CN112552744A - Water-based polyurethane ink composition and preparation method thereof - Google Patents

Water-based polyurethane ink composition and preparation method thereof Download PDF

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CN112552744A
CN112552744A CN202011460702.XA CN202011460702A CN112552744A CN 112552744 A CN112552744 A CN 112552744A CN 202011460702 A CN202011460702 A CN 202011460702A CN 112552744 A CN112552744 A CN 112552744A
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aqueous polyurethane
ink composition
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water
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贺笑笑
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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
    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

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Abstract

The invention relates to the technical field of ink, and discloses a water-based polyurethane ink composition and a preparation method thereof. Comprises the following components in parts by weight: 60-70 parts of waterborne polyurethane emulsion, 15-20 parts of pigment, 5-10 parts of fluorescent composite particles, 0.5-1 part of dispersing agent, 0.3-0.6 part of defoaming agent, 0.5-1 part of wetting agent and 50-60 parts of water; the preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 20-30min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 30-40min to obtain the aqueous polyurethane ink composition. According to the invention, the silicon dioxide-metal organic framework composite nanosheet is used as a carrier of europium ions, so that the waterborne polyurethane ink has a good fluorescent effect.

Description

Water-based polyurethane ink composition and preparation method thereof
Technical Field
The invention relates to the technical field of ink, in particular to a water-based polyurethane ink composition and a preparation method thereof.
Background
With the development of society, fluorescent ink is more and more widely applied. Especially the printing technology of the packing products such as bills, securities, scratch cards, trademarks, book covers, cigarettes, wines and the like, adopts the anti-counterfeiting fluorescent ink to print, can improve the printing technology level, and can achieve a certain anti-counterfeiting effect. Fluorescent ink is ink made of fluorescent material. The layout printed by the fluorescent ink has the characteristic of converting ultraviolet short waves into longer visible light and reflecting attractive colors, so that the anti-counterfeiting effect is certain. The fluorescent ink can be divided into the following components according to the printing process: there are silk screen fluorescent ink, gravure fluorescent ink, offset fluorescent ink, letterpress fluorescent ink and flexo fluorescent ink. According to the performance of the ink, the fluorescent ink is used for printing general products, and the fluorescent anti-counterfeiting ink is specially used for anti-counterfeiting printing of special products. When in use, the fluorescent ink is designed according to the characteristics of the printing process, and the effect of the printing process can be ensured not to be influenced. Fluorescent inks are further classified into invisible anti-counterfeiting inks and visible anti-counterfeiting inks. Rare earth metal is also called rare earth element, rare earth ions can be changed into corresponding excited states from a ground state in a certain transition mode when being stimulated by external energy due to the special molecular structure of the rare earth ions, so that absorbed energy can be decayed to the excited state 4f configuration in a non-radiation mode, and then the excited energy state is radiatively transitioned to a low energy state, so that the special fluorescence of the rare earth can be emitted. However, rare earth particles have small ultraviolet absorption coefficient and weak fluorescence intensity, and sensitized rare earth ion luminescent ligands are designed for improving the fluorescence emission intensity of rare earth ions so as to achieve the purpose of changing the luminescent property.
Chinese patent publication No. CN106928774 discloses a tiger fluorescent anti-counterfeiting ink and a preparation method thereof, the tiger fluorescent anti-counterfeiting ink comprises fluorescent powder, pigment, a connecting material, a diluent, a filler and an auxiliary agent, the aging-resistant fluorescent powder comprises a europium ligand complex and a high-molecular adhesive medium material, and the technical scheme directly utilizes europium and an organic ligand to prepare the fluorescent powder by complexing; for another example, chinese patent publication No. CN107474633 discloses a modified ultraviolet fluorescent anti-counterfeit offset printing ink, which is prepared by mixing rare earth ion europium particles with thiophene formyl trifluoroacetone and phenol to obtain fluorescent agent powder, and then adding the fluorescent agent into the printing ink to endow the printing ink with fluorescent property. However, in the technical scheme, a large amount of europium ions are embedded in the fluorescent powder, so that the fluorescent intensity of the fluorescent powder is reduced, more rare earth europium raw materials are wasted, and the generation cost is high.
