CN116589884B - Mechanochromatic ink and preparation method and application thereof - Google Patents
Mechanochromatic ink and preparation method and application thereof Download PDFInfo
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- CN116589884B CN116589884B CN202310408239.1A CN202310408239A CN116589884B CN 116589884 B CN116589884 B CN 116589884B CN 202310408239 A CN202310408239 A CN 202310408239A CN 116589884 B CN116589884 B CN 116589884B
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 230000008859 change Effects 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000002077 nanosphere Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- LCDOENXNMQXGFS-UHFFFAOYSA-N phenoxybenzene;prop-2-enoic acid Chemical compound OC(=O)C=C.C=1C=CC=CC=1OC1=CC=CC=C1 LCDOENXNMQXGFS-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 229920000193 polymethacrylate Polymers 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 239000004038 photonic crystal Substances 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 39
- 239000002105 nanoparticle Substances 0.000 description 19
- 230000003287 optical effect Effects 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- -1 amino- Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000012704 polymeric precursor Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000238367 Mya arenaria Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001486 SU-8 photoresist Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IMXQXDJNRPLNKQ-UHFFFAOYSA-N [P].C1(=CC=CC=C1)C=1C(=C(C(=C(C1C)C(=O)[O])C)C1=CC=CC=C1)C Chemical compound [P].C1(=CC=CC=C1)C=1C(=C(C(=C(C1C)C(=O)[O])C)C1=CC=CC=C1)C IMXQXDJNRPLNKQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- 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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of ink, in particular to a mechanochromatic ink and a preparation method and application thereof. The mechanochromatic ink comprises nano microspheres, a high molecular precursor and a photoinitiator. The nano microsphere forms a photonic crystal structure through self-assembly, so that the material has structural color, and the elastic polymer is endowed with the characteristic that the material deforms under the action of external force, so that the structural color changes. And the structural color change characteristic of the technology does not need to depend on dark background, so that the application range of the technology is widened.
Description
Technical Field
The invention relates to the technical field of ink, in particular to a mechanochromatic ink and a preparation method and application thereof.
Background
The concept of photonic crystals (photonic crystal) was defined in 1987 by scientists s.john and e.yablonovtech. The micro-nano structure metamaterial with the dielectric constant periodically changing along with the space can modulate photons, and when the photons enter the periodically arranged dielectric material to propagate, the photons are modulated to form a photon energy band structure, namely a photon band gap due to Bragg scattering of the light waves at different medium interfaces. At this time, photons of the corresponding wavelength cannot propagate in the photonic crystal material and are reflected, so that structural colors can be observed. Since the diffraction of photons in the crystal conforms to the bragg formula, i.e. by changing the corresponding bragg constants (interlayer spacing, incident light and viewing angle, refractive index of the material), different colors can be seen by the observer. The use of photonic crystal materials to prepare inks has natural decorative or anti-counterfeit efficacy.
By applying external force to the photonic crystal material, the Bragg parameters of the photonic crystal material are changed, and further the structural color is changed, so that the mechanochromatic photonic crystal material is formed. Meanwhile, the mechanochromatic characteristic can be used for constructing anti-counterfeiting labels. The following ways of constructing the mechanochromatic photonic crystal are provided: first, a positive phase photonic crystal is built up from deformable nano-microspheres. Under the action of external force, the nano microsphere is deformed, so that the interlayer spacing of the photonic crystal is changed, and finally the structural color is changed. Common elastic nanospheres are generally composed of a hard core and a soft shell, such as SiO 2 @PEGPEA, PS-ALMA@PEA, PMMA@P (BA-AA-AAm), and the like. Secondly, the reverse-phase photonic crystal structure is constructed by elastic high polymer materials, such as SU-8, polyurethane, PVDF and the like, then the reverse-phase photonic crystal is constructed by a hard template method, and then the hard template is removed, so that the preparation process and difficulty are greatly increased, and the material tolerance is also influenced. And only the third mode, namely, taking common nano-microspheres as a main body and matching elastic polymer precursors as fillers, can construct the mechanochromic photonic crystal at one time, so that the complexity of the preparation process and the practicability of the use process can be balanced.
