Self-emulsifying dispersion, method for preparing the same, and use thereof

Abstract

This invention discloses a self-emulsifying dispersion, its preparation method, and its applications, relating to the field of dispersion technology. A self-emulsifying dispersion comprises: dye resin particles and water; wherein the dye resin particles include solvent dye, resin, and alkali, the acid value of the resin is 70~300 mg·KOH / g, and the mass ratio of solvent dye to resin is (1~5):1. The dispersion of this invention does not require the addition of emulsifiers, effectively improving the water resistance and migration problems of emulsifiers. Simultaneously, the increased dye coating capacity solves the problem of insufficient color density in high-speed printing of single-channel inkjet printers. Furthermore, resin coating of the dye improves the lightfastness of the dye, resulting in good color fastness and printing quality, showing promising application prospects in digital inkjet, digital printing, and digital printing fields.

Description

Technical Field

[0001] This invention relates to the field of dispersion technology, and in particular to a self-emulsifying dispersion, its preparation method, and its application. Background Technology

[0002] This invention relates to the field of ink technology, specifically to a self-emulsifying dispersion and its preparation method and application, aiming to solve the problems faced by existing dye inks, including insufficient color concentration in single-channel inkjet printers during high-speed printing, and the application bottleneck of poor water / light resistance in outdoor environments. It is applicable to digital inkjet, digital printing, digital printing and other fields.

[0003] Traditional scanning inkjet printers require 4-8 repeated inkjet prints at the same location to improve color density and resolution. This not only consumes a large amount of ink but also requires significant heat for drying, resulting in low production efficiency, high ink consumption, and high energy consumption, limiting their large-scale application. Furthermore, while the dyes commonly used in inks offer vibrant colors and good water solubility, they have poor water and light resistance, easily smudging and migrating when exposed to water, and fading with prolonged outdoor exposure, further limiting outdoor applications. Therefore, even though water-based dye inkjet technology is non-toxic and environmentally friendly, it cannot be widely adopted due to these multiple problems.

[0004] To improve printing efficiency, the industry has developed single-scan (single-channel) printers, where each ink dot is ejected only once, significantly reducing ink volume and printing time. Conversely, this requires a significant increase in ink density to ensure print quality. While this device, equipped with high-density ink, solves the efficiency, cost, and energy consumption problems of traditional models, it does not address the core defects of dyes, such as poor water and lightfastness, and still cannot overcome the limitations of outdoor applications.

[0005] The prior art discloses a method of dissolving resin and dye in a solvent and then dispersing and emulsifying them in water with the aid of an emulsifier to prepare a resin-coated high-concentration dye dispersion, which can meet the high color concentration requirements of high-speed inkjet printing. However, it has obvious limitations: the emulsifier is easily desorbed by the ambient temperature and ink additives, which reduces the stability of the dispersion; and the emulsifier is hydrophilic, which leads to a decrease in water resistance and cannot meet the needs of emerging scenarios such as outdoor use.

[0006] In summary, existing dye ink technologies suffer from limitations in application scenarios (poor water and light resistance), high costs, and high energy consumption, failing to meet market demands for efficient, environmentally friendly, energy-saving, and low-cost inks. Therefore, developing a self-emulsifying dispersion of resin-coated high-concentration dyes that exhibits uniform aqueous dispersion, excellent water resistance, stability under light, and meets environmental protection, non-toxicity, high efficiency, waste reduction, and energy-saving requirements, without the addition of emulsifiers, has become a pressing technical challenge in this field. Summary of the Invention

[0007] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a self-emulsifying dispersion.

[0008] The present invention also provides a method for preparing the above-mentioned self-emulsifying dispersion.

[0009] The present invention also provides applications of the above-described self-emulsifying dispersion.

[0010] The present invention also provides an ink comprising the above-described self-emulsifying dispersion.

[0011] A self-emulsifying dispersion according to a first aspect of the present invention comprises: dye resin particles and water; The dye resin particles include solvent dyes, resins, and alkalis; The acid value of the resin is 70~300 mg KOH / g; The mass ratio of the solvent dye to the resin is (1~5):1.

[0012] The dispersion according to embodiments of the present invention has at least the following beneficial effects: Eliminating the need for emulsifiers reduces functional and water resistance degradation caused by emulsifiers, saving costs. The resin's acid value is neutralized by alkali to form a water-dissociable salt. The electrostatic repulsion generated by the dissociation of this salt controls the stability of the dye resin particles in water, preventing desorption and inactivation due to ambient temperature and ink additives. Solvent solubilization of the dye allows for resin coating of high-concentration dyes, forming a stable dye resin particle dispersion. High-concentration ink reduces ink consumption, addressing cost and energy consumption issues. Furthermore, resin coating of the dye effectively improves lightfastness, water resistance, and resistance to smudging and migration, while also providing good color fastness and print quality, making it a promising application in digital inkjet, digital printing, and digital printing industries.