Chinese patent publication No. CN105037662 discloses a method for preparing europium-bonded fluorescent nano-silica microspheres by photocuring, which bonds acrylic acid europium into a nano-silica microsphere matrix by an ultraviolet curing method to prepare the europium-bonded fluorescent nano-silica microspheres, but europium ions are randomly dispersed in the matrix in the bonding process, the bonding effect of the silica microspheres and the europium ions is poor, the content of europium bonded on the surface of nano-silica is low, and the generated fluorescent effect is weak.
Disclosure of Invention
The present invention has been made to overcome the above problems of the prior art, and provides an aqueous polyurethane ink composition.
The invention also provides a preparation method of the aqueous polyurethane ink composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
the aqueous polyurethane ink composition comprises the following components in parts by weight:
60-70 parts of waterborne polyurethane emulsion, 15-20 parts of pigment, 5-10 parts of fluorescent composite particles, 0.5-1 part of dispersing agent, 0.3-0.6 part of defoaming agent, 0.5-1 part of wetting agent and 50-60 parts of water.
Preferably, the pigment is at least one of rutile titanium dioxide, anatase titanium dioxide and furnace black.
Preferably, the dispersant is at least one of sodium polyacrylate, polyoxyethylene ether and sodium maleate.
Preferably, the defoaming agent is at least one of polyoxypropylene glycerol ether, silicone emulsion and pentaerythritol stearate.
Preferably, the wetting agent is at least one of sodium dodecyl benzene sulfonate and polyethylene glycol ether.
Preferably, the preparation method of the fluorescent composite particle comprises the following steps:
1) adding nano-silica and an epoxy silane coupling agent into a mixed solution of ethanol and water, adjusting the pH value of the system to 4-6, heating in a water bath to 40-60 ℃, stirring and reacting for 1-3h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding the coupling agent modified nano-silica into a sodium carboxymethyl fiber aqueous solution, then adding stannic chloride, heating in a water bath to 80-85 ℃, stirring and reacting for 3-6h, performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing N, N-dimethylformamide and deionized water to obtain a mixed solvent, adding zinc nitrate hexahydrate and 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding surface-modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion, heating to 80-90 ℃, carrying out heat preservation reaction, carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding the silicon dioxide-metal organic framework composite nanosheets into deionized water, uniformly dispersing by ultrasonic oscillation, then adding europium trichloride, heating to 70-80 ℃, stirring for reaction for 20-30min, and performing suction filtration, washing and drying to obtain the fluorescent composite particles.
In the prior art, two methods are generally adopted for preparing europium-containing fluorescent materials, firstly, europium ions are matched with organic compounds to prepare polymer rare earth complexes, but a large number of europium ions in the obtained polymer rare earth complex fluorescent materials are embedded in the polymer rare earth complexes, so that the fluorescent effect of the fluorescent materials is reduced; secondly, europium is loaded on the nano particles, so that the problem of large-scale embedding of europium ions is solved, the nano particles are easy to agglomerate, the surface of the agglomerated nano particles (such as nano silicon dioxide) is difficult to complex the europium ions through coordination, and the europium ions are randomly dispersed in the solution, so that the europium ion content loaded on the surface of the nano particles is low, and the obtained fluorescent particles have weak fluorescence intensity. In order to solve the problems, the invention uses a silicon dioxide-metal organic framework composite nanosheet as a carrier of europium ions, zinc nitrate hexahydrate and 5-chlorobenzimidazole react to generate a metal organic framework nanosheet with a porous structure, surface organic modified nano-silica is added in the preparation process of the metal organic framework nanosheet, the surface organic modified nano-silica is deposited and combined on the surface of the metal organic framework nanosheet, and then the europium ions are coordinated with an organic compound on the surface of the nano-silica, so that the europium ions are combined on the surface of the silicon dioxide-metal organic framework composite nanosheet, the europium ions are prevented from being embedded in a ligand, the fluorescence intensity of fluorescent particles is improved, and the fluorescence effect of ink is further improved; on the other hand, the nano silicon dioxide is combined on the surface of the metal organic framework nanosheet, and the porous structure on the surface of the metal organic framework nanosheet can adsorb europium ions in the solution, so that the concentration of the europium ions near the surface of the silicon dioxide-metal organic framework composite nanosheet is increased, more europium ions are coordinated with the organic compound on the surface of the nano silicon dioxide, the fluorescence intensity of fluorescent particles is improved, and the fluorescence effect of the ink is further improved.
