CN102173203A - Method for improving resolution of inkjet printing by inducing de-infiltration of ink droplets based on external stimulus - Google Patents
Method for improving resolution of inkjet printing by inducing de-infiltration of ink droplets based on external stimulus Download PDFInfo
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Abstract
The invention belongs to the technical field of inkjet printing and relates to a method for improving the printing resolution by inducing de-infiltration of ink droplets based on external stimulus. The method comprises the following steps: firstly dispersing inorganic particles or a polymer with external stimulus response in an appropriate substrate to get ink with the external stimulus responsiveness, then spraying the ink with the external stimulus responsiveness through an inkjet printing device, enabling the ink droplets to generate shape change and volume contraction or only generate the volume contraction due to induction of the external stimulus before curing so as to generate de-infiltration on the substrate, further reducing the deposition area of the ink droplets on the substrate, appropriately curing the ink droplets, and finally improving the printing resolution of inkjet printed contents. The method for improving the printing resolution of the inkjet printed contents is simple to operate, has the characteristics of low cost, no special requirements on equipment, greatly improved resolution and the like.
Description
Technical field
The invention belongs to the inkjet technology field, relate to and use ink, relate in particular to based on environmental stimuli and induce ink droplet to go to soak into the method that improves print resolution to improve the print resolution of inkjet printing content significantly with special environmental stimuli response.
Background technology
In recent years, paid close attention to very much in the application aspect the high-resolution manufacturing industry based on the graphic printing technology of inkjet printing.Inkjet printing is one of the most promising method that optionally deposits functional material, its large tracts of land that can realize complexity, precise pattern is directly write, and is widely used in the meticulous accurate preparation of micro semiconductor, electronic device, biosystem because of advantages such as graphic designs convenience, low operation cost.Print resolution during these are used is defined as stable minimum print point, the narrowest continuous lines or minimum breach, and generally, this resolution ratio is relevant with the diameter of the ink droplet of inkjet printing.High-resolution inkjet technology can be realized the accurate location of ink droplet, for the fineness that improves the little pattern of gained, improve the functional most important of micro element.
At present the method about the print resolution that improves the inkjet printing content mainly comprises three aspects: one, and from the angle of equipment, by reducing the shower nozzle diameter or improving ejector principle and improve resolution ratio.The Rogers seminar in illinois university Urbana branch school (Nat.Mater., 2007,6,782) has developed electrodynamics inkjet printing principle, utilizes charged ink, has obtained the resolution ratio in 8 μ m points footpaths with the shower nozzle aperture of 30 μ m.Poulikakos (the Adv.Mater.2010 of Zurich, SUI ETH, 22,4701) seminar has developed the dielectrophoresis inkjet technology, makes the ink dispersate in the shower nozzle concentrate on the shower nozzle middle part, after printing the solvent evaporates in the deposition sample, obtain the resolution ratio suitable with the shower nozzle aperture.Its two, from the angle of base material, by the physics and/or the chemical confinement effect of base material, restriction sprawling of ink-jet drop and reduce resolution ratio.(the Nat.Mater. of Sirringhau seminar of Cambridge University, 2004,3,171) method by etching obtains narrow hydrophobic pattern on hydrophilic base material, induce ink droplet to go to soak into by physics and chemical confinement effect, thereby reduce single volume raising resolution ratio.Its three, from the angle of ink, adjust ink and form.(the J.Mater.Chem. of Schubert seminar of Holland Ai Ende Huo Wen University of Science and Technology, 2007,17,677) selected a kind of stable phase parting material, the instantaneous solidification by ink droplet has improved resolution ratio, (the Adv.Mater.2008 of this seminar, 20,343) also developed a kind of hot substrate printing technique, stoped it further to sprawl, thereby improved resolution ratio by the curing of quickening ink-jet drop.Can improve resolution ratio by a relatively large margin though improve shower nozzle and ejector principle, the universality of method is not strong; Base material treatment improves resolution ratio needs mask and accurate etching usually, and process is loaded down with trivial details, and cost is higher; Adjust ink and form that to improve the resolution ratio process simple, but present report is less relatively, and the amplitude of the raising resolution ratio of having reported is still little.
The present invention adopts the ink with environmental stimuli response to carry out inkjet printing, after ink droplet is sprayed by shower nozzle, because of induced by environmental stimuli to take place the variation of shape, size, cause ink droplet on base material, to produce and remove infiltration phenomenon, thereby reduce the sedimentation diameter of ink droplet, after taking certain mechanism to solidify, realize the raising of the print resolution of inkjet printing content.The response speed that this ink stimulates to external world is fast, satisfies the range request of crossing of inkjet printing; Simultaneously, the responsiveness that ink stimulates to external world is big, and the degree of ink droplet change of shape is big, or the degree of dispersate change in size is big in the ink droplet, thereby has realized the raising of the print resolution of inkjet printing content significantly.This method is simple to operate, and universality is strong, and is with low cost, and the preparation of high-resolution, high performance little pattern and micro element is had important directive significance.
