CN110577769A - Water-based up-conversion fluorescent ink-jet ink and preparation method and application thereof - Google Patents
Water-based up-conversion fluorescent ink-jet ink and preparation method and application thereof Download PDFInfo
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- CN110577769A CN110577769A CN201910964603.6A CN201910964603A CN110577769A CN 110577769 A CN110577769 A CN 110577769A CN 201910964603 A CN201910964603 A CN 201910964603A CN 110577769 A CN110577769 A CN 110577769A
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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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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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
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Abstract
The invention relates to an aqueous up-conversion fluorescent ink-jet ink, a preparation method and an application thereof, wherein the aqueous up-conversion fluorescent ink-jet ink comprises the following components in percentage by mass: 0.5-10% of up-conversion fluorescent material, 20-35% of binder, 50-60% of water, 4-10% of alcohol solvent and 0.23-5% of auxiliary agent; the up-conversion fluorescent material comprises rare earth element doped water-based up-conversion fluorescent nanoparticles, and polyethyleneimine is modified on the water-based up-conversion fluorescent nanoparticles. The water-based up-conversion fluorescent ink-jet ink provided by the invention has the advantages of good environmental protection performance, adjustable fluorescent color, suitability for various printing materials, simple preparation process, strong concealment, capability of realizing individuation, private customization and variable information hiding, capability of being printed on bills, trademarks or high-grade packages in batches, wide application range and strong anti-counterfeiting force, thereby realizing the replacement and supplement of the existing anti-counterfeiting printing technology.
Description
Technical Field
The invention relates to the technical field of rail transit, in particular to water-based up-conversion fluorescent ink-jet ink, a preparation method and application thereof, and particularly relates to water-based up-conversion fluorescent ink-jet ink suitable for multi-medium digital proofing, and a preparation method and application thereof.
Background
The counterfeit goods seriously harm the human health, and the close combination of the anti-counterfeiting technology and the digital printing has important significance for fighting against illegal counterfeiting and maintaining the market order of fair competition. The anti-counterfeiting ink is an important branch in anti-counterfeiting technology, namely, the anti-counterfeiting mark is printed on a ticket, a product trademark or a package in an ink mode, and the anti-counterfeiting ink has the advantages of low cost, good concealment, easiness in detection, high flexibility and the like. In recent years, with the increasing awareness of environmental protection, some printed matters have made higher demands on anti-counterfeiting printing technology in order to pursue unique artistic effects. Therefore, the development of environment-friendly and digital anti-counterfeiting ink becomes a hot spot and direction for improving competitiveness and developing roads continuously in the industry.
the invisible anti-counterfeiting ink has strong concealment, confidentiality and disguise, and can realize the concealment and reproduction of the anti-counterfeiting mark on the basis of keeping the original appearance of the surface picture. According to different excitation modes, the invisible anti-counterfeiting ink can be divided into ultraviolet light excited anti-counterfeiting ink (down-conversion fluorescent ink) and infrared light excited anti-counterfeiting ink (up-conversion fluorescent ink). The ultraviolet light excited anti-counterfeiting ink has wide application, the materials, the preparation process and the excitation light source are easy to imitate, most ultraviolet light excited fluorescent materials are organic dyes or quantum dots, the environment-friendly performance is poor, the resistance and the stability are poor, and the long-term storage of anti-counterfeiting prints is not facilitated. In addition, most of the printing materials (containing fluorescent whitening agents) or surface coatings absorb ultraviolet light to a certain extent, so that the final anti-counterfeiting effect is influenced.
compared with the prior art, the up-conversion fluorescent ink shows the invisible anti-counterfeiting characteristic only under the specific wavelength, has the advantages of low toxicity, long fluorescence life, good light stability, no background fluorescence interference, strong anti-counterfeiting strength and the like, and is a key point and a hotspot of the current research.
CN201610308927.0 and CN201710335455.2 disclose preparation methods of rare earth up-conversion luminescent ink and up/down-conversion dual-mode luminescent ink for screen printing and anti-counterfeiting application thereof. The up-conversion fluorescent material prepared by the method has a complex preparation process and poor compatibility with ink binder, the prepared solvent-based ink has poor environmental protection performance and poor stability, the printing precision of screen printing is low, and personalized and variable information hiding cannot be realized.
CN201810115493.1 discloses an aqueous rare earth up-conversion fluorescent ink, a preparation method thereof and anti-counterfeiting application. The printing ink prepared by the method obtains anti-counterfeiting patterns on a printing stock in a stamping or gravure mode, has good environmental protection performance, wide printing range and strong anti-counterfeiting strength, but can not realize variable data and printing according to requirements.
CN201410718694.2 discloses an up-conversion fluorescent ink for inkjet printer and a preparation method thereof. The method relates to a two-step method for preparing rare earth-doped up-conversion nanoparticles, chloroform with high toxicity is needed for water-soluble surface modification, and particle aggregation and fluorescence intensity reduction are easily caused in the water-soluble modification process. In addition, the printing ink system takes glycerol or ethylene glycol as a thickening agent, so that high adhesive force is difficult to obtain on printing materials such as synthetic paper, PET, BOPP and the like, and the requirement of multi-medium digital proofing cannot be met.
in addition, the up-conversion fluorescent ink is easy to blacken by a three-roll rolling method or a stainless steel high-speed grinding method commonly adopted in the existing preparation method, and the addition of the light calcium carbonate can improve the covering power of the ink, so that the transparency is reduced, and the final fluorescence emission is influenced.