In the experimental process, the common organic compound is used for modifying the nano silicon dioxide, and then the fluorescent composite particles obtained by coordination of the organic compound and europium ions have a relatively common fluorescent effect, and a large amount of experimental research and analysis prove that the problem is caused by uneven deposition and combination of the nano silicon dioxide on the surface of the metal organic framework nanosheet in the preparation process of the silicon dioxide-metal organic framework composite nanosheet.
Preferably, the mass ratio of the coupling agent modified nano silicon dioxide to the sodium carboxymethyl cellulose is controlled to be 1: 0.7-1.2.
The mass ratio of the coupling agent modified nano silicon dioxide to the sodium carboxymethyl cellulose must be controlled within the range of 1:0.7-1.2, when the mass ratio of the coupling agent modified nano silicon dioxide to the sodium carboxymethyl cellulose is more than 1:0.7, the amount of the carboxymethyl cellulose participating in the reaction is insufficient, so that the electrostatic repulsive force formed between the nano silicon dioxide is insufficient, the dispersibility of the nano silicon dioxide on the surface of the metal organic framework nanosheet is influenced, and when the mass ratio of the coupling agent modified nano silicon dioxide to the sodium carboxymethyl cellulose is less than 1:1.2, the solution viscosity is larger due to the excessive sodium carboxymethyl cellulose, and the ring-opening reaction between the sodium carboxymethyl cellulose and the coupling agent modified nano silicon dioxide is not facilitated.
Preferably, the mass ratio of the zinc nitrate hexahydrate to the 5-chlorobenzimidazole in the step 2) is 1: 3-6.
Preferably, the mass ratio of the silica-metal organic framework composite nanosheets to the europium trichloride in the step 3) is 1: 0.2-0.5.
The preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 20-30min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 30-40min to obtain the aqueous polyurethane ink composition.
Therefore, the invention has the following beneficial effects: (1) the silicon dioxide-metal organic framework composite nanosheets are used as carriers of europium ions, so that the europium ions are prevented from being embedded in ligands, the fluorescence intensity of fluorescent particles is improved, and the fluorescence effect of the ink is further improved; (2) the nanometer silicon dioxide is combined on the surface of the metal organic framework nanosheet, the porous structure on the surface of the metal organic framework nanosheet can adsorb europium ions in a solution, so that the concentration of the europium ions near the surface of the silicon dioxide-metal organic framework composite nanosheet is increased, more europium ions are coordinated with an organic compound on the surface of the nanometer silicon dioxide, the fluorescence intensity of fluorescent particles is further improved, and the fluorescence effect of the ink is further improved.
Drawings
FIG. 1 shows fluorescence excitation spectra of aqueous polyurethane inks of example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. In the present invention, unless otherwise specified, raw materials, equipment, and the like used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the fluorescent composite particle comprises the following steps:
1) uniformly mixing 150mL of ethanol and 30mL of water to obtain a mixed solution of ethanol and water, adding 8g of nano-silica and 2g of epoxy silane coupling agent KH560 into the mixed solution of ethanol and water, adjusting the pH value of the system to 6, heating in a water bath to 60 ℃, stirring for reaction for 2.5h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding 5g of carboxymethyl cellulose into 120mL of deionized water, stirring for dissolution to obtain carboxymethyl cellulose solution, adding 5g of coupling agent modified nano-silica into sodium carboxymethyl cellulose solution, then adding 0.05g of stannic chloride catalyst, heating in a water bath to 85 ℃, stirring for reaction for 5h, and performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing 60mL of N, N-dimethylformamide and 5mL of deionized water to obtain a mixed solvent, adding 0.5g of zinc nitrate hexahydrate and 2.5g of 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding 0.3g of surface modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion liquid, heating to 90 ℃, carrying out heat preservation reaction for 48 hours, and carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding 5g of silicon dioxide-metal organic framework composite nanosheet into 80mL of deionized water, uniformly dispersing by ultrasonic oscillation, then adding 2g of europium trichloride, heating to 80 ℃, stirring for reacting for 28min, and carrying out suction filtration, washing and drying to obtain the fluorescent composite particle.