[0013] According to some embodiments of the present invention, the self-emulsifying dispersion does not contain an emulsifier. Exemplarily, the emulsifier may be selected from anionic emulsifiers, such as sulfate esters, sulfonates, etc.; cationic emulsifiers, such as quaternary ammonium salts, imidazoline salts, etc.; and nonionic emulsifiers, such as polyoxyethylene sorbitan fatty acid esters, etc.

[0014] According to some embodiments of the present invention, the pH of the self-emulsifying dispersion is 8 to 10. For example, it can be any value or a range between 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.

[0015] According to some embodiments of the present invention, the solid content of the self-emulsifying dispersion is 30% to 50%, for example, it can be any value or a range between any two of 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, or 49%.

[0016] According to some embodiments of the present invention, the solvent dye accounts for no less than 50 wt% of the mass percentage of the dye resin particles. The mass of "dye resin particles" refers to the total mass of the solvent dye, resin, and alkali in the particles. For example, it can be any value or a range between any two of the following: 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, or 95 wt%. If the solvent dye content is less than 50 wt%, it will result in a low solvent dye content and a high resin ratio, which will lead to masking of dye color development and insufficient color concentration of the dispersion, which is not conducive to applications such as digital inkjet. If the solvent dye content is too high, the resin will not be able to completely encapsulate the dye, and the stability, water resistance and migration resistance of the dispersion will decrease.

[0017] According to some embodiments of the present invention, the solvent dye accounts for 20% to 30% of the mass percentage of the self-emulsifying dispersion, for example, any value or a range between 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, and 29%.

[0018] According to some embodiments of the present invention, the solvent dye includes, but is not limited to, at least one of solvent dye yellow, solvent dye orange, solvent dye red, solvent dye purple, solvent dye blue, solvent dye green, solvent dye brown, and solvent dye black.

[0019] According to some embodiments of the present invention, the solvent dye yellow includes, but is not limited to, at least one of solvent dye yellow 1, 2, 3, 5, 12, 14, 16, 18, 19, 21, 33, 34, 43, 44, 56, 72, 77, 82, 93, 98, 114, 145, 163, 167, 176, 185, and 189.

[0020] According to some embodiments of the present invention, the solvent dye orange includes, but is not limited to, at least one of solvent dye orange 2, 3, 7, 20, 45, 54, 56, 60, 62, 63, 86, 99, and 107.

[0021] According to some embodiments of the present invention, the solvent dye red includes, but is not limited to, at least one of the following solvent dye reds: 1, 8, 23, 24, 25, 26, 27, 30, 32, 41, 49, 52, 79, 89, 102, 111, 119, 122, 132, 135, 146, 149, 160, 164, 168, 169, 172, 179, 195, 196, 197, 207, 218, 229, and 242.

[0022] According to some embodiments of the present invention, the solvent dye violet includes, but is not limited to, at least one of solvent dye violets 8, 9, 11, 13, 14, 26, 28, 31, 36, 37, 38, 49, and 59.

[0023] According to some embodiments of the present invention, the solvent dye blue includes, but is not limited to, at least one of solvent dye blues 4, 5, 6, 35, 36, 38, 45, 58, 59, 70, 78, 97, 101, 104, and 122.

[0024] According to some embodiments of the present invention, the solvent dye green includes, but is not limited to, at least one of solvent dye green 1, 3, 5, 20, and 28.

[0025] According to some embodiments of the present invention, the solvent dye brown includes, but is not limited to, at least one of solvent dye brown 5, 20, 41, 43, and 53.

[0026] According to some embodiments of the present invention, the solvent dye black includes, but is not limited to, at least one of solvent dye black 3, 5, 27, 28, 29, and 34.

[0027] According to some embodiments of the present invention, the resin includes, but is not limited to, at least one of acrylate resin, polyurethane resin, styrene-acrylic resin, rosin resin (rosin esterification polymerized resin), maleic rosin resin (resin polymerized by esterification reaction of maleic acid (anhydride) and rosin), and styrene-maleic anhydride resin.

