Micellar phase change type reactive dye ink based on cationic polymer regulation and control

Abstract

The invention relates to the technical field of ink-jet printing, and discloses micelle phase change type reactive dye ink based on cationic polymer regulation and control. On the basis of a cationic compound with the relative molecular weight of 1000-400000 in an ink system, an anionic surfactant aggregate structure is induced to be converted by means of an ionic bond effect, the rheological property and the dynamic surface tension of the reactive dye ink are regulated and controlled without adding a viscosity regulator, the dynamic surface tension response rate is increased, and the reactive dye ink is prepared. Therefore, the uniformity and the stability of the morphology of ink-jet printing ink droplets are improved, the dynamic wetting behavior in the process that the ink droplets collide with a base material is improved, high-precision ink-jet printing of reactive dye ink on textile fabric is achieved, and the ink-jet printing device has the advantages of being efficient, low in energy consumption and good in finishing effect and has extremely good popularization value.

Description

Technical Field

[0001] The present invention relates to the technical field of inkjet printing, in particular to a micellar phase-change reactive dye ink regulated by a cationic polymer. Background Art

[0002] As a key technology in digital manufacturing, inkjet printing integrates the achievements of multiple disciplines, including computer science, precision mechanical engineering, and materials science. With its high production efficiency, environmental friendliness, and flexible adaptability, it is gradually replacing traditional printing techniques and occupying a core position in industries such as textiles, packaging, and decoration. Driven by the deep synergy of artificial intelligence and the Internet of Things, this technology is accelerating its evolution towards intelligent control and ultra-precision. This requires ink systems to meet more stringent performance standards, maintaining rheological stability during ultra-high-speed jetting, and simultaneously ensuring ink droplet landing accuracy and substrate penetration efficiency, achieving indicators related to submicron pattern contour clarity.

[0003] At present, the performance optimization of inkjet ink mainly relies on the following technical routes, but there are still significant limitations: Viscosity regulator addition method (such as patent CN114016306A): The viscosity of the ink is adjusted by introducing thickeners such as polyvinyl pyrrolidone or carboxymethyl chitosan, but excessive addition will cause satellite particles to be generated during the flight of the ink droplets, resulting in blurred pattern edges. Surface tension regulation method: The micelle morphology is changed by adjusting the concentration of silicone oil contained in a single surfactant and the carbon content of the alkyl group (such as patent CN119640604A), but there is a problem of low dynamic surface tension response rate, which causes uneven spreading of the ink droplets when in contact with the substrate, affecting the fineness. For traditional regulators, PEG compounds, PVP compounds, etc. are difficult to degrade and will pollute water and soil; substances such as ethylene glycol ethers and toluene are neurotoxic and carcinogenic, and the EU REACH regulations have restricted their use (such as patent CN117988133A). The above methods are difficult to take into account the technical indicators of low viscosity, high dynamic response and low satellite point incidence, which restricts the application of inkjet printing in high-precision scenarios (such as microcircuit printing and high-end textiles).

[0004] Therefore, it is necessary to develop a micellar phase change reactive dye ink based on cationic polymer regulation. Without adding an external viscosity regulator, the ionic association between the cationic polymer and the anionic surfactant can be used to induce the structural transformation of the surfactant aggregate, thereby achieving precise control of the rheological properties and dynamic surface tension of the ink, improving the dynamic surface tension response rate, and inhibiting the generation of satellite points of the jetted ink droplets. At the same time, it ensures that the ink droplets spread quickly after hitting the substrate, thereby achieving the industrial goals of high-speed inkjet printing ink droplet stability and high pattern fineness. Summary of the Invention

