CN108424684B - Thermochromic emissivity-variable printing ink and preparation method and application thereof - Google Patents

Thermochromic emissivity-variable printing ink and preparation method and application thereof Download PDF

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CN108424684B
CN108424684B CN201810365517.9A CN201810365517A CN108424684B CN 108424684 B CN108424684 B CN 108424684B CN 201810365517 A CN201810365517 A CN 201810365517A CN 108424684 B CN108424684 B CN 108424684B
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thermochromic
emissivity
printing ink
ink
deionized water
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CN108424684A (en
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程海峰
谢东津
刘东青
王楠楠
张朝阳
嵇海宁
汤丹
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National University of Defense Technology
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks

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  • Life Sciences & Earth Sciences (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention provides a thermochromic emissivity printing ink and a preparation method and application thereof, wherein the printing ink is composed of a thermochromic material, a thermochromic emissivity material, a binder, an antibacterial agent, an anti-settling dispersant and deionized water, and is prepared by selecting [ (C)2H5)2NH2]2CuCl4The ink is a thermochromic material, an acrylic resin emulsion and/or a polyvinyl alcohol aqueous solution are/is matched as a binder, and deionized water is used as a solvent, so that the ink does not cause nozzle blockage, the printing performance is stable, a coating printed by the ink can be green at room temperature (25 ℃), yellow at higher temperature (52 ℃) and can restore green when the temperature is reduced, and meanwhile, the coating can have the characteristic of reducing emissivity along with the increase of the temperature within a certain temperature range (60-100 ℃) by matching with the thermochromic material, so that the high-temperature weapon equipment can realize self-adaptive camouflage at an infrared band.

Description

Thermochromic emissivity-variable printing ink and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ink-jet printing, and particularly relates to thermochromic emissivity-changing ink-jet printing ink for preparing a self-adaptive camouflage coating, and a preparation method and application thereof.
Background
The ink-jet printing technology is a non-contact digital printing technology which inputs the required pattern into a computer in a digital form, directly sprays ink onto a printing stock through image processing and prints various patterns. The technology gets rid of the difficulties of high energy consumption, high emission, high pollution and low added value of the traditional printing process, and has the obvious advantages of simple production process, breaking the limitation of traditional color register and pattern return, low energy consumption, small pollution and the like.
One of the keys to inkjet printing technology is the printing of ink. The ink-jet printing ink mainly comprises two types of dye type ink and pigment type ink, wherein the dye type ink has bright color and good stability, is not easy to block a spray head, has complete chromatogram, but has poor water resistance and light resistance, and cannot meet the outdoor use requirement; the pigment type ink can just make up the defects of the dye type ink, has good light resistance, water resistance and heat resistance, is not easily influenced by weather, and is mostly used for outdoor spray painting. Therefore, how to improve the formulation and/or preparation process of the existing pigment-based ink to overcome the above defects has become an important research topic in the field.
In the military camouflage field, the camouflage coating is used for concealing military targets, so that the military targets show spectral reflection performance close to that of a combat environment, and at present, the camouflage coating is designed by coping with enemy reconnaissance measures in visible light, ultraviolet light, near infrared light, intermediate infrared light and other wave bands. However, with frequent change of combat regions and continuous widening of military detector wave bands in modern high-tech wars, the camouflage coating with a single spectrum band cannot meet the requirements of camouflage protection, so that the research on visible/infrared compatible camouflage coatings is gradually developed to be a necessary trend.
For example, chinese patent document CN107141907A discloses a visible/infrared compatible self-adaptive camouflage coating and a preparation method thereof, wherein the coating has a layered structure and sequentially comprises a substrate layer, a bottom layer, a thermally variable infrared emission layer and a camouflage pattern layer from inside to outside. According to the prior art, dye molecules with large tinting strength are adopted in the camouflage pattern layer, so that the thickness of the camouflage pattern layer is 2-3 microns, on one hand, light in a far infrared waveband (7.5-14 microns) can be transmitted, the change of the infrared emissivity of the thermotropic infrared emissivity layer can be reflected, on the other hand, the thickness of the camouflage pattern layer is larger than the wavelength of a visible light waveband, the color of the thermotropic infrared emissivity layer cannot be reflected, and the whole coating has visible/infrared compatible self-adaptive camouflage performance. However, the coating in the technology has a complex structure, and accordingly, the preparation process of the coating is complicated, which is not beneficial to industrial production.
