CN112126280B - Perovskite quantum dot invisible ink-jet printing ink - Google Patents
Perovskite quantum dot invisible ink-jet printing ink Download PDFInfo
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- CN112126280B CN112126280B CN202011014347.3A CN202011014347A CN112126280B CN 112126280 B CN112126280 B CN 112126280B CN 202011014347 A CN202011014347 A CN 202011014347A CN 112126280 B CN112126280 B CN 112126280B
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- 238000007641 inkjet printing Methods 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 41
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
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- 239000007788 liquid Substances 0.000 claims description 20
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 112
- 238000007639 printing Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 3
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- 239000000049 pigment Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
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- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides perovskite quantum dot invisible ink-jet printing ink which comprises the following components: polymethyl methacrylate/perovskite quantum dot resin powder, resin, a defoaming agent, a surfactant and an ink solvent. The polymethyl methacrylate/perovskite quantum dot resin powder prepared by the method is of a core-shell structure, and the polymethyl methacrylate is coated outside the perovskite quantum dots, so that the stability of the perovskite quantum dots is improved, and the quantum yield is improved. Compared with the traditional anti-counterfeiting ink, the invisible ink-jet printing ink prepared from polymethyl methacrylate/perovskite quantum dot resin powder has better dispersibility, adhesiveness and stability when being used as the anti-counterfeiting mark, so that the fluorescent stability is good, the color development range is wide, and the decay is not easy to occur.
Description
Technical Field
The invention relates to the technical field of ink, in particular to perovskite quantum dot invisible ink-jet printing ink.
Background
The anti-fake printing ink is an important part in anti-fake technology, and is one kind of anti-fake printing ink comprising pigment, binder and ink assistant, and is especially one kind of special printing ink with special anti-fake material added into the binder and through special technological process. It can prevent forgery by using colorant and binder with special function in ink.
The anti-counterfeiting printing ink comprises fluorescent ink, color-changing ink, heat-sensitive anti-counterfeiting ink, chemical reaction color-changing ink, optical variable anti-counterfeiting ink, magnetic anti-counterfeiting ink, water-sensitive anti-counterfeiting ink and other special anti-counterfeiting ink. The fluorescent ink is one of the more applied inks in ticket printing, and the main component of the fluorescent ink is a fluorescent pigment. The original color fluorescent ink is colored by mixing multiple fluorescent powders, the multiple fluorescent powders can be mutually absorbed, the color brightness is poor, the stability of the existing fluorescent ink is poor, the fluorescent ink can be attenuated along with time, the monochromaticity of fluorescence is poor, and the color is impure.
Disclosure of Invention
The application aims to solve the problems that the traditional fluorescent ink used for anti-counterfeiting marks at present is poor in color brightness, poor in stability, impure in color and capable of being attenuated along with time, and provides perovskite quantum dot invisible ink-jet printing ink.
In order to achieve the purpose, the application provides a perovskite quantum dot invisible ink-jet printing ink which comprises the following components: polymethyl methacrylate/perovskite quantum dot resin powder, resin, a defoaming agent, a surfactant and an ink solvent.
As a further improvement of the application, the perovskite quantum dot invisible ink-jet printing ink comprises the following components in percentage by mass: 15-30% of polymethyl methacrylate/perovskite quantum dot resin powder, 15-25% of resin, 0.1-1.0% of defoaming agent, 0.05-7% of surfactant and the balance of ink solvent.
As a further improvement of the application, the perovskite quantum dot invisible ink-jet printing ink comprises the following components in percentage by mass: 25-30% of polymethyl methacrylate/perovskite quantum dot resin powder, 20-25% of resin, 0.5-0.7% of defoaming agent, 2.5-5% of surfactant and the balance of ink solvent.
As a further improvement of the present application, the resin is a vinyl chloride-vinyl acetate resin; the surfactant is sodium hexadecylbenzene sulfonate; the printing ink solvent is prepared by mixing n-hexane, acetone and butanone.
As a further improvement of the present application, the ink solvent is prepared from a mixed solution of 40% by volume of n-hexane and 60% by volume of acetone and butanone.