[0028] According to some embodiments of the present invention, the mass ratio of the solvent dye to the resin is (1-5):1. For example: It could be 1: 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2: 1, 2.1: 1, 2.2: 1, 2.3: 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1, 3: 1, 3.1: 1, 3.2: 1, 3.3: 1, 3.4: 1, 3.5: 1, 3.6: 1, 3.7: 1, 3.8: 1, 3.9: 1, 4: 1, 4.1: 1, 4.2: 1, 4.3: 1, 4.4: 1, 4.5: 1, 4.6: 1, 4.7: 1, 4.8: 1, 4.9: 1 or 5: 1, or a range of values ​​between any two.

[0029] According to some embodiments of the present invention, the acid value of the resin is 70-300 mg KOH / g; preferably 100-250 mg KOH / g. For example, the acid value can be any value or a range between any two of 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300. If the acid value of the resin is too low, sufficient base dissociation cannot be generated, and the stability of the dispersion will deteriorate; if the acid value of the resin is too high (too hydrophilic), the affinity of the resin for the dye deteriorates, the dye is easily precipitated, and the water resistance of the resin also deteriorates.

[0030] According to some embodiments of the present invention, the alkali agent includes at least one selected from dimethylethanolamine (DMEA), 2-amino-2-methyl-1-propanol (AMP-95), triethanolamine, diethanolamine, monoethanolamine, ethylenediamine, triethylenediamine, tetramethyltriethylenediamine, tetramethylethylenediamine, hexamethylenetetramine, N,N-dimethylbenzylamine, and pyridine. The alkali agent is used to salify the resin, neutralize the resin acid value, and adjust the pH of the dispersion.

[0031] According to some embodiments of the present invention, the amount of alkali agent added is calculated as follows: Alkali addition amount = [acid value] Resin weight Alkali equivalent Neutralization / 56100; Wherein, the base equivalent is equal to [base molecular weight] / [number of bases]. For example, triethanolamine has 1 base, so the base equivalent is equal to the molecular weight of triethanolamine; monoethanolamine has 1 base, so the base equivalent is equal to the molecular weight of monoethanolamine. The alkali neutralizes with the resin to form a water-soluble salt. Further, the alkali is added to a neutralization degree of 70% to 100% (i.e., the equivalent of the alkali is 70% to 100% of all acidic groups on the resin), for example, any value or a range between 70%, 75%, 80%, 85%, 90%, 95%, and 100%.

[0032] Preferably, the mass ratio of the alkali agent to the resin is 1:1.5 to 10, for example, any value or a range between 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, and 1:10.

[0033] According to some embodiments of the present invention, the water is deionized water.

[0034] A method for preparing a self-emulsifying dispersion as described in the first aspect embodiment of the present invention includes the following steps: A first mixed solution of the solvent, dye, resin, and organic solvent is prepared; the alkali is added to the first mixed solution to obtain a second mixed solution; water is mixed with the second mixed solution and homogenized to form an emulsion; the organic solvent is then removed to obtain the final product.

[0035] The preparation method according to embodiments of the present invention has at least the following beneficial effects: The preparation method of this embodiment utilizes an organic solvent to liquefy and solubilize the resin and solvent dye, then uses an alkali to generate bases in the acid-valued resin. The mixture of the base-containing resin and solvent dye is then homogenized with water to form self-emulsifying nanodroplets. After removing the organic solvent, the resin in the droplets solidifies and coats the dye. This method does not require polymerization, is simple, safe, and can increase the dye coating amount in the resin particles.

[0036] According to some embodiments of the present invention, the organic solvent is capable of dissolving at least one of the resin or solvent dye, including at least one of alcohols, ketones, esters, ethers, alcohol ethers, aromatic hydrocarbons, and haloalkanes.

[0037] According to some embodiments of the present invention, the alcohols include, but are not limited to, at least one of methanol, ethanol, propanol, isopropanol, butanol, and isobutanol.

[0038] According to some embodiments of the present invention, the ketones include, but are not limited to, at least one of acetone, butanone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol.

[0039] According to some embodiments of the present invention, the esters include, but are not limited to, at least one of ethyl acetate, propyl acetate, and propylene glycol acetate.

[0040] According to some embodiments of the present invention, the ethers include, but are not limited to, methyl tert-butyl ether.

[0041] According to some embodiments of the present invention, the alcohol ethers include, but are not limited to, at least one of methoxypropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0042] According to some embodiments of the present invention, the aromatic hydrocarbons include, but are not limited to, at least one of benzene, toluene, and xylene.

[0043] According to some embodiments of the present invention, the haloalkane includes, but is not limited to, at least one of dichloromethane and dichloroethane.