Disclosure of Invention
The invention aims to overcome the defects of complex multilayer structure and complex preparation process of the existing visible/infrared compatible self-adaptive camouflage coating, and further provides the thermochromic variable-emissivity ink-jet printing ink which has a simple structure and a simple and convenient preparation process and can be used for producing the self-adaptive camouflage coating.
Further, the invention also provides a method for preparing the thermochromic emissivity ink-jet printing ink.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the thermochromic emissivity-changing printing ink comprises the following raw materials in parts by mass:
10-30% of thermochromic material, 2-10% of thermochromic emissivity material, 10-40% of binder, 0.1-0.6% of antibacterial agent, 0.1-0.6% of anti-settling dispersant and the balance of deionized water;
the thermochromic material is [ (C)2H5)2NH2]2CuCl4；
The binder is acrylic resin emulsion and/or polyvinyl alcohol aqueous solution.
Preferably, the thermochromic emissivity-changing printing ink comprises the following raw materials:
10% of thermochromic material, 5% of thermochromic emissivity material, 35% of bonding material, 0.1% of antibacterial agent, 0.5% of anti-settling dispersant and the balance of deionized water; or
20% of thermochromic material, 3% of thermochromic emissivity material, 30% of bonding material, 0.2% of antibacterial agent, 0.2% of anti-settling dispersant and the balance of deionized water; or
25% of thermochromic material, 7% of thermochromic emissivity material, 25% of bonding material, 0.1% of antibacterial agent, 0.5% of anti-settling dispersant and the balance of deionized water.
Preferably, the [ (C)2H5)2NH2]2CuCl4The purity of the crystal is more than 99.9 percent, the grain size is 1-100 mu m, and the relative humidity is 10-20 percent.
Preferably, the [ (C)2H5)2NH2]2CuCl4The preparation method comprises the following steps:
dissolving copper dichloride and diethylamine hydrochloride in deionized water according to the molar ratio of 1 (1.5-2.5), uniformly stirring, heating to 50-70 ℃, reacting for 2 hours, cooling, filtering, collecting solids, recrystallizing with absolute ethyl alcohol, and drying crystals to obtain the copper dichloride-diethylamine hydrochloride crystal.
Preferably, the crystals are dried under vacuum at 60 ℃ for 3 h.
Preferably, the antibacterial agent is one or more of acylaniline antibacterial agents, imidazole antibacterial agents, thiazole antibacterial agents and isothiazolone derivative antibacterial agents; and/or
The anti-settling dispersant is one or more of BYK-2155, BYK-161, BYK-2173, BYK-420 and BYK-8420.
Preferably, the material with thermal variable emissivity is VO2And/or a perovskite-type composite oxide, which may be La1-xSrxMnO3、La1-xCaxMnO3Or Sm1-xCaxMnO3、Nd1-xEuxNiO3Wherein 1 > x > 0.
The thermochromic emissivity-changing printing ink is applied to the field of military camouflage.
The method for preparing the thermochromic emissivity-changing printing ink comprises the following steps:
and adding the anti-settling dispersing agent into the deionized water, stirring, adding the thermochromic emissivity material, the thermochromic material, the binder and the antibacterial agent, and continuously stirring to obtain the material.