Summary of the invention
One of purpose of the present invention is to utilize shape or the change in size of ink under environmental stimuli is induced with environmental stimuli response, provides a kind of and induces ink droplet to go to soak into the method that improves inkjet printing resolution ratio based on environmental stimuli.
Two of purpose of the present invention provides ink with environmental stimuli response and preparation method thereof.
Method of inducing ink droplet to go to soak into raising inkjet printing resolution ratio based on environmental stimuli of the present invention is, earlier will have the inorganic particulate of environmental stimuli response or polymer dispersed and in suitable matrix, obtain ink with environmental stimuli response with certain dispersal mechanism, spray ink by ink jet printing device then with environmental stimuli response, ink droplet is induced because of environmental stimuli before curing change of shape and volume contraction is taken place, or volume contraction only takes place; Thereby on base material, go to soak into, cause ink droplet the reducing of depositional area on base material, ink droplet is carried out suitable curing after, finally realize the raising of the print resolution of inkjet printing content.The method of above-mentioned raising inkjet printing resolution ratio has simple to operate, with low cost, and equipment is not had specific (special) requirements, and resolution ratio is improved characteristics such as amplitude is big.
Method of inducing ink droplet to go to soak into raising inkjet printing resolution ratio based on environmental stimuli of the present invention is: the ink that will have the environmental stimuli response is loaded in the print cartridge of single shower nozzle ink jet printing device, according to conventional inkjet printing methods, base material is carried out printing of the ejected ink drop, apply environmental stimuli to arriving substrate surface and uncured ink droplet, make ink droplet that change of shape and volume contraction take place before still uncured, or volume contraction only takes place (induce because of environmental stimuli and to make ink droplet generation change of shape and volume contraction, or volume contraction only takes place), this variation can cause the ink droplet on the base material to go to soak into, the depositional area of ink droplet on base material reduces, ink droplet is cured, ink droplet promptly obtains the inkjet printing result that resolution ratio improves after solidifying.The raising extent and scope of the print resolution of inkjet printing content is 20～80%.
Described ink with environmental stimuli response is the ink with magnetic field responsiveness, the ink that has the ink of electric field response or have the pH response.
The described environmental stimuli that applies is provided with magnetic field above perpendicular to base material, apply magnetic field to arriving substrate surface and the uncured ink droplet with magnetic field responsiveness; Perhaps
The described environmental stimuli that applies is provided with electric field above perpendicular to base material, apply electric field to arriving substrate surface and the uncured ink droplet with electric field response; Perhaps
The described environmental stimuli that applies is that the base material that will just print places acid atmosphere or alkaline atmosphere, and substrate surface and the uncured ink droplet with pH response carry out acid atmosphere or alkaline atmosphere is handled to arriving.
Described ink with magnetic field responsiveness is under the effect that applies magnetic field, and the ink droplet that spreads over substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change of shape and volume contraction.
Described ink with electric field response is applying under the effect of electric field, and the ink droplet that spreads over substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change of shape and volume contraction.
Described ink with pH response is under the processing of acid atmosphere or alkaline atmosphere, and the pH of ink droplet changes, and spreads over the ink droplet generation volume contraction of substrate surface, and the ink droplet spreading area after solidifying is less than the ink droplet spreading area before solidifying.
The described magnetic field that applies is that to make the magnetic field intensity scope in the magnetic field that is applied to substrate surface be 100～200 Gausses; The described electric field that applies is that to make the electric-field intensity scope of the electric field that is applied to substrate surface be 200～400V/cm; Described acid atmosphere is to be 1～3 acid atmosphere by the pH value scope that hydrochloric acid produces, and described alkaline atmosphere is to be 9～11 alkaline atmosphere by the pH value scope that ammoniacal liquor produces.
Described magnetic field is the magnetic field that the block Ru-Fe-Mn permanent magnet of magnetic field, sintering of permanent-magnet ferrite generation produces, or the electromagnetic field of hot-wire coil generation; Described electric field is the flat field that plate condenser produces.
Described ink jet printing device is piezoelectric ink jet printer or industry point colloid system etc., and the aperture of their shower nozzle is preferably 10 μ m, 20 μ m, 50 μ m or 150 μ m.
Described base material is preferably sheet glass, polyethylene film, polychloroethylene film, PET film or the PDMS film of poly-polytetrafluoroethylene film, hydrophobization.
Described volume contraction is that the depositional area of the ink droplet that when not having environmental stimuli under the same conditions (or) obtains when the depositional area that obtains the ink droplet after solidifying on the base material just has been ejected on the base material than ink droplet reduces 20～80%.
The mode of described curing is solvent evaporates curing mode, heat cure mode or photocuring mode.
Described solvent evaporates curing mode is that the solvent under the printing environment condition volatilizees naturally; Described heat cure mode is heated substrate to 60～90 ℃; Described photocuring mode for wavelength be the uviol lamp of 200～400nm as light source, intensity of illumination is 1～2W/cm
2Carry out illumination.
