CN116731553A - Preparation method of long-acting fluorescent ink - Google Patents
Preparation method of long-acting fluorescent ink Download PDFInfo
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- CN116731553A CN116731553A CN202310661722.0A CN202310661722A CN116731553A CN 116731553 A CN116731553 A CN 116731553A CN 202310661722 A CN202310661722 A CN 202310661722A CN 116731553 A CN116731553 A CN 116731553A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 67
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 63
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 63
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 50
- 229910021485 fumed silica Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920005732 JONCRYL® 678 Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 10
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 39
- 239000000976 ink Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 19
- 238000009210 therapy by ultrasound Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000010926 purge Methods 0.000 description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000272168 Laridae Species 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Classifications
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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
- C09D11/02—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
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to the technical field of ink, and particularly relates to a preparation method of long-acting fluorescent ink, which comprises the following steps of: 30-50 parts of aqueous polyurethane resin, 20-30 parts of aqueous acrylic resin, 4-6 parts of modified fluorescent material, 100-150 parts of water, 5-10 parts of ethanol, 3-5 parts of glycerol, 1-2 parts of surfactant and 0.5-1 part of anti-settling agent, and a specific preparation method is provided. The invention solves the problem of poor fluorescence stability of the existing zinc sulfide, utilizes the silicon-oxygen material to wrap the zinc sulfide to form a stable wrapping structure, not only improves the stability of the phosphorescent zinc sulfide, but also has excellent light transmittance, and does not influence the light storage and light emitting functions of the phosphorescent zinc sulfide.
Description
Technical Field
The invention belongs to the technical field of ink, and particularly relates to a preparation method of long-acting fluorescent ink.
Background
Fluorescent ink is one of the inks used in ticket printing, and the main component of the fluorescent ink is fluorescent pigment. Fluorescent pigments are functional luminescent pigments, which are different from general pigments in that they absorb energy of a certain form when irradiated with external light (including ultraviolet light), and excite photons to release the absorbed energy in the form of low visible light, thereby generating fluorescent phenomena of different hues. The light of different colors combines to form an abnormally vivid color, and when the light stops being irradiated, the luminescence phenomenon disappears, and thus is called a fluorescent pigment. The fluorescent pigment, the high polymer resin binder, the solvent and the auxiliary agent are mixed and ground to prepare the fluorescent ink. Zinc sulfide is one of the most commonly used fluorescent materials, and is often used in ink, but zinc sulfide is extremely susceptible to the influence of heavy metal substances in the air, and can deteriorate and lose light emission.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the preparation method of the long-acting fluorescent ink, which solves the problem of poor fluorescence stability of the traditional zinc sulfide, utilizes the silica material to wrap the zinc sulfide to form a stable wrapping structure, not only improves the stability of the phosphorescent zinc sulfide, but also has excellent light transmittance, and does not influence the light storage and light emitting functions of the phosphorescent zinc sulfide.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of long-acting fluorescent ink comprises the following steps of:
30-50 parts of aqueous polyurethane resin, 20-30 parts of aqueous acrylic resin, 4-6 parts of modified fluorescent material, 100-150 parts of water, 5-10 parts of ethanol, 3-5 parts of glycerol, 1-2 parts of surfactant and 0.5-1 part of anti-settling agent.
The viscosity value of the aqueous polyurethane resin is less than or equal to 500 mpa.s, the solid content is 35%, and the model of the aqueous polyurethane resin is AH-1502E13, which is available from Anhui Anhua Huatai New Material Co.
The aqueous acrylic resin adopts Joncryl 678 which is an aqueous acrylic solid resin of Pasteur.
