Preparation method for and use of digital inkjet ink having micron / nano-sized fluoro-silicon polymer-coated colored hard spheres

Abstract

The present invention relates to the field of fine chemical engineering. Disclosed are a preparation method for and use of a digital inkjet ink having micron / nano-sized fluoro-silicon polymer-coated colored hard spheres. The preparation of the digital inkjet ink having fluoro-silicon polymer-coated colored hard spheres is as follows: preparing a polystyrene-based colored hard sphere seed emulsion by dissolving a high-solubility reactive dye in a styrene monomer and performing free radical polymerization, then injecting an organofluorosilane monomer and an acrylate monomer into the seed emulsion as a shell layer, and performing free radical polymerization and cationic ring-opening polymerization to prepare the digital inkjet ink having fluoro-silicon polymer-coated colored hard spheres. The digital inkjet ink having fluoro-silicon polymer-coated colored hard spheres has the advantages of small particle size, good storage stability, controllable latex ink structure, etc. This digital inkjet ink having micron / nano-sized fluoro-silicon polymer-coated colored hard spheres can be applied to digital printing to endow fabrics with excellent waterproofness, breathability, and soft properties.

Description

Preparation method and application of micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink TECHNICAL FIELD

[0001] The present application relates to the field of textiles, in particular to a preparation method and application of micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink BACKGROUND

[0002] The inkjet printing technology makes up for the defects and gaps of traditional printing in technology due to its high printing accuracy, color design, and green environmental protection. In recent years, the consumption of digital inkjet ink has shown a continuous growth trend, and the cost of inkjet ink accounts for 30% of the cost of inkjet. In order to adapt to this technology, the development of inkjet ink has become the research focus of scholars and enterprises, and the development of high-stable ink is an inevitable trend of inkjet printing. Compared with dye ink, pigment ink has great potential for development due to its versatility. However, pigment ink still has problems to be solved, and pigment ink has large and small particles, uneven distribution, which makes the formation of ink droplets complex and easy to block the nozzle of traditional printing. Color hard ball can become a new type of colorant to replace pigment due to its nanoscale particle size and high stability.

[0003] Color hard ball, that is, high polymerization of low molecular dye, directly adheres to the surface of fabric by the adhesion of high polymer, without the need for additional dye and film-forming agent, which meets the market demand for safety and environmental protection, and is considered as one of the effective ways to solve the above-mentioned problems of pigment ink. By introducing dye parent into the main chain or side group of high polymer through polymerization reaction, the dye retains the characteristics of light absorption and color development, and also has the characteristics of high polymer, such as migration resistance and processability. However, the solubility of reactive dye in polymer monomer is low, resulting in shallow printing color depth; the hand feeling and air permeability of printed fabric are not good, which limits the large-scale use of hard ball ink.

[0004] The introduction of fluorosilicon segment into color hard ball can significantly improve the hand feeling of printed fabric and give the fabric good hydrophobic properties. For example, Yang Yi et al. successfully introduced vinyl trimethoxysilane and anthraquinone dye monomer into the acrylate segment through emulsion polymerization reaction to prepare self-crosslinking silicone modified self-coloring latex, but the organic fluorine segment was not introduced, resulting in poor migration ability of the latex film, and the hand feeling, color fastness and air permeability of the coated fabric still need to be improved. In addition, due to the poor solubility of reactive anthraquinone dye in monomer, the color depth of printed fabric is shallow. Lixiaoqi et al. first synthesized fluorosilicon macromonomer with vinyl end-capping, prepared fluorosilicon modified polyacrylate emulsion through emulsion polymerization reaction, and applied it to liquid disperse dye printing to improve the hydrophobic and soft properties of printed fabric, but due to the thermal migration of small dye molecules, the rubbing fastness of printed fabric is not good. SUMMARY

[0005] The application provides a preparation method of micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink, which modifies traditional disperse dyes, prepares high-solubility polymerizable dyes, then prepares color hard ball emulsion through free radical copolymerization, then introduces organic fluorosilicon monomers and soft monomers as a shell layer to coat the hard ball seed emulsion through cationic ring-opening polymerization and free radical polymerization, and finally, micro-nano fluorosilicon polymer coated color hard ball ink is obtained by adjusting inkjet parameters. The micro-nano fluorosilicon polymer coated color hard ball ink has the advantages of small particle size, good storage stability, excellent dry and wet rubbing performance, good hydrophobicity of printed fabric, good hand feeling and the like. It can be adapted to various digital printing equipment, breaks the monopoly of foreign ink, and has good market application prospect.

