Preparation method and application of color microsphere ink for digital inkjet printing

Abstract

The application discloses a preparation method and application of color microsphere ink for digital inkjet printing, and belongs to the fine chemical field. The color microsphere is prepared as follows: firstly, traditional disperse dyes are modified to prepare high-solubility polymerizable dyes; subsequently, the color microsphere emulsion is prepared through free radical copolymerization; finally, the color microsphere ink is obtained by regulating inkjet parameters. The color microsphere ink has the advantages of high dye content, small particle size, good storage stability, excellent dry and wet rubbing performance and the like. The color microsphere ink can be adapted to various digital printing equipment, breaks the monopoly of foreign inks, and has a good market application prospect.

Description

Technical Field

[0001] The present invention relates to the field of textiles, and in particular to a preparation method and application of color microsphere ink for digital inkjet printing. Background Art

[0002] Digital inkjet printing, with its advantages of high printing precision, low pollution, low cost, and reduced water and energy consumption, is a popular choice for small-scale custom production and is gaining widespread popularity in textile applications. It reduces the burden on businesses, meets environmental protection requirements, and addresses the technical shortcomings and gaps of traditional printing. Printing ink, as a key component and primary consumable of digital inkjet printing, is a key factor influencing its development. Commonly used inks are primarily dye inks and pigment inks. Inkjet printing inks generally consist of a colorant (dye or pigment), a dispersion medium (water or organic solvent), and additives (such as pH adjusters, biocides, and humectants). Pigment inks also require dispersants and binders. While there are many types of traditional dyes, not all are suitable for the formulation of digital inkjet printing inks. Reactive dyes, acid dyes, and disperse dyes are currently the primary colorants in dye inks. While dye-based digital inkjet printing inks are currently in production and application, their shortcomings are evident for digital inkjet textile printing. For example, dye inks lack universality, requiring different inks for different fibers. The production process is complex and carries a degree of environmental pollution. Dye inks require fiber modification or pretreatment before inkjet printing, as well as the application of dye fixatives and printing pastes. Post-printing fabric treatments such as steaming and washing are also required, which is environmentally unfavorable. These drawbacks of dye inks have hindered the development of digital printing technology, leading numerous researchers both domestically and internationally to conduct extensive research on pigment inks. Compared to dye inks, pigment inks offer greater versatility and are non-selective for fiber. The process is simpler, with no emissions, contributing to environmental benefits. They require no complex pre- and post-treatment processes and can be directly inkjet printed on fabrics, followed by simple baking. They also exhibit excellent lightfastness and are resistant to degradation by light. However, these inks also present several challenges. First, pigment inks prepared using existing grinding and dispersion techniques exhibit a mix of large and small particles, which can affect droplet morphology. Second, using polymer encapsulation for pigment particles is extremely costly and difficult to maintain ink stability, making them difficult to commercialize. Furthermore, the presence of the polymer shell can affect the ink's color. Therefore, in order to solve the shortcomings of traditional pigment inks in applications, developing new colorant particles to replace pigments may be an effective way.

[0003] Colored microspheres are colorful polymer particles with a regular morphology, formed by physically or chemically combining a colorant component with a polymer component. They are characterized by their small size and stable distribution, combining the vibrant color of dyes with the durability of pigments. They are a promising alternative to dyes and pigments as a new type of colorant, and are being used in textile inkjet printing. However, due to the limited solubility of the dye in the polymer monomer, colored microsphere inks have been unable to achieve high color depths, a key issue for the industrial production of microsphere inks.

[0004] For example, Song Yawei et al. used disperse dyes to dye poly(styrene-methyl acrylic nitrate) nanospheres to prepare high-performance colored nanospheres, and used them for screen printing; Zhao Le et al. first prepared reactive anthraquinone dyes, and prepared colored latex particles by copolymerizing them with acrylonitrile monomers for use in cotton fabric printing processes; Zhou Lan et al. prepared nanosphere structured color-producing ink for digital printing by mixing dispersion media, nanospheres and dyes and adding additives, and constructed structural color photonic crystal films on the fabric surface.

[0005] The process described in the above method does not involve the preparation of highly soluble reactive anthraquinone disperse dyes or the structural design of colored microspheres for digital inkjet printing. Summary of the Invention

[0006] This invention provides a method for preparing and applying a colored microsphere ink for digital inkjet printing. Conventional disperse dyes are modified to produce highly soluble polymerizable dyes. Subsequently, a colored microsphere emulsion is prepared through free radical copolymerization. Finally, the colored microsphere ink is obtained by adjusting inkjet parameters. This colored microsphere ink exhibits advantages such as small particle size, good storage stability, and excellent wet and dry friction properties. It is compatible with various digital printing equipment, breaking the monopoly of foreign inks and possessing promising market application prospects.