[0044] According to some embodiments of the present invention, the mass ratio of water to the organic solvent is (2-3):1. For example, it can be any value or a range between 2:1, 2.05:1, 2.1:1, 2.15:1, 2.2:1, 2.25:1, 2.3:1, 2.35:1, 2.4:1, 2.45:1, 2.5:1, 2.55:1, 2.6:1, 2.65:1, 2.7:1, 2.75:1, 2.8:1, 2.85:1, 2.9:1, 2.95:1, or 3:1.

[0045] According to some embodiments of the present invention, the homogenization process includes at least one of high-pressure homogenization, high-shear homogenization, microfluidic homogenization, and ultrasonic homogenization.

[0046] According to some embodiments of the present invention, the homogenization process includes high-shear homogenization; the high-shear homogenization rotation speed is 10,000 rpm to 30,000 rpm. For example, it can be any value or a range between 10,000 rpm, 11,000 rpm, 12,000 rpm, 13,000 rpm, 14,000 rpm, 15,000 rpm, 16,000 rpm, 17,000 rpm, 18,000 rpm, 19,000 rpm, 20,000 rpm, 21,000 rpm, 22,000 rpm, 23,000 rpm, 24,000 rpm, 25,000 rpm, 26,000 rpm, 27,000 rpm, 28,000 rpm, 29,000 rpm, or 30,000 rpm.

[0047] According to some embodiments of the present invention, the homogenization process includes ultrasonic homogenization; the ultrasonic power of the ultrasonic homogenization is 400 W-800 W. For example, it can be any value from 400 W, 410 W, 420 W, 430 W, 440 W, 450 W, 460 W, 470 W, 480 W, 490 W, 500 W, 510 W, 520 W, 530 W, 540 W, 550 W, 560 W, 570 W, 580 W, 590 W, 600 W, 610 W, 620 W, 630 W, 640 W, 650 W, 660 W, 670 W, 680 W, 690 W, 700 W, 710 W, 720 W, 730 W, 740 W, 750 W, 760 W, 770 W, 780 W, 790 W, or 800 W, or a range between any two.

[0048] According to some embodiments of the present invention, the homogenization process includes ultrasonic homogenization; the ultrasonic frequency of the ultrasonic homogenization is 10 kHz to 30 kHz. For example, it can be any value or a range between 10 kHz, 11 kHz, 12 kHz, 13 kHz, 14 kHz, 15 kHz, 16 kHz, 17 kHz, 18 kHz, 19 kHz, 20 kHz, 21 kHz, 22 kHz, 23 kHz, 24 kHz, 25 kHz, 26 kHz, 27 kHz, 28 kHz, 29 kHz, or 30 kHz.

[0049] According to some embodiments of the present invention, the method for removing organic solvents includes at least one of distillation, vacuum distillation, and freeze drying.

[0050] According to some embodiments of the present invention, the average particle size of the emulsion is 50 nm to 500 nm. Preferably, it is 80 nm to 400 nm. More preferably, it is 100 nm to 300 nm. For example, it can be any value from 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, or 500 nm, or a range of any two.

[0051] Application of the self-emulsifying dispersion as described in the first aspect embodiment of the present invention in ink.

[0052] According to some embodiments of the present invention, the ink is inkjet ink.

[0053] According to some embodiments of the present invention, the ink is a digital inkjet ink.

[0054] An ink according to a fourth aspect embodiment of the present invention includes a self-emulsifying dispersion as described in the first aspect embodiment above. Since the ink employs all the technical solutions of the self-emulsifying dispersion of the above embodiments, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments.

[0055] According to some embodiments of the present invention, the ink further includes water and additives.

[0056] According to some embodiments of the present invention, the ink comprises, by weight parts: 5-85 parts water; The self-emulsifying dispersion is 10-90 parts; Additives: 5-30 parts.

[0057] According to some embodiments of the present invention, the ink comprises, by weight parts: 40-70 parts water; 20-40 parts of the self-emulsifying dispersion; Additives: 10-20 parts.

[0058] According to some embodiments of the present invention, the ink comprises, by mass fraction: Water 40wt%-70wt%; The self-emulsifying dispersion is 20wt%-40wt%; Additives 10wt%-20wt%.

[0059] For example, in the ink, the mass fraction of water can be 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, or 70wt%; the mass fraction of the self-emulsifying dispersion can be... The mass fraction of the additives can be any value or a range between 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, or 40wt%;

[0060] According to some embodiments of the present invention, the additives include at least one of defoamers, surface tension modifiers, bactericides, wetting agents, humectants, penetrants, leveling agents, and gloss agents.

[0061] According to some embodiments of the present invention, the additives include, by weight, 0.1-0.5 parts of defoamer, 0.3-0.7 parts of surface tension modifier, 0.05-0.5 parts of bactericide, 0.5-2 parts of wetting agent, and 10-15 parts of humectant.