In order to achieve the above object, the present application also provides a method for preparing polymethyl methacrylate/perovskite quantum dot resin powder, comprising the following steps: s1, carrying out reduced pressure distillation treatment on methyl methacrylate; s2, dissolving the methyl methacrylate and the sodium dodecyl benzene sulfonate in the step S1 into n-hexane through continuous stirring in a nitrogen atmosphere until the methyl methacrylate and the sodium dodecyl benzene sulfonate are completely dissolved into light yellow clear liquid, adding the perovskite quantum dot n-hexane dispersion liquid into the light yellow clear liquid, and uniformly dispersing to form a reaction system; and S3, adding an initiator into the reaction system in the step S2, fully reacting at 50-70 ℃ to obtain flocculent precipitate, repeatedly centrifuging, washing, and drying in vacuum to obtain the polymethyl methacrylate/perovskite quantum dot.
As a further improvement of the application, the mass ratio of the sodium dodecyl benzene sulfonate to the methyl methacrylate is 10.
As a further improvement of the application, the stirring speed is 120 r/min-170 r/min, and the stirring time is 10 min-30 min.
As a further refinement of the present application, the initiator is benzoyl peroxide.
As a further improvement of the application, the perovskite quantum dot is CsPbX 3 Wherein X is at least one of Cl, br and I.
The application has the beneficial effects that the invisible ink-jet printing ink containing the perovskite quantum dots is provided, and comprises the following components: compared with the traditional anti-counterfeiting ink, the polymethyl methacrylate/perovskite quantum dot resin powder, the resin, the defoaming agent, the surfactant and the ink solvent have better dispersibility, adhesiveness and stability, so that the fluorescence stability is good. Meanwhile, the perovskite quantum dot has high luminous efficiency and narrow luminous spectral line, and the fluorescence spectrum of the quantum dot can be changed by changing the type of the halogen element, so that the printing ink prepared from the polymethyl methacrylate/perovskite quantum dot resin powder has the following advantages when being used for anti-counterfeiting marking: good monochromaticity, good color rendering property, wide color rendering range and difficult decay.
Drawings
FIG. 1 shows CsPbX 3 A fluorescence spectrogram of the perovskite quantum dot, wherein X is Cl, br or I;
FIG. 2 shows CsPbX 3 Testing and analyzing the surface tension and viscosity of the invisible perovskite quantum dot ink-jet printing ink;
FIG. 3 CsPbX using different surface tensions and viscosities 3 Sample layout prepared from perovskite quantum dot invisible ink-jet printing ink。
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
In order to prepare the anti-counterfeiting printing ink with excellent performance, the invention provides the invisible perovskite quantum dot ink-jet printing ink which comprises the following components: polymethyl methacrylate/perovskite quantum dot resin powder, resin, a defoaming agent, a surfactant and an ink solvent.
In the present application, a preferred first embodiment is as follows: the perovskite quantum dot invisible ink-jet printing ink comprises the following components in percentage by mass: 15% -30% of polymethyl methacrylate/perovskite quantum dot resin powder; 15 to 25 percent of resin; 0.1 to 1.0 percent of defoaming agent; 0.05 to 7 percent of surfactant; the balance being ink solvent. The preferred second embodiment is as follows: the invisible perovskite quantum dot ink-jet printing ink comprises the following components in percentage by mass: 20-30% of polymethyl methacrylate/perovskite quantum dot resin powder; 20 to 25 percent of resin; 0.5 to 0.7 percent of defoaming agent; 2 to 5 percent of surfactant; the balance being ink solvent. The preferred third embodiment is as follows: the invisible perovskite quantum dot ink-jet printing ink comprises the following components in percentage by mass: 25-30% of polymethyl methacrylate/perovskite quantum dot resin powder; 20 to 25 percent of resin; 0.5 to 0.7 percent of defoaming agent; 2.5 to 4 percent of surfactant; the balance being ink solvent.