Described ink with environmental stimuli response is prepared by following method: will have in the inorganic particulate of environmental stimuli response or the resinous substrates or pH buffer solution that polymer is dispersed in certain viscosity, optionally add crosslinking agent and initator and form mixed liquor, promptly obtain described ink with environmental stimuli response.
Described inorganic particulate with environmental stimuli response is the particle that has the particle of magnetic field responsiveness or have electric field response, and described polymer with environmental stimuli response is the polymer with pH response.
The ink with environmental stimuli response that is obtained by above-mentioned particle with magnetic field responsiveness is the ink with magnetic field responsiveness, and the content of the particle with magnetic field responsiveness in the ink is 5～15wt%; The ink with environmental stimuli response that is obtained by above-mentioned particle with electric field response is the ink with electric field response, and the content of the particle with electric field response in the ink is 5～15wt%; The ink with environmental stimuli response that is obtained by the polymer of the above-mentioned pH of having response is the ink with pH response, and the content of the polymer with pH response in the ink is 10～20wt%.
Described particle with magnetic field responsiveness is the commercially available prod, and its particle diameter is 20～100nm; Be selected from tri-iron tetroxide particle or di-iron trioxide particle.
Described particle with electric field response is the commercially available prod, and its particle diameter is 20～100nm; Be selected from barium titanate particles or TiO 2 particles.
The polymer of the described pH of having response is the commercially available prod, is selected from polyacrylic acid, styrene-propene acid block copolymer, poly 2 vinyl pyridine or styrene-2-vinylpyridine block copolymer.
The range of viscosities of described resinous substrates is 300～1500mPas; The concentration range of described resinous substrates is 20～30wt%.Described resinous substrates is selected from polyurethane solutions, the polyethylene glycol aqueous solution, the polyethylene glycol-diacrylate aqueous solution, polyvinyl alcohol water solution or epoxy resin.
Described polyurethane solutions forms in the vinylacetate for the commercial polyurethane particle is dissolved in; The described polyethylene glycol aqueous solution is that commercially available polyethylene glycol particle is scattered in and forms in the water; Described polyethylene glycol-diacrylate aqueous solution is that commercially available polyethylene glycol-diacrylate particle is scattered in and forms in the water; Described polyvinyl alcohol water solution is preferably commercially available 1788 type polyvinyl alcohol and is scattered in and forms in the water; Described epoxy resin is the commercially available prod, and model is preferably E-44 and E-51.
Described pH buffer solution is selected from known products, is that to be selected from pH be that 10 boric acid-potassium chloride-sodium hydrate buffer solution, pH are that 9.1 ammonium chloride-ammoniacal liquor buffer solution, pH are that 6.8 potassium dihydrogen phosphate-sodium hydrate buffer solution, pH are that 4.8 Potassium Hydrogen Phthalate-sodium hydrate buffer solution, pH are that 3.6 Potassium Hydrogen Phthalate-hydrochloride buffer or pH are amion acetic acid-hydrochloride buffer of 2.3.
Described crosslinking agent is N, the N-methylene-bisacrylamide, its content in the ink with environmental stimuli response is 0～10wt%, and described initator is thermal initiator or light trigger, and its content in the ink with environmental stimuli response is 0～5wt%.
Described thermal initiator is a kind of in water miscible ammonium persulfate, the water miscible potassium peroxydisulfate etc.; Or a kind of in the water miscible azo-initiators such as azo-bis-isobutyrate hydrochloride, azo diisopropyl imidazoline salt hydrochlorate etc.Described light trigger is 2-hydroxy-2-methyl-1-phenyl-1-acetone or 1-hydroxy-cyclohexyl phenyl ketone etc.
Described process for dispersing is mechanical oscillation and ultrasonic dispersion.
It is ink that the present invention adopts the mixed liquor with environmental stimuli response, under certain environmental stimuli effect, by inkjet printing with deposit of ink to base material.Ink droplet is induced because of environmental stimuli before curing and is produced change of shape or volume contraction, cause ink droplet the reducing of depositional area on base material, acquisition is solidified ink droplet under certain mechanism much smaller than the droplet deposition sample in shower nozzle aperture, finally obtains the inkjet printing result that resolution ratio improves.Method of the present invention is not appeared in the newspapers at present in the prior art.Induce ink droplet to go to soak into that the method that improves inkjet printing resolution ratio is simple to operate, cost is low by provided by the invention based on environmental stimuli, the amplitude that resolution ratio improves is big.The raising of the print resolution of the inkjet printing content that is realized by the method for the invention has great importance for the high-quality patterning functional membrane of preparation.This method provides guidance for the preparation of high-quality little pattern and micro element, improves significant for the accurate deposition of functional material and the performance of function element.
Description of drawings
Fig. 1. of the present inventionly in the presence of electric field or magnetic field, carry out inkjet printing, have the mechanism schematic diagram that the ink of electric field or magnetic field responsiveness changes on base material.
Fig. 2. inkjet printing of the present invention has the mechanism schematic diagram that the ink of pH response changes on base material.