[0006] A preparation method of micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink, comprising the following steps: (1) using anthraquinone type disperse dye as raw material, introducing double bond monomer and aromatic hydrocarbon monomer, synthesizing reaction type anthraquinone type dye composed of anthraquinone matrix-linker-polymerizable group; (2) using styrene as a comonomer, adding high-solubility reaction type anthraquinone type dye, initiator, water and emulsifier and fully ultrasonic dissolving, preparing seed color hard ball emulsion through free radical polymerization process; (3) transferring the styrene color hard ball seed emulsion to a reactor, using organic fluorosilicon monomer and soft monomer as a shell layer, injecting initiator, crosslinking agent, water, emulsifier and cationic ring-opening agent into the reactor to prepare micro-nano fluorosilicon polymer coated color hard ball emulsion through free radical polymerization and cationic ring-opening miniemulsion polymerization process; (4) adding moisturizing agent, PH regulator and surface tension regulator to the fluorosilicon polymer coated color hard ball emulsion for adjustment, and finally preparing micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink.

[0007] Further, a preparation method of micro-nano fluorosilicon polymer coated color hard ball digital inkjet ink, which comprises the following steps:

[0008] (1) Preparation of high-solubility reaction type anthraquinone dye: a certain amount of hydroxyethyl methacrylate, acid binding agent and toluene are weighed into a reaction kettle provided with a stirrer, nitrogen inlet and outlet line and a thermometer. The solution is cooled to near 0 DEG C under a nitrogen atmosphere. At a temperature of 0-5 DEG C, trichloro cyanuric acid is added, and stirred for 48 h. Then CI disperse red 60 is added, and stirred at 40-50 DEG C for 48 h, and then the temperature is raised to 100 DEG C, phenol is added, and the temperature is kept for 8 h. After cooling to room temperature, the solution is filtered through a sand core funnel, and the filtrate is evaporated. The residue is stirred with distilled water, filtered through a sand core funnel, and the filtrate is evaporated and dried to obtain high-solubility reaction type anthraquinone dye. The structure of the high-solubility reaction type anthraquinone dye is as follows:

[0009] (2) Color hard sphere emulsion preparation: dissolve high solubility reactive anthraquinone dye and initiator in acrylate monomer to form oil phase, dissolve emulsifier in deionized water to form water phase, pour oil phase into water phase to form coarse emulsion after pre-emulsification for 20 min. After pre-emulsification, the emulsion is placed in an ice water bath for ultrasonic treatment for 20 min. The obtained pre-emulsified liquid is transferred to a reaction equipped with a condenser and a mechanical stirrer and N2 is introduced for 15 min. Finally, the emulsion is reacted in a 70℃ water bath for 8h to prepare color hard sphere seed emulsion.

[0010] (3) Micro-nano fluorosilicon polymer coated color hard sphere emulsion preparation: add color hard sphere seed emulsion into the reaction kettle, take organic fluorosilicon monomer, soft monomer, initiator and crosslinking agent as oil phase, and take water, emulsifier and cationic ring-opening agent as water phase, pour oil phase into water phase for emulsification for 20 min, after pre-emulsification, inject the emulsion into the reaction kettle after ultrasonic treatment for 20 min in ice water bath to react at 75℃ for 8h to prepare micro-nano fluorosilicon polymer coated color hard sphere emulsion.