In the application, the resin is a main film forming substance of the ink, the more the content of the resin is, the better the film quality is, the faster the fixation is, and the resin is greatly helpful for the gloss, the water resistance, the rheological property and the printability (good film forming fastness and friction resistance) of the ink. Further, the resin is vinyl chloride-vinyl acetate resin, and the vinyl chloride-vinyl acetate resin has excellent adhesive force and adhesive force. Defoaming agent: the ink is mixed with air during stirring to generate a large amount of bubbles, which can affect the viscosity of the ink, and the defoaming agent mainly eliminates the bubbles. Surfactant (b): the function is to help the perovskite quantum dot resin powder to be uniformly dispersed in the whole ink system and prevent agglomeration and sedimentation. In the present application, sodium hexadecylbenzene sulfonate is further preferable as the surfactant, and is an anionic surfactant having good surface activity, lipophilicity, thermal stability and fluidity.
In this application, the dynamic surface tension of the ink can affect different properties of the ink, such as: wetting, drop size, permeability, drying and leveling capabilities. Viscosity and surface tension: viscosity, i.e., the resistance to flow of the liquid, and the surface tension of the liquid are related to the ability to form droplets, and in general, ink-jet inks have a low viscosity and a high surface tension to ensure good flow properties and droplet morphology. Ink surface tension also affects the dot diameter and ink drying time produced by a given size of ink. Ink viscosity strongly affects the geometry of the ink flow path, which affects ink refill time and also affects the size of the dots formed by the ink droplets striking the surface of the paper, and thus print quality.
In the present application, the role of the solvent: 1) The organic solvent dissolves the resin or the additive, so that the ink becomes uniform liquid, has fluidity, can disperse pigment, is beneficial to transferring the ink to a printed material during printing and is beneficial to improving the adhesive force of the ink; 2) The ink has good stability to the ink and has no adverse effect on color hue change, tinting strength, printing, color distribution, precipitation, agglomeration and the like; 3) The organic solvent is low-viscosity liquid, and is added into the ink to reduce the viscosity of the ink so as to achieve the best effect; 4) The drying speed of the ink is adjusted by the factors such as the adjusting capability of the drying speed, the jet printing speed, the drying capability, the weather condition, the pattern area size and the like, so that the ideal requirement can be met, and the adjustment can be generally carried out by a standard solvent; 5) The wetting of the ink to the printed material is improved, the surface of some printed materials is not easy to be wetted by the ink, the transfer of the ink is hindered, the printing effect is damaged, and the fastness is not good. In this case, an organic solvent with surface tension similar to that of the material to be printed can be used, so that the surface of the material to be printed can be soaked by the ink, and the defects can be overcome; 6) The dissolving power or the penetrability of the printing material is improved, for example, the adhesion power is improved due to the dissolution of the solvent in the printing ink on the surface of the printing material, and the printing fastness is good. If the material is insoluble, its affinity for the solvent increases the cohesive force as the solvent swells. Therefore, the choice of solvent plays a crucial role. In the application, the solvent is prepared from n-hexane, acetone and butanone, the solvent has strong volatility, the solubility is high, the film forming is fast, and the ink prepared from the solvent is suitable for high-speed production. Preferably, when the solvent is prepared from a mixed solvent of 40% by volume of n-hexane and 60% by volume of acetone and butanone, wherein the acetone and the butanone are mixed in any proportion, the solvent prepared from the components has optimal volatility, solubility and film-forming property.
In order to prepare the anti-counterfeiting printing ink with stable performance, the application also provides a preparation method of the polymethyl methacrylate/perovskite quantum dot resin powder, which comprises the following steps: s1, processing methyl methacrylate by reduced pressure distillation; the step S1 is used for removing polymerization inhibitors such as hydroquinone and the like in the methyl methacrylate; further preferably, the temperature of the reduced pressure distillation is controlled to be 50-60 ℃; s2, dissolving the methyl methacrylate and the sodium dodecyl benzene sulfonate treated in the step S1 into n-hexane by continuously stirring in a nitrogen atmosphere until the methyl methacrylate and the sodium dodecyl benzene sulfonate are completely dissolved into light yellow clear liquid; more preferably, the mass ratio of the sodium dodecyl benzene sulfonate to the methyl methacrylate is 10-15, the stirring speed is 120 r/min-170 r/min, and the stirring time is 10 min-30 min; adding a perovskite quantum dot n-hexane dispersion liquid into the faint yellow clear liquid, continuously stirring, and uniformly dispersing to form a reaction system; further preferably, the mass ratio of the methyl methacrylate to the perovskite quantum dots is 6; s3, adding an initiator into the reaction system in the step S2, fully reacting at 50-70 ℃ for 6-8 h to obtain flocculent precipitate, repeatedly carrying out centrifugal washing for at least 3 times, and carrying out vacuum drying to obtain polymethyl methacrylate/perovskite quantum dot resin powder; further preferably, the initiator is benzoyl peroxide.