Fig. 3. ink-jet print drops in the deposition shape variation of effect front and back, magnetic field in the embodiment of the invention 3.
The specific embodiment
At room temperature (25 ℃) are the Fe of 20nm with particle diameter
3O
4Particle is scattered in the polyurethane solutions that viscosity is 700mPas (20wt%), Fe
3O
4The content of particle in polyurethane solutions is 5wt%.After the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of magnetic field responsiveness.As shown in Figure 1, the ink that will have magnetic field responsiveness is loaded in the print cartridge of industry point colloid system, and being equipped with the aperture is the Picodot shower nozzle of 150 μ m.Above perpendicular to poly-polytetrafluoroethylene film base material block permanent-magnet ferrite is set, magnetic field intensity is 100 Gausses.Ink sprays from shower nozzle and arrives on the poly-polytetrafluoroethylene film, and the poly-polytetrafluoroethylene film that will just print places under the above-mentioned permanent-magnet ferrite, the ink droplet that is ejected into poly-polytetrafluoroethylene film surface is before curing, because the magnetic field intensity that is subjected to applying thereon is the attraction of 100 Gausses' magnetic field force, the ink droplet that spreads over poly-polytetrafluoroethylene film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on poly-polytetrafluoroethylene film.After making the solvent natural evaporation curing in the ink droplet under the printing environment condition, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the poly-polytetrafluoroethylene film just has been ejected on the poly-polytetrafluoroethylene film than ink droplet reduces 60%, and the print resolution of inkjet printing content has improved 60%.
Embodiment 2
At room temperature, with particle diameter be the Fe of 50nm
3O
4Particle is scattered in the polyethylene glycol aqueous solution (50wt%) that viscosity is 500mPas, Fe
3O
4The content of particle in the polyethylene glycol aqueous solution is 10wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in the polyethylene glycol aqueous solution is 10wt%) and light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (content in the polyethylene glycol aqueous solution is 5wt%), after the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of magnetic field responsiveness.The ink that will have magnetic field responsiveness is loaded in the print cartridge of industry point colloid system, and being equipped with the aperture is the Picodot shower nozzle of 150 μ m.Above perpendicular to the polyethylene film base material the block Ru-Fe-Mn permanent magnet of sintering is set, magnetic field intensity is 150 Gausses.Ink sprays from shower nozzle and arrives on the polyethylene film, and the polyethylene film that will just print places under the above-mentioned Ru-Fe-Mn permanent magnet, the ink droplet that is ejected into the polyethylene film surface is before curing, because the magnetic field intensity that is subjected to applying thereon is the attraction of 150 Gausses' magnetic field force, the ink droplet that spreads over the polyethylene film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on polyethylene film.(wavelength is 200nm, and intensity of illumination is 1W/cm at uviol lamp
2) solidify down after, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the polyethylene film just has been ejected on the polyethylene film than ink droplet reduces 20%, the print resolution of inkjet printing content has improved 20%.
Embodiment 3
At room temperature, with particle diameter be the Fe of 100nm
2O
3Particle is scattered in the polyethylene glycol that viscosity is 300mPas-diacrylate aqueous dispersion (20wt%), Fe
2O
3The content of particle in polyethylene glycol-diacrylate aqueous dispersion is 15wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in polyethylene glycol-diacrylate aqueous dispersion is 5wt%) and light trigger 1-hydroxy-cyclohexyl phenyl ketone (content in polyethylene glycol-diacrylate aqueous dispersion is 1wt%), after the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of magnetic field responsiveness.To have the magnetic field responsiveness ink and be loaded in the print cartridge of industry point colloid system, it is the Picodot shower nozzle of 150 μ m that this colloid system is equipped with the aperture.Above perpendicular to the PDMS film base material the block Ru-Fe-Mn permanent magnet of sintering is set, magnetic field intensity is 150 Gausses.Ink sprays from shower nozzle and arrives on the PDMS film, and the PDMS film that will just print places under the above-mentioned Ru-Fe-Mn permanent magnet, the ink droplet that is ejected into PDMS film surface is before curing, because the magnetic field intensity that is subjected to applying thereon is the attraction of 150 Gausses' magnetic field force, the ink droplet that spreads into PDMS film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on the PDMS film.(wavelength is 300nm, and intensity of illumination is 1.5W/cm at uviol lamp
2) solidify down after, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the PDMS film just has been ejected on the PDMS film than ink droplet reduces 40%, the print resolution of inkjet printing content has improved 40%.Fig. 3 a and Fig. 3 b are respectively the shape changing figure of inkjet printing ink droplet ink droplet before and after the effect of magnetic field.Wherein the sedimentation diameter of ink droplet reduces 20% before acting on than magnetic field, and the depositional area of ink droplet reduces 40% before acting on than magnetic field.