The modified fluorescent material adopts silicon dioxide to wrap phosphorescent zinc sulfide (ZnS: cu), the phosphorescent zinc sulfide belongs to light storage powder, the light-emitting state of the phosphorescent zinc sulfide is kept for 1-2h after full light storage, and under normal use, the light storage and light emitting function of the material can last for 3-5 years, but in the actual use process, the light storage and light emitting function cannot be kept for a long time, and the reason is that the phosphorescent zinc sulfide is extremely easy to pollute, and is deactivated, so that the light storage and light emitting function is lost. The silicon dioxide is used as a shell material for surface wrapping, the phosphorescent zinc sulfide is wrapped on the inner layer of the silica structure, the influence of air on the phosphorescent zinc sulfide is avoided, the influence of impurities in the air on the zinc sulfide is prevented, and meanwhile, the silicon dioxide shell has good light transmittance, and a light storage and emitting system of the phosphorescent zinc sulfide is not influenced. The preparation method of the modified fluorescent material comprises the following steps of: adding ethyl silicate into diethyl ether, stirring uniformly to form a silyl ether solution, performing ultrasonic treatment for 10-20min, and performing expansion dissolution to obtain a dispersion, wherein the concentration of the ethyl silicate in the diethyl ether is 50-100g/L, the stirring speed of uniform stirring is 100-200r/min, the ultrasonic frequency of ultrasonic treatment is 50-70kHz, the ultrasonic temperature is 30-36 ℃, the volume of the dispersion is 170-280% of that of the silyl ether solution, the step utilizes the solubility of ethanol to the ethyl silicate to form liquid phase dispersion, the ethyl silicate is homogenized in an ultrasonic mode, and meanwhile, part of diethyl ether is volatilized at the instantaneous temperature of ultrasonic, and the dissolution solution is further dispersed in a diffusion dispersion mode according to the time; a2, placing the phosphorescent zinc sulfide into the dispersion liquid, stirring for 20-30min at a low temperature, then performing ultrasonic treatment at a low temperature for 20-30min, filtering to be semi-dry to obtain coated phosphorescent zinc sulfide, wherein the concentration of the phosphorescent zinc sulfide in the dispersion liquid is 10-20g/L, the stirring temperature at the low temperature is 5-10 ℃, the stirring speed is 100-200r/min, the temperature of the low-temperature ultrasonic treatment is 0-5 ℃, and the ultrasonic frequency is 60-80kHz; the method comprises the steps of wetting the surface of phosphorescent zinc sulfide in a stirring manner, removing bubbles on the surface of the zinc sulfide in an ultrasonic process, and ensuring that diethyl ether is uniformly adhered to the specific surface of the phosphorescent zinc sulfide, so that an excellent wetting and adhering effect is achieved; a3, placing the coated phosphorescent zinc sulfide into a reaction kettle, standing for 1-3h, carrying out heating treatment after purging to obtain the silicon dioxide coated phosphorescent zinc sulfide, wherein the atmosphere in the reaction kettle is a mixed atmosphere of water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 1:10-15, the standing temperature is 10-20 ℃, the purging adopts nitrogen purging at 50-60 ℃, and the temperature of the heating treatment is 180-200 ℃; the step utilizes the slightly soluble characteristic of diethyl ether on water molecules to form low-quantity dispersion of water molecules in diethyl ether, and simultaneously ethyl silicate and water molecules can form hydrolysis, and the ethyl silicate is continuously converted by being matched with continuous consumption of water molecules and reabsorbing air water molecules; during the purging process, diethyl ether is evaporated into steam and is removed by nitrogen, and meanwhile, the subsequent temperature rising treatment can convert silicic acid obtained by in-situ hydrolysis into silicon dioxide to obtain a silicon-oxygen structure on the surface. The silicon-oxygen structure prepared by the process is tightly adhered to the surface of the phosphorescent zinc sulfide, and the in-situ hydrolysis system ensures that the silicon-oxygen structure is in a film shape.
The surfactant adopts sodium dodecyl sulfonate or sodium dodecyl sulfate.
The anti-settling agent adopts fumed silica, the particle size of the fumed silica is 12-15nm, the fumed silica is selected from A200 or A150 of De-solid plug, the fumed silica has small self particle size and large specific surface area, and silanol groups are arranged on the surface of the fumed silica. These silanol groups can interact with adjacent fumed silica particles to form hydrogen bonds that cause them to form thixotropic structures. Aiming at the modified titanium dioxide and the modified fluorescent material which belong to inorganic solid fillers, the precipitation is easy to occur, particles are aggregated, and the fumed silica is added into the ink, so that the suspension characteristics of the modified titanium dioxide and the modified fluorescent material can be effectively improved, and the stability of the ink is improved. Meanwhile, the fumed silica belongs to a silica material, has the characteristics of small granularity and good light transmittance, and ensures light transmission in the whole ink system. Furthermore, the surfaces of the silicon dioxide coated phosphorescent zinc sulfide and the fumed silica are both silicon dioxide materials, so that the silicon dioxide coated phosphorescent zinc sulfide has good light transmissibility and a good homogenized light treatment system.