In the application, the polymethyl methacrylate/perovskite quantum dot resin powder prepared by the method is of a core-shell structure, and the perovskite quantum dots are coated in the shell by the polymethyl methacrylate, so that the increase and phase change of crystal grains caused by the agglomeration of nano materials are avoided, and the active material can still keep good fluorescence characteristics and excellent catalytic activity for a long time under the complex environmental condition and the stability of structure and performance. The perovskite quantum dots are coated with the polymethyl methacrylate in the application because the polymethyl methacrylate can be used as an ester film-forming aid for preparing ink. The prepared polymethyl methacrylate/perovskite quantum dot resin powder is dissolved in a solvent of the ink-jet printing ink, and other components such as a surfactant and the like can be added after the polymethyl methacrylate/perovskite quantum dot resin powder with proper addition amount is dissolved in the solvent, so that the ink meeting the requirements of ink-jet printing viscosity and surface tension is obtained.
All-inorganic perovskite CsPbX 3 The (X is halogen element) nanocrystal has unique physicochemical properties, such as high absorption coefficient, adjustable band gap width, excellent fluorescence property and the like, and is widely concerned by researchers. Therefore, the perovskite quantum dots in the present application are preferably CsPbX 3 The perovskite quantum dot is prepared by using at least one of Cl, br and I and different halogen elements 3 The perovskite quantum dots have different wavelengths and fluorescence properties, as shown in figure 1, csPbX of the patent 3 Perovskite quantum dots, 1) replacement of X in halogen elements with I, the obtained quantum dots wavelength rangeUnder the excitation of ultraviolet light around 690nm, the fluorescence spectrum is red; 2) X in the halogen elements is replaced by Br, so that the wavelength range of the obtained quantum dots is about 550nm, and the fluorescence spectrum of the quantum dots is green under the excitation of ultraviolet light; 3) When X in the halogen element is replaced by Cl, the wavelength range of the obtained quantum dot is about 450nm, and the fluorescence spectrum of the quantum dot is blue under the excitation of ultraviolet light. The fluorescence spectrum of the quantum dots can be changed by changing the types and the element proportions of halogen elements, so that CsPbX can be obtained 3 The quantum dots are combined with polymethyl methacrylate, so that the fluorescence efficiency, stability and catalytic activity of the perovskite quantum dots can be improved, and the fluorescence characteristic can meet the requirement of anti-counterfeiting identification.
The present application is also directed to an all-inorganic perovskite CsPbX 3 A set of examples for preparing polymethylmethacrylate/perovskite quantum dot resin powders is provided, as follows:
firstly, adding 100ml of n-hexane into a 500ml three-neck flask, adding 2.5g of sodium dodecyl benzene sulfonate and 0.2g of Methyl Methacrylate (MMA) subjected to reduced pressure distillation treatment into the three-neck flask to obtain a mixed solution, continuously introducing nitrogen into the three-neck flask, and stirring the mixed solution at a speed of 150r/min for 20min under the nitrogen atmosphere until the mixed solution is completely dissolved into a light yellow clear liquid; secondly, adding 100ml of perovskite quantum dot n-hexane dispersion liquid into the faint yellow clear liquid, continuously stirring and uniformly dispersing to obtain uniform dispersion liquid, wherein the concentration of the perovskite quantum dot n-hexane dispersion liquid is 0.25mg/ml, and the perovskite quantum dot is CsPbX 3 Wherein, X is at least one of Cl, br and I; and thirdly, adding 0.3g of benzoyl peroxide into the uniform dispersion liquid, quickly stirring, continuously reacting for 6-8 hours at 50-70 ℃ to obtain flocculent precipitate, centrifugally washing the flocculent precipitate for three times, and drying in vacuum to obtain the polymethyl methacrylate/perovskite quantum dot resin powder. The polymethyl methacrylate/perovskite quantum dot resin powder is stored at normal temperature and is used for preparing invisible ink-jet printing ink.