[0007] A method for preparing a color microsphere ink for digital inkjet printing comprises the following steps: (1) using anthraquinone disperse dyes as raw materials, introducing double bond-containing monomers and aromatic hydrocarbon monomers, and synthesizing a highly soluble reactive anthraquinone dye consisting of anthraquinone matrix, a linker, and a polymerizable group; (2) using acrylate monomers as comonomers, adding a highly soluble reactive anthraquinone dye, an initiator, water, and an emulsifier, and fully ultrasonically dissolving the mixture, and preparing a color microsphere emulsion by a free radical polymerization process; (3) adding an alcohol surface tension regulator, a surfactant, a pH regulator, and an adhesive to the color microsphere emulsion, and filtering the mixture through a PVDF membrane to obtain the color microsphere ink for digital inkjet printing.

[0008] Furthermore, a method for preparing colored microsphere ink for digital inkjet printing comprises the following steps:

[0009] (1) Preparation of highly soluble reactive anthraquinone dye: Weigh one of hydroxyethyl methacrylate / hydroxyethyl acrylate, an acid binder, and toluene into a reactor equipped with a stirrer, nitrogen inlet and outlet lines, and a thermometer. The solution is cooled to near 0°C under a nitrogen atmosphere. Add cyanuric chloride at a temperature of 0-5°C and stir for 48 hours. Then add CI Disperse Red 60 and stir at 40-50°C for 48 hours. Then heat to 100°C and add one of phenol / methylphenol / o-methylphenol / p-methylphenol. Keep the temperature for reaction for 8 hours. After cooling to room temperature, filter with a sand core funnel and evaporate the filtrate. Stir the residue with distilled water, filter with a sand core funnel, and evaporate the filtrate to dryness to obtain a highly soluble reactive anthraquinone dye. The structure of the highly soluble reactive anthraquinone dye is as follows:

[0010]

[0011] Wherein, R is a polymerizable double bond group, and X is an aromatic hydrocarbon solubilizing group.

[0012] (2) Preparation of colored microsphere emulsion: A highly soluble reactive anthraquinone dye and an initiator were dissolved in an acrylate monomer to form an oil phase. The emulsifier was dissolved in deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 minutes to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 minutes. The obtained pre-emulsion was transferred to a reactor equipped with a condenser and a mechanical stirrer and nitrogen was introduced for 15 minutes. Finally, the emulsion was reacted in a 70°C water bath for 8 hours to prepare a colored microsphere emulsion.

[0013] (3) Regulation of color microsphere ink for code inkjet printing: Add alcohol surface tension regulator, surfactant, Ph regulator, and adhesive to the color microsphere emulsion to control the ink surface tension, viscosity, and Ph to meet the requirements of inkjet printing to prepare color microsphere ink for inkjet printing and enable it to be firmly bonded to the fabric.

[0014] Furthermore, the double bond-containing monomer in step (1) is one of hydroxyethyl methacrylate and hydroxyethyl acrylate; and the aromatic hydrocarbon monomer is one of phenol, methylphenol and o-methylphenol.

[0015] Furthermore, the solid content of the colored microsphere emulsion in step (2) is 15 wt% to 35 wt%. The acrylic ester monomer in step (2) is any one of styrene, acrylonitrile, and methyl methacrylate.

[0016] Furthermore, the initiator in step (2) is any one of azobiscyanovaleric acid, azobisisobutylamidine hydrochloride, azobisisobutyronitrile, and potassium persulfate, and the amount used is 1 wt% to 3 wt% of the total monomers.

[0017] Furthermore, the amount of the reactive anthraquinone dye used in step (2) is 1 wt% to 9 wt% of the total monomers.

[0018] Furthermore, the emulsifier in step (2) is an anionic surfactant, which is any one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the amount used is 3wt% to 5wt% of the total monomers.

[0019] Furthermore, the alcohol surface tension regulator in step (3) is any one or more of ethylene glycol, glycerol, and diethylene glycol butyl ether, and the total amount is 20wt%-40wt% of the color microsphere ink; the surfactant regulator is a non-ionic defoaming wetting agent, and the amount is 0.05wt%-1wt% of the color microsphere ink; the pH regulator is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium carbonate, and the pH of the color microsphere ink is controlled to be 7-9.

[0020] Furthermore, the binder of the colored microsphere ink in step (3) is water-soluble polyurethane, and the amount used is 10wt%-25wt% of the colored microsphere ink.