The preparation method of the long-acting fluorescent ink comprises the following steps:
step 1, magnetically stirring aqueous polyurethane resin and aqueous acrylic resin until the aqueous polyurethane resin and the aqueous acrylic resin are milky white to obtain mixed resin;
step 2, adding water, ethanol and glycerol into a reaction kettle, uniformly mixing to obtain a mixed solvent, sequentially adding a surfactant, an anti-settling agent and a modified fluorescent material, and continuously stirring until the mixture is uniformly dispersed to obtain a mixed solution, wherein the stirring speed is 200-300r/min;
step 3, gradually adding the mixed resin into the mixed solution, and rapidly stirring until the mixed resin is uniformly dispersed to obtain the long-acting fluorescent ink, wherein the gradually adding speed is 3-6mL/min, and the rapid stirring speed is 1000-2000r/min.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of poor fluorescence stability of the existing zinc sulfide, utilizes the silicon-oxygen material to wrap the zinc sulfide to form a stable wrapping structure, not only improves the stability of the phosphorescent zinc sulfide, but also has excellent light transmittance, and does not influence the light storage and light emitting functions of the phosphorescent zinc sulfide.
2. According to the invention, the fumed silica is used as an anti-settling agent, so that the suspension property of the modified fluorescent material can be effectively improved, meanwhile, the fumed silica has excellent light transmittance, and a light transmission system of a silica system is formed by the fumed silica and the phosphorescent zinc sulfide wrapped by silica, so that the light storage and light emitting performance of the zinc sulfide is ensured.
3. The invention uses the aqueous polyurethane and the aqueous acrylic resin as the adhesive resin, has good adhesion to the common summer gull, and simultaneously the polyurethane resin and the acrylic resin are provided with a large number of active groups, can form chemical fixed connection with the surface of the modified phosphorescent zinc sulfide exposed by the silicon oxygen, and has excellent long-term stability.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1
A preparation method of long-acting fluorescent ink comprises the following steps of:
30 parts of aqueous polyurethane resin, 20 parts of aqueous acrylic resin, 4 parts of modified fluorescent material, 100 parts of water, 5 parts of ethanol, 3 parts of glycerol, 1 part of surfactant and 0.5 part of anti-settling agent.
The viscosity value of the aqueous polyurethane resin is less than or equal to 500 mpa.s, the solid content is 35%, and the model of the aqueous polyurethane resin is AH-1502E13, which is available from Anhui Anhua Huatai New Material Co.
The aqueous acrylic resin adopts Joncry l 678 which is an aqueous acrylic solid resin of Pasteur.
The modified fluorescent material adopts silicon dioxide to wrap phosphorescent zinc sulfide (ZnS: cu), the phosphorescent zinc sulfide adopts small-particle-size zinc sulfide, and the preparation method of the modified fluorescent material comprises the following steps: a1, adding ethyl silicate into diethyl ether, uniformly stirring to form a silyl ether solution, then carrying out ultrasonic treatment for 10min, and carrying out expansion dissolution to obtain a dispersion, wherein the concentration of the ethyl silicate in the diethyl ether is 50g/L, the uniform stirring speed of stirring is 100r/min, the ultrasonic frequency of ultrasonic treatment is 50kHz, the ultrasonic temperature is 30 ℃, and the volume of the dispersion is 170% of that of the silyl ether solution; a2, placing the phosphorescent zinc sulfide into a dispersion liquid, stirring for 20min at a low temperature, then carrying out ultrasonic treatment at a low temperature for 20min, filtering to be semi-dry to obtain coated phosphorescent zinc sulfide, wherein the concentration of the phosphorescent zinc sulfide in the dispersion liquid is 10g/L, the stirring temperature at the low temperature is 5 ℃, the stirring speed is 100r/min, the temperature of the low-temperature ultrasonic treatment is 0 ℃, and the ultrasonic frequency is 60kHz; a3, placing the coated phosphorescent zinc sulfide into a reaction kettle, standing for 1h, carrying out heating treatment after purging, and obtaining the silicon dioxide coated phosphorescent zinc sulfide, wherein the atmosphere in the reaction kettle is a mixed atmosphere of water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 1:10, the standing temperature is 10 ℃, the purging adopts nitrogen purging at 50 ℃, and the temperature of the heating treatment is 180 ℃.