[0005] To enhance the fineness and process stability of inkjet printing patterns, the present invention provides a cationic polymer-mediated micellar phase-change reactive dye ink. This innovative approach incorporates a cationic polymer-mediated micellar phase-change mechanism into the reactive dye ink system, overcoming the limitations of traditional methods that rely on a single component to modulate the ink's rheological properties and dynamic surface tension. The core of this approach lies in incorporating the cationic polymer-mediated micellar phase-change mechanism into the reactive dye ink. Without the addition of a viscosity modifier, this approach leverages the structural transformation of surfactant aggregates to precisely control the ink's rheological properties and dynamic surface tension, improving the dynamic surface tension response rate. This approach achieves two key innovations: 1. Formula innovation, eliminating exogenous additives such as polyethylene glycol, reducing raw material costs and simplifying the process; and 2. Performance enhancement, through dynamic micelle reconstruction, simultaneously optimizing rheological properties and interfacial response, suppressing satellite dot formation, ensuring ink droplet spread and finalization within 5ms, and enhancing the clarity of inkjet patterns. No prior art method has disclosed a solution for optimizing reactive dye ink systems based on a cationic polymer-induced micellar phase-change strategy. The present invention achieves targeted performance control through a multi-level molecular-micelle structure collaborative design, demonstrating substantial innovation. At the same time, the system can adapt to continuous production needs. As a common solution for inkjet printing, it will help the industry transform to low-carbon precision manufacturing.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] The present invention proposes a micellar phase change reactive dye ink regulated by a cationic polymer, which is composed of the following components by mass percentage: 1% to 50% of a cationic polymer, 5% to 50% of a reactive dye, 0.1% to 20% of an anionic surfactant, 0% to 20% of a cosolvent, 0% to 20% of a moisturizer, 0% to 10% of a pH regulator, 0% to 2% of an antibacterial agent, and the balance being deionized water.

[0008] The cationic polymer-modulated micellar phase-change reactive dye ink contains 1% to 50% cationic polymer. Prepared within this concentration range, the cationic polymer-modulated micellar phase-change reactive dye ink achieves controlled transformation of the surfactant's self-assembled structure by regulating the electrostatic interaction between the cationic polymer and the anionic surfactant. This intermolecular interaction effectively optimizes the rheological properties and dynamic surface tension behavior of the ink system, significantly improving the ink's jetting stability and substrate wetting while reducing the amount of traditional viscosity modifiers used.

[0009] The cationic polymer refers to a polymer compound with a stable positively charged group on the molecular chain, and its charge center can contain a variety of nitrogen- and phosphorus-containing organic structural units. In addition to conventional primary / secondary / tertiary amino groups, quaternary ammonium salts, quaternary phosphonium salts and guanidinium structures, novel cationic groups such as imidazolium salts and pyridinium structures can also be introduced. Such polymers usually have reactive sites, including but not limited to traditional functional groups such as carboxyl, acid anhydride, halogenated acyl, carbon-carbon double bond, and epoxy groups, and can also be expanded to introduce novel reactive groups such as sulfonate, isocyanate, and maleimide. Depending on the application requirements, its degree of polymerization can be flexibly regulated, and the relative molecular weight covers a wide range of 1000-400000. Specifically, poly(styrene-butyl acrylate-vinylbenzyltrimethylammonium chloride), poly(ethylene oxide-methacryloyloxyethyl trimethylammonium chloride), poly(styrene-ethyl acrylate-vinylbenzyltriethylammonium chloride), poly(hydroxyethyl acrylate sulfonate-vinylbenzyltrimethylammonium chloride), poly(N,N-dimethylacrylamide-benzyl ammonium chloride), poly(styrene-butyl acrylate-dimethylbutyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethylhexyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethyloctyl alkyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethyldodecyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethyloctadecyl allyl ammonium chloride), poly(ethyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(butyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(ethylene oxide-methacryloyloxyethyl trimethyl ammonium chloride), poly(octadecyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(maleimide ethyl acrylate-acryloyloxyethyl trimethyl ammonium chloride), poly(propylene acrylate-acryloyloxyethyl trimethyl ammonium chloride), poly(styrene-butyl acrylate-vinylbenzyl triethyl ammonium chloride), poly(butyl acrylate-diethylaminoethyl methacrylate quaternary ammonium salt), poly(divinylbenzene-dimethylaminoethyl methacrylate quaternary ammonium salt), poly(acrylamide-diallyl dimethyl ammonium chloride), poly(dimethylaminopropyl methacrylamide-butyl ammonium bromide), poly(dimethylaminopropyl methacrylamide-hexyl ammonium bromide), poly(dimethylaminopropyl methacrylamide-benzylammonium bromide), poly(vinyl pyrrolidone-methyl acrylate The invention also includes one or more of the following: poly(vinyl imidazolium chloride-styrene), poly(dimethylsiloxane-dimethylaminoethyl methacrylate quaternary ammonium salt), poly(N-vinyl pyrrolidone-vinyl pyridinium methyl sulfate), poly(polyethylene glycol-isocyanate acrylate-vinyl imidazolium chloride), poly(hydroxyethyl acrylate-vinyl pyridinium benzyl chloride), poly(polyethylene glycol methyl ether acrylate-4-vinyl pyridinium ethyl bromide), and poly(glycerol dimethacrylate-vinyl pyridinium butyl ammonium bromide).