Embodiment 4
At room temperature, with particle diameter be the Fe of 60nm
2O
3Particle is scattered in the polyvinyl alcohol aqueous dispersion (25wt%) that viscosity is 500mPas, Fe
2O
3The content of particle in the polyvinyl alcohol aqueous dispersion is 10wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in the polyvinyl alcohol aqueous dispersion is 8wt%) and light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (content in the polyvinyl alcohol aqueous dispersion is 3wt%), after the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of magnetic field responsiveness.The ink that will have magnetic field responsiveness is loaded in the print cartridge of industry point colloid system, and being equipped with the aperture is the Picodot shower nozzle of 50 μ m.Above perpendicular to the PET film base material electromagnetic field that electric coil produces is set, the intensity of electromagnetic field is 200 Gausses.Ink sprays from shower nozzle and arrives on the PET film, and the PET film that will just print places under the above-mentioned electromagnetic field, the ink droplet that is ejected into PET film surface is before curing, because the electromagnetic field intensity that is subjected to applying thereon is the attraction of 200 Gausses' magnetic field force, the ink droplet that spreads into PET film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on the PET film.(wavelength is 400nm, and intensity of illumination is 2W/cm at uviol lamp
2) solidify down after, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the PET film just has been ejected on the PET film than ink droplet reduces 80%, the print resolution of inkjet printing content has improved 80%.
Embodiment 5
At room temperature, be that the barium titanate particles of 80nm is scattered in the polyurethane solutions that viscosity is 800mPas (30wt%) with particle diameter, the content of barium titanate particles in polyurethane solutions is 5wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in polyurethane solutions is 5wt%) and thermal initiator azo-bis-isobutyrate hydrochloride (content in polyurethane solutions is 1wt%), after the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of electric field response.The ink that will have electric field response is loaded in the print cartridge of industry point colloid system, and being equipped with the aperture is the Picodot shower nozzle of 50 μ m.Above perpendicular to the PVC film base material flat field that is produced by plate condenser is set, electric-field intensity is 200V/cm.Ink sprays from shower nozzle and arrives on the PVC film, and the PVC film that will just print places under the above-mentioned electric field, the ink droplet that is ejected into PVC film surface is before curing, because the electric-field intensity that is subjected to applying thereon is the attraction of the electric field force of 200V/cm, the ink droplet that spreads into PVC film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on the PVC film.Behind heating PVC film to the 60 ℃ curing ink droplet, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the PVC film just has been ejected on the PVC film than ink droplet reduces 60%, and the print resolution of inkjet printing content has improved 60%.
Embodiment 6
At room temperature, be that the barium titanate particles of 100nm is scattered in the epoxy resin E-44 that viscosity is 1200mPas (30wt%) with particle diameter, the content of barium titanate particles in epoxy resin E-44 is 10wt%.After the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of electric field response.The ink that will have electric field response is loaded in the print cartridge of industry point colloid system, and being equipped with the aperture is the Picodot shower nozzle of 50 μ m.Above perpendicular to the PVC film base material flat field that is produced by plate condenser is set, electric-field intensity is 300V/cm.Ink sprays from shower nozzle and arrives on the PVC film, and the PVC film that will just print places under the above-mentioned electric field, the ink droplet that is ejected into PVC film surface is before curing, because the electric-field intensity that is subjected to applying thereon is the attraction of the electric field force of 200V/cm, the ink droplet that spreads into PVC film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on the PVC film.After under the printing environment condition, making the solvent natural evaporation curing in the ink droplet, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the PVC film just has been ejected on the PVC film than ink droplet reduces 40%, and the print resolution of inkjet printing content has improved 40%.
Embodiment 7
At room temperature, be that the TiO 2 particles of 20nm is scattered in the polyethylene glycol that viscosity is 400mPas-diacrylate aqueous dispersion (50wt%) with particle diameter, the content of TiO 2 particles in polyethylene glycol-diacrylate aqueous solution is 15wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in polyethylene glycol-diacrylate aqueous solution is 5wt%) and thermal initiator azo-bis-isobutyrate hydrochloride (content in polyethylene glycol-diacrylate aqueous solution is 1wt%), after the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of electric field response.The ink that will have electric field response is loaded in the print cartridge of commercial Epson R series printer, and the shower nozzle aperture is 20 μ m.Above perpendicular to the sheet glass base material flat field that is produced by plate condenser is set, electric-field intensity is 350V/cm.Ink sprays from shower nozzle and arrives on the hydrophobic sheet glass, and the sheet glass that will just print places under the above-mentioned electric field, the ink droplet that is ejected into glass sheet surface is before curing, because the electric-field intensity that is subjected to applying thereon is the attraction of the electric field force of 350V/cm, the ink droplet that spreads into glass sheet surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on sheet glass.Behind heating glass sheet to the 90 ℃ curing ink droplet, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the sheet glass just has been ejected on the sheet glass than ink droplet reduces 80%, and the print resolution of inkjet printing content has improved 80%.