[0062] According to some embodiments of the present invention, the method for preparing the ink includes the following steps: Mix the components of the ink.

[0063] According to some embodiments of the present invention, the method for preparing the ink further includes mixing followed by filtration and degassing.

[0064] According to some embodiments of the present invention, the filtration process includes sequentially using a 0.8 μm-1.2 μm glass fiber filter membrane, a 0.3 μm-0.7 μm glass fiber filter membrane, and a 0.8 μm-1.2 μm PVDF filter membrane.

[0065] According to some embodiments of the present invention, the degassing treatment includes at least one of negative pressure degassing and degassing membrane degassing.

[0066] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Detailed Implementation

[0067] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0068] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0069] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike mass fractions, the sum of the mass parts of all components is not limited to 100 parts.

[0070] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0071] Unless otherwise specified, "room temperature" in this invention means (25±5)℃.

[0072] Unless otherwise specified, “about” in this invention means ±2%.

[0073] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0074] Example 1 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 30 g of ethyl acetate, 7.5 g of maleic rosin resin M115 (Guangdong Deqing, acid value 220 mg KOH / g) and 15 g of solvent dye red 122 until they are evenly dissolved to obtain the first mixture. Then mix 4.4 g of triethanolamine with the first mixture and stir for 30 min to obtain the second mixture.

[0075] (2) 73.1g of deionized water was mixed with the second mixture and homogenized and dispersed using an ultrasonic homogenizer at 20KHz / 600W to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm±50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP1 with pH=8.5±0.5 and a solid content of 40.2%.

[0076] The theoretical content of dye in the dispersion is 22.4 wt%; the theoretical mass ratio of dye to resin is 2.

[0077] Example 2 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 30 g of butanone, 7.5 g of maleic rosin resin M115 (Guangdong Deqing, acid value 220 mg KOH / g) and 17.5 g of solvent red 122 and stir until dissolved to obtain the first mixture. Then mix 4.4 g of triethanolamine with the first mixture and stir for 30 min to obtain the second mixture.

[0078] (2) 70.6g of deionized water was mixed with the second mixture and homogenized and dispersed using a high-shear homogenizer at 20,000 rpm to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm ± 50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP2 with pH = 8.5 ± 0.5 and a solid content of 43.9%.

[0079] The theoretical content of dye in the dispersion is 26.2 wt%; the theoretical mass ratio of dye to resin is 2.3.

[0080] Example 3 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 30g of butanone, 4g of styrene-maleic anhydride resin SMA1440 (Créville, France, acid value 180 mgKOH / g) with 20g of solvent red 122 and stir until dissolved to obtain the first mixture. Then mix 1.1g of dimethylethanolamine with the first mixture and stir for 30min to obtain the second mixture.

[0081] (2) 74.9g of deionized water was mixed with the second mixture and homogenized and dispersed using an ultrasonic homogenizer at 20KHz / 600W to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm±50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP3 with pH=8.5±0.5 and solid content of 37.5%.

[0082] The theoretical content of dye in the dispersion is 29.9 wt%; the theoretical mass ratio of dye to resin is 5.

[0083] Example 4 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 20g ethyl acetate, 15g butanone, 5g styrene-acrylic resin Joncryl 682 (BASF, Germany, acid value 240 mg KOH / g) with 15g Solvent Red 122 and stir until dissolved to obtain the first mixture. Then mix 1.9g dimethylethanolamine with the first mixture and stir for 30min to obtain the second mixture.

[0084] (2) 78.1g of deionized water was mixed with the second mixture and homogenized and dispersed using an ultrasonic homogenizer at 20KHz / 600W to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm±50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP4 with pH=8.5±0.5 and a solid content of 32.7%.

[0085] The theoretical content of dye in the dispersion is 22.4 wt%; the theoretical mass ratio of dye to resin is 3.

[0086] Example 5 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 32g of ethyl acetate, 10g of styrene-acrylic resin Joncryl 586 (BASF, Germany, acid value 110mg·KOH / g) and 16g of Solvent Red 122 and stir until dissolved to obtain the first mixture. Then mix 1.2g of monoethanolamine with the first mixture and stir for 30min to obtain the second mixture.

[0087] (2) 72.8g of deionized water was mixed with the second mixture and homogenized and dispersed using a high shear homogenizer at 20,000 rpm to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm ± 50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP5 with pH = 8.5 ± 0.5 and a solid content of 40.7%.

[0088] The theoretical content of dye in the dispersion is 23.9 wt%; the theoretical mass ratio of dye to resin is 1.6.