The surfactant adopts sodium dodecyl sulfonate.
The anti-settling agent adopts fumed silica, the particle size of the fumed silica is 12nm, and the fumed silica is selected from A200 of De-solid plug.
The preparation method of the long-acting fluorescent ink comprises the following steps:
step 1, magnetically stirring aqueous polyurethane resin and aqueous acrylic resin until the aqueous polyurethane resin and the aqueous acrylic resin are milky white to obtain mixed resin;
step 2, adding water, ethanol and glycerol into a reaction kettle, uniformly mixing to obtain a mixed solvent, sequentially adding a surfactant, an anti-settling agent and a modified fluorescent material, and continuously stirring until the mixture is uniformly dispersed to obtain a mixed solution, wherein the stirring speed is 200r/min;
step 3, gradually adding the mixed resin into the mixed solution, and rapidly stirring until the mixed resin is uniformly dispersed to obtain the long-acting fluorescent ink, wherein the gradually adding speed is 3mL/min, and the rapid stirring speed is 1000r/min.
Example 2
A preparation method of long-acting fluorescent ink comprises the following steps of:
50 parts of aqueous polyurethane resin, 30 parts of aqueous acrylic resin, 6 parts of modified fluorescent material, 150 parts of water, 10 parts of ethanol, 5 parts of glycerol, 2 parts of surfactant and 1 part of anti-settling agent.
The viscosity value of the aqueous polyurethane resin is less than or equal to 500 mpa.s, the solid content is 35%, and the model of the aqueous polyurethane resin is AH-1502E13, which is available from Anhui Anhua Huatai New Material Co.
The aqueous acrylic resin adopts Joncry l 678 which is an aqueous acrylic solid resin of Pasteur.
The modified fluorescent material adopts silicon dioxide to wrap phosphorescent zinc sulfide (ZnS: cu), the phosphorescent zinc sulfide adopts small-particle-size zinc sulfide, and the preparation method of the modified fluorescent material comprises the following steps: a1, adding ethyl silicate into diethyl ether, uniformly stirring to form a silyl ether solution, then performing ultrasonic treatment for 20min, and performing expansion dissolution to obtain a dispersion, wherein the concentration of the ethyl silicate in the diethyl ether is 100g/L, the uniform stirring speed of stirring is 200r/min, the ultrasonic frequency of ultrasonic treatment is 70kHz, the ultrasonic temperature is 36 ℃, and the volume of the dispersion is 280% of that of the silyl ether solution; a2, placing the phosphorescent zinc sulfide into a dispersion liquid, stirring for 30min at a low temperature, then carrying out ultrasonic treatment at a low temperature for 30min, filtering to be semi-dry to obtain coated phosphorescent zinc sulfide, wherein the concentration of the phosphorescent zinc sulfide in the dispersion liquid is 20g/L, the stirring temperature at the low temperature is 10 ℃, the stirring speed is 200r/min, the temperature of the low-temperature ultrasonic treatment is 5 ℃, and the ultrasonic frequency is 80kHz; a3, placing the coated phosphorescent zinc sulfide into a reaction kettle, standing for 3 hours, carrying out heating treatment after purging, and obtaining the silicon dioxide coated phosphorescent zinc sulfide, wherein the atmosphere in the reaction kettle is a mixed atmosphere of water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 1:15, the standing temperature is 20 ℃, the purging adopts nitrogen purging at 60 ℃, and the temperature of the heating treatment is 200 ℃.
The surfactant adopts sodium dodecyl sulfate.
The anti-settling agent adopts fumed silica, the particle size of the fumed silica is 15nm, and the fumed silica is selected from A150 of De-solid plug.