[0011] (4) Micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink regulation: add humectant, PH regulator and surface tension regulator to the fluorosilicon polymer coated color hard sphere emulsion for regulation, and finally prepare micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink.

[0012] Further, in steps (2) and (3), the concentration of the color hard sphere seed emulsion is 15wt%-30wt%, and the concentration of the shell emulsion is 10wt%-25wt%.

[0013] Further, in steps (2) and (3), the emulsifier is an anionic surfactant, which is one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the amount used is 3wt%-5wt% of the monomer.

[0014] Further, in steps (2) and (3), the initiator is one or two of azobis cyanovaleric acid, azobis diisobutyl amidine hydrochloride, azobis diisobutyl cyanide and potassium persulfate, the amount of initiator used in steps (2) and (3) is 1%-5% of the hard monomer and reactive dye, and the amount of initiator used in steps (3) and (3) is 1%-3% of the organic fluorosilicon monomer and soft monomer.

[0015] Further, the amount of reactive anthraquinone dye used in step (2) is 9wt% of the total monomer.

[0016] Further, the emulsifier in step (2) is an anionic surfactant, which is any one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the amount used is 3wt%-5wt% of the total monomer.

[0017] Further, the organic fluorine monomer and the organic silicon monomer in step (2) are octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane, the ratio is 1:0-0:1, the cationic ring-opening agent is dodecylbenzenesulfonic acid, the crosslinking agent is vinyltrimethoxysilane, and one of the vinyltrimethoxysilane.

[0018] Further, the humectant in step (3) is octadecyl fatty alcohol polyoxyethylene ether, and the total amount is 3wt%-5wt% of the fluorosilicon coated seed color hard ball ink; the surface active regulator is a non-ionic defoaming wetting agent, and the amount is 0.05wt%-1wt% of the fluorosilicon coated seed color hard ball ink; and the pH regulator is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium carbonate, and the pH of the micro-nano fluorosilicon polymer coated color hard ball ink is controlled to be 7-9.

[0019] Further, the surface tension of the fluorosilicon coated seed color hard ball ink in step (3) is controlled to be 20mN / m-35mN / m, and the viscosity is controlled to be 2-5cp.

[0020] In detail, the application provides a preparation method of a color hard ball ink for digital inkjet printing, mainly including the following steps:

[0021] (1) Color hard ball emulsion preparation: 9wt% of high solubility reactive anthraquinone dye and 1wt%-5wt% of initiator in total monomers are dissolved in styrene to form an oil phase, 3wt%-5wt% of emulsifier in total monomers is dissolved in deionized water to form an aqueous phase, the oil phase is poured into the aqueous phase, pre-emulsified for 20min (power is 650W) to form a coarse emulsion. After pre-emulsification, the emulsion is placed in an ice water bath and ultrasonicated for 20min. The obtained pre-emulsified liquid is transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 is introduced for 15min. Finally, the emulsion is reacted in a 70℃ water bath for 8h to prepare a color hard ball emulsion.

[0022] (2) Micro-nano fluorosilicon polymer coated color hard ball emulsion preparation: the color hard ball seed emulsion is added to a reaction kettle, the organic fluorosilicon monomer, soft monomer, 1wt%-3wt% of initiator in total monomers, and the crosslinking agent are the oil phase; the water, 3wt%-5wt% of emulsifier and the cationic ring-opening agent are the aqueous phase, the oil phase is poured into the aqueous phase and emulsified for 20min, after pre-emulsification, the emulsion is placed in an ice water bath and ultrasonicated for 20min, and then injected into the reaction kettle for reaction at 75℃ for 8h to prepare a micro-nano fluorosilicon polymer coated color hard ball emulsion.

[0023] (3) The micro-nano fluorosilicon polymer coated color hard sphere ink: the micro-nano fluorosilicon polymer coated color hard sphere emulsion (the balance) is added into 3wt%-5wt% humectant, 0.05wt%-1wt% surfactant, and Ph regulator (adjusted to 7-9) to prepare the micro-nano fluorosilicon polymer coated color hard sphere ink (the total mass percentage is 100%).