The thermochromic emissivity-changing printing ink prepared by the method is applied to the field of military camouflage.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the thermochromic emissivity printing ink provided by the invention consists of a thermochromic material, a thermochromic emissivity material, a binder, an antibacterial agent, an anti-settling dispersant and deionized water, and is prepared by selecting [ (C)2H5)2NH2]2CuCl4The ink is used as a thermochromic material, and is matched with acrylic resin emulsion and/or polyvinyl alcohol aqueous solution as a binder and deionized water as a solvent, and the synergistic cooperation effect of the acrylic resin emulsion and/or the polyvinyl alcohol aqueous solution enables a coating printed by the ink to be green at room temperature (25 ℃), yellow at higher temperature (52 ℃) and above, and recover green when the temperature is reduced to below 52 ℃, so that the ink meets the self-adaptive camouflage characteristic that a low-temperature jungle environment displays jungle camouflage dominant colors and a high-temperature desert area displays desert camouflage dominant colors; meanwhile, by matching with a thermal variable emissivity material, the coating printed by the ink disclosed by the invention has the characteristic of reducing emissivity along with temperature increase within a certain temperature range (60-100 ℃), so that the high-temperature weapon equipment can realize self-adaptive camouflage in an infrared band. Besides, the raw materials except the binder and the thermal variable emissivity material are dissolved in water in a molecular level, the binder exists in an emulsion form, and the thermal variable emissivity material can be stably dispersed in an ink system under the dispersion action of the anti-settling dispersant, so that the ink disclosed by the invention cannot cause nozzle blockage, has stable printing performance, and can be used for carrying out ink-jet printing on printing materials such as paper, coated cloth and the like. Therefore, the ink can be used for printing military camouflage coatings, so that the military camouflage coatings can realize self-adaptive camouflage in visible and infrared wave bands.
The ink of the invention is also added with an antibacterial agent, which has the function of keeping the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae, viruses and the like) below a necessary level within a certain period of time so as to ensure the long-term stability of the ink and be harmless to human bodies. If not, the ink may cause mass propagation of microorganisms due to problems such as a storage method and the like, and a nozzle may be blocked in the ink-jet printing process, thereby affecting the film forming quality or the thermochromic performance.
2. The preparation method of the thermochromic emissivity printing ink provided by the invention can be prepared by uniformly mixing all the raw materials, and the thermochromic emissivity coating can be obtained by utilizing an ink-jet printing technology, so that the preparation method is simple and convenient in preparation process, strong in operability and convenient for industrialization.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a photograph (25 ℃) printed with the thermochromic emissivity printing ink provided in example 1;
FIG. 2 is a photograph (52 ℃) printed with the thermochromic emissivity printing ink provided in example 1;
FIG. 3 is a graph of the absorption of the visible spectrum at 25 deg.C and 52 deg.C of a coating printed with the thermochromic emissivity printing ink provided in example 1;
FIG. 4 is a graph of the change of infrared emissivity of a coating printed by the thermochromic emissivity printing ink provided in example 1 in a wavelength band of 3-5 μm with temperature;
FIG. 5 is a graph showing the variation of infrared emissivity with temperature of a coating printed by the thermochromic emissivity printing ink provided in example 1 in a wavelength band of 8-14 μm.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the thermochromic emissivity-changing printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4Preparation of
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving 21.2g of NH & HCl in 140g of deionized water, stirring and mixing uniformly, carrying out a constant-temperature water bath reaction at 70 ℃ for 2h, taking out, cooling to room temperature, carrying out suction filtration on absolute ethyl alcohol after solid is separated out, collecting the solid, recrystallizing for 2 times by using the absolute ethyl alcohol, putting the crystal into a vacuum drying oven, and drying for 3h at 60 ℃ to obtain 38g of bright green needle-like crystals, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.99%, the grain size is 18-31 μm, and the relative humidity is 15%.
(2) Preparing printing ink
0.25g of BYK-2155 (manufactured by Bick chemical Co., Germany) was slowly added to 24.7g of deionized water, and stirred for 20min, and 2.5g of VO was slowly added while stirring2Powder, 5g of [ (C)2H5)2NH2]2CuCl417.5g of acrylic resin emulsion (the solid content of the acrylic resin emulsion is 40%) and 0.05g of 1, 2-benzisothiazolin-3-one, and after continuously stirring for 1h, filtering by using a filter membrane with the pore diameter of 1 mu m, wherein the filtrate is the thermochromic emissivity printing ink.
Fig. 1 is a photograph of a thermochromic emissivity printing ink prepared according to this example printed at 25 ℃, which clearly shows that the photograph at 25 ℃ is green, which is similar to RAL6018 in color and RGB R101G148B68, as compared to RAL color chart.
Fig. 2 is a photograph of the thermochromic emissivity printing ink prepared according to this example at 52 ℃, which clearly shows that the photograph at 52 ℃ is yellow, which is similar to RAL1018 in color and has an RGB value of R249G206B82, as seen by comparing with RAL color chart. When the temperature is reduced to below 52 ℃, the green color is recovered.