[0010] The micellar phase change reactive dye ink based on cationic polymer regulation is characterized in that the anionic surfactant is one or a mixture of several of sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium stearate, sodium laurate, sodium lauryl ether carboxylate, sodium dioctyl sulfosuccinate, sodium toluene sulfonate, sodium xylene sulfonate, sodium lauryl polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium α-olefin sulfonate, sodium alkyl diphenyl ether disulfonate, sodium naphthalenesulfonic acid formaldehyde condensate, sodium tetradecyl sulfate, sodium N-lauroyl sarcosinate, disodium sulfosuccinate monoester, sodium hexadecylbenzenesulfonate, sodium nonylbenzenesulfonate, sodium sulfonated polyacrylate, sodium oleic acid sulfate, sodium dinonylnaphthalenesulfonate, sodium octyl sulfate, and sodium cocoyl glutamate.

[0011] The reactive dye is one or a mixture of reactive blue 19, reactive red 198, reactive orange 16, reactive green 12, reactive yellow 17, reactive blue 49, reactive black 31, reactive red 24, reactive blue 72, reactive gray 4, reactive violet 23, reactive yellow 145, reactive orange 7, reactive red 141, reactive blue 4, reactive black 5, reactive red 120, reactive green 19, reactive violet 33, reactive yellow 95, reactive blue 221, reactive brown 21, reactive black 39, reactive red 195, reactive yellow 84, reactive blue 13, reactive orange 122, reactive red 11, reactive blue 21, reactive yellow 37, reactive black 8, reactive blue 194, reactive red 194, reactive violet 5, reactive orange 84, reactive green 8, reactive yellow 176, reactive red 218, reactive brown 9, and reactive yellow 160.

[0012] Preferably, the anionic surfactant is sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium stearate, sodium laurate, sodium lauryl ether carboxylate, sodium dioctyl sulfosuccinate, sodium toluene sulfonate, sodium xylene sulfonate, sodium lauryl polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium α-olefin sulfonate, sodium alkyl diphenyl ether disulfonate, sodium naphthalenesulfonic acid formaldehyde condensate, sodium tetradecyl sulfate, sodium N-lauroyl sarcosinate, disodium sulfosuccinate monoester, sodium hexadecylbenzenesulfonate, sodium nonylbenzenesulfonate, sodium sulfonated polyacrylate, sodium oleate sulfate, sodium dinonylnaphthalenesulfonate, sodium octyl sulfate, and sodium cocoyl glutamate, or a mixture of more thereof.

[0013] Preferably, the reactive dye is one or more of reactive blue 19, reactive red 198, reactive orange 16, reactive green 12, reactive yellow 17, reactive blue 49, reactive black 31, reactive red 24, reactive blue 72, reactive gray 4, reactive violet 23, reactive yellow 145, reactive orange 7, reactive red 141, reactive blue 4, reactive black 5, reactive red 120, reactive green 19, reactive violet 33, reactive yellow 95, reactive blue 221, reactive brown 21, reactive black 39, reactive red 195, reactive yellow 84, reactive blue 13, reactive orange 122, reactive red 11, reactive blue 21, reactive yellow 37, reactive black 8, reactive blue 194, reactive red 194, reactive violet 5, reactive orange 84, reactive green 8, reactive yellow 176, reactive red 218, reactive brown 9, and reactive yellow 160.

[0014] Preferably, the cosolvent is one or a mixture of ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monobutyl ether, N-methylpyrrolidone, dimethyl sulfoxide, cyclohexanone, dimethyl imide, propylene glycol methyl ether, ethylene glycol phenyl ether, ethylene glycol monobutyl ether, and ethyl lactate.

[0015] Preferably, the moisturizing agent is one or a mixture of glycerol, ethylene glycol, diethylene glycol, polyethylene glycol, sorbitol, propylene glycol, 1,2-hexanediol, xylitol, urea, and triethylene glycol.

[0016] Preferably, the pH adjuster is one or a mixture of citric acid, sodium hydroxide, triethanolamine, sodium dihydrogen phosphate, sodium bicarbonate, ammonia water, acetic acid, borax, 2-amino-2-methyl-1-propanol, and hydrochloric acid.