Embodiment 8
At room temperature, be that the TiO 2 particles of 50nm is scattered among the epoxy resin E-51 that viscosity is 1500mPas with particle diameter, the content of TiO 2 particles in epoxy resin E-51 is 10wt%.After the mechanical dispersion ultrasonic about 1 hour, obtain to have the ink of electric field response.The ink that will have electric field response is loaded in the print cartridge of commercial Epson R series printer, and the shower nozzle aperture is 20 μ m.Above perpendicular to poly-polytetrafluoroethylene film base material the flat field that is produced by plate condenser is set, electric-field intensity is 400V/cm.Ink sprays from shower nozzle and arrives on the poly-polytetrafluoroethylene film, and the poly-polytetrafluoroethylene film that will just print places under the above-mentioned electric field, the ink droplet that is ejected into poly-polytetrafluoroethylene film surface is before curing, because the electric-field intensity that is subjected to applying thereon is the attraction of the electric field force of 400V/cm, the ink droplet that spreads into poly-polytetrafluoroethylene film surface is drawn as cone-shaped ink droplet, make ink droplet generation change of shape and volume contraction, ink droplet goes to soak on poly-polytetrafluoroethylene film.After under the printing environment condition, making the solvent natural evaporation curing in the ink droplet, the depositional area of the ink droplet that has obtained when the depositional area that obtains the ink droplet after solidifying on the poly-polytetrafluoroethylene film just has been ejected on the poly-polytetrafluoroethylene film than ink droplet reduces 20%, and the print resolution of inkjet printing content has improved 20%.
Embodiment 9
At room temperature, commercially available polyacrylic acid being scattered in pH is that the content of polyacrylic acid in buffer solution is 10wt% in boric acid-potassium chloride-sodium hydrate buffer solution of 10.0.Add crosslinking agent N, N-methylene-bisacrylamide (content in buffer solution is 5wt%) and thermal initiator ammonium persulfate (content in buffer solution is 1wt%), after the mechanical dispersion ultrasonic about 1 hour, the ink that acquisition has the pH response.As shown in Figure 2, the ink that will have the pH response is loaded in the print cartridge of commercial Epson R series printer, and the shower nozzle aperture is 20 μ m, is base material with the polychloroethylene film.Ink with pH response sprays from shower nozzle and arrives on the polychloroethylene film, and the polychloroethylene film that will just print to place the pH value be 1 hydrogen chloride gas atmosphere, the ink droplet that is ejected into the polychloroethylene film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 1 hydrogen chloride gas, the pH of ink droplet is reduced to 5.0 from 10.0, spreads over the ink droplet generation volume contraction on polychloroethylene film surface.Behind heating polychloroethylene film to the 60 ℃ curing ink droplet, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the polychloroethylene film than ink droplet reduces 60%, and the print resolution of inkjet printing content has improved 60%.
Embodiment 10
At room temperature, it is in ammonium chloride-ammoniacal liquor buffer solution of 9.1 that commercial styrene-acrylic block copolymers is scattered in pH, and the content of styrene-propene acid block copolymer in buffer solution is 15wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in buffer solution is 8wt%) and thermal initiator potassium peroxydisulfate (content in buffer solution is 3wt%), after the mechanical dispersion ultrasonic about 1 hour, the ink that acquisition has the pH response.The ink that will have the pH response is loaded in the print cartridge of commercial Epson R series printer, and the shower nozzle aperture is 20 μ m, is base material with the PET film.Ink sprays from shower nozzle and arrives on the PET film, and the PET film that will just print to place the pH value be 2 hydrogen chloride gas atmosphere, the ink droplet that is ejected into PET film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 2 hydrogen chloride gas, the pH of ink droplet is reduced to 5.5 from 9.1, spreads over the ink droplet generation volume contraction on PET film surface.Behind heating PET film to the 60 ℃ curing ink droplet, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the PET film than ink droplet reduces 80%, and the print resolution of inkjet printing content has improved 80%.
Embodiment 11
At room temperature, it is in potassium dihydrogen phosphate-sodium hydrate buffer solution of 6.8 that commercial styrene-acrylic block copolymers is scattered in pH, and the content of styrene-propene acid block copolymer in buffer solution is 20wt%.Add crosslinking agent N, N-methylene-bisacrylamide (content in buffer solution is 10wt%) and thermal initiator potassium peroxydisulfate (content in buffer solution is 5wt%), after the mechanical dispersion ultrasonic about 1 hour, the ink that acquisition has the pH response.The ink that will have the pH response is loaded in the print cartridge of commercial Epson R series printer, and the shower nozzle aperture is 20 μ m, is base material with the polychloroethylene film.Ink sprays from shower nozzle and arrives on the polychloroethylene film, and the polychloroethylene film that will just print to place the pH value be 3 hydrogen chloride gas atmosphere, the ink droplet that is ejected into the polychloroethylene film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 3 hydrogen chloride gas, the pH of ink droplet is reduced to 4.5 from 6.8, spreads over the ink droplet generation volume contraction on polychloroethylene film surface.Behind heating polychloroethylene film to the 60 ℃ curing ink droplet, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the polychloroethylene film than ink droplet reduces 20%, and the print resolution of inkjet printing content has improved 20%.