The aqueous polyurethane ink composition comprises the following components in parts by weight:
68 parts of aqueous polyurethane emulsion, 18 parts of rutile titanium dioxide pigment, 7 parts of fluorescent composite particles, 0.8 part of sodium polyacrylate dispersant, 0.5 part of polyoxypropylene glycerol ether defoamer, 0.8 part of sodium dodecyl benzene sulfonate wetting agent and 57 parts of water.
The preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 20min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 30min to obtain the aqueous polyurethane ink composition.
Example 2
The preparation method of the fluorescent composite particle comprises the following steps:
1) uniformly mixing 150mL of ethanol and 30mL of water to obtain a mixed solution of ethanol and water, adding 8g of nano-silica and 2g of epoxy silane coupling agent KH560 into the mixed solution of ethanol and water, adjusting the pH value of the system to 4, heating in a water bath to 40 ℃, stirring for reaction for 1.5h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding 4g of carboxymethyl cellulose into 120mL of deionized water, stirring for dissolution to obtain carboxymethyl cellulose solution, adding 5g of coupling agent modified nano-silica into sodium carboxymethyl cellulose solution, then adding 0.05g of stannic chloride catalyst, heating in a water bath to 80 ℃, stirring for reaction for 4h, and performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing 60mL of N, N-dimethylformamide and 5mL of deionized water to obtain a mixed solvent, adding 0.5g of zinc nitrate hexahydrate and 2g of 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding 0.3g of surface modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion, heating to 80 ℃, carrying out heat preservation reaction for 48 hours, and carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding 5g of silicon dioxide-metal organic framework composite nanosheet into 80mL of deionized water, uniformly dispersing by ultrasonic oscillation, then adding 1.5g of europium trichloride, heating to 70 ℃, stirring for reaction for 22min, and carrying out suction filtration, washing and drying to obtain the fluorescent composite particle.
The aqueous polyurethane ink composition comprises the following components in parts by weight:
65 parts of aqueous polyurethane emulsion, 16 parts of anatase titanium dioxide pigment, 6 parts of fluorescent composite particles, 0.6 part of polyoxyethylene ether dispersing agent, 0.4 part of silicone emulsion defoamer, 0.6 part of polyethylene glycol ether wetting agent and 53 parts of water.
The preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 30min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 40min to obtain the aqueous polyurethane ink composition.
Example 3
The preparation method of the fluorescent composite particle comprises the following steps:
1) uniformly mixing 150mL of ethanol and 30mL of water to obtain a mixed solution of ethanol and water, adding 8g of nano-silica and 2g of epoxy silane coupling agent KH560 into the mixed solution of ethanol and water, adjusting the pH value of the system to 5, heating in a water bath to 50 ℃, stirring for reaction for 3h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding 6g of carboxymethyl cellulose into 120mL of deionized water, stirring for dissolution to obtain carboxymethyl cellulose solution, adding 5g of coupling agent modified nano-silica into sodium carboxymethyl cellulose solution, then adding 0.05g of stannic chloride catalyst, heating in a water bath to 83 ℃, stirring for reaction for 6h, and performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing 60mL of N, N-dimethylformamide and 5mL of deionized water to obtain a mixed solvent, adding 0.5g of zinc nitrate hexahydrate and 3g of 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding 0.3g of surface modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion, heating to 85 ℃, carrying out heat preservation reaction for 48 hours, and carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding 5g of silicon dioxide-metal organic framework composite nanosheet into 80mL of deionized water, uniformly dispersing by ultrasonic oscillation, then adding 2.5g of europium trichloride, heating to 75 ℃, stirring for reacting for 30min, and performing suction filtration, washing and drying to obtain the fluorescent composite particle.
The aqueous polyurethane ink composition comprises the following components in parts by weight:
70 parts of aqueous polyurethane emulsion, 20 parts of furnace black pigment, 10 parts of fluorescent composite particles, 1 part of sodium maleate dispersing agent, 0.6 part of pentaerythritol stearate defoaming agent, 1 part of polyethylene glycol ether wetting agent and 60 parts of water.
The preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 25min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 35min to obtain the aqueous polyurethane ink composition.