[0017] Preferably, the antibacterial agent is one or a mixture of isothiazolinone, benzisothiazolinone, 2-methyl-4-isothiazolin-3-one, glutaraldehyde, sodium benzoate, sodium dehydroacetate, DMDM hydantoin, bronopol, and silver ion antibacterial agents.

[0018] The present invention also provides a method for preparing the above-mentioned micellar phase change reactive dye ink based on cationic polymer regulation, comprising the following steps:

[0019] The invention discloses a method for preparing a micellar phase-change active dye ink regulated by a cationic polymer. The method comprises the following steps: taking various raw material components, uniformly mixing the components except the cationic polymer in proportion, slowly adding the cationic polymer dropwise with stirring using a peristaltic pump, stirring for 1-3 hours, and filtering through a 0.10-1.00 micron filter membrane to prepare a micellar phase-change active dye ink regulated by a cationic polymer. The prepared micellar phase-change active dye ink regulated by a cationic polymer has a viscosity of 1-100 cP, a surface tension of 20-100 mN / m, a pH value of 3-9, a dynamic surface tension response rate of 1-300 mN / (m·s), a uniform morphology of ejected ink droplets, and can be continuously printed without ink for 3 months. Based on cryo-transmission observation, the aggregate structure of anionic surfactants includes spherical, worm-like, lamellar micelles and vesicle structures. Due to the differences in the aggregate structures, the average particle size distribution is 10 nm to 150 nm. The micellar phase-change active dye ink regulated by the cationic polymer is uniformly mixed according to the component proportions and then filtered through a 0.10-1.00 micron filter membrane.

[0020] In order to more clearly understand the technical solution of the present invention, the invention mechanism of the present technical solution is explained as follows:

[0021] (1) The ionic association of cationic polymers can be controlled by the anion / cation concentration ratio. When the concentration of anionic surfactants is higher than that of cationic polymers, the excess anions completely neutralize the positive charge of the polymer chains through electrostatic adsorption, resulting in a significant shielding of the electrostatic repulsion between cationic segments. The intermolecular interaction is dominated by the van der Waals force of the surfactant hydrophobic chain, forming a weakly bound micelle-polymer complex. When the anion / cation ratio reaches an equimolar ratio, the two form a high-strength electrostatic association through charge complementarity. The positively charged groups of the cationic polymers and the anionic groups of the surfactants produce localized strong dipole interactions, which promote the construction of a through-type three-dimensional electrostatic cross-linked network between the polymer backbone and the micelle units. When the concentration of cationic polymers is dominant, the unbound cationic groups form long-range electrostatic repulsion domains in the solution, forcing the polymer chains to stretch and produce a spatial repulsion effect. At the same time, the surfactant micelles are anchored to the polymer chains through charge matching, forming a "rigid-flexible" composite structure stabilized by the electrostatic repulsion and micelle steric hindrance.

[0022] (2) The change in cationic polymer concentration systematically regulates the fluidity, surface tension, and dynamic response behavior of the ink through the coupling of charge interaction and fluid mechanics. When the polymer concentration increases, the excess cationic groups increase the ionic strength of the system through the Donnan effect, compress the double layer thickness of the colloidal particles, and reduce the Zeta potential, resulting in a decrease in dispersion stability. At the same time, the polymer chains entangle to form a transient network structure, causing the zero-shear viscosity to increase exponentially with concentration. The network disentanglement at high shear rates triggers a significant shear thinning effect, achieving an adaptive switch between static anti-settling and dynamic low viscosity of the ink. At the level of dynamic surface tension response, high-concentration polymers limit the migration rate of surfactant monomers to the gas-liquid interface through electrostatic capture, resulting in an increase in static surface tension. However, during the transient process of high-speed shear or ink droplet impact on the substrate, the external force field induces the disassociation of the polymer-surfactant complex, and the released free surfactant is rapidly adsorbed to the three-phase contact line, accelerating the spreading of the liquid film by reducing the dynamic surface tension gradient. In addition, when the polymer concentration exceeds the critical entanglement concentration, its molecular chains form a viscoelastic adsorption layer at the gas-liquid interface, generating a normal stress difference through changes in conformational entropy. This stress field synergistically dissipates the kinetic energy of ink droplet impact and suppresses capillary wave oscillations. At the same time, with the help of the Marangoni effect, it compensates for the local surface tension differences during the wetting process, ultimately achieving the dual suppression of uniform liquid film spreading and satellite point generation, and achieving cross-scale collaborative optimization of ink rheological properties, interfacial behavior and dynamic response.