Aiming at the polymethyl methacrylate/perovskite quantum dot resin powder prepared by the embodiment, the application also provides anti-counterfeiting ink-jet printing ink with a group of specific components, which comprises the following components in percentage by mass: 15-30% of polymethyl methacrylate/perovskite quantum dot resin powder; 15% -25% of vinyl chloride-vinyl acetate copolymer; 0.5 percent of defoaming agent; 2.5 to 5 percent of hexadecyl benzene sulfonic acid sodium; the balance being ink solvent; the ink solvent is prepared from 40% of n-hexane by volume and 60% of a mixed solvent of acetone and butanone by volume, wherein the acetone and the butanone are mixed in any proportion. In order to prove that the anti-counterfeiting ink-jet printing ink has excellent performance, the application also provides a series of performance experimental data aiming at the anti-counterfeiting ink-jet printing ink, and the data comprise the following data:
1) Measurement of viscosity and surface tension of anti-counterfeit ink-jet printing ink
The physical properties of the ink affect the ink jet printing process, in particular viscosity and surface tension, and in general the physical properties of the printed ink should be in the following ranges: the viscosity is between 1cps and 20cps, the surface tension is between 35mN/m and 60mN/m, and printing ink outside the range is not suitable for printing because independent stable liquid drops are not easy to form. The measured surface tension of the anti-counterfeiting ink-jet printing ink prepared by the scheme of the application is basically controlled to be about 45mN/m, and the measured viscosity is basically controlled to be about 15cps, as shown in figure 2.
The application also provides a sample layout clean condition data analysis prepared by applying inks with different surface tensions and viscosities, as shown in fig. 3, the Ink1 layout is prepared by applying Ink drops with small viscosities and small surface tensions, the Ink2 layout is prepared by applying normal Ink drops, and the Ink3 layout is prepared by applying Ink drops with too large viscosities and surface tensions. It can be seen from fig. 3 that the long tail of the print nozzle occurs with low viscosity and low surface tension; when both the viscosity and the surface tension are too large, the nozzle ink droplet volume is too large, and poor fluidity is also liable to occur. Therefore, the ink drop formed by the anti-counterfeiting ink-jet printing ink prepared by the scheme of the application has good fluidity, and can flow smoothly when passing through the nozzle, and the prepared sample has a clean surface.
2) Analysis of adhesion and dispersibility of anti-counterfeit ink-jet printing inks
Adhesion: the anti-counterfeiting ink-jet printing ink prepared by the method has the advantages of common solvent resistance (such as ethanol), detergent resistance and rubbing resistance, and can not be removed by repeatedly rubbing the surface of a jet printing product with alcohol with the concentration of 75% for 25 times by 1 kilogram; and covering the printed part with gummed paper, flattening to ensure that no bubble exists in the covered part, then tearing off, continuously performing for 3 times, having no printing shedding phenomenon and excellent adhesiveness.
Dispersibility: and (3) standing the prepared anti-counterfeiting ink-jet printing ink, and observing the states of the ink after standing for 7 days, 14 days and 30 days respectively, wherein no precipitate is observed to be generated by observation, which indicates that the anti-counterfeiting ink-jet printing ink has good dispersibility and stability.
In the application, the invisible ink-jet printing ink containing the perovskite quantum dots is provided, and the components of the invisible ink-jet printing ink comprise polymethyl methacrylate/perovskite quantum dot resin powder, resin, a defoaming agent, a surfactant and an ink solvent. The application also provides a preparation method of the polymethyl methacrylate/perovskite quantum dot resin powder for the invisible ink-jet printing ink, the polymethyl methacrylate/perovskite quantum dot resin powder prepared by the method is of a core-shell structure, perovskite quantum dots are coated in the shell by the polymethyl methacrylate, the polymethyl methacrylate can protect the perovskite quantum dots from being corroded by water and oxygen, the problem of poor stability of the perovskite quantum dots is solved, the perovskite quantum dots can be prevented from being influenced by anion exchange reaction, meanwhile, the agglomeration among the quantum dots is avoided, and the quantum yield is improved. The polymethyl methacrylate/perovskite quantum dot resin powder has high luminous efficiency and narrow luminous spectral line, and the fluorescence spectrum of the quantum dot can be changed by changing the type of the halogen element, so that when the printing ink prepared from the polymethyl methacrylate/perovskite quantum dot resin powder is used for anti-counterfeiting marks, the polymethyl methacrylate/perovskite quantum dot resin powder has the following advantages: good monochromaticity, good color rendering property, wide color rendering range and difficult decay. The invisible ink-jet printing ink prepared by the scheme of the application has wide application range: suitable for a variety of ink jet printing, such as: dot matrix ink jet numbering machines, high resolution ink jet numbering machines, various industrial grade spray heads, etc.