Therefore, the up-conversion fluorescent inkjet ink has the effects of good environmental protection performance, adjustable fluorescent color, suitability for various printing materials, simple preparation process, strong concealment, batch printing, personalized customization, variable information hiding and the like.
disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide an aqueous upconversion fluorescent inkjet ink, and in particular, to provide an aqueous upconversion fluorescent inkjet ink suitable for multimedia digital proofing, and a preparation method and an application thereof. The water-based up-conversion fluorescent ink-jet ink is good in environmental protection performance, adjustable in fluorescent color, suitable for various printing materials, simple in preparation process, strong in concealment, capable of achieving individuation, private customization and variable information hiding, capable of being printed on bills, trademarks or high-grade packages in batches, wide in application range and strong in anti-counterfeiting strength, and accordingly replacement and supplement of the existing anti-counterfeiting printing technology are achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides water-based up-conversion fluorescent ink-jet ink which comprises the following components in percentage by mass:
The up-conversion fluorescent material comprises rare earth element doped water-based up-conversion fluorescent nanoparticles, and Polyethyleneimine (PEI) is modified on the water-based up-conversion fluorescent nanoparticles.
in the aqueous upconversion fluorescent inkjet ink, the mass percentage of an upconversion fluorescent material is 0.5-10%, such as 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% and the like;
In the aqueous up-conversion fluorescent inkjet ink, the mass percentage of the binder is 20-35%, such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% and the like;
in the aqueous up-conversion fluorescent inkjet ink, the mass percentage of water is 50-60%, such as 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% and the like;
In the aqueous up-conversion fluorescent inkjet ink, the mass percentage of the alcohol solvent is 4-10%, such as 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% and the like;
In the water-based up-conversion fluorescent inkjet ink, the mass percentage of the auxiliary agent is 0.23-5%, such as 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.48% and the like.
an upconversion fluorescent material refers to a material that is capable of emitting fluorescence upon excitation by infrared light.
According to the invention, the rare earth element doped water-based up-conversion fluorescent nanoparticles are selected, and the polyethyleneimine is modified on the water-based up-conversion fluorescent nanoparticles, so that the fluorescent material has better water dispersibility due to the introduction of the polyethyleneimine, has good compatibility with a water-based ink binder, and is matched with other components, so that the stability and the adhesive force of the ink are improved.
in addition, the rare earth element is doped in the water-based up-conversion fluorescent nanoparticles, so that the light emitting color and the wavelength of the fluorescent material can be adjusted by adjusting the doping type and the doping amount of the rare earth element. And through a specific ink formula design, the types of the fluorescent materials and the proportion among various fluorescent materials are further adjusted to obtain the ink with a specific emission color and wavelength, the emission color can be accurately displayed only under the specific formula design and a certain excitation condition, the concealment is strong, the printing ink is more difficult to copy compared with the traditional fluorescent ink, the anti-counterfeiting strength of a printed product is greatly improved, and the individuation, the private customization and the variable information hiding can be realized through a spray printing mode. And when the excitation wavelength is 980nm, 380-780 nm fluorescence is emitted.
The water-based up-conversion fluorescent ink-jet ink provided by the invention is suitable for various printing media, and the types of the printing media do not influence the absorption and fluorescence emission of near infrared light, and the ink-jet ink is environment-friendly and pollution-free.
The rare earth element doped waterborne up-conversion fluorescent nanoparticle refers to that the rare earth element is doped on the basis of a fluorescent nanoparticle base material, and the base material can also be composed of a compound containing the rare earth element.
preferably, the rare earth element includes a combination of at least two of erbium, thulium, and ytterbium.
In a preferred embodiment, at least two of the rare earth metals are selected to facilitate the adjustment of the fluorescence color.
Preferably, the aqueous upconversion fluorescent nanoparticles comprise sodium yttrium tetrafluoride nanoparticles.
the invention selects sodium yttrium tetrafluoride nano particles as the matrix of the fluorescent nano material, and rare earth elements are doped on the basis, so that the fluorescent nano material can be matched with the rare earth elements to realize the adjustment of the fluorescent color.
Preferably, the up-conversion fluorescent material includes any one or at least two combinations of a red up-conversion fluorescent material, a green up-conversion fluorescent material, and a blue up-conversion fluorescent material.
preferably, the red up-conversion fluorescent material comprises erbium and thulium co-doped sodium yttrium tetrafluoride nanoparticles, wherein the molar contents of erbium and thulium are respectively 10% and 2%.
preferably, the red up-conversion fluorescent material emits red fluorescence under excitation of near infrared light with a wavelength of 980 nm.
Preferably, the green up-conversion fluorescent material comprises ytterbium and erbium co-doped sodium yttrium tetrafluoride nanoparticles, wherein the molar contents of ytterbium and erbium are respectively 20% and 2%.
Preferably, the green up-conversion fluorescent material emits green fluorescence under excitation of near infrared light with a wavelength of 980 nm.
Preferably, the blue up-conversion fluorescent material comprises ytterbium and thulium co-doped sodium yttrium tetrafluoride nanoparticles, wherein the molar contents of ytterbium and thulium are 20% and 0.5%, respectively.
Preferably, the blue up-conversion fluorescent material emits blue fluorescence under excitation of near infrared light with a wavelength of 980 nm.
The molar content mentioned above refers to the proportion of this element to the total mass of rare earth elements, and illustratively, the molar content of erbium in the red up-conversion fluorescent material is 10%, meaning that the mass of erbium accounts for 10% of the total mass of yttrium, erbium and thulium.
When the doping type and the doping proportion of the rare earth elements are changed according to the scheme, red, green and blue fluorescent materials can be obtained respectively, the three materials can be independently added into the printing ink or added into the printing ink in a combined mode, the fluorescent emission is adjusted by adjusting the adding type and the adding proportion of the fluorescent materials, and therefore spot-color fluorescent anti-counterfeiting can be achieved by adopting an ink jet channel.