[0023] Compared with related technologies, the micellar phase change reactive dye ink based on cationic polymer regulation provided by the present invention has the following beneficial effects:

[0024] (1) The present invention constructs an adaptive rheological control system by using cationic polymers and anionic surfactants. Without adding an external viscosity modifier, the system relies on the dynamic cross-linked network formed by intermolecular electrostatic interaction to achieve directional control of the rheological properties of the ink under static storage and high-speed shear conditions, thereby improving the dynamic surface tension response rate and suppressing the generation of satellite points of the jetted ink droplets. During the pipeline transmission stage, the system maintains the structural viscosity of the ink through a three-dimensional network structure, ensuring the stability of ink sedimentation, while meeting the fluid dynamic conditions for continuous injection and the requirements for precise formation of ink droplets on the substrate surface. This mechanism breaks through the injection lag effect caused by the reliance on external viscosity modifiers in traditional inks, thereby improving the clarity and color rendering accuracy of the pattern contour.

[0025] (2) Based on the surfactant aggregate phase transition mechanism regulated by ionic association strength, the precise coupling of dynamic interfacial behavior and ink droplet dynamics is achieved. By adjusting the polymer-surfactant charge density ratio, the aggregate is guided to evolve from a spherical micelle to a lamellar structure, and a non-equilibrium surface tension response window is established. At the moment the ink droplet hits the substrate, the interfacial active components generated by the disassociation of the aggregate quickly migrate to the three-phase contact line, accelerating the spreading of the liquid film by reducing the dynamic surface tension gradient; at the same time, the fluid elastic effect triggered by the structural transformation of the aggregate can effectively dissipate the energy of the ink droplet impact and inhibit the generation of satellite points. This dual-path control mechanism solves the contradiction between ink droplet penetration and positioning accuracy in high-speed printing, and provides an interfacial chemical theoretical basis for the controllable fixation of reactive dye inks. DETAILED DESCRIPTION

[0026] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0027] Example 1:

[0028] Formulating cationic polymer-regulated micellar phase-change reactive dye ink and reactive dye ink;

[0029] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 2 wt% of poly (styrene-butyl acrylate-vinylbenzyltrimethylammonium chloride) (solid content of 45%), 3.0 wt% of dioctyl sodium sulfosuccinate, 8.0 wt% of reactive blue 19, 9.0 wt% of ethylene glycol, 0.2 wt% of triethanolamine and 0.1 wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are uniformly mixed in proportion, and a peristaltic pump is used to slowly pump the mixture while stirring. Add a cationic polymer dropwise, stir for 1-2 hours, and filter through a 0.22-micron filter membrane to obtain a cationic polymer-regulated micellar phase-change reactive dye ink. The prepared cationic polymer-regulated micellar phase-change reactive dye ink has a viscosity of 4 cP, a surface tension of 45 mN / m, a dynamic surface tension response rate of 120 mN / (m·s), a uniform droplet morphology, and can be continuously printed without ink within 3 months. Based on cryo-transmission observation, the structural transformation of anionic surfactant aggregates (spherical, worm-like, etc.) was observed, and the average particle size was 110 nm.

[0030] Example 2:

[0031] Formulating cationic polymer-regulated micellar phase-change reactive dye inks and reactive dye inks;

[0032] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 5.0wt% of poly(styrene-ethyl acrylate-vinylbenzyltriethylammonium chloride) (solid content is 45%), 10.0wt% of sodium dodecylbenzenesulfonate, 8.0wt% of Reactive Red 198, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are evenly mixed in proportion, and stirred using a peristaltic The cationic polymer is slowly added dropwise through a pump. After the addition is completed, the mixture is stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer is 8 cP, the surface tension is 62 mN / m, the dynamic surface tension response rate is 85 mN / (m·s), the droplet morphology is uniform, and continuous printing without ink is required within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 60 nm.

[0033] Example 3:

[0034] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 10.0wt% of poly(styrene-butyl acrylate-dimethyloctyl allyl ammonium chloride) (solid content of 45%), 2.0wt% of sodium lauryl ether carboxylate, 11.0wt% of reactive black 31, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are mixed uniformly in proportion, and a peristaltic pump is used while stirring. The cationic polymer is slowly added dropwise. After the addition is completed, the mixture is stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer is 3 cP, the surface tension is 40 mN / m, the dynamic surface tension response rate is 259 mN / (m·s), the droplet morphology is uniform, and continuous printing without ink is required within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) is observed, and the average particle size is 37 nm.