[0021] Furthermore, the surface tension of the colored microsphere ink in step (3) is controlled to be 25mN / m-35mN / m, and the viscosity is controlled to be 2-8cp.

[0022] In detail, the present invention provides a method for preparing colored microsphere ink for digital inkjet printing, which mainly includes the following steps:

[0023] (2) Preparation of colored microsphere emulsion: 1-9 wt% of a highly soluble reactive anthraquinone dye and 1 wt% to 5 wt% of an initiator were dissolved in an acrylate monomer to form an oil phase. 3 wt% to 5 wt% of an emulsifier were dissolved in deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0024] (3) Regulation of color microsphere ink for digital inkjet printing: add 20wt%-30wt% of alcohol surface tension regulator, 0.05wt%-1wt% of surfactant, Ph regulator (adjusted to 7-9), and 10wt%-25wt% of water-soluble polyurethane binder color microsphere ink for inkjet printing (total mass percentage 100%) to the color microsphere emulsion (balance).

[0025] The present invention provides a color microsphere ink for digital inkjet printing, which has the following four main advantages:

[0026] (1) The present invention successfully prepares a highly soluble reactive anthraquinone dye, which has high solubility in acrylate monomers, so that the colored microsphere emulsion prepared by polymerization reaction has a higher color depth, solving the key problem of low dye content and light coloring of traditional colored microspheres.

[0027] (2) The prepared reactive anthraquinone dye has an active carbon-carbon double bond and can be copolymerized with acrylate monomers to form a strong chemical bond, which greatly improves the color fastness of the microsphere ink. With the help of the adhesion of the polymer, it is directly attached to the surface of the fabric without the need for additional dyes and film-forming agents. The process is simple and meets the market demand for safety and environmental protection.

[0028] (3) The color microsphere ink prepared by the present invention has a regular spherical shape and is evenly dispersed. There are no extremely large particles, which has little effect on the morphology of the ink droplets and effectively solves the problem of easy clogging of the nozzle.

[0029] (4) The invention uses acrylic monomers, which have a high glass transition temperature, so that the prepared colored microsphere ink has good thermal stability and is difficult to form a film and clog the nozzle at room temperature.

[0030] The preparation method and application of colored microsphere ink for digital inkjet printing meet the development needs of textiles in the era. The preparation process is wastewater-free and does not require chemical colorants. It is green and pollution-free, and has huge development potential and broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The particle size distribution diagram (a) and transmission electron microscopy image (b) of the colored microspheres;

[0032] Figure 2 Schematic diagram of the solubility of highly soluble and non-grafted solubilizing group reactive anthraquinone dyes in styrene monomer;

[0033] Figure 3 This is a synthesis diagram of highly soluble reactive anthraquinone dyes;

[0034] Figure 4 The NMR characterization and IR spectrum of the highly soluble reactive anthraquinone dye are shown;

[0035] Figure 5 Print physical images for colored microsphere inks; DETAILED DESCRIPTION

[0036] The following description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will appreciate that they may modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

[0037] The preparation method of the dye used in this application is as follows (see Figure Figure 3 The figure shows the synthesis of highly soluble reactive anthraquinone dyes):

[0038] Preparation of highly soluble reactive anthraquinone dye: Weigh 0.52g HEMA, 10g anhydrous sodium carbonate, and 200ml toluene into a three-necked round-bottom flask equipped with an overhead stirrer, nitrogen inlet and outlet lines, and a thermometer. The solution was cooled to close to 0°C under a nitrogen atmosphere. At a temperature of 0-5°C, 1.48g of cyanuric chloride was added and stirred for 48h. Then 2.64g CI Disperse Red 60 was added and stirred at 40-50°C for 48h, then the temperature was raised to 100°C, 0.753g of phenol was weighed and added and the reaction was continued for 8h. After cooling to room temperature, it was filtered with a sand core funnel, and the filtrate was evaporated to obtain a red solid, which was purified by column chromatography with an ethyl acetate: dichloromethane = 2:1 (v / v) solvent to obtain a highly soluble reactive anthraquinone dye (structural characterization is shown in the attached figure). Figure 4 shown).

[0039] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to specific embodiments and accompanying drawings.