[0089] Example 6 This example provides a self-emulsifying dispersion, the preparation method of which is as follows: (1) Mix 21g ethyl acetate, 6g butanone, 3g methanol, 9g styrene-acrylic resin Joncryl 586 (BASF, Germany, acid value 110 mg KOH / g) with 18g Solvent Red 122 and stir until dissolved to obtain the first mixture. Then mix 1.1g monoethanolamine with the first mixture and stir for 30min to obtain the second mixture.

[0090] (2) 71.9g of deionized water was mixed with the second mixture and homogenized and dispersed using an ultrasonic homogenizer at 20KHz / 600W to form an emulsion. Homogenization was stopped when the average particle size of the emulsion reached 150 nm±50 nm. The organic solvent and some water were removed by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion CRP6 with pH=8.5±0.5 and solid content of 42.0%.

[0091] The theoretical content of dye in the dispersion is 26.9 wt%; the theoretical mass ratio of dye to resin is 2.

[0092] Comparative Example 1 This example provides a self-emulsifying dispersion NRP1, which is prepared in a manner similar to that of Example 1, except that: no alkali triethanolamine is added; and because the resin is not salted, it cannot be stably emulsified, resulting in an unstable dispersion with precipitates layering.

[0093] Comparative Example 2 This example provides a self-emulsifying dispersion NRP2, which is prepared in the same way as in Example 1, except that the resin in step (1) is replaced with maleic rosin resin 424 (Guangdong Deqing, acid value 10 mg KOH / g). Because the resin acid value is too low, the number of bases formed is too small, and it cannot be emulsified stably. The dispersion is unstable and there is stratification of precipitates.

[0094] Comparative Example 3 This example provides a self-emulsifying dispersion NRP3, the preparation method of which is basically the same as that of Example 3, except that the resin in step (1) is replaced with styrene maleic anhydride resin SMA1000 (French Créville, acid value 475 mg KOH / g); because the resin acid value is too high, it is easy to cause the coating to become less water resistant, and the dye compatibility with the resin decreases, making it impossible to emulsify stably, the dispersion is unstable, and there are precipitates.

[0095] Comparative Example 4 This example refers to Example 1 of patent CN122213723A to prepare a dispersion, and the steps are as follows: (1) Mix 55.8 g of deionized water, 0.6 g of sodium bicarbonate buffer, and 3.6 g of SR-10 reactive anionic emulsifier (sulfonated ammonium salt of allyl and C10-C14 alkyl alcohol and ethylene oxide adduct, Aidi Co., Japan) and stir until dissolved to obtain premix A. Mix 11.6 g of Solvent Red 122, 23.2 g of ethyl acetate, and 5.2 g of aldehyde resin F80 (Yueyang Dongrun, China, Mw=423) and stir until dissolved to obtain premix B.

[0096] (2) Mix premixed liquid A and premixed liquid B, and homogenize and disperse them using an ultrasonic homogenizer at 20KHz / 600W power to form an emulsion. Stop homogenization when the average particle size of the emulsion reaches 150 nm±50 nm. Remove organic solvent and some water by vacuum distillation at room temperature using a water flow pump for 24 hours to obtain a dispersion NRP4 with pH=8.5±0.5 and solid content of 40%.

[0097] The theoretical content of dye in the dispersion is 22.1 wt%; the dye coating amount accounts for 69 wt% of the total dye resin particles; and the theoretical mass ratio of dye to resin is 2.2.

[0098] Application Example 1 This application example provides an inkjet ink INK1, which is composed of the following raw materials: 35.7 g of the dispersion CRP1 from Example 1; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 54.3g of deionized water.

[0099] This application example also provides a method for preparing the inkjet ink, the steps of which are as follows: Take the formula amount of each component, mix and stir evenly to obtain ink semi-finished product; then filter the ink semi-finished product through a 1.0μm glass fiber filter membrane, a 0.5 μm glass fiber filter membrane and a 1.0 μm PVDF filter membrane in sequence and degas under negative pressure to obtain inkjet ink INK1.

[0100] Application Example 2 This application example provides an inkjet ink INK2, which is composed of the following raw materials: 30.5 g of the CRP2 dispersion from Example 2; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 59.5g of deionized water.

[0101] The preparation method of this inkjet ink is the same as in application example 1.

[0102] Application Example 3 This application example provides an inkjet ink INK3, which is composed of the following raw materials: 26.8g of the CRP3 dispersion from Example 3; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 63.2 g of deionized water.

[0103] The preparation method of this inkjet ink is the same as in application example 1.