Preferably, the weight average molecular weight of the polyethyleneimine is 8000 to 10000, for example, 8200, 8500, 8600, 8900, 9000, 9200, 9500, 9700, 9800 and the like.
preferably, the binder includes a synthetic resin.
Preferably, the synthetic resin comprises any one or at least two of aqueous polyurethane resin, aqueous acrylic resin, polyvinyl alcohol resin and aqueous polyester resin, preferably aqueous polyurethane resin and/or aqueous acrylic resin.
Preferably, the alcoholic solvent includes any one or a combination of at least two of ethanol, isopropanol, n-propanol and n-butanol, preferably ethanol and/or isopropanol.
Preferably, the auxiliary agent comprises any one or at least two of a pH adjuster, a defoaming agent and a leveling agent.
preferably, the pH regulator comprises any one or a combination of at least two of ammonia, sodium hydroxide, triethanolamine and triethylamine, preferably triethanolamine.
preferably, the defoaming agent comprises any one or at least two of a silicone defoaming agent, a polyether modified defoaming agent and a polysiloxane-polyether copolymer emulsion defoaming agent, and the polysiloxane-polyether copolymer emulsion defoaming agent is preferred.
preferably, the leveling agent comprises an acrylic modified non-silicon leveling agent.
Preferably, the aqueous upconversion fluorescent inkjet ink comprises the following components in percentage by mass:
in the aqueous upconversion fluorescent inkjet ink, the mass percentage of the pH regulator is 0.2-2%, such as 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.8%, and the like.
In the aqueous up-conversion fluorescent inkjet ink, the mass percent of the defoaming agent is 0.02-2%, such as 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18% and the like.
Preferably, the emission wavelength of the up-conversion fluorescent material under the excitation of near infrared light with the wavelength of 980nm is 380-780 nm, such as 385nm, 390nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm and the like.
preferably, the pH of the aqueous upconversion fluorescent inkjet ink is 7.02 to 8.68, such as 7.05, 7.1, 7.5, 7.7, 7.9, 8.2, 8.5, and the like.
preferably, the viscosity of the aqueous upconversion fluorescent inkjet ink is 2.52 to 4.00mpa.s, such as 2.6mpa.s, 2.8mpa.s, 3mpa.s, 3.2mpa.s, 3.5mpa.s, 3.6mpa.s, 3.8mpa.s, and the like.
Preferably, the surface tension of the aqueous upconversion fluorescent inkjet ink is 28.23 to 35.47mN/m, such as 29mN/m, 30mN/m, 31mN/m, 32mN/m, 33mN/m, 34mN/m, 35mN/m, and the like.
Preferably, the aqueous upconversion fluorescent inkjet ink has an adhesion on paper > 98%, such as 98.5%, 99%, 99.1%, 99.5%, etc.
the second object of the present invention is to provide a method for preparing an aqueous upconversion fluorescent inkjet ink according to the first object, comprising the steps of:
s1: preparing an up-conversion fluorescent material by a solvothermal method: dissolving rare earth nitrate or rare earth chloride, polyethyleneimine and NaF in a solvent, stirring, transferring to a stainless steel reaction kettle, heating at a speed of 8-15 ℃/min (such as 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min and the like), carrying out heat preservation reaction, cooling to room temperature, precipitating, centrifuging and washing to obtain the up-conversion fluorescent material;
s2: dispersing at least one up-conversion fluorescent material in weak alkaline water for 20-40 min (such as 22min, 24min, 26min, 28min, 30min, 32min, 35min, 38min, etc.) to obtain an up-conversion fluorescent material aqueous dispersion;
S3: dispersing the binder in water, stirring and standing to obtain a binder dispersion liquid;
s4: adding the up-conversion fluorescent material aqueous dispersion into the binder dispersion, stirring, homogenizing and grinding to obtain a mixed dispersion;
S5: and adding an alcohol solvent and an auxiliary agent in a formula amount into the mixed dispersion liquid, and stirring to obtain the water-based up-conversion fluorescent ink-jet ink.
The PEI modified water-soluble rare earth doped up-conversion fluorescent nanoparticle prepared by the one-step solvothermal method has the advantages of good water dispersibility, good compatibility with a water-based ink binder, strong adhesive force and simple preparation process, and is beneficial to improving the environmental protection property, the spray printability, the storage stability and the anti-counterfeiting effect of the up-conversion fluorescent ink-jet ink.
preferably, in step S1, the rare earth nitrate or chloride salt includes any three or more of erbium nitrate, yttrium chloride, ytterbium chloride, erbium chloride and thulium chloride, and preferably includes yttrium chloride.
the kind of the above-mentioned rare earth nitrate or rare earth chloride is selected according to the desired luminescent color of the upconversion fluorescent material, for example, yttrium chloride, erbium nitrate and thulium chloride may be selected when preparing a red upconversion fluorescent material; when the green light up-conversion fluorescent material is prepared, yttrium chloride, ytterbium chloride and erbium nitrate can be selected; when preparing blue up-conversion fluorescent materials, yttrium chloride, ytterbium chloride and thulium chloride may be selected.
one upconversion fluorescent material may be added in step S2, or two or more upconversion fluorescent materials may be added.
preferably, in step S1, the solvent includes water and ethylene glycol.
Preferably, in step S1, the stirring is magnetic stirring, and the stirring time is preferably 0.5 to 1 hour, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, and the like.
preferably, in step S1, the target temperature for heating is 200-220 deg.C, such as 202 deg.C, 203 deg.C, 204 deg.C, 205 deg.C, 206 deg.C, 207 deg.C, 208 deg.C, 210 deg.C, 212 deg.C, 215 deg.C, 216 deg.C, 218 deg.C, etc.
Preferably, in step S1, the reaction time is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, etc.
Preferably, in step S1, the precipitated precipitant includes ethanol.