The present application has been described in connection with only the presently preferred embodiments with the understanding that the present disclosure is not to be considered as limiting, and the present application is not limited to the examples described above, but rather, it is to be understood that changes, modifications, additions or substitutions that are within the spirit and scope of the application by one of ordinary skill in the art are included.
Claims (8)
1. The invisible perovskite quantum dot ink-jet printing ink is characterized by comprising the following components in percentage by mass: 15 to 30 percent of polymethyl methacrylate/perovskite quantum dot resin powder, 15 to 25 percent of resin, 0.1 to 1.0 percent of defoaming agent, 0.05 to 7 percent of surfactant and the balance of ink solvent;
the resin is vinyl chloride-vinyl acetate resin; the surfactant is sodium dodecyl benzene sulfonate;
the polymethyl methacrylate/perovskite quantum dot resin powder is prepared by the following steps:
s1, carrying out reduced pressure distillation treatment on methyl methacrylate;
s2, dissolving the methyl methacrylate and the sodium dodecyl benzene sulfonate in the step S1 in n-hexane under the nitrogen atmosphere by continuously stirring until the methyl methacrylate and the sodium dodecyl benzene sulfonate are completely dissolved into light yellow clear liquid, adding perovskite quantum dot n-hexane dispersion liquid into the light yellow clear liquid, and uniformly dispersing to form a reaction system;
and S3, adding an initiator into the reaction system in the step S2, fully reacting at 50-70 ℃ to obtain flocculent precipitate, repeatedly centrifuging, washing, and drying in vacuum to obtain the polymethyl methacrylate/perovskite quantum dot.
2. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 1, which comprises the following components in percentage by mass:
polymethyl methacrylate/perovskite quantum dot resin powder 25-30%
20 to 25 percent of resin
0.5 to 0.7 percent of defoaming agent
2.5 to 5 percent of surfactant
The balance being ink solvent.
3. The perovskite quantum dot invisible ink-jet printing ink as claimed in any one of claims 1 to 2, wherein the ink solvent is prepared by mixing n-hexane, acetone and butanone.
4. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 3, wherein the ink solvent is prepared from a mixed solution of 40% by volume of n-hexane and 60% by volume of acetone and butanone.
5. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 1, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the methyl methacrylate is 10-15.
6. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 1, wherein the stirring speed is 120r/min to 170r/min, and the stirring time is 10min to 30min.
7. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 1, wherein the initiator is benzoyl peroxide.
8. The perovskite quantum dot invisible ink-jet printing ink as claimed in claim 1, wherein the perovskite quantum dot is CsPbX 3 Wherein X is at least one of Cl, br and I.
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| CN113306326A (en) * | 2021-05-18 | 2021-08-27 | 江苏第二师范学院 | Fluorescent anti-counterfeiting material based on copper-based halogen perovskite and preparation method and application thereof |
| CN113698814A (en) * | 2021-09-17 | 2021-11-26 | 义乌清越光电科技有限公司 | Quantum dot ink and application thereof |
| CN116731559A (en) * | 2022-03-03 | 2023-09-12 | 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) | Printing ink with fluorescent effect and preparation method and application thereof |
| CN114634735B (en) * | 2022-04-27 | 2023-05-09 | 广州市麦修拓包装设备有限公司 | Ink paste for small character code spraying, preparation method thereof and ink |
| CN116589885A (en) * | 2023-06-02 | 2023-08-15 | 厦门大学 | Preparation method of stable fluorescent PeQD ink suitable for EHD ink-jet printing |
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