The preparation method of the long-acting fluorescent ink comprises the following steps:
step 1, magnetically stirring aqueous polyurethane resin and aqueous acrylic resin until the aqueous polyurethane resin and the aqueous acrylic resin are milky white to obtain mixed resin;
step 2, adding water, ethanol and glycerol into a reaction kettle, uniformly mixing to obtain a mixed solvent, sequentially adding a surfactant, an anti-settling agent and a modified fluorescent material, and continuously stirring until the mixture is uniformly dispersed to obtain a mixed solution, wherein the stirring speed is 300r/min;
step 3, gradually adding the mixed resin into the mixed solution, and rapidly stirring until the mixed resin is uniformly dispersed to obtain the long-acting fluorescent ink, wherein the gradually adding speed is 6mL/min, and the rapid stirring speed is 2000r/min.
Example 3
A preparation method of long-acting fluorescent ink comprises the following steps of:
40 parts of aqueous polyurethane resin, 25 parts of aqueous acrylic resin, 5 parts of modified fluorescent material, 130 parts of water, 8 parts of ethanol, 4 parts of glycerol, 2 parts of surfactant and 0.8 part of anti-settling agent.
The viscosity value of the aqueous polyurethane resin is less than or equal to 500 mpa.s, the solid content is 35%, and the model of the aqueous polyurethane resin is AH-1502E13, which is available from Anhui Anhua Huatai New Material Co.
The aqueous acrylic resin adopts Joncry l 678 which is an aqueous acrylic solid resin of Pasteur.
The modified fluorescent material adopts silicon dioxide to wrap phosphorescent zinc sulfide (ZnS: cu), the phosphorescent zinc sulfide adopts small-particle-size zinc sulfide, and the preparation method of the modified fluorescent material comprises the following steps: a1, adding ethyl silicate into diethyl ether, uniformly stirring to form a silyl ether solution, then performing ultrasonic treatment for 15min, and performing expansion dissolution to obtain a dispersion, wherein the concentration of the ethyl silicate in the diethyl ether is 80g/L, the uniform stirring speed of stirring is 150r/min, the ultrasonic frequency of ultrasonic treatment is 60kHz, the ultrasonic temperature is 34 ℃, and the volume of the dispersion is 230% of the silyl ether solution; a2, placing the phosphorescent zinc sulfide into a dispersion liquid, stirring for 25min at a low temperature, then carrying out ultrasonic treatment at a low temperature for 25min, filtering to be semi-dry to obtain coated phosphorescent zinc sulfide, wherein the concentration of the phosphorescent zinc sulfide in the dispersion liquid is 15g/L, the stirring temperature at the low temperature is 8 ℃, the stirring speed is 150r/min, the temperature of the low-temperature ultrasonic treatment is 3 ℃, and the ultrasonic frequency is 70kHz; a3, placing the coated phosphorescent zinc sulfide into a reaction kettle, standing for 2h, carrying out heating treatment after purging, and obtaining the silicon dioxide coated phosphorescent zinc sulfide, wherein the atmosphere in the reaction kettle is a mixed atmosphere of water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 1:13, the standing temperature is 15 ℃, the purging adopts nitrogen purging at 55 ℃, and the temperature of the heating treatment is 190 ℃.
The surfactant adopts sodium dodecyl sulfonate.
The anti-settling agent adopts fumed silica, the particle size of the fumed silica is 12nm, and the fumed silica is selected from A200 of De-solid plug.
The preparation method of the long-acting fluorescent ink comprises the following steps:
step 1, magnetically stirring aqueous polyurethane resin and aqueous acrylic resin until the aqueous polyurethane resin and the aqueous acrylic resin are milky white to obtain mixed resin;
step 2, adding water, ethanol and glycerol into a reaction kettle, uniformly mixing to obtain a mixed solvent, sequentially adding a surfactant, an anti-settling agent and a modified fluorescent material, and continuously stirring until the mixture is uniformly dispersed to obtain a mixed solution, wherein the stirring speed is 250r/min;
step 3, gradually adding the mixed resin into the mixed solution, and rapidly stirring until the mixed resin is uniformly dispersed to obtain the long-acting fluorescent ink, wherein the gradually adding speed is 5mL/min, and the rapid stirring speed is 1500r/min.
Stability test
The ink products prepared in examples 1-3 were used as test examples.