Preferably, in step S1, the washed detergent includes ethanol and water.
preferably, in step S1, the heating rate is 10 deg.C/min.
preferably, in step S2, the dispersing method includes ultrasound.
Preferably, in step S2, the dispersion time is 30 min.
Preferably, in step S3, the stirring is magnetic stirring, and the stirring time is preferably 0.5 to 1.5h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, and the like.
preferably, in step S4, the aqueous dispersion of the upconversion fluorescent material is added dropwise with stirring.
Preferably, in step S4, the homogenization is performed in a homogenizer.
preferably, in step S4, the homogenization time is 0.5-1.5 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, etc.
preferably, in step S4, the grinding is performed in a ceramic high speed mixer.
Preferably, in step S4, the ceramic high-speed stirrer includes a ceramic grinding bowl, a ceramic grinding rod, and a ceramic grinding bead.
Preferably, in step S4, the grinding time is 3 to 5 hours, such as 3.2 hours, 3.5 hours, 3.6 hours, 3.8 hours, 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, and the like.
Preferably, in step S5, the alcohol solvent and the auxiliary are added sequentially.
preferably, in step S5, the auxiliary agent includes an antifoaming agent and a pH adjusting agent, and the antifoaming agent and the pH adjusting agent are added sequentially.
Preferably, in step S5, the auxiliary agent further includes a leveling agent.
Preferably, in step S5, the stirring time is 0.5-1.5 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, etc.
preferably, in step S5, after the stirring, the pH, viscosity, surface tension and drying performance of the ink system are adjusted to meet the requirements of inkjet printing.
preferably, the preparation method specifically comprises the following steps:
s1: dissolving rare earth nitrate or rare earth chloride, polyethyleneimine and NaF in a mixed solution of water and ethylene glycol, magnetically stirring for 0.5-1 h, transferring to a stainless steel reaction kettle, heating to 200-220 ℃ at the speed of 8-15 ℃/min, carrying out heat preservation reaction for 2-3 h, cooling to room temperature, adding ethanol for precipitation to obtain a product, centrifuging, and washing with ethanol and water for 3 times to obtain the up-conversion fluorescent material;
S2: ultrasonically dispersing at least one up-conversion fluorescent material in weak alkaline water for 20-40 min to obtain an up-conversion fluorescent material water dispersion;
Wherein, the ultrasonic dispersion is carried out until the uniform fluorescent light beam appears under the excitation of near infrared light with the wavelength of 980 nm;
S3: dispersing the binder in water, magnetically stirring for 0.5-1.5 h, and standing to obtain a binder dispersion liquid;
S4: dropwise adding the up-conversion fluorescent material water dispersion into the connecting material dispersion while stirring, dispersing and homogenizing for 0.5-1.5 h by using a homogenizer, and grinding for 3-5 h on a ceramic high-speed stirrer to obtain a mixed dispersion;
s5: and sequentially adding an alcohol solvent and an auxiliary agent in a formula amount into the mixed dispersion liquid, stirring for 0.5-1.5 h, and adjusting the pH value, viscosity, surface tension and drying performance of an ink system to meet the requirements of ink-jet printing to obtain the water-based up-conversion fluorescent ink-jet ink.
The third purpose of the invention is to provide an anti-counterfeiting color block, which is formed by spraying and printing the water-based up-conversion fluorescent ink-jet ink.
compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the rare earth element doped water-based up-conversion fluorescent nanoparticles are selected and modified with the polyethyleneimine, and the introduction of the polyethyleneimine can enable the fluorescent material to have better water dispersibility, and the fluorescent material has good compatibility with a water-based ink binder, so that the stability and the adhesive force of the ink are improved.
(2) The rare earth elements are doped in the waterborne up-conversion fluorescent nanoparticles, so that the luminous color and wavelength of the fluorescent material can be adjusted by adjusting the doping type and the doping amount of the rare earth elements. And the type of the fluorescent material is further adjusted through a specific ink formula design to obtain the ink with a specific emission color and wavelength, the emission color can be accurately displayed only under the specific formula design and a certain excitation condition, the concealment is strong, the printing ink is more difficult to copy compared with the traditional fluorescent ink, the anti-counterfeiting strength of a printed product is greatly improved, and the individuation, the private customization and the variable information hiding can be realized through a spray printing mode. And when the excitation wavelength is 980nm, 380-780 nm fluorescence is emitted.
(3) The water-based up-conversion fluorescent ink-jet ink provided by the invention is suitable for various printing media, and the types of the printing media do not influence the absorption and fluorescence emission of near infrared light, and the ink-jet ink is environment-friendly and pollution-free.
In conclusion, the water-soluble rare earth doped up-conversion fluorescent nanoparticles are added into the water-based ink-jet ink system by adopting a simple process method, and a better anti-counterfeiting effect is obtained by a spray printing mode, so that a new thought is provided for further developing high-performance environment-friendly functional packaging materials, and the method has very important research significance and far-reaching prospect.
drawings
FIG. 1 is an upconversion fluorescence spectrum of the ink of example 4 under excitation by 980nm wavelength near infrared light.
FIG. 2 is an upconversion fluorescence spectrum of the ink of example 5 under excitation by 980nm wavelength near infrared light.