Example 4
The preparation method of the fluorescent composite particle comprises the following steps:
1) uniformly mixing 150mL of ethanol and 30mL of water to obtain a mixed solution of ethanol and water, adding 8g of nano-silica and 2g of epoxy silane coupling agent KH560 into the mixed solution of ethanol and water, adjusting the pH value of the system to 5, heating in a water bath to 50 ℃, stirring for reaction for 1h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding 3.5g of carboxymethyl cellulose into 120mL of deionized water, stirring for dissolution to obtain carboxymethyl cellulose solution, adding 5g of coupling agent modified nano-silica into sodium carboxymethyl cellulose solution, then adding 0.05g of stannic chloride catalyst, heating in a water bath to 83 ℃, stirring for reaction for 3h, and performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing 60mL of N, N-dimethylformamide and 5mL of deionized water to obtain a mixed solvent, adding 0.5g of zinc nitrate hexahydrate and 1.5g of 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding 0.3g of surface modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion liquid, heating to 85 ℃, carrying out heat preservation reaction for 48 hours, and carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding 5g of silicon dioxide-metal organic framework composite nanosheet into 80mL of deionized water, uniformly dispersing by ultrasonic oscillation, then adding 1g of europium trichloride, heating to 75 ℃, stirring for reacting for 20min, and carrying out suction filtration, washing and drying to obtain the fluorescent composite particle.
The aqueous polyurethane ink composition comprises the following components in parts by weight:
60 parts of aqueous polyurethane emulsion, 15 parts of anatase titanium dioxide pigment, 5 parts of fluorescent composite particles, 0.5 part of sodium polyacrylate dispersant, 0.3 part of pentaerythritol stearate defoaming agent, 0.5 part of polyethylene glycol ether wetting agent and 50 parts of water.
The preparation method of the aqueous polyurethane ink composition comprises the following steps: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 25min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 35min to obtain the aqueous polyurethane ink composition.
Comparative example 1
Comparative example 1 is different from example 1 in that the preparation method of the fluorescent composite particle includes the steps of:
1) uniformly mixing 150mL of ethanol and 30mL of water to obtain a mixed solution of ethanol and water, adding 8g of nano-silica and 2g of epoxy silane coupling agent KH560 into the mixed solution of ethanol and water, adjusting the pH value of the system to 6, heating in a water bath to 60 ℃, stirring for reaction for 2.5h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding 5g of carboxymethyl cellulose into 120mL of deionized water, stirring for dissolution to obtain carboxymethyl cellulose solution, adding 5g of coupling agent modified nano-silica into sodium carboxymethyl cellulose solution, then adding 0.05g of stannic chloride catalyst, heating in a water bath to 85 ℃, stirring for reaction for 5h, and performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) adding 5g of surface-modified nano silicon dioxide into 80mL of deionized water, uniformly dispersing by ultrasonic oscillation, then adding 2g of europium trichloride, heating to 80 ℃, stirring for reacting for 28min, and carrying out suction filtration, washing and drying to obtain the fluorescent composite particles.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the mass ratio of the modified nano silicon dioxide to the sodium carboxymethyl cellulose is controlled to be 1:0.3 in the preparation process of the fluorescent composite particle.
1. Detection of fluorescence property of the ink: placing the water-based polyurethane ink into a printability tester to grind uniformly, wherein the selected density is 120g/m2The non-fluorescent offset paper is cut into a 55 x 350mm paper pattern for later use. Then, under the conditions of constant temperature and humidity test, a certain amount of ink is added on an IGT printability tester, the ink is homogenized for 10s at the speed of 1.1m/s, the ink is transferred onto a grinding roller in the time of 5s, and then a paper strip is mounted on the tester, and an ink sample strip is printed at the pressure of 625N and the printing speed of 0.20 m/s. The fluorescence spectra of the ink bars were measured by PL and the fluorescence quantum yield was measured using a fluoroSens fluorescence spectrometer from GILDEN photosonics, UK.