[0035] Example 4:

[0036] The invention relates to a micellar phase change type reactive dye ink regulated by a cationic polymer, wherein the micellar phase change type reactive dye ink comprises 1.0 wt% of poly (dimethylsiloxane-dimethylaminoethyl methacrylate quaternary ammonium salt) (solid content is 45%), 1.5 wt% of sodium lauryl sulfate, 12.0 wt% of reactive red 24, 9.0 wt% of ethylene glycol, 0.2 wt% of triethanolamine and 0.1 wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are uniformly mixed in proportion, and a peristaltic pump is used to slowly pump the mixture while stirring. The cationic polymer was slowly added dropwise. After the addition was completed, the mixture was stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer was 4 cP, the surface tension was 38 mN / m, the dynamic surface tension response rate was 129 mN / (m·s), the droplet morphology was uniform, and continuous printing without ink was possible within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 60 nm.

[0037] Example 5:

[0038] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 2wt% of poly(styrene-butyl acrylate-dimethylbutyl allyl ammonium chloride) (solid content of 45%), 10.0wt% of sodium dibutylnaphthalene sulfonate, 7.0wt% of reactive blue 221, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are mixed uniformly in proportion, and a peristaltic pump is used while stirring. The cationic polymer is slowly added dropwise. After the addition is completed, the mixture is stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer is 7 cP, the surface tension is 55 mN / m, the dynamic surface tension response rate is 39 mN / (m·s), the droplet morphology is uniform, and continuous printing without ink is required within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) is observed, and the average particle size is 53 nm.

[0039] Example 6:

[0040] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 8wt% of poly(dimethylaminopropylmethacrylamide-butylammonium bromide) (solid content is 45%), 15.0wt% of sodium stearate, 13.0wt% of Reactive Red 11, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are evenly mixed in proportion, and then slowly added dropwise using a peristaltic pump while stirring. After the cationic polymer is added dropwise, the mixture is stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a cationic polymer-regulated micellar phase-change reactive dye ink. The prepared cationic polymer-regulated micellar phase-change reactive dye ink has a viscosity of 6 cP, a surface tension of 50 mN / m, a dynamic surface tension response rate of 207 mN / (m·s), a uniform droplet morphology, and can be continuously printed without ink within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 72 nm.

[0041] Example 7:

[0042] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 5.0wt% of poly(butyl acrylate-methacryloyloxyethyltrimethylammonium chloride) (solid content of 45%), 3.0wt% of sodium lauryl sulfate, 14.0wt% of reactive blue 21, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are uniformly mixed in proportion, and a peristaltic pump is used to slowly pump the mixture while stirring. The cationic polymer was slowly added dropwise. After the addition was completed, the mixture was stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer was 4 cP, the surface tension was 35 mN / m, the dynamic surface tension response rate was 92 mN / (m·s), the droplet morphology was uniform, and continuous printing without ink was possible within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 82 nm.

[0043] Example 8:

[0044] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 10.0wt% of poly(dimethylaminopropylmethacrylamide-benzylammonium bromide) (solid content is 45%), 15.0wt% of sodium dodecylbenzenesulfonate, 9.0wt% of Reactive Orange 84, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are uniformly mixed in proportion, and a peristaltic pump is used to slowly pump the mixture while stirring. Cationic polymers were added dropwise, and after the addition was completed, the mixture was stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The prepared micellar phase-change reactive dye ink regulated by the cationic polymer had a viscosity of 15 cP, a surface tension of 42 mN / m, a dynamic surface tension response rate of 142 mN / (m·s), a uniform droplet morphology, and could be continuously printed without ink for 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregates (spherical, worm-like, etc.) was observed, and the average particle size was 105 nm.

[0045] Example 9:

[0046] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 15.0wt% of poly(styrene-butyl acrylate-dimethyl dodecyl allyl ammonium chloride) (solid content is 45%), 10.0wt% of sodium stearate, 13.0wt% of Reactive Red 218, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are mixed uniformly in proportion, and stirred using a peristaltic The cationic polymer is slowly added dropwise through a pump. After the addition is completed, the mixture is stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The prepared micellar phase-change reactive dye ink regulated by the cationic polymer has a viscosity of 9 cP, a surface tension of 65 mN / m, a dynamic surface tension response rate of 22 mN / (m·s), and a uniform droplet morphology. It can be continuously printed without ink for 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 133 nm.