[0024] The present application provides a micro-nano fluorosilicon polymer coated color hard sphere ink for digital inkjet printing, which has the following five main advantages:

[0025] (1) The present application uses high-solubility reactive anthraquinone dyes, which have high solubility in styrene monomers, so that the color hard sphere emulsion prepared by polymerization reaction has higher color depth, solving the key problem of low dye content and light dyeing of traditional color hard sphere dyes.

[0026] (2) The prepared reactive anthraquinone dyes have active carbon-carbon double bonds, which can copolymerize with styrene monomers to form a firm chemical bond, greatly improving the color fastness of the hard sphere ink. With the adhesion of the low glass transition temperature of the acrylate soft monomer, 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 it meets the market demand for safety and environmental protection.

[0027] (3) The micro-nano fluorosilicon polymer coated color hard sphere ink prepared by the present application has a regular spherical micro-morphology and is uniformly dispersed, without large particles, which has little effect on the shape of the ink droplets, and well solves the problem of easy clogging of the inkjet head.

[0028] (4) The present application uses organic fluorosilicon monomers and acrylate soft monomers as shell monomers to coat styrene color hard spheres. The introduction of organic fluorosilicon segments gives the inkjet printed fabric excellent hydrophobic properties, softness and color fastness.

[0029] (5) The present application uses octadecyl fatty alcohol polyoxyethylene ether as a humectant. Compared with alcohol humectants, a smaller amount can make the ink have excellent moisturizing properties, relatively increase the content of fluorosilicon coated color hard spheres, and further improve the wearability of the inkjet printed fabric.

[0030] The preparation method and application of the micro-nano fluorosilicon polymer coated color hard sphere ink for digital inkjet printing meet the development needs of textiles, have no wastewater in the preparation process, do not require chemical colorants, are green and pollution-free, have great development potential and broad market prospects. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is a nuclear magnetic resonance characterization diagram and infrared spectrum of high-solubility reactive anthraquinone dyes;

[0032] Figure 2 is a reaction flow diagram of styrene seed color hard sphere emulsion and fluorosilicon shell emulsion;

[0033] Figure 3 is a TEM transmission electron microscope image of styrene seed color hard sphere emulsion and fluorosilicon shell layer emulsion;

[0034] Figure 4 is a micro-nano fluorosilicon polymer coated color hard sphere inkjet printed fabric hydrophobic image. DETAILED DESCRIPTION

[0035] The following description is only preferred embodiments of the present application, and is not intended to limit the present application, although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to part of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

[0036] The dye preparation method used in the present application is as follows:

[0037] Preparation of high solubility reactive anthraquinone dye: 0.52 g of HEMA, 10 g of anhydrous sodium carbonate, and 200 ml of 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. At a temperature of 0-5°C, 1.48 g of cyanuric chloride was added, and stirred for 48 h. Then 2.64 g of CI Disperse Red 60 was added, and stirred at 40-50°C for 48 h, followed by heating to 100°C, and 0.753 g of phenol was weighed in for continuous reaction for 8 h. After cooling to room temperature, it was filtered with a sand core funnel, and the filtrate was evaporated to a red solid, which was purified by column chromatography with ethyl acetate: dichloromethane = 2:1 (v / v) as the developing agent, and a high solubility reactive anthraquinone dye was obtained (structure characterization as shown in Figure 1).

[0038] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the present application will be further described in detail below with reference to specific embodiments and drawings.

[0039] Example 1

[0040] (1) Color hard ball seed emulsion preparation: 1.08 g (9 wt%) of high solubility reactive anthraquinone dye and 0.2616 g (1 wt%) of azobisisobutyronitrile of total monomers were dissolved in 12 g of styrene to form an oil phase, 0.36 g of sodium dodecyl sulfate was dissolved in 36 g of deionized water (25 wt%) to form an aqueous phase, the oil phase was poured into the water phase, 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 color hard ball seed emulsion.

