction solution was rotary evaporated at 30°C until no acetone was detected. Pure water was added to precipitate the solid, which was then centrifuged, washed, and dried under vacuum to obtain modified disperse black 7.
[0062] (2) Preparation of polymer microspheres Take 0.03g of sodium chloride and 5g of aminostyrene monomer, add them to deionized water and ultrasonically disperse until homogeneous. After purging with nitrogen to remove oxygen, slowly add 1mL of potassium persulfate aqueous solution (0.001g / mL). After the addition is complete, sonicate under nitrogen atmosphere for 30 min, raise the temperature to 70℃ and polymerize at a constant temperature under nitrogen atmosphere for 10 h to generate polymer microspheres.
[0063] After the reaction was completed, the obtained polymer microspheres were repeatedly centrifuged and washed 5 times with deionized water, and then redispersed in deionized water to prepare a 10% (w / w) polymer microsphere aqueous solution.
[0064] (3) Preparation of modified organic black dyes Take 7 mL of the above-mentioned 10% (w / w) polymer microsphere aqueous solution, sonicate for 30 min, and add 50 mL of 1.5% (w / w) modified dispersible black 7-acetone solution while stirring. Adjust the pH to 9 with 1 mol / L NaOH and react at room temperature for 10 h to generate modified organic black dye.
[0065] After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with pure water, filtered, washed five times with water, and dried under vacuum to obtain the modified organic black dye.
[0066] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing a modified organic black dye, characterized in that, Includes the following steps: (1) The linker is reacted with N-hydroxysuccinimide in the presence of a condensing agent to obtain an active ester; then an organic black dye is reacted with the active ester to obtain a modified black dye; the linker is selected from one of chlorohexanoic acid, bromohexanoic acid, and iodohexanoic acid. (2) Polymer microspheres were prepared by soap-free emulsion polymerization; (3) The modified black dye obtained in step (1) is chemically bonded with the polymer microspheres obtained in step (2) to obtain spherical modified organic black dye.
2. The method for preparing the modified organic black dye according to claim 1, characterized in that, The condensing agent is N,N'-dicyclohexylcarbodiimide.
3. The method for preparing the modified organic black dye according to claim 1, characterized in that, The organic black dye is Disperse Black 3, Disperse Black 6, or Disperse Black 7.
4. The method for preparing the modified organic black dye according to claim 1, characterized in that, The reaction between the organic black dye and the reactive ester is specifically carried out by reacting the organic black dye and the reactive ester in acetone at 4-8°C for 6-10 hours.
5. The method for preparing the modified organic black dye according to claim 1, characterized in that, Step (2) includes: adding sodium chloride and aminostyrene monomer to deionized water, ultrasonically dispersing them, adding an initiator dropwise under nitrogen protection, and obtaining polymer microspheres through soap-free emulsion polymerization.
6. The method for preparing the modified organic black dye according to claim 5, characterized in that, The initiator is potassium persulfate or sodium persulfate.
7. The method for preparing the modified organic black dye according to claim 1, characterized in that, In step (3), the polymer microsphere dispersion is mixed with the modified black dye solution, the pH is adjusted to 8-11, and after the reaction, the mixture is separated, washed, and dried to obtain the modified organic black dye.
8. The method for preparing the modified organic black dye according to claim 7, characterized in that, The polymer microsphere dispersion is an aqueous solution of polymer microspheres with a mass content of 8-12%; the modified black dye solution is an acetone solution of modified black dye with a mass content of 1-2%.
9. A modified organic black dye obtained by the preparation method according to any one of claims 1-9, characterized in that, The dye is in the form of spherical particles with a particle size of 1-10 μm.
10. The application of the modified organic black dye according to claim 9 in laser printing toner, cosmetics, liquid crystal displays, or medical testing.