FIG. 3 is an upconversion fluorescence spectrum of the ink of example 6 under excitation by 980nm wavelength near infrared light.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
the embodiment provides a preparation method of a red up-conversion fluorescent material, which comprises the following steps:
s1, dissolving 0.88mmol of yttrium chloride, 0.1mmol of erbium nitrate, 0.02mmol of thulium chloride and 0.5g of PEI (weight average molecular weight of 8000) in 6mL of water and 12mL of Ethylene Glycol (EG), and fully mixing to form a transparent solution A;
S2, dissolving 12mmol of NaF in 12mL of EG to form a uniform solution B;
S3, dropwise adding the solution A into the solution B under the action of magnetic stirring, transferring the mixed solution into a 50mL stainless steel reaction kettle containing a polytetrafluoroethylene lining after stirring the mixed solution for 30min, heating to 220 ℃ at the speed of 10 ℃/min, and carrying out heat preservation reaction for 3 h;
S4, cooling to room temperature, adding ethanol for precipitation to obtain a product, centrifuging at a high speed of 10000rpm for 15min, and using a mixed solvent (V)ethanol：VWater (W)1:1) and cleaning for 3 times to prepare the water-soluble red up-conversion fluorescent nanoparticles which emit red fluorescence under the excitation of near infrared light with the wavelength of 980 nm.
Example 2
the embodiment provides a preparation method of a green up-conversion fluorescent material, which comprises the following steps:
s1, dissolving 0.78mmol of yttrium chloride, 0.2mmol of ytterbium chloride, 0.02mmol of erbium nitrate and 0.5g of PEI (weight-average molecular weight of 10000) in 6mL of water and 12mL of EG, and fully mixing to form a transparent solution A;
S2, dissolving 12mmol of NaF in 12mL of EG to form a uniform solution B;
S3, dropwise adding the solution A into the solution B under the action of magnetic stirring, transferring the mixed solution into a 50mL stainless steel reaction kettle containing a polytetrafluoroethylene lining after stirring the mixed solution for 1h, heating to 200 ℃ at the speed of 10 ℃/min, and carrying out heat preservation reaction for 2 h;
s4, cooling to room temperature, adding ethanol for precipitation to obtain a product, centrifuging at a high speed of 10000rpm for 15min, and using a mixed solvent (V)Ethanol：Vwater (W)1:1) and (3) cleaning for 3 times to prepare the water-soluble green up-conversion fluorescent nanoparticles which emit green fluorescence under the excitation of near infrared light with the wavelength of 980 nm.
Example 3
the embodiment provides a preparation method of a blue up-conversion fluorescent material, which comprises the following steps:
S1, dissolving 0.795mmol of yttrium chloride, 0.2mmol of ytterbium chloride, 0.005mmol of thulium chloride and 0.5g of PEI (weight-average molecular weight of 9000) in 6mL of water and 12mL of EG, and fully mixing to form a transparent solution A;
S2, dissolving 12mmol of NaF in 12mL of EG to form a uniform solution B;
s3, dropwise adding the solution A into the solution B under the action of magnetic stirring, transferring the mixed solution into a 50mL stainless steel reaction kettle containing a polytetrafluoroethylene lining after stirring the mixed solution for 1h, heating to 220 ℃ at the speed of 10 ℃/min, and carrying out heat preservation reaction for 2 h;
S4, cooling to room temperature, adding ethanol for precipitation to obtain a product, centrifuging at a high speed of 10000rpm for 15min, and using a mixed solvent (V)ethanol：Vwater (W)1:1) and cleaning for 3 times to prepare the water-soluble blue up-conversion fluorescent nanoparticles which emit blue fluorescence under the excitation of near infrared light with the wavelength of 980 nm.
Example 4
(1) The embodiment provides a preparation method of an aqueous up-conversion fluorescent inkjet ink suitable for multi-media digital proofing, which comprises the following steps:
s1, ultrasonically dispersing 0.5g of the green up-conversion fluorescent material prepared in the embodiment 2 in 20g of weak alkaline water for 30min, and enabling the dispersion liquid to show stable fluorescence output under the excitation of near infrared light with the wavelength of 980 nm.
S2, dispersing 35g of connecting material in 40g of water, wherein the mass ratio of the water-based polyurethane (HK-718, Jinninghuaka resin company) to the water-based acrylic resin (AZR, Tianjin Atakz company) in the connecting material is 2: 1. magnetically stirring for 1.5h, standing for 10min to form a uniformly dispersed stable carrier;
S3, dropwise adding the water dispersion of the up-conversion fluorescent material into the dispersion of the connecting material while stirring, dispersing and homogenizing for 0.5h by using a homogenizer, and then grinding for 3h on a ceramic high-speed stirrer;
s4, sequentially adding 4g of alcohol solvent (the mass ratio of ethanol to isopropanol is 1:1), 0.02g of defoaming agent (polysiloxane-polyether copolymer emulsion defoaming agent, tego810, Germany dike high auxiliary agent), 0.2g of pH regulator (ammonia water) and 0.01g of flatting agent (acrylic acid modified non-silicon flatting agent, KYC-616, Germany Keying chemistry), stirring for 0.5h, and testing the pH value, viscosity, adhesive force and drying performance of the ink-jet ink system;
(2) Preparing a fluorescent anti-counterfeiting color block by spray printing: designing a 2.0cm multiplied by 2.0cm fluorescent spot color block, carrying out jet printing on the prepared water-based up-conversion fluorescent ink-jet ink in a spray printing mode to obtain a required pattern on coated paper, and naturally drying.
FIG. 1 is a graph showing the upconversion fluorescence spectrum of the printed pattern of example 4 excited by 980nm near infrared light, the main emission peak wavelength shown in FIG. 1 is 540nm, and Er3+Energy level transition of (1:2S3/2→2I15/2) The fluorescence was green.
The printed patterns were irradiated with near infrared light having wavelengths of 808nm, 850nm, 900nm, 950nm, and 1100nm, respectively, without emitting fluorescence.
The upconversion fluorescence spectrum of the invention is measured by an external 980nm near infrared exciter (Changchun new industry photoelectric technology Co., Ltd.) of an F-4500 type fluorescence spectrophotometer produced by Hitachi.