[0041] (2) Preparation of micro-nano fluorosilicon polymer coated color hard ball emulsion: 40.72 g of the above color hard ball seed emulsion was transferred to a reaction kettle, 4.8 g of octamethylcyclotetrasiloxane, 1.2 g of trifluoropropylmethylcyclotrisiloxane, 3 g of butyl acrylate, 0.18 g of azobisisobutyronitrile, and 0.18 g of vinyltrimethoxysilane were used as the oil phase; 34 g of water (15 wt%), 0.27 g of sodium dodecyl sulfate, and 0.6 g of dodecylbenzenesulfonic acid were used as the aqueous phase, the oil phase was poured into the water phase and emulsified for 20 min, after pre-emulsification, the emulsion was placed in an ice water bath and ultrasonicated for 20 min (650 W) and then injected (10 ml / h) into the reaction kettle at 75°C for 8 h to prepare a micro-nano fluorosilicon polymer coated color hard ball emulsion.

[0042] (3) Preparation of micro-nano fluorosilicon polymer coated color hard ball ink: based on 100% of the total mass of the color hard ball ink, the micro-nano fluorosilicon polymer coated color hard ball (balance) was added to 3 wt% of octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yangsong Technology), 0.05 wt% of non-ionic defoaming wetting agent surfactant 104e (Yingchuang Base), and sodium carbonate Ph adjuster (adjusted to 8), filtered through a PVDF membrane with a pore size of 1 um to prepare an inkjet printing micro-nano fluorosilicon polymer coated color hard ball ink.

[0043] Example 2

[0044] (1) Color hard ball seed emulsion preparation: 1.08 g (9 wt%) of high solubility reactive anthraquinone dye and 0.2616 g (1 wt%) of azobisisobutyronitrile of total monomers were dissolved in 12 g of styrene to form an oil phase, 0.36 g of sodium dodecyl sulfate was dissolved in 36 g of deionized water (25 wt%) to form an aqueous phase, the oil phase was poured into the water phase, 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 color hard ball seed emulsion.

[0045] (2) Preparation of micro-nano fluorosilicone polymer coated color hard sphere emulsion: 24.72 g of the above color hard sphere seed emulsion was transferred to a reaction kettle, 6 g of octamethylcyclotetrasiloxane, 0 g of trifluoropropylmethylcyclotrisiloxane, 3 g of butyl acrylate, 0.18 g of azobisisobutyronitrile, and 0.18 g of vinyltrimethoxysilane were used as the oil phase; 27 g of water (25 wt%), 0.27 g of sodium dodecyl sulfate, and 0.6 g of dodecylbenzenesulfonic acid were used as the water phase, the oil phase was poured into the water phase and emulsified for 20 min, after pre-emulsification, the emulsion was placed in an ice water bath and ultrasonicated for 20 min (650 W) and then injected (10 ml / h) into the reaction kettle at 75°C for 8 h to prepare the micro-nano fluorosilicone polymer coated color hard sphere emulsion.

[0046] (3) Preparation of micro-nano fluorosilicone polymer coated color hard sphere ink: 3 wt% of octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yangsong Technology) and 0.05 wt% of non-ionic defoaming wetting agent surfactant 104e (Yingchuang Base Material) were added to the micro-nano fluorosilicone polymer coated color hard sphere (balance) to prepare the inkjet printing micro-nano fluorosilicone polymer coated color hard sphere ink, which was filtered through a PVDF membrane with a pore size of 1 um.

[0047] Example 3

[0048] (1) Preparation of color hard sphere seed emulsion: 1.08 g (9 wt%) of high solubility reactive anthraquinone dye and 0.2616 g (1 wt%) of azobisisobutyronitrile were dissolved in 12 g of styrene to form an oil phase, 0.36 g of sodium dodecyl sulfonate was dissolved in 36 g of deionized water (25 wt%) 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 the color hard sphere seed emulsion.