Embodiment 12
At room temperature, it is in Potassium Hydrogen Phthalate-sodium hydrate buffer solution of 4.8 that commercially available poly 2 vinyl pyridine is scattered in pH, the content of poly 2 vinyl pyridine in buffer solution is 20wt%, after the mechanical dispersion ultrasonic about 1 hour, obtains the ink with pH response.The ink that will have the pH response is loaded in the print cartridge of the commercial PIXUS of Canon series printer, and the shower nozzle aperture is 10 μ m, is base material with the PDMS film.Ink sprays from shower nozzle and arrives on the PDMS film, and the PDMS film that will just print to place the pH value be 11 ammonia gas atmosphere, the ink droplet that is ejected into PDMS film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 11 ammonia gas, the pH of ink droplet is elevated to 5.5 from 4.8, spreads over the ink droplet generation volume contraction on PDMS film surface.Make the solvent natural evaporation curing in the ink droplet under the printing environment condition after, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the PDMS film than ink droplet reduces 20%, and the print resolution of inkjet printing content has improved 20%.
Embodiment 13
At room temperature, it is in Potassium Hydrogen Phthalate-hydrochloride buffer of 3.6 that commercial styrene-2-vinylpyridine block copolymer is scattered in pH, styrene-the content of 2-vinylpyridine block copolymer in buffer solution is 15wt%, after the mechanical dispersion ultrasonic about 1 hour, obtain ink with pH response.The ink that will have the pH response is loaded in the print cartridge of the commercial PIXUS of Canon series printer, and the shower nozzle aperture is 10 μ m, is base material with the PDMS film.Ink sprays from shower nozzle and arrives on the PDMS film, and the PDMS film that will just print to place the pH value be 10 ammonia gas atmosphere, the ink droplet that is ejected into PDMS film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 10 ammonia gas, the pH of ink droplet is elevated to 5.0 from 3.6, spreads over the ink droplet generation volume contraction on PDMS film surface.Make the solvent natural evaporation curing in the ink droplet under the printing environment condition after, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the PDMS film than ink droplet reduces 40%, and the print resolution of inkjet printing content has improved 40%.
Embodiment 14
At room temperature, it is in amion acetic acid-hydrochloride buffer of 2.3 that commercial styrene-2-vinylpyridine block copolymer is scattered in pH, styrene-the content of 2-vinylpyridine block copolymer in buffer solution is 10wt%, after the mechanical dispersion ultrasonic about 1 hour, obtain ink with pH response.The ink that will have the pH response is loaded in the print cartridge of the commercial PIXUS of Canon series printer, and the shower nozzle aperture is 10 μ m, is base material with the polyethylene film.Ink sprays from shower nozzle and arrives on the polyethylene film, and the polyethylene film that will just print to place the pH value be 9 ammonia gas atmosphere, the ink droplet that is ejected into the polyethylene film surface is before ink droplet solidifies, owing to be subjected to the pH value is the effect of 9 ammonia gas, the pH of ink droplet is elevated to 5.0 from 2.3, spreads over the ink droplet generation volume contraction on polyethylene film surface.After under the printing environment condition, making the solvent natural evaporation curing in the ink droplet, the depositional area of the ink droplet that has obtained when the depositional area of the ink droplet after solidifying just has been ejected on the polyethylene film than ink droplet reduces 80%, and the print resolution of inkjet printing content has improved 80%.
Claims (12)
1. induce ink droplet to go to soak into the method that improves inkjet printing resolution ratio based on environmental stimuli for one kind, it is characterized in that: the ink that will have the environmental stimuli response is loaded in the print cartridge of single shower nozzle ink jet printing device, base material is carried out printing of the ejected ink drop, apply environmental stimuli to arriving substrate surface and uncured ink droplet, make ink droplet that change of shape and volume contraction take place before still uncured, or volume contraction only takes place; Ink droplet is cured;
Described ink with environmental stimuli response is the ink with magnetic field responsiveness, the ink that has the ink of electric field response or have the pH response.
2. method according to claim 1 is characterized in that: the described environmental stimuli that applies is provided with magnetic field above perpendicular to base material, applies magnetic field to arriving substrate surface and the uncured ink droplet with magnetic field responsiveness; Perhaps
The described environmental stimuli that applies is provided with electric field above perpendicular to base material, apply electric field to arriving substrate surface and the uncured ink droplet with electric field response; Perhaps
The described environmental stimuli that applies is that the base material that will just print places acid atmosphere or alkaline atmosphere, and substrate surface and the uncured ink droplet with pH response carry out acid atmosphere or alkaline atmosphere is handled to arriving.
3. method according to claim 1 and 2 is characterized in that: described ink with magnetic field responsiveness is under the effect that applies magnetic field, and the ink droplet that spreads over substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change of shape and volume contraction;
Described ink with electric field response is applying under the effect of electric field, and the ink droplet that spreads over substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change of shape and volume contraction;
Described ink with pH response is under the processing of acid atmosphere or alkaline atmosphere, and the pH of ink droplet changes, and spreads over the ink droplet generation volume contraction of substrate surface.