Example 5
(1) the embodiment provides a preparation method of an aqueous up-conversion fluorescent inkjet ink suitable for multi-media digital proofing, which comprises the following steps:
S1, ultrasonically dispersing 4g of red up-conversion fluorescent material, 2g of green up-conversion fluorescent material and 4g of blue up-conversion fluorescent material respectively prepared in examples 1, 2 and 3 in 20g of weak alkaline water for 30min, and enabling dispersion liquid to show stable fluorescence output under the excitation of near infrared light with the wavelength of 980 nm.
s2, dispersing 20g of binder in 40g of water, wherein the mass ratio of the aqueous polyurethane (HK-718, Jinninghuaka resin company) to the aqueous acrylic resin (AZR, Tianjin Atlantic company) in the binder is 1: 2. magnetically stirring for 0.5h, standing for 10min to form a uniformly dispersed stable carrier;
s3, dropwise adding the water dispersion of the up-conversion fluorescent material into the dispersion of the connecting material while stirring, dispersing and homogenizing for 1.5h by using a homogenizer, and then grinding for 5h on a ceramic high-speed stirrer;
S4, sequentially adding 5g of alcohol solvent (the mass ratio of ethanol to isopropanol is 1:1), 2g of defoaming agent (polysiloxane-polyether copolymer emulsion type defoaming agent, tego810, Germany dikao auxiliary), 2g of pH regulator (triethanolamine) and 1g of leveling agent (acrylic acid modified non-silicon leveling agent, KYC-616, Germany Keying chemistry), stirring for 1.5h, and testing the pH value, viscosity, adhesive force and drying performance of the ink-jet ink system.
(2) Preparing a fluorescent anti-counterfeiting color block by spray printing: designing a 2.0cm multiplied by 2.0cm fluorescent spot color block, adopting a spray printing mode to the prepared water-based up-conversion fluorescent ink-jet ink to obtain a required pattern on synthetic paper, and naturally drying.
FIG. 2 is the upconversion fluorescence spectrum of the printed pattern of example 5 under the excitation of 980nm wavelength near infrared light, and the integrated areas of the fluorescence spectrum shown in FIG. 2 in the wavelength ranges of 400-500nm, 500-600nm and 600-700nm are approximately equal, and white fluorescence appears.
The printed patterns were irradiated with near infrared light having wavelengths of 808nm, 850nm, 900nm, 950nm, and 1100nm, respectively, without emitting fluorescence.
example 6
(1) The embodiment provides a preparation method of an aqueous up-conversion fluorescent inkjet ink suitable for multi-media digital proofing, which comprises the following steps:
s1, ultrasonically dispersing 3g of green up-conversion fluorescent material and 5g of blue up-conversion fluorescent material respectively prepared in examples 2 and 3 in 20g of weak alkaline water for 30min, and enabling dispersion liquid to show stable fluorescence output under the excitation of near infrared light with the wavelength of 980 nm.
s2, dispersing 30g of binder in 30g of water, wherein the mass ratio of the waterborne polyurethane (HK-718, Jining Huaka resin company) to the waterborne acrylic resin (AZR, Tianjin Atlantic company) in the binder is 2: 1. magnetically stirring for 1h, standing for 10min to form a uniformly dispersed stable carrier;
S3, dropwise adding the water dispersion of the up-conversion fluorescent material into the dispersion of the connecting material while stirring, dispersing and homogenizing for 1.5h by using a homogenizer, and then grinding for 5h on a ceramic high-speed stirrer;
S4, sequentially adding 10g of alcohol solvent (the mass ratio of ethanol to isopropanol is 1:1), 1g of defoaming agent (polysiloxane-polyether copolymer emulsion defoaming agent, tego810, Germany dikao auxiliary agent), 0.95g of pH regulator (sodium hydroxide) and 0.05g of leveling agent (acrylic acid modified non-silicon leveling agent, KYC-616, Germany Keying chemistry), stirring for 1.5h, and testing the pH value, viscosity, adhesive force and drying performance of the ink-jet ink system.
(2) preparing a fluorescent anti-counterfeiting color block by spray printing: designing a 2.0cm multiplied by 2.0cm fluorescent spot color block, carrying out spray printing on the prepared water-based up-conversion fluorescent ink-jet ink to obtain a required pattern on the white cardboard, and naturally drying.
FIG. 3 is a graph showing the up-conversion fluorescence spectra of the printed pattern of example 6 under excitation by 980nm near infrared light showing main emission peak wavelengths of 475nm and 540nm, respectively, and Tm3+(1G4→3H6) And Er3+energy level transition of (1:2S3/2→2I15/2) The integrated areas of the spectra in the wavelength ranges of 400-500nm and 500-600nm are approximately equal, and the blue fluorescence is shown.
The printed patterns were irradiated with near infrared light having wavelengths of 808nm, 850nm, 900nm, 950nm, and 1100nm, respectively, without emitting fluorescence.
In the above examples 5 to 6, different fluorescent materials are used, and the fluorescence emission spectra of the finally obtained inks are also different, thereby realizing the adjustment of the emitted fluorescence.
Comparative example 1
the difference from example 4 is that the green up-conversion phosphor obtained in example 2 was replaced by an equal mass of up-conversion phosphor D1;
the preparation method of the up-conversion fluorescent material D1 only differs from that of example 2 in that no PEI is added.
The 980nm wavelength near infrared light is used for exciting the printed pattern to emit green fluorescence, but the water dispersibility is poor, and the storage stability of the ink is poor.
comparative example 2
the difference from example 4 is that the green up-conversion phosphor obtained in example 2 was replaced by an equal mass of up-conversion phosphor D1;
the preparation method of the up-conversion fluorescent material D1 only differs from that of example 2 in that ytterbium chloride and erbium nitrate are not added.