2. Solid content test: accurately weighing 2g of an aqueous polyurethane ink sample, placing the aqueous polyurethane ink sample in a weighed container, volatilizing a part of a solvent at room temperature, then placing the aqueous polyurethane ink sample in a 105 ℃ constant-temperature drying oven to be heated for 2 hours, taking out the aqueous polyurethane ink sample, weighing the aqueous polyurethane ink sample on an analytical electronic balance, then placing the aqueous polyurethane ink sample in the 105 ℃ constant-temperature drying oven to be heated, taking out the aqueous polyurethane ink sample at an interval of 25min, weighing the aqueous polyurethane ink sample again, repeating the steps for several times until the mass difference between two successive times of weighing:
W＝(m2-m0/m1-m0) X is 100%; wherein W represents solid content/%; m is0Represents the mass of the vessel/g; m is1Is the total mass/g of the sample and the vessel before drying; m is2Is the total mass/g of the dried sample and vessel.
3. And (3) testing adhesion fastness: uniformly coating the water-based polyurethane ink on a BOPP film by using a 10-micron wire rod, putting the BOPP film into a 50-DEG C oven to dry ink marks of the water-based ink to obtain a water-based ink scratch sample, and storing the scratch sample in the 40-DEG C oven for subsequent testing. And marking a scratch sample on the ink film, peeling off the ink film by using a transparent adhesive tape, judging the adhesive force grade of the ink film according to the damage degree, and classifying into a grade of 0-5 according to the damage degree, wherein the grade of 0-5 shows that the adhesive force is gradually deteriorated.
Example 1 Example 2 Example 3 Example 4
Solid content (%) 40.36 40.53 41.42 40.76
Fastness to adhesion Level 1 Level 1 Level 1 Level 1
The fluorescence excitation intensity of the aqueous polyurethane ink of example 1 at the wavelength of 615nm is higher than that of the aqueous polyurethane ink of comparative example 1 and comparative example 2, which can be obtained by the fluorescence excitation spectra of the aqueous polyurethane inks of example 1, comparative example 1 and comparative example 2 in FIG. 1.
The fluorescence excitation intensity of the embodiment 1 at the wavelength of 615nm is higher than that of the aqueous polyurethane ink of the comparative example 1, and the fluorescence effect obtained by using the silica-metal organic framework composite nanosheet as the europium ion carrier is better than that obtained by using silica as the europium ion carrier, because the nanosilicon dioxide is combined on the surface of the metal organic framework nanosheet in the embodiment 1, the porous structure on the surface of the metal organic framework nanosheet can adsorb the europium ion in the solution, so that the europium ion concentration near the surface of the silica-metal organic framework composite nanosheet is increased, and further more europium ions are coordinated with the organic compound on the surface of the nanosilicon dioxide, and further the fluorescence intensity of the ink is improved. The fluorescence excitation intensity at the wavelength of 615nm of example 1 is higher than that of the aqueous polyurethane ink of comparative example 1, which proves that the ratio of the modified nano-silica to the sodium carboxymethyl cellulose has a great influence on the fluorescence intensity of the ink, and when the amount of the carboxymethyl cellulose participating in the reaction is insufficient, the electrostatic repulsive force formed between the nano-silicas is insufficient, so that the dispersibility of the nano-silica on the surface of the metal organic framework nanosheet is influenced, and the fluorescence intensity of the ink is further reduced.
By testing the solid content and the adhesion fastness of the waterborne polyurethane ink in the embodiment, the solid content of the waterborne polyurethane ink reaches more than 40%, the adhesion reaches grade 1, and the use standard of the ink is met.
The principle and the embodiments of the present invention are explained in the above embodiments, and the above embodiments are only used to help understanding the method and the core idea of the present invention, and meanwhile, for a person skilled in the art, there are variations in the embodiments and the application scope according to the idea of the present invention, and the content of the present specification should not be construed as limiting the present invention.

Claims (10)

1. The water-based polyurethane ink composition is characterized by comprising the following components in parts by weight:
60-70 parts of waterborne polyurethane emulsion, 15-20 parts of pigment, 5-10 parts of fluorescent composite particles, 0.5-1 part of dispersing agent, 0.3-0.6 part of defoaming agent, 0.5-1 part of wetting agent and 50-60 parts of water.
2. The aqueous polyurethane ink composition of claim 1, wherein the pigment is at least one of rutile titanium dioxide, anatase titanium dioxide, and furnace black.
3. The aqueous polyurethane ink composition of claim 1, wherein the dispersant is at least one of sodium polyacrylate, polyoxyethylene ether, and sodium maleate.