Fig. 3 is a graph of the absorption of the coating printed by the thermochromic emissivity printing ink prepared in this embodiment at 25 ℃ and 52 ℃, and it can be seen from the graph that the coating absorbs weak visible light around 580nm at 25 ℃, which indicates that the coating is green; the coatings have weak absorption of visible light above 550nm at 52 ℃, which indicates that the coatings are yellow brown.
The thermochromic emissivity-changing printing ink prepared by the embodiment is printed on a nylon textile fabric by adopting an ink-jet printing technology to form a coating, and the infrared emissivity of the coating at different temperatures is tested by adopting the following specific test method:
heating the constant-temperature water bath to a temperature to be measured, adhering a coating sample to the side surface of the water bath by using a heat-conducting adhesive, wherein the position is below the water surface and close to the center, and carrying out heat balance for 30 min; and (3) turning on the FLIR thermal infrared imager, starting an automatic shooting function to record an IR chart, reading the radiation temperature of the surface of the sample by using the attached software of the IR thermal infrared imager, calculating to obtain the IR emittances of the coating at 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, and further drawing the variation curves of the IR emittances with the temperature, wherein the variation curves are respectively shown in fig. 4 and 5.
As can be seen from FIG. 4, in the wave band of 3-5 μm, the emissivity of the coating is suddenly reduced at 65-70 ℃, and the maximum mutation value is 0.3. As can be seen from FIG. 5, the emissivity of the coating decreases sharply at 65-70 ℃ in the wavelength range of 8-14 μm, and the maximum strain value is 0.22.
Example 2
The preparation method of the thermochromic emissivity-changing printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4System of (1)Prepare for
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving 19.7g of NH & HCl in 120g of deionized water, stirring and mixing uniformly, carrying out a constant-temperature water bath reaction at 60 ℃ for 2h, taking out, cooling to room temperature, carrying out suction filtration on absolute ethyl alcohol after solid is separated out, collecting the solid, recrystallizing for 2 times by using the absolute ethyl alcohol, putting the crystal into a vacuum drying oven, and drying for 3h at 60 ℃ to obtain 34.1g of bright green needle-like crystal, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.9%, the grain size is 10-39 μm, and the relative humidity is 12%.
(2) Preparing printing ink
0.1g of BYK-161 (manufactured by Bick chemical Co., Germany) was slowly added to 23.3g of deionized water, and stirred for 30min, and 1.5g of VO was slowly added while stirring2Powder, 10g of [ (C)2H5)2NH2]2CuCl415g of acrylic resin emulsion (the solid content of the acrylic resin emulsion is 40%) and 0.1g of 1, 2-benzisothiazolin-3-one, and after continuously stirring for 1h, filtering by using a filter membrane with the aperture of 1 mu m, wherein the filtrate is the thermochromic emissivity printing ink.
Example 3
The preparation method of the thermochromic printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4Preparation of
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving 16.4g of NH & HCl in 120g of deionized water, stirring and mixing uniformly, carrying out a constant-temperature water bath reaction at 65 ℃ for 2h, taking out, cooling to room temperature, carrying out suction filtration on absolute ethyl alcohol after solid is separated out, collecting the solid, recrystallizing for 2 times by using the absolute ethyl alcohol, putting the crystal into a vacuum drying oven, and drying for 3h at 60 ℃ to obtain 29g of bright green needle-like crystals, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.99%, the grain size is 16-42 μm, and the relative humidity is 20%.
(2) Preparing printing ink
0.25g of BYK-2173 (manufactured by Bikk Chemicals, Germany) was slowly added to 21.2g of deionized water, stirred for 30min, and 3.5g of VO was slowly added with stirring2Powder, 12.5g of [ (C)2H5)2NH2]2CuCl412.5g of acrylic resin emulsion (the solid content of the acrylic resin emulsion is 40%) and 0.05g of 1, 2-benzisothiazolin-3-one, and after continuously stirring for 1.5h, filtering by using a filter membrane with the aperture of 1 mu m, wherein the filtrate is the thermochromic emissivity printing ink.