[0047] Example 10:

[0048] Based on the total weight of the cationic polymer-regulated micellar phase-change reactive dye ink, the cationic polymer-regulated micellar phase-change reactive dye ink includes 1.0wt% of poly(dimethylaminopropylmethacrylamide-hexylammonium bromide) (solid content of 45%), 3.0wt% of sodium dibutylnaphthalenesulfonate, 11.0wt% of Reactive Yellow 160, 9.0wt% of ethylene glycol, 0.2wt% of triethanolamine and 0.1wt% of sodium sorbate, and the balance is water; first, the other components except the cationic polymer are uniformly mixed in proportion, and a peristaltic pump is used to slowly pump the mixture while stirring. The cationic polymer was slowly added dropwise. After the addition was completed, the mixture was stirred for 1-2 hours and then filtered through a 0.22-micron filter membrane to obtain a micellar phase-change reactive dye ink regulated by the cationic polymer. The viscosity of the prepared micellar phase-change reactive dye ink regulated by the cationic polymer was 3 cP, the surface tension was 30 mN / m, the dynamic surface tension response rate was 31 mN / (m·s), the droplet morphology was uniform, and continuous printing without ink was possible within 3 months. Based on cryo-transmission observation, the structural transformation of the anionic surfactant aggregate (spherical, worm-like, etc.) was observed, and the average particle size was 85 nm.

[0049] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent process transformations made using the description of the present invention, or any direct or indirect application in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A micellar phase change reactive dye ink regulated by a cationic polymer, characterized in that: The composition by mass percentage is as follows: Cationic polymer 1% to 50%, reactive dye 5% to 50%, anionic surfactant 0.1 to 20%, cosolvent 0 to 20%, moisturizer 0 to 20%, pH regulator 0 to 10%, antibacterial agent 0 to 2%, and the balance is deionized water; Cationic polymers are polymer compounds with stable positively charged groups on their molecular chains, and their charge centers contain a variety of nitrogen- and phosphorus-containing organic structural units. In addition to conventional primary / secondary / tertiary amino groups, quaternary ammonium salts, quaternary phosphonium salts, and guanidinium structures, novel cationic groups such as imidazolium salts and pyridinium structures are also introduced. Such polymers generally have reactive sites, including traditional functional groups such as carboxyl groups, acid anhydrides, halogenated acyl groups, carbon-carbon double bonds, and epoxy groups, and can also be expanded to introduce novel reactive groups such as sulfonate groups, isocyanate groups, and maleimide groups. Their degree of polymerization can be flexibly controlled, and the relative molecular weight covers a wide range of 1,000-400,000. The molecular structure of the anionic surfactant contains anionic groups, hydrophobic groups and counterions, wherein the anionic groups include one or more structures such as sulfonic acid groups, sulfate groups, carboxyl groups, phosphate groups, methylsulfonate groups, and sulfosuccinic acid diester groups, the hydrophobic groups include one or more of alkyl groups, aryl groups, alkenyl groups, and alkynyl groups, and the counterions include one or more of sodium ions, potassium ions, and ammonium ions.

2. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The cationic polymers are poly(styrene-butyl acrylate-vinylbenzyltrimethylammonium chloride), poly(ethylene oxide-methacryloyloxyethyl trimethylammonium chloride), poly(styrene-ethyl acrylate-vinylbenzyltriethylammonium chloride), poly(hydroxyethyl acrylate sulfonate-vinylbenzyltrimethylammonium chloride), poly(N,N-dimethylacrylamide-benzyl ammonium chloride), poly(styrene-butyl acrylate-dimethylbutyl alkyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethylhexyl allyl ammonium chloride), poly(styrene-butyl acrylate -dimethyloctyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethyldodecyl allyl ammonium chloride), poly(styrene-butyl acrylate-dimethyloctadecyl allyl ammonium chloride), poly(ethyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(butyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(ethylene oxide-methacryloyloxyethyl trimethyl ammonium chloride), poly(octadecyl acrylate-methacryloyloxyethyl trimethyl ammonium chloride), poly(maleimide ethyl acrylate-acryloyloxyethyl trimethyl ammonium chloride), Poly(butyl acrylate-acryloyloxyethyl trimethyl ammonium chloride), poly(styrene-butyl acrylate-vinyl benzyl triethyl ammonium chloride), poly(butyl acrylate-diethylaminoethyl methacrylate quaternary ammonium salt), poly(divinylbenzene-dimethylaminoethyl methacrylate quaternary ammonium salt), poly(acrylamide-diallyl dimethyl ammonium chloride), poly(dimethylaminopropyl methacrylamide-butyl ammonium bromide), poly(dimethylaminopropyl methacrylamide-hexyl ammonium bromide), poly(dimethylaminopropyl methacrylamide-benzylammonium bromide), poly(vinyl pyrrolidone-methyl The invention also includes one or more of the following: poly(vinyl imidazolium chloride-styrene), poly(dimethylsiloxane-dimethylaminoethyl methacrylate quaternary ammonium salt), poly(N-vinyl pyrrolidone-vinyl pyridinium methyl sulfate), poly(polyethylene glycol-isocyanate acrylate-vinyl imidazolium chloride), poly(hydroxyethyl acrylate-vinyl pyridinium benzyl chloride), poly(polyethylene glycol methyl ether acrylate-4-vinyl pyridinium ethyl bromide), and poly(glycerol dimethacrylate-vinyl pyridinium butyl ammonium bromide).

3. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The anionic surfactant is one or a mixture of the following: sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium stearate, sodium laurate, sodium lauryl ether carboxylate, sodium dioctyl sulfosuccinate, sodium toluene sulfonate, sodium xylene sulfonate, sodium lauryl polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium α-olefin sulfonate, sodium alkyl diphenyl ether disulfonate, sodium naphthalenesulfonic acid formaldehyde condensate, sodium tetradecyl sulfate, sodium N-lauroyl sarcosinate, disodium sulfosuccinate monoester, sodium hexadecylbenzenesulfonate, sodium nonylbenzenesulfonate, sodium sulfonated polyacrylate, sodium oleate sulfate, sodium dinonylnaphthalenesulfonate, sodium octyl sulfate, and sodium cocoyl glutamate.

4. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The reactive dye is one or a mixture of reactive blue 19, reactive red 198, reactive orange 16, reactive green 12, reactive yellow 17, reactive blue 49, reactive black 31, reactive red 24, reactive blue 72, reactive gray 4, reactive violet 23, reactive yellow 145, reactive orange 7, reactive red 141, reactive blue 4, reactive black 5, reactive red 120, reactive green 19, reactive violet 33, reactive yellow 95, reactive blue 221, reactive brown 21, reactive black 39, reactive red 195, reactive yellow 84, reactive blue 13, reactive orange 122, reactive red 11, reactive blue 21, reactive yellow 37, reactive black 8, reactive blue 194, reactive red 194, reactive violet 5, reactive orange 84, reactive green 8, reactive yellow 176, reactive red 218, reactive brown 9, and reactive yellow 160.

5. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The cosolvent is one or a mixture of ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monobutyl ether, N-methyl pyrrolidone, dimethyl sulfoxide, cyclohexanone, dimethyl imide, propylene glycol methyl ether, ethylene glycol phenyl ether, ethylene glycol monobutyl ether, and ethyl lactate.

6. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The moisturizing agent is one or a mixture of glycerol, ethylene glycol, diethylene glycol, polyethylene glycol, sorbitol, propylene glycol, 1,2-hexanediol, xylitol, urea, and triethylene glycol.

7. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The pH regulator is one or a mixture of citric acid, sodium hydroxide, triethanolamine, sodium dihydrogen phosphate, sodium bicarbonate, ammonia water, acetic acid, borax, 2-amino-2-methyl-1-propanol, and hydrochloric acid.

8. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The antibacterial agent is one or a mixture of isothiazolinone, benzisothiazolinone, 2-methyl-4-isothiazolin-3-one, glutaraldehyde, sodium benzoate, sodium dehydroacetate, DMDM hydantoin, bronopol and silver ion antibacterial agents.

9. The micellar phase change reactive dye ink based on cationic polymer regulation according to claim 1, characterized in that: The micellar phase-change reactive dye ink regulated by a cationic polymer has a viscosity of 1 to 100 cP, a surface tension of 20 to 100 mN / m, a pH value of 3 to 9, a dynamic surface tension response rate of 1 to 300 mN / (m·s), a uniform morphology of ejected ink droplets, and continuous ink printing within three months. Based on cryo-transmission observation, the aggregate structure of anionic surfactants includes spherical, worm-like, lamellar micelles and vesicle structures. Based on the differences in aggregate structure, the average particle size distribution is 10 nm to 150 nm. The micellar phase-change reactive dye ink regulated by a cationic polymer is mixed evenly according to the component ratio and then filtered through a 0.10 to 1.00 micron filter membrane.