[0104] Application Example 4 This application example provides an inkjet ink INK4, which is composed of the following raw materials: 35.7 g of the CRP4 dispersion from Example 4; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 54.3 g of deionized water.

[0105] The preparation method of this inkjet ink is the same as in application example 1.

[0106] Application Example 5 This application example provides an inkjet ink INK5, which is composed of the following raw materials: 33.4 g of the CRP5 dispersion from Example 5; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 56.6 g of deionized water.

[0107] The preparation method of this inkjet ink is the same as in application example 1.

[0108] Application Example 6 This application example provides an inkjet ink INK6, which is composed of the following raw materials: 29.7 g of the CRP6 dispersion from Example 6; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1.0 g wetting agent BYK465; 8 g of humectant glycerin; 60.3 g of deionized water.

[0109] The preparation method of this inkjet ink is the same as in application example 1.

[0110] Application Comparative Example 1 This application example provides an inkjet ink INK1-CP, which is composed of the following raw materials: 5 g Acid Red 35; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1 g wetting agent BYK465; 8 g of humectant glycerin; 85 g of deionized water.

[0111] The preparation method of this inkjet ink is the same as in application example 1.

[0112] Application Comparative Example 2 This application example provides an inkjet ink INK2-CP, which is composed of the following raw materials: 36.2 g of NPR4 dispersion from Comparative Example 4; 0.3 g of defoamer Surfynol 420; 0.5 g surface tension modifier BYK346; 0.2 g of fungicide BIT-20; 1 g wetting agent BYK465; 8 g of humectant glycerin; 53.8 g of deionized water.

[0113] The preparation method of this inkjet ink is the same as in application example 1.

[0114] Test Example 1 Functional tests were conducted on the dispersions obtained in Examples 1-6 and Comparative Examples 1-4. Samples were obtained by scraping ink onto 200g coated paper with a No. 15 thread stick, and allowed to stand for 24 hours until completely dry. The following tests were then performed: (1) Color concentration test: The color concentration was measured using an X-Rite Ci7600 spectrophotometer. Based on Example 1, the color concentration of the sample was compared. A color concentration ratio greater than 95% was grade A, 90%-95% was grade B, and less than 90% was unqualified.

[0115] (2) Emulsifier migration test: After placing the sample at room temperature for 0hr and 24hr, drop pure water onto the sample surface and take a picture to detect the change in water contact angle before and after standing. If the change in contact angle is less than 5%, it is grade A; less than 10%, it is grade B; less than 15%, it is grade C; and greater than 15%, it is unqualified.

[0116] (3) Stability test: The accelerated aging test was conducted at 60℃ for 7 days. The particle size D50 of the dispersion was measured using a Malvern ZS-90 particle size analyzer. A change of less than 10% was grade A, 10-20% was grade B, 20-30% was grade C, and more than 30% was unqualified.

[0117] The relevant test results are shown in Table 1.

[0118] Table 1

[0119] The self-emulsifying dispersions prepared in Examples 1-6 all achieved Grade A in terms of color concentration, emulsifier migration resistance, and stability.

[0120] Comparative Example 1 resin was not alkali-treated, therefore the resin acid value could not be dissociated and self-emulsified, and it could not stably form an emulsion. The dispersion precipitated and separated, making it impossible to test color concentration and emulsifier migration, and the dispersion stability was poor.

[0121] Comparative Example 2 used resin with too low an acid value, resulting in too few saltable cleavage radicals in the resin, which could not self-emulsify to form a stable emulsion. The dispersion precipitated and separated, making it impossible to test color concentration and emulsifier migration, and the dispersion stability was poor.

[0122] Comparative Example 3 used a resin with an excessively high acid value, which resulted in excessive salt-soluble ionization of the resin, decreased water resistance and dye compatibility, easy dye precipitation, inability to test color concentration and emulsifier migration, and unstable dispersion with layering.

[0123] Comparative Example 4 uses traditional emulsifiers to emulsify the resin / dye solution, which easily leads to the migration of emulsifiers to the interface, resulting in a decrease in contact angle, moisture absorption, whitening, and poor adhesion of the coating surface; in addition, high-temperature aging can easily cause the emulsifier to desorb and reduce dispersion stability.

[0124] Test Example 2 Functional tests were conducted on the inkjet inks prepared using Application Examples 1-6 and Comparative Examples 1-2. Samples were obtained by scraping the ink onto an acrylic board with a No. 15 ink stick and allowing them to stand for 24 hours until completely dry. The following tests were then performed: (1) Color concentration test: The color concentration was measured using an X-Rite Ci7600 spectrophotometer. Based on Application Example 1, the color concentration of the sample was compared. A color concentration ratio greater than 95% was grade A, 90%-95% was grade B, and less than 90% was unqualified.