Example 4
The preparation method of the thermochromic printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4Preparation of
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving 27.4g of NH & HCl in 150g of deionized water, stirring and mixing uniformly, carrying out a constant-temperature water bath reaction at 65 ℃ for 2h, taking out, cooling to room temperature, carrying out suction filtration on absolute ethyl alcohol after solid is separated out, collecting the solid, recrystallizing for 2 times by using the absolute ethyl alcohol, putting the crystal into a vacuum drying oven, and drying for 3h at 60 ℃ to obtain 38.2g of bright green needle-like crystal, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.99%, the grain size is 22-50 μm, and the relative humidity is 10%.
(2) Preparing printing ink
0.05g of BYK-420 (manufactured by Bick chemical Co., Germany) was slowly added to 17.15g of deionized water, and stirred for 10min, and 5g of La was slowly added thereto with stirring0.825Sr0.175MnO3Powder, 7.5g of [ (C)2H5)2NH2]2CuCl420g of acrylic resin emulsion (the solid content of the acrylic resin emulsion is 40%) and 0.3g of 1, 2-benzisothiazolin-3-one, and after continuously stirring for 1.5h, filtering by using a filter membrane with the pore diameter of 1 mu m, wherein the filtrate is the thermochromic emissivity printing ink.
Example 5
The preparation method of the thermochromic printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4Preparation of
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving NH & HCl 25.5g in deionized water 150g, stirring and mixing uniformly, reacting in 50 ℃ constant temperature water bath for 2h, taking out, cooling to room temperature, after solid precipitation, carrying out suction filtration by absolute ethyl alcohol, collecting solid, recrystallizing for 2 times by absolute ethyl alcohol, putting the crystal into a vacuum drying oven, drying for 3h at 60 ℃ to obtain 38.1g bright green needle-like crystal, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.99%, the grain size is 25-62 μm, and the relative humidity is 18%.
(2) Preparing printing ink
0.3g of BYK-8420 (manufactured by Bick chemical Co., Germany) was slowly added to 28.5g of deionized water, and stirred for 10min, and 1g of La was slowly added thereto with stirring0.7Ca0.3MnO3Powder, 15g of [ (C)2H5)2NH2]2CuCl45g of acrylic resin emulsion (the solid content of the acrylic resin emulsion is 40%) and 0.175g of 1, 2-benzisothiazolin-3-one, and after continuously stirring for 1.5h, filtering by using a filter membrane with the pore diameter of 1 mu m, wherein the filtrate is the thermochromic emissivity printing ink.
Example 6
The preparation method of the thermochromic printing ink provided by the embodiment comprises the following steps of:
(1) thermochromic material [ (C)2H5)2NH2]2CuCl4Preparation of
Adding CuCl2·2H2O17 g and (C)2H5)2Dissolving NH & HCl 22.9g in deionized water 150g, stirring and mixing uniformly, reacting in a 55 ℃ constant temperature water bath for 2h, taking out, cooling to room temperature, after solid precipitation, carrying out suction filtration by absolute ethyl alcohol, collecting the solid, recrystallizing for 2 times by absolute ethyl alcohol, putting the crystal into a vacuum drying oven, drying for 3h at 60 ℃ to obtain 38.2g bright green needle-shaped crystals, namely [ (C)2H5)2NH2]2CuCl4。
Detected, [ (C)2H5)2NH2]2CuCl4The purity of the crystal is 99.99%, the grain size is 15-45 mu m, and the relative humidity is 17%.
(2) Preparing printing ink
0.15g of BYK-2155 (manufactured by Bick chemical Co., Germany) was slowly added to 26.75g of deionized water, and stirred for 10min, and 3g of VO was slowly added while stirring2Powder, 10g of [ (C)2H5)2NH2]2CuCl410g of polyvinyl alcohol aqueous solution and 0.1g of 1, 2-benzisothiazolin-3-one, continuously stirring for 1h, and filtering by using a filter membrane with the aperture of 1 mu m to obtain filtrate, namely the thermochromic emissivity printing ink.
Comparative example 1
Comparative example thermochromic Material [ (C)2H5)2NH2]2CuCl4The preparation method is the same as that of example 1 of the present invention.