Comparative example 1 was identical to the preparation method of example 3, except that an unmodified fluorescent material was used for comparative example 1.
Comparative example 2 the same preparation as comparative example 1 was carried out, except that organobentonite was used as an anti-settling agent in comparative example 2.
The ink was sprayed on paper and compared for brightness as follows: (unit: MCD/m 2 )
| 1min | 2min | 5min | 10min | |
| Example 1 | 160 | 50 | 30 | 10 |
| Example 2 | 170 | 60 | 30 | 10 |
| Example 3 | 160 | 60 | 30 | 10 |
| Comparative example 1 | 140 | 50 | 20 | 9 |
| Comparative example 2 | 130 | 40 | 15 | 8 |
| Standard of | ＞120 | ＞40 | ＞15 | ＞8 |
After the ink was subjected to light-accumulating and light-emitting treatment 200 times for 3 months, the light-emitting luminance of examples 1 to 3 was relatively stable, the change was not significant, and comparative examples 1 and 2 were slightly degraded, i.e., examples 1 to 3 were superior to comparative examples 1 and 2, and comparative example 1 was slightly superior to comparative example 2.
The ink spray samples of examples 1-3 and comparative examples 1-2 were placed in a vented environment, the inks of examples 1-3 remained stable, while the inks of comparative examples 1-2 failed and comparative example 2 preceded comparative example 1.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (9)
1. A preparation method of long-acting fluorescent ink is characterized by comprising the following steps: the fluorescent ink comprises the following components in percentage by mass:
30-50 parts of aqueous polyurethane resin, 20-30 parts of aqueous acrylic resin, 4-6 parts of modified fluorescent material, 100-150 parts of water, 5-10 parts of ethanol, 3-5 parts of glycerol, 1-2 parts of surfactant and 0.5-1 part of anti-settling agent; the modified fluorescent material adopts silicon dioxide to wrap phosphorescent zinc sulfide.
2. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the viscosity value of the aqueous polyurethane resin is less than or equal to 500 mpa.s, and the solid content is 35%.
3. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the aqueous acrylic resin adopts Joncryl 678 which is an aqueous acrylic solid resin of Pasteur.
4. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the phosphorescent zinc sulfide adopts zinc sulfide with small particle size.
5. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the surfactant adopts sodium dodecyl sulfonate or sodium dodecyl sulfate.
6. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the anti-settling agent adopts fumed silica, and the particle size of the fumed silica is 12-15nm.
7. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the preparation method of the long-acting fluorescent ink comprises the following steps:
step 1, magnetically stirring aqueous polyurethane resin and aqueous acrylic resin until the aqueous polyurethane resin and the aqueous acrylic resin are milky white to obtain mixed resin;
step 2, adding water, ethanol and glycerol into a reaction kettle, uniformly mixing to obtain a mixed solvent, sequentially adding a surfactant, an anti-settling agent and a modified fluorescent material, and continuously stirring until the mixture is uniformly dispersed to obtain a mixed solution;
step 3, gradually adding the mixed resin into the mixed solution, and rapidly stirring until the mixed resin is uniformly dispersed to obtain the long-acting fluorescent ink.
8. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the stirring speed in the step 2 is 200-300r/min.
9. The method for preparing the long-acting fluorescent ink according to claim 1, wherein the method comprises the following steps: the gradual adding speed in the step 3 is 3-6mL/min, and the rapid stirring speed is 1000-2000r/min.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229363A (en) * | 2009-03-30 | 2010-10-14 | Econet Engineering:Kk | Water resistant light accumulating material and fluorescent material, method of producing thereof, coating material composition and ink composition using these |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229363A (en) * | 2009-03-30 | 2010-10-14 | Econet Engineering:Kk | Water resistant light accumulating material and fluorescent material, method of producing thereof, coating material composition and ink composition using these |
Non-Patent Citations (2)
| Title |
|---|
| 方小牛等: "《生土类建筑保护技术与策略-以井冈山刘氏房祠保护与修缮为例》", vol. 1, 31 January 2018, 同济大学出版社, pages: 19 - 23 * |
| 朱万强主编: "《涂料基础教程》", vol. 1, 30 June 2012, 西南交通大学出版社, pages: 143 - 145 * |
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