[0125] (2) Lightfastness test: Six Philips TUV F17T8 UV-C lamps with wavelengths of 200-280 nm were used. The lamps were placed 15 cm away from the object being irradiated. The temperature of the test chamber was 45±3℃ and the exposure time was 1 h. The color difference (ΔE) of the samples before and after exposure was measured using an X-Rite Ci7600 spectrophotometer. ΔE≤2 was grade A, ΔE≤3 was grade B, ΔE≤4 was grade C, and ΔE>4 was unqualified.

[0126] (3) Water resistance test: After soaking the sample in water for 24 hours, it is qualified if the coating does not bubble.

[0127] (4) Color difference test: The sample is soaked in water for 24 hours and then taken out and dried. The coating is qualified if it does not turn white, fade or migrate (the color difference △E≤2 is grade A, △E≤3 is grade B, △E≤4 is grade C, and △E>4 is unqualified).

[0128] (5) Stability test: The accelerated aging test was conducted at 60℃ for 7 days. The particle size D50 of the dispersion was measured using a Malvern ZS-90 particle size analyzer. A change of less than 10% was grade A, 10-20% was grade B, 20-30% was grade C, and more than 30% was unqualified.

[0129] The relevant test results are shown in Table 2.

[0130] Table 2

[0131] The inkjet inks prepared in Application Examples 1-6 are superior to the conventional water-soluble dye inks in Application Comparative Example 1 in terms of color concentration, lightfastness, water fastness, and water adhesion; at the same time, they are superior to Application Comparative Example 2, which uses a conventional emulsifier system, in terms of water adhesion and dispersion stability.

[0132] The above description, in conjunction with specific embodiments, provides a detailed explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A self-emulsifying dispersion, characterized in that, include: Dye resin particles and water; The dye resin particles include solvent dye, resin and alkali agent; The acid value of the resin is 70~300 mg·KOH / g; The mass ratio of the solvent dye to the resin is (1~5):

1.

2. The self-emulsifying dispersion according to claim 1, characterized in that, The solvent dye accounts for no less than 50 wt% of the mass percentage of the dye resin particles.

3. The self-emulsifying dispersion according to claim 1, characterized in that, The solvent dyes include at least one of solvent dye yellow, solvent dye orange, solvent dye red, solvent dye purple, solvent dye blue, solvent dye green, solvent dye brown, and solvent dye black.

4. The self-emulsifying dispersion according to claim 1, characterized in that, The resin includes at least one of acrylate resin, polyurethane resin, styrene-acrylic resin, rosin resin, maleic rosin resin, and styrene-maleic anhydride resin.

5. The self-emulsifying dispersion according to claim 1, characterized in that, The alkali agent includes at least one selected from dimethylethanolamine, 2-amino-2-methyl-1-propanol, triethanolamine, diethanolamine, monoethanolamine, ethylenediamine, triethylenediamine, tetramethyltriethylenediamine, tetramethylethylenediamine, hexamethylenetetramine, N,N-dimethylbenzylamine, and pyridine; optionally, the alkali agent is neutralized with the resin to form a water-soluble salt; optionally, the alkali agent is added to a neutralization degree of 70% to 100%.

6. The method for preparing the self-emulsifying dispersion according to any one of claims 1 to 5, characterized in that, Includes the following steps: A first mixed solution of the solvent, dye, resin, and organic solvent is prepared; the alkali is added to the first mixed solution to obtain a second mixed solution; water is mixed with the second mixed solution and homogenized to form an emulsion; the organic solvent is then removed to obtain the final product.

7. The preparation method according to claim 6, characterized in that, The organic solvent includes at least one of alcohols, ketones, esters, ethers, alcohol ethers, aromatic hydrocarbons, and haloalkanes; preferably, the alcohols include at least one of methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; preferably, the ketones include at least one of acetone, butanone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol; preferably, the esters include at least one of ethyl acetate, propyl acetate, and propylene glycol acetate; preferably, the ethers include methyl tert-butyl ether; preferably, the alcohol ethers include at least one of methoxypropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monobutyl ether; preferably, the aromatic hydrocarbons include at least one of benzene, toluene, and xylene; preferably, the haloalkanes include at least one of dichloromethane and dichloroethane.

8. The preparation method according to claim 6, characterized in that, The mass ratio of water to the organic solvent is (2~3):

1.

9. The use of the self-emulsifying dispersion as described in any one of claims 1 to 5 in ink.

10. An ink, characterized in that, Includes the self-emulsifying dispersion according to any one of claims 1 to 5.

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