The preparation method of the thermochromic emissivity-changing printing ink in the comparative example is as follows:
0.25g of BYK-2155 (produced by Bick chemical Co., Germany) was slowly added to 22.2g of deionized water, and stirred for 20min, and 2.5g of VO was slowly added while stirring2Powder, 5g of [ (C)2H5)2NH2]2CuCl417.5g of aqueous polyurethane (with a solid content of 40%) and 0.05g of 1, 2-benzisothiazolin-3-one, and stirring was continued, a large amount of polyurethane precipitates, and the ink obtained by filtration showed no significant color development due to the low solid content.
Examples of the experiments
The printing inks prepared in the embodiments 1 to 6 of the present invention were added to the ink cartridge of the inkjet printer EPSON style pro 1390 having a piezoelectric nozzle, and the printer was used, and the nozzle detection function was performed after 0h, 12h, and 24h, and the results showed that the printed pattern had no broken line.
After one week of use, the above test was repeated to find that the printed pattern was still unbroken.
Thus, the printing ink of the present invention does not cause clogging of the head of the ink jet printer.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. The thermochromic emissivity-changing printing ink is characterized by comprising the following raw materials in parts by mass:
10-30% of thermochromic material, 2-10% of thermochromic emissivity material, 10-40% of binder, 0.1-0.6% of antibacterial agent, 0.1-0.6% of anti-settling dispersant and the balance of deionized water;
the thermochromic material is [ (C)2H5)2NH2]2CuCl4；
The material with thermally variable emissivity is VO2Or VO2And the perovskite type composite oxide, so that the coating printed by the ink has the characteristic of reducing emissivity along with the increase of temperature within 60-100 ℃;
the binder is acrylic resin emulsion and/or polyvinyl alcohol aqueous solution.
2. The thermochromic emissivity printing ink of claim 1,
10% of thermochromic material, 5% of thermochromic emissivity material, 35% of bonding material, 0.1% of antibacterial agent, 0.5% of anti-settling dispersant and the balance of deionized water; or
20% of thermochromic material, 3% of thermochromic emissivity material, 30% of bonding material, 0.2% of antibacterial agent, 0.2% of anti-settling dispersant and the balance of deionized water; or
25% of thermochromic material, 7% of thermochromic emissivity material, 25% of bonding material, 0.1% of antibacterial agent, 0.5% of anti-settling dispersant and the balance of deionized water.
3. The thermochromic emissivity printing ink of claim 1 or 2, wherein the [ (C) is2H5)2NH2]2CuCl4The purity of the crystal is more than 99.9 percent, the grain size is 1-100 mu m, and the relative humidity is 10-20 percent.
4. The thermochromic emissivity printing ink of claim 1 or 2, wherein the [ (C) is2H5)2NH2]2CuCl4The preparation method comprises the following steps:
dissolving copper dichloride and diethylamine hydrochloride in deionized water according to the molar ratio of 1 (1.5-2.5), uniformly stirring, heating to 50-70 ℃, reacting for 2 hours, cooling, filtering, collecting solids, recrystallizing with absolute ethyl alcohol, and drying crystals to obtain the copper dichloride-diethylamine hydrochloride crystal.
5. Thermochromic emissivity printing ink according to claim 4, wherein the crystals are vacuum dried at 60 ℃ for 3 h.
6. The thermochromic emissivity printing ink of claim 1 or 2, wherein the antimicrobial agent is one or more of an anilide antimicrobial agent, an imidazole antimicrobial agent, a thiazole antimicrobial agent, an isothiazolone derivative antimicrobial agent; and/or
The anti-settling dispersant is one or more of BYK-2155, BYK-161, BYK-2173, BYK-420 and BYK-8420.
7. Method for preparing a thermochromic emissivity printing ink according to any of claims 1-6, comprising:
and adding the anti-settling dispersing agent into the deionized water, stirring, adding the thermochromic emissivity material, the thermochromic material, the binder and the antibacterial agent, and continuously stirring to obtain the material.
8. Use of the thermochromic emissivity printing ink of any one of claims 1 to 6 in the field of military camouflage.
9. Use of the thermochromic emissivity printing ink made by the method of claim 7 in the field of military camouflage.
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