[0040] Example 1

[0041] (1) Preparation of colored microsphere emulsion: 0.12 g (1 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.1212 g (1 wt%) of azobisisobutyronitrile were dissolved in 12 g of styrene to form an oil phase, and 0.36 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and ultrasonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0042] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion (balance) was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0043] Example 2

[0044] (1) Preparation of colored microsphere emulsion: 0.12 g (1 wt%) of highly soluble reactive anthraquinone dye and 0.1212 g (1 wt%) of azobisisobutyronitrile were dissolved in 12 g of methyl methacrylate to form the oil phase. 0.36 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the water phase. The oil phase was poured into the water phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0045] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0046] Example 3

[0047] (1) Preparation of colored microsphere emulsion: 0.12 g (1 wt%) of highly soluble reactive anthraquinone dye and 0.1212 g of azobisisobutyronitrile were dissolved in 12 g of acrylonitrile to form an oil phase. 0.36 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0048] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0049] Example 4

[0050] (1) Preparation of colored microsphere emulsion: 0.6 g (5 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of benzophenone were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the water phase. The oil phase was poured into the water phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h and filtered through a PVDF membrane to prepare a colored microsphere emulsion.

[0051] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0052] Example 5

[0053] (1) Preparation of colored microsphere emulsion: 0.6 g (5 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of benzophenone were dissolved in 12 g of styrene to form an oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0054] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0055] Example 6

[0056] (1) Preparation of colored microsphere emulsion: 1.08 g (9 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 68 g of deionized water to form the aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0057] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0058] Example 7

[0059] (1) Preparation of colored microsphere emulsion: 1.08 g (9 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0060] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% propylene glycol, 5 wt% glycerol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0061] Example 8

[0062] (1) Preparation of colored microsphere emulsion: 1.08 g (9 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0063] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 20 wt% propylene glycol, 10 wt% glycerol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0064] Example 9

[0065] (1) Preparation of colored microsphere emulsion: 1.08 g (9 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0066] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 10 wt% propylene glycol, 10 wt% glycerol, 10 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0067] Example 10

[0068] (1) Preparation of colored microsphere emulsion: 1.08 g (9 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of were dissolved in 12 g of styrene to form the oil phase. 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form the aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and sonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0069] (2) Regulation of color microsphere ink for digital inkjet printing: Based on the total mass percentage of color microsphere ink as 100%, the color microsphere emulsion was added with 20 wt% propylene glycol, 10 wt% glycerol, 10 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.1 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 8), and 20 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0070] Comparative Example 1

[0071] Preparation of a highly soluble reactive anthraquinone dye: 0.52g HEMA, 10g anhydrous sodium carbonate, and 200ml toluene were weighed into a three-necked round-bottom flask equipped with an overhead stirrer, nitrogen inlet and outlet lines, and a thermometer. The solution was cooled to near 0°C under a nitrogen atmosphere. 1.48g of cyanuric chloride was added at 0-5°C and stirred for 48 hours. Then, 2.64g of CI Disperse Red 60 was added and stirred at 40-50°C for 48 hours. The mixture was then heated to 100°C, cooled to room temperature, and filtered through a fritted funnel. The filtrate was evaporated to yield a red solid, which was purified by column chromatography using ethyl acetate:dichloromethane (v / v) in a ratio of 2:1 to obtain the reactive anthraquinone dye.

[0072] (1) Preparation of colored microsphere emulsion: 0.36 g (3 wt%) of the total monomers of a highly soluble reactive anthraquinone dye and 0.3924 g of benzophenone were dissolved in 12 g of styrene to form an oil phase, and 0.6 g of sodium dodecylsulfonate was dissolved in 36 g of deionized water to form an aqueous phase. The oil phase was poured into the aqueous phase and pre-emulsified for 20 min (power 650 W) to form a coarse emulsion. After pre-emulsification, the emulsion was placed in an ice-water bath and ultrasonicated for 20 min. The obtained pre-emulsion was transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 was introduced for 15 min. Finally, the emulsion was reacted in a 70°C water bath for 8 h to prepare a colored microsphere emulsion.

[0073] (2) Regulation of color microsphere ink for digital inkjet printing: The color microsphere emulsion was added with 10 wt% ethylene glycol, 10 wt% propylene glycol, 5 wt% diethylene glycol butyl ether alcohol surface tension regulator, 0.05 wt% non-ionic defoaming wetting agent surfactant 104e, sodium carbonate Ph regulator (adjusted to 7-9), and 10 wt% water-soluble polyurethane adhesive (G702, Wenzhou Guoshibang Polymer Materials Co., Ltd.) and filtered through a PVDF membrane with a pore size of 1 μm to prepare color microsphere ink for inkjet printing.

[0074] The comparative example is a colored microsphere ink using a reactive anthraquinone dye without a grafted aromatic hydrocarbon solubilizing group, and the maximum solubility is only 3%.