4. method according to claim 3 is characterized in that: described volume contraction is that the depositional area of the ink droplet of acquisition when the depositional area that obtains the ink droplet after solidifying on the base material just has been ejected on the base material than ink droplet reduces 20～80%.
5. method according to claim 3 is characterized in that: the described magnetic field that applies is that to make the magnetic field intensity scope in the magnetic field that is applied to substrate surface be 100～200 Gausses; The described electric field that applies is that to make the electric-field intensity scope of the electric field that is applied to substrate surface be 200～400V/cm; Described acid atmosphere is to be 1～3 acid atmosphere by the pH value scope that hydrochloric acid produces, and described alkaline atmosphere is to be 9～11 alkaline atmosphere by the pH value scope that ammoniacal liquor produces.
6. method according to claim 5 is characterized in that: described magnetic field is the magnetic field that the block Ru-Fe-Mn permanent magnet of magnetic field, sintering of permanent-magnet ferrite generation produces, or the electromagnetic field of hot-wire coil generation; Described electric field is the flat field that plate condenser produces.
7. method according to claim 5 is characterized in that: described base material is sheet glass, polyethylene film, polychloroethylene film, PET film or the PDMS film of poly-polytetrafluoroethylene film, hydrophobization.
8. method according to claim 1, it is characterized in that: described ink with environmental stimuli response is prepared by following method: the inorganic particulate or the polymer that will have the environmental stimuli response are dispersed in resinous substrates or the pH buffer solution, add crosslinking agent and initator and form mixed liquor, promptly obtain described ink with environmental stimuli response;
The range of viscosities of described resinous substrates is 300～1500mPas; Described resinous substrates is selected from polyurethane solutions, the polyethylene glycol aqueous solution, the polyethylene glycol-diacrylate aqueous solution, polyvinyl alcohol water solution or epoxy resin;
It is that 10 boric acid-potassium chloride-sodium hydrate buffer solution, pH are that 9.1 ammonium chloride-ammoniacal liquor buffer solution, pH are that 6.8 potassium dihydrogen phosphate-sodium hydrate buffer solution, pH are that 4.8 Potassium Hydrogen Phthalate-sodium hydrate buffer solution, pH are that 3.6 Potassium Hydrogen Phthalate-hydrochloride buffer or pH are amion acetic acid-hydrochloride buffer of 2.3 that described pH buffer solution is selected from pH;
Described inorganic particulate with environmental stimuli response is the particle that has the particle of magnetic field responsiveness or have electric field response, and described polymer with environmental stimuli response is the polymer with pH response;
The ink with environmental stimuli response that is obtained by above-mentioned particle with magnetic field responsiveness is the ink with magnetic field responsiveness, the ink with environmental stimuli response that is obtained by above-mentioned particle with electric field response is the ink with electric field response, and the ink with environmental stimuli response that is obtained by the polymer of the above-mentioned pH of having response is the ink with pH response.
9. method according to claim 8 is characterized in that: the content of the particle with magnetic field responsiveness in the described ink with magnetic field responsiveness is 5～15wt%, and the content of crosslinking agent is 0～10wt%, and the content of initator is 0～5wt%; The content of the particle with electric field response in the described ink with electric field response is 5～15wt%, and the content of crosslinking agent is 0～10wt%, and the content of initator is 0～5wt%; The content of the polymer with pH response in the ink of the described pH of having response is 10～20wt%, and the content of crosslinking agent is 0～10wt%, and the content of initator is 0～5wt%.
10. according to Claim 8 or 9 described methods, it is characterized in that: described particle diameter with particle of magnetic field responsiveness is 20～100nm; Be selected from tri-iron tetroxide particle or di-iron trioxide particle;
Described particle diameter with particle of electric field response is 20～100nm; Be selected from barium titanate particles or TiO 2 particles;
The polymer of the described pH of having response is selected from polyacrylic acid, styrene-propene acid block copolymer, poly 2 vinyl pyridine or styrene-2-vinylpyridine block copolymer.
11. method according to claim 8 is characterized in that: the concentration range of described resinous substrates is 20～30wt%.
12. according to Claim 8 or 9 described methods, it is characterized in that: described crosslinking agent is N, the N-methylene-bisacrylamide; Described initator is thermal initiator or light trigger;
Described thermal initiator is a kind of in water miscible ammonium persulfate, the water miscible potassium peroxydisulfate; Or a kind of in the water miscible azo-bis-isobutyrate hydrochloride, water miscible azo diisopropyl imidazoline salt hydrochlorate; Described light trigger is 2-hydroxy-2-methyl-1-phenyl-1-acetone or 1-hydroxy-cyclohexyl phenyl ketone.
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| CN114475036A (en) * | 2022-02-17 | 2022-05-13 | 北京航空航天大学 | Method for improving ink-jet printing quality based on liquid drop boiling |
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