[0049] (2) Micro-nano fluorosilicon polymer coated color hard ball emulsion preparation: 24.72 g of the above color hard ball seed emulsion was transferred to a reaction kettle, 4.8 g of octamethylcyclotetrasiloxane, 1.2 g of trifluoropropylmethylcyclotrisiloxane, 3 g of butyl acrylate, 0.18 g of azobisisobutyronitrile, and 0.18 g of vinyltrimethoxysilane were used as the oil phase; 27 g of water (25 wt%), 0.27 g of sodium dodecyl sulfate, and 0.6 g of dodecylbenzenesulfonic acid were used as the water phase, the oil phase was poured into the water phase and emulsified for 20 min, after pre-emulsification, the emulsion was placed in an ice water bath and ultrasonicated for 20 min (650 W), then injected (10 ml / h) into the reaction kettle at 75°C for 8 h to prepare the micro-nano fluorosilicon polymer coated color hard ball emulsion.

[0050] (3) Preparation of micro-nano fluorosilicon polymer coated color hard ball ink: based on 100% of the total mass percentage of the color hard ball ink, the micro-nano fluorosilicon polymer coated color hard ball (balance) was added to 3 wt% of octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yangsong Technology), 0.05 wt% of non-ionic defoaming wetting agent surfactant 104e (Yingchuang Base Material), and sodium carbonate Ph adjuster (adjusted to 8), filtered through a PVDF membrane with a pore size of 1 um to prepare the micro-nano fluorosilicon polymer coated color hard ball ink for inkjet printing.

[0051] Example 4

[0052] (1) Color hard ball seed emulsion preparation: 1.08 g (9 wt%) of high solubility reactive anthraquinone dye and 0.2616 g (1 wt%) of azobisisobutyronitrile were dissolved in 12 g of styrene to form an oil phase, 0.36 g of sodium dodecyl sulfonate was dissolved in 36 g of deionized water (25 wt%) to form an aqueous 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 ultrasonicated for 20 min. The obtained pre-emulsified liquid 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 the color hard ball seed emulsion.

[0053] (2) Micro-nano fluorosilicon polymer coated color hard ball emulsion preparation: 24.72 g of the above color hard ball seed emulsion was transferred to a reaction kettle, 3 g of octamethylcyclotetrasiloxane, 3 g of trifluoropropylmethylcyclotrisiloxane, 3 g of butyl acrylate, 0.18 g of azobisisobutyronitrile, and 0.18 g of vinyltrimethoxysilane were used as the oil phase; 27 g of water (25 wt%), 0.27 g of sodium dodecyl sulfate, and 0.6 g of dodecylbenzenesulfonic acid were used as the water phase, the oil phase was poured into the water phase and emulsified for 20 min, after pre-emulsification, the emulsion was placed in an ice water bath and ultrasonicated for 20 min (650 W), then injected (10 ml / h) into the reaction kettle at 75°C for 8 h to prepare the micro-nano fluorosilicon polymer coated color hard ball emulsion.

[0054] (3) Preparation of micro-nano fluorosilicon polymer coated color hard sphere ink: with 100% of the total mass of color hard sphere ink, micro-nano fluorosilicon polymer coated color hard sphere (balance) is added to 3wt% octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yang Song Technology), 0.05wt% non-ionic defoaming wetting agent surfactant 104e (Yingchuang base), sodium carbonate Ph adjuster (adjusted to 8), filtered by PVDF membrane with pore size of 1um to prepare micro-nano fluorosilicon polymer coated color hard sphere ink for inkjet printing.

[0055] Example 5

[0056] (1) Preparation of color hard sphere seed emulsion: 1.08g (9wt%) of high solubility reactive anthraquinone dye and 0.2616g (1wt%) of azobisisobutyronitrile are dissolved in 12g of styrene to form an oil phase, 0.36g of sodium dodecyl sulfonate is dissolved in 36g of deionized water (25wt%) to form an aqueous phase, the oil phase is poured into the water phase, pre-emulsified for 20min (power is 650W) to form a coarse emulsion. After pre-emulsification, the emulsion is placed in an ice water bath and ultrasonicated for 20min. The obtained pre-emulsion is transferred to a three-necked round-bottom flask equipped with a condenser and a mechanical stirrer for reaction and N2 is introduced for 15min. Finally, the emulsion is reacted in a 70℃ water bath for 8h to prepare the color hard sphere seed emulsion.