The printed pattern was excited using near infrared light of 980nm wavelength, and no fluorescence was emitted.
the results prove that the ink provided by the invention can be accurately displayed only under the specific formula design and certain excitation conditions, has strong concealment and adjustable emission spectrum, is more difficult to copy compared with the traditional fluorescent ink, greatly improves the anti-counterfeiting strength of printed products, and can realize individuation, private customization and variable information concealment by a spray printing mode.
And (3) performance testing:
The following performance tests were performed on the upconversion fluorescent inkjet inks obtained in the examples and comparative examples:
(1) surface tension test
The test was carried out using a K100 model static surface tensiometer manufactured by Kruss, Germany. (2) And (3) viscosity testing:
The test was carried out according to GB/T13217.4-2008 "method for testing viscosity of liquid inks".
(3) And (3) testing the adhesive force:
The test was carried out according to GB/T13217.7-2009 test method for fastness to liquid ink adhesion.
(4) Initial drying test:
The test was carried out according to GB/T13217.5-2008 "detection method for initial drying of liquid ink".
(5) And (3) pH test:
Testing by adopting a PHS-3CB type pH meter produced by Shanghai Yueping scientific instruments and instruments Limited;
(6) And (3) stability testing:
After the sample was left at room temperature for 1 month, the physical states of the sample such as color, dispersibility, and the like were observed, and the fluorescence intensities of the upper and lower layer liquids were compared.
the results of the performance tests are shown in table 1.
TABLE 1
As can be seen from table 2, the aqueous upconversion fluorescent inkjet inks in the examples have good stability and high adhesion to paper.
the fluorescent material of comparative example 1 is different from that of example 4 only in that PEI is not modified, and although the obtained ink can emit fluorescence under the excitation of near infrared light with the wavelength of 980nm, the stability of the ink is poor, and the adhesion force is also reduced. Therefore, the method for modifying the fluorescent nanoparticles by adopting the PEI can effectively improve the stability and the adhesive force of the ink.
The fluorescent material of comparative example 2 is different from example 4 only in that it is not doped with a rare earth element, and although the stability and adhesion of the fluorescent material of comparative example 2 are comparable to example 4, it cannot emit fluorescence under excitation of near infrared light having a wavelength of 980 nm.
in addition, the inks of examples 4-5 were not capable of emitting fluorescence when excited by near infrared light of other wavelengths.
therefore, the ink can emit fluorescence under the excitation of near infrared light with the wavelength of 980nm only by adding the waterborne upconversion fluorescent nanoparticles doped with the rare earth elements and modified with the PEI and controlling the proportion of the fluorescent material, and the ink is strong in concealment and high in stability and adhesion.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. the water-based up-conversion fluorescent inkjet ink is characterized by comprising the following components in percentage by mass:
The up-conversion fluorescent material comprises rare earth element doped water-based up-conversion fluorescent nanoparticles, and polyethyleneimine is modified on the water-based up-conversion fluorescent nanoparticles.
2. The aqueous upconversion fluorescent inkjet ink according to claim 1, wherein the rare earth element comprises a combination of at least two of erbium, thulium and ytterbium;
Preferably, the aqueous upconversion fluorescent nanoparticles comprise sodium yttrium tetrafluoride nanoparticles.
3. The aqueous upconversion fluorescent inkjet ink according to claim 1 or 2, wherein the upconversion fluorescent material comprises any one or at least two combinations of a red upconversion fluorescent material, a green upconversion fluorescent material, and a blue upconversion fluorescent material.
4. the aqueous upconversion fluorescent inkjet ink according to claim 3, wherein the red upconversion fluorescent material comprises erbium and thulium co-doped sodium yttrium tetrafluoride nanoparticles, wherein the molar content of erbium and thulium is 10% and 2%, respectively;
preferably, the red up-conversion fluorescent material emits red fluorescence under excitation of near infrared light with a wavelength of 980 nm;
preferably, the green up-conversion fluorescent material comprises ytterbium and erbium co-doped sodium yttrium tetrafluoride nano-particles, wherein the molar contents of ytterbium and erbium are respectively 20% and 2%;
Preferably, the green up-conversion fluorescent material emits green fluorescence under the excitation of near infrared light with the wavelength of 980 nm;
Preferably, the blue up-conversion fluorescent material comprises ytterbium and thulium co-doped sodium yttrium tetrafluoride nanoparticles, wherein the molar contents of ytterbium and thulium are respectively 20% and 0.5%;
Preferably, the blue up-conversion fluorescent material emits blue fluorescence under excitation of near infrared light with a wavelength of 980 nm.
5. The aqueous upconversion fluorescent inkjet ink according to any one of claims 1 to 4, wherein the weight average molecular weight of the polyethyleneimine is 8000 to 10000;
Preferably, the binder comprises a synthetic resin;
preferably, the synthetic resin comprises any one or at least two of aqueous polyurethane resin, aqueous acrylic resin, polyvinyl alcohol resin and aqueous polyester resin, preferably aqueous polyurethane resin and/or aqueous acrylic resin.