[0075] Table 2 shows the properties of colored microsphere emulsions with different formulations

[0076] Particle size (nm) PDI Potential (mv) Example 1 66.46 0.056 -65.4 Example 2 68.55 0.102 -64.5 Example 3 72.45 0.098 -60.5 Example 4 69.81 0.086 -70.2 Example 5 73.22 0.066 -58.7

[0077] Table 3 shows the effects of different dye contents and additive amounts on the performance of color microsphere inks

[0078]

[0079] As can be seen from Table 2, the particle size of the microsphere emulsion is less than 100 nm. The particle size distribution index is low, the absolute potential is high, and the stability is excellent.

[0080] Figure 1 The particle size and transmittance of the styrene colored microspheres prepared in Example 4 were characterized. Figure 1 As shown in FIG, the particle size of the colored microspheres is 69.81 nm, the PDI is 0.086, and the particle size meets the requirements of inkjet printing (≤200 nm). Transmission electron microscopy images show that the prepared colored microspheres are uniformly spherical and evenly distributed.

[0081] Figure 2Schematic diagram of the solubility of highly soluble and non-grafted solubilizing group reactive anthraquinone dyes. The maximum solubility of the highly soluble reactive anthraquinone dye can reach 9% at room temperature, while the solubility of the non-grafted solubilizing group reactive anthraquinone dye is only 3%.

[0082] Figure 4 These are the nuclear magnetic resonance hydrogen spectrum and infrared spectrum images of the highly soluble reactive anthraquinone dye, indicating the successful synthesis of the highly soluble reactive anthraquinone dye.

[0083] Figure 5 The inkjet printed font prepared in Example 4 shows clear printed fonts.

[0084] The embodiment described above is only a preferred solution of the present invention and does not limit the present invention in any form. Other variations and modifications are possible without exceeding the technical solution described in the claims.

Claims

1. A method for preparing colored microsphere ink for digital inkjet printing, characterized in that: The following steps are involved: (1) Using anthraquinone disperse dyes as raw materials, double bond-containing monomers and aromatic hydrocarbon monomers are introduced to synthesize highly soluble reactive anthraquinone dyes consisting of anthraquinone matrix-linker-polymerizable group; The structure of the highly soluble reactive anthraquinone dye is as follows: ； Wherein, R is a polymerizable double bond group, and X is an aromatic hydrocarbon solubilizing group; ； ； (2) Using acrylate monomers as comonomers, adding highly soluble reactive anthraquinone dyes, initiators, water and emulsifiers and fully ultrasonically dissolving them, a colored microsphere emulsion was prepared by free radical polymerization; (3) The colored microsphere emulsion was added with an alcohol surface tension regulator, a surfactant, a pH regulator and an adhesive, and filtered through a PVDF membrane to obtain colored microsphere ink for digital inkjet printing.

2. The preparation method according to claim 1, characterized in that In step (1), the double bond-containing monomer is one of hydroxyethyl methacrylate and hydroxyethyl acrylate; and the aromatic hydrocarbon monomer is one of phenol, methylphenol and o-methylphenol.

3. The preparation method according to claim 1, characterized in that In step (2), the amount of the highly soluble reactive anthraquinone dye used is 1-9 wt% of the mass of the comonomer.

4. The preparation method according to claim 1, characterized in that In step (2), the acrylic ester monomer is one or more of styrene, acrylonitrile, and methyl methacrylate; The emulsifier is any one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the amount of the emulsifier is 3 wt% to 5 wt% of the mass of the comonomer.

5. The preparation method according to claim 1, characterized in that In step (2), the initiator is any one of azobiscyanovaleric acid, azobisisobutylamidine hydrochloride, azobisisobutyronitrile, and potassium persulfate, and the amount of the initiator is 1 wt% to 3 wt% of the total monomers.

6. The preparation method according to claim 1, characterized in that In step (3), the alcohol surface tension regulator is any one or more of ethylene glycol, propylene glycol, and diethylene glycol butyl ether; The surfactant is a nonionic defoaming wetting agent; The pH regulator is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium carbonate; The adhesive is water-soluble polyurethane.

7. The preparation method according to claim 1, characterized in that In step (3), the color microsphere ink for digital inkjet printing is made of the following raw materials in percentage by weight: Alcohol surface tension regulator 20 wt%-40 wt%; Surfactant 0.05 wt%-1 wt%; Adhesive 10wt%-25wt%; Colored microsphere emulsion residue; The pH value of the color microsphere ink for digital inkjet printing is 7-9.

8. Use of the colored microsphere ink for digital inkjet printing prepared according to the preparation method according to any one of claims 1 to 7 in digital inkjet printing.

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