[0057] (2) Preparation of micro-nano fluorosilicon polymer coated color hard sphere emulsion: 24.72g of the above color hard sphere seed emulsion is transferred to a reaction kettle, 0g octamethylcyclotetrasiloxane, 6g trifluoropropylmethylcyclotrisiloxane, 3g butyl acrylate, 0.18g azobisisobutyronitrile, and 0.18g vinyltrimethoxysilane are used as the oil phase; 27g water (25wt%), 0.27g sodium dodecyl sulfate, and 0.6g dodecylbenzenesulfonic acid are used as the aqueous phase, the oil phase is poured into the water phase and emulsified for 20min, after pre-emulsification, the emulsion is placed in an ice water bath and ultrasonicated for 20min (650W) and then injected (10ml / h) into the reaction kettle at 75℃ for 8h to prepare the micro-nano fluorosilicon polymer coated color hard sphere emulsion.

[0058] (3) Preparation of micro-nano fluorosilicon polymer coated color hard sphere ink: with 100% of the total mass of color hard sphere ink, micro-nano fluorosilicon polymer coated color hard sphere (balance) is added to 3wt% octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yang Song Technology), 0.05wt% non-ionic defoaming wetting agent surfactant 104e (Yingchuang base), sodium carbonate Ph adjuster (adjusted to 8), filtered by PVDF membrane with pore size of 1um to prepare micro-nano fluorosilicon polymer coated color hard sphere ink for inkjet printing.

[0059] Comparative Example 1

[0060] (1) Color hard-sphere seed emulsion preparation: 0.36 g (9 wt%) of high-solubility reactive anthraquinone dye and 0.3924 g of AIBN of total monomers were dissolved in 12 g of styrene to form an oil phase, 0.6 g of sodium dodecyl sulfonate was dissolved in 36 g (25 wt%) of deionized water to form an aqueous phase, the oil phase was poured into the water phase, 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 the color hard-sphere emulsion.

[0061] (2) Color hard-sphere ink for digital inkjet printing: The color hard-sphere emulsion was added to 3 wt% of octadecyl fatty alcohol polyoxyethylene ether (FDC, Guangzhou Yangsong Technology), 0.05 wt% of non-ionic defoaming wetting agent surfactant 104e (Yingchuang Base), sodium carbonate Ph adjuster (adjusted to 8), filtered through a PVDF membrane with a pore size of 1 um to prepare a micro-nano fluorosilicon polymer coated color hard-sphere ink for inkjet printing.

[0062] Comparative Example 1 is a color hard-sphere ink without fluorosilicon coating.

[0063] Table 2 is the performance of micro-nano fluorosilicon polymer coated color hard-sphere ink with different formulations

[0064]

[0065] As can be seen from Table 2, the micro-nano fluorosilicon polymer coated color hard-sphere emulsion has a particle size of less than 100 nm. The particle size distribution index is low, the absolute potential value is high, and the stability is excellent.

[0066] Figure 1 is the nuclear magnetic resonance and infrared characterization of the high-solubility reactive anthraquinone dye, which proves that the dye is successfully synthesized

[0067] Figure 3 is a transmission characterization of the styrene color hard-sphere prepared in Example 5, and the results are shown in Table 1. The particle size of the micro-nano fluorosilicon polymer coated color hard-sphere emulsion is 77.81 nm, and the PDI is 0.076. The particle size meets the requirements of inkjet printing (≤200 nm). As can be seen from the transmission electron microscope photo, the prepared color hard-sphere is uniform spherical and uniformly distributed.

[0068] Figure 4 is the inkjet printed cotton fabric prepared in Example 5, which shows that the fabric sample printed using the micro-nano fluorosilicon polymer coated color hard-sphere ink has an excellent water contact angle.