4. The aqueous polyurethane ink composition of claim 1, wherein the defoamer is at least one of polyoxypropylene glycerol ether, silicone emulsion, pentaerythritol stearate.
5. The aqueous polyurethane ink composition of claim 1, wherein the wetting agent is at least one of sodium dodecylbenzene sulfonate and polyethylene glycol ether.
6. The aqueous polyurethane ink composition of claim 1, wherein the fluorescent composite particles are prepared by a method comprising the steps of:
1) adding nano-silica and an epoxy silane coupling agent into a mixed solution of ethanol and water, adjusting the pH value of the system to 4-6, heating in a water bath to 40-60 ℃, stirring and reacting for 1-3h, performing centrifugal separation, washing and drying to obtain coupling agent modified nano-silica, adding the coupling agent modified nano-silica into a sodium carboxymethyl fiber aqueous solution, then adding stannic chloride, heating in a water bath to 80-85 ℃, stirring and reacting for 3-6h, performing centrifugal separation, washing and drying to obtain surface modified nano-silica;
2) mixing N, N-dimethylformamide and deionized water to obtain a mixed solvent, adding zinc nitrate hexahydrate and 5-chlorobenzimidazole into the mixed solvent, stirring for dissolving, then adding surface-modified nano-silica, continuously stirring and uniformly mixing to obtain a dispersion, heating to 80-90 ℃, carrying out heat preservation reaction, carrying out suction filtration, washing and drying to obtain a silica-metal organic framework composite nanosheet;
3) adding the silicon dioxide-metal organic framework composite nanosheets into deionized water, uniformly dispersing by ultrasonic oscillation, then adding europium trichloride, heating to 70-80 ℃, stirring for reaction for 20-30min, and performing suction filtration, washing and drying to obtain the fluorescent composite particles.
7. The aqueous polyurethane ink composition as claimed in claim 6, wherein the mass ratio of the coupling agent modified nano-silica to the sodium carboxymethyl cellulose in the step 1) is controlled to be 1: 0.7-1.2.
8. The aqueous polyurethane ink composition of claim 6, wherein the mass ratio of zinc nitrate hexahydrate to 5-chlorobenzimidazole in step 2) is 1: 3-6.
9. The aqueous polyurethane ink composition as claimed in claim 6, wherein the mass ratio of the silica-metal organic framework composite nanosheets to europium trichloride in step 3) is 1: 0.2-0.5.
10. A method of making the aqueous polyurethane ink composition of any one of claims 1-9, comprising the steps of: adding the aqueous polyurethane emulsion, the pigment and the dispersing agent into water, stirring and mixing for 20-30min, then adding the fluorescent composite particles, the defoaming agent and the wetting agent, and continuing stirring for 30-40min to obtain the aqueous polyurethane ink composition.
CN202011460702.XA 2020-12-11 2020-12-11 Water-based polyurethane ink composition and preparation method thereof Withdrawn CN112552744A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114592373A (en) * 2022-01-17 2022-06-07 惠州市沃碧特化工有限公司 Offset printing touch oil and preparation method thereof
CN115160850A (en) * 2022-07-26 2022-10-11 黄山豪泰塑胶有限公司 Water-based ink for decorative paper and preparation method thereof
CN116496662A (en) * 2023-03-04 2023-07-28 惠州德斯坤化工有限公司 Environment-friendly photosensitive color-changing ink for smart card and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114592373A (en) * 2022-01-17 2022-06-07 惠州市沃碧特化工有限公司 Offset printing touch oil and preparation method thereof
CN115160850A (en) * 2022-07-26 2022-10-11 黄山豪泰塑胶有限公司 Water-based ink for decorative paper and preparation method thereof
CN115160850B (en) * 2022-07-26 2023-07-21 黄山豪泰塑胶有限公司 Water-based ink for decorative paper and preparation method thereof
CN116496662A (en) * 2023-03-04 2023-07-28 惠州德斯坤化工有限公司 Environment-friendly photosensitive color-changing ink for smart card and preparation method thereof
CN116496662B (en) * 2023-03-04 2023-12-08 惠州德斯坤化工有限公司 Environment-friendly photosensitive color-changing ink for smart card and preparation method thereof

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Application publication date: 20210326