6. The aqueous upconversion fluorescent inkjet ink according to any one of claims 1 to 5, wherein the alcohol solvent comprises any one or a combination of at least two of ethanol, isopropanol, n-propanol and n-butanol, preferably ethanol and/or isopropanol;
Preferably, the auxiliary agent comprises any one or at least two of pH regulator, defoaming agent and leveling agent;
Preferably, the pH regulator comprises any one or at least two of ammonia water, sodium hydroxide, triethanolamine and triethylamine, preferably triethanolamine;
Preferably, the defoaming agent comprises any one or at least two of organic silicon defoaming agent, polyether modified defoaming agent and polysiloxane-polyether copolymer emulsion defoaming agent, preferably polysiloxane-polyether copolymer emulsion defoaming agent;
Preferably, the leveling agent comprises an acrylic modified non-silicon leveling agent;
Preferably, the aqueous upconversion fluorescent inkjet ink comprises the following components in percentage by mass:
7. The aqueous upconversion fluorescent inkjet ink according to any one of claims 1 to 6, wherein the upconversion fluorescent material has an emission wavelength of 380 to 780nm under excitation of near infrared light having a wavelength of 980 nm;
preferably, the pH of the aqueous upconversion fluorescent inkjet ink is 7.02-8.68;
preferably, the viscosity of the aqueous upconversion fluorescent inkjet ink is 2.52 to 4.00 mPa.s;
Preferably, the surface tension of the aqueous upconversion fluorescent inkjet ink is 28.23-35.47 mN/m;
Preferably, the adhesion of the aqueous up-conversion fluorescent inkjet ink on paper is > 98%.
8. A method for preparing an aqueous upconversion fluorescent inkjet ink according to any one of claims 1 to 7, comprising the steps of:
S1: preparing an up-conversion fluorescent material by a solvothermal method: dissolving rare earth nitrate or rare earth chloride, polyethyleneimine and NaF in a solvent, stirring, transferring to a stainless steel reaction kettle, heating at the speed of 8-15 ℃/min, carrying out heat preservation reaction, cooling to room temperature, precipitating, centrifuging, and washing to obtain the up-conversion fluorescent material;
s2: dispersing at least one up-conversion fluorescent material in weak alkaline water for 20-40 min to obtain an up-conversion fluorescent material water dispersion;
S3: dispersing the binder in water, stirring and standing to obtain a binder dispersion liquid;
s4: adding the up-conversion fluorescent material aqueous dispersion into the binder dispersion, stirring, homogenizing and grinding to obtain a mixed dispersion;
S5: and adding an alcohol solvent and an auxiliary agent in a formula amount into the mixed dispersion liquid, and stirring to obtain the water-based up-conversion fluorescent ink-jet ink.
9. the method according to claim 8, wherein in step S1, the rare earth nitrate or chloride salt includes any three or more of erbium nitrate, yttrium chloride, ytterbium chloride, erbium chloride, and thulium chloride, preferably includes yttrium chloride;
preferably, in step S1, the solvent includes water and ethylene glycol;
preferably, in the step S1, the stirring is magnetic stirring, and preferably the stirring time is 0.5 to 1 hour;
Preferably, in step S1, the target temperature of heating is 200-220 ℃;
preferably, in the step S1, the time of the heat preservation reaction is 2-3 h;
Preferably, in step S1, the precipitated precipitating agent includes ethanol;
Preferably, in step S1, the washed detergent includes ethanol and water;
preferably, in step S1, the heating rate is 10 ℃/min;
preferably, in step S2, the dispersing method includes ultrasound;
Preferably, in step S2, the dispersing time is 30 min;
Preferably, in the step S3, the stirring is magnetic stirring, and preferably the stirring time is 0.5 to 1.5 hours;
preferably, in step S4, the aqueous dispersion of the upconversion fluorescent material is added dropwise with stirring;
Preferably, in step S4, the homogenizing is performed in a homogenizer;
preferably, in step S4, the homogenization time is 0.5-1.5 h;
preferably, in step S4, the grinding is performed in a ceramic high-speed stirrer;
preferably, in step S4, the ceramic high-speed stirrer comprises a ceramic grinding bowl, a ceramic grinding rod and ceramic grinding beads;
Preferably, in the step S4, the grinding time is 3-5 hours;
Preferably, in step S5, the alcohol solvent and the auxiliary are sequentially added;
Preferably, in step S5, the auxiliary agent includes an antifoaming agent and a pH adjusting agent, and the antifoaming agent and the pH adjusting agent are added sequentially;
Preferably, in step S5, the auxiliary agent further includes a leveling agent;
Preferably, in the step S5, the stirring time is 0.5-1.5 h;
preferably, in step S5, after the stirring, the pH, viscosity, surface tension and drying performance of the ink system are adjusted to meet the requirements of inkjet printing;
Preferably, the preparation method specifically comprises the following steps:
s1: dissolving rare earth nitrate or rare earth chloride, polyethyleneimine and NaF in a mixed solution of water and ethylene glycol, magnetically stirring for 0.5-1 h, transferring to a stainless steel reaction kettle, heating to 200-220 ℃ at the speed of 8-15 ℃/min, carrying out heat preservation reaction for 2-3 h, cooling to room temperature, adding ethanol for precipitation to obtain a product, centrifuging, and washing with ethanol and water for 3 times to obtain the up-conversion fluorescent material;
S2: ultrasonically dispersing at least one up-conversion fluorescent material in weak alkaline water for 20-40 min to obtain an up-conversion fluorescent material water dispersion;
S3: dispersing the binder in water, magnetically stirring for 0.5-1.5 h, and standing to obtain a binder dispersion liquid;
s4: dropwise adding the up-conversion fluorescent material water dispersion into the connecting material dispersion while stirring, dispersing and homogenizing for 0.5-1.5 h by using a homogenizer, and grinding for 3-5 h on a ceramic high-speed stirrer to obtain a mixed dispersion;
s5: and sequentially adding an alcohol solvent and an auxiliary agent in a formula amount into the mixed dispersion liquid, stirring for 0.5-1.5 h, and adjusting the pH value, viscosity, surface tension and drying performance of an ink system to meet the requirements of ink-jet printing to obtain the water-based up-conversion fluorescent ink-jet ink.
10. An anti-counterfeiting color block, which is prepared by spray-printing the aqueous up-conversion fluorescent ink-jet ink according to any one of claims 1 to 7.
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