[0069] The above-described embodiments are only the preferred ones of the present application, and do not limit the present application in any form, and other variants and modifications can be made without departing from the technical solutions recited in the claims.

Claims

1. A method for preparing micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink, characterized in that, The method comprises the following steps: (1) introducing polymerizable double bonds and solubilizing groups to anthraquinone parent compounds to synthesize reactive anthraquinone dyes composed of anthraquinone parent compounds-linking groups-polymerizable groups-solubilizing groups; (2) dissolving the reactive anthraquinone dyes in styrene monomers, adding water, emulsifiers and initiators, and preparing color hard sphere seed emulsions through free radical polymerization; (3) transferring the color hard sphere seed emulsions to a reactor, using organic fluorosilicon monomers and soft monomers as shell layers, and adding initiators, crosslinking agents, water, emulsifiers and cationic ring-opening agents to the reactor to perform free radical polymerization and cationic ring-opening miniemulsion polymerization processes to prepare micro-nano fluorosilicon polymer coated color hard sphere emulsions; (4) adding moisturizers, pH regulators and surface tension regulators to the micro-nano fluorosilicon polymer coated color hard sphere emulsions to perform regulation, and finally preparing micro-nano fluorosilicon polymer coated color hard sphere digital inkjet inks.

2. The production method according to claim 1, characterized by, In step (2), the concentration of the color hard sphere seed emulsion is 15wt%-30wt%; In step (3), the concentration of the micro-nano fluorosilicon polymer coated color hard sphere emulsion is 10wt%-25wt%.

3. The preparation method according to claim 1, characterized in that, In step (2), the emulsifier is one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the amount is 3wt%-5wt% of the styrene monomers; In step (3), the emulsifier is one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the amount is 3wt%-5wt% of the total mass of the organic fluorosilicon monomers and the soft monomers.

4. The production method according to claim 1, characterized by, In step (2), the initiator is one or two of azobis cyanovaleric acid, azobis diisobutyl amidine hydrochloride, azobis isobutyronitrile and potassium persulfate, and the amount is 1%-5% of the mass of the styrene monomers and the reactive anthraquinone dyes; In step (3), the initiator is one or two of azobis cyanovaleric acid, azobis diisobutyl amidine hydrochloride, azobis isobutyronitrile and potassium persulfate, and the amount is 1%-3% of the total mass of the organic fluorosilicon monomers and the soft monomers.

5. The preparation method of core-shell type color hard sphere ink according to claim 1, characterized in that, In step (3), the soft monomer is one or more of butyl acrylate, ethyl acrylate and isooctyl acrylate.

6. The method of claim 1, wherein, In step (3), the organic fluorosilicon monomer is one or more of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane, and the mass ratio is 1:0-0:1; The cationic ring-opening agent is dodecyl benzene sulfonic acid; The crosslinking agent is one of vinyl trimethoxysilane and vinyl trimethoxysilane.

7. The preparation method according to claim 1, characterized in that, In step (3), the organic fluorosilicon monomers, the soft monomers, the initiators, the crosslinking agents, water, the emulsifiers and the cationic ring-opening agents are mixed and then added to the reactor through injection at 70-80℃ for 4-12h, and the injection speed is 10-30ml / h.

8. The method of claim 1, wherein, In step (4), the surface tension regulator is a non-ionic defoaming wetting agent; The pH regulator is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium carbonate; The moisturizer is octadecyl fatty alcohol polyoxyethylene ether.

9. The method of claim 1, wherein, In step (4), the micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink is prepared from the following raw materials with the following mass percentages: moisturizing agent 3wt%-5wt%; surface tension regulator 0.05wt%-1wt%; micro-nano fluorosilicon polymer coated color hard sphere emulsion balance; adjusting the pH of the micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink to 7-9 with a pH regulator.

10. The application of the micro-nano fluorosilicon polymer coated color hard sphere digital inkjet ink prepared by the preparation method according to any one of claims 1-9 in digital inkjet printing.

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