The difficulty in constructing the mechanochromatic anti-counterfeiting label is to obtain a high polymer material with proper elasticity so as to ensure the capability of endowing the photonic crystal structure with force-induced deformation, and the requirement is that the color change can be quickly caused after the external force is applied and the external force is withdrawn, so that the selection of the high polymer material becomes the most critical place in order to obtain better mechanochromatic effect. Firstly, the nano microsphere has proper affinity with the selected nano microsphere, so that a photonic crystal structure is easy to construct; secondly, under the condition of smaller deformation pressure, the change of the comprehensive refractive index is as large as possible, which is beneficial to the perception of color change; thirdly, the polymer can also meet the tolerance requirement of physical and chemical conditions in the use of the banknote.
There has been some research on the aspect of the mechanochromatic materials at home and abroad, including the aspects of preparation methods, performance research, application and the like of the mechanochromatic materials. Some operations similar to the present operation but with different points will now be briefly described:
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a mechanochromatic ink, and a preparation method and application thereof, for solving the problems in the prior art.
To achieve the above and other related objects, one aspect of the present invention provides a mechanochromatic ink, which includes a nanoparticle, a polymer precursor, and a photoinitiator, wherein the volume ratio of the nanoparticle, the polymer precursor, and the photoinitiator is (20-60): (40-80): (2-10).
In some embodiments of the present invention, the nanoparticle is selected from one of a silica nanoparticle and its derivatives, a polystyrene nanoparticle and its derivatives, a polymethacrylate nanoparticle and its derivatives, a polyacrylamide nanoparticle, a zinc oxide nanoparticle, a zirconium oxide nanoparticle, a cadmium sulfide nanoparticle, an iron oxide nanoparticle, and a cerium oxide nanoparticle.
In some embodiments of the invention, the nanoparticle has a particle size of 100 to 900nm; the nano microsphere has monodispersity; the variation coefficient of the nano microsphere is less than 15%.
In some embodiments of the invention, the polymeric precursor is selected from one or a mixture of two of diethylene glycol ethyl ether acrylate and polyethylene glycol phenyl ether acrylate.
In some embodiments of the invention, the polymeric precursor is selected from the group consisting of a mixture of diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate; the high polymer precursor is selected from diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate with the volume ratio of 1-4: 1 to 4.
In some embodiments of the invention, the photoinitiator is selected from one of 2-hydroxy-2-methyl-1-phenylpropion and diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus.
In another aspect, the present invention provides a method for preparing the mechanochromatic ink according to the first aspect of the present invention, wherein the method comprises the following steps:
1) Dispersing the nano microspheres in an organic solution to prepare a dispersion liquid A;
2) Mixing a macromolecule precursor and a photoinitiator to prepare a solution B;
3) Mixing the dispersion liquid A and the solution B, and then heating to volatilize the organic solution to obtain a mixed solution C;
4) And (3) standing the mixed solution C, and then irradiating under an ultraviolet lamp to finish curing to obtain the target material.
In some embodiments of the invention, in step 1), the volume ratio of the nanoparticle to the organic solvent is 1-2: 1.
In some embodiments of the invention, in step 1), the organic solvent is selected from ethanol, propanol, butanol.
In some embodiments of the present invention, in step 2), the volume ratio of the polymer precursor and the photoinitiator is 10 to 15:1 to 2.
In some embodiments of the invention, in step 3), the volume ratio of dispersion a and solution B is 3 to 5: 7-8.
In some embodiments of the invention, in step 4), the ultraviolet lamp curing conditions include a mercury lamp UV light source with a power of 0.075J/cm 2-0.085J/cm2 and a curing time of 0.05-0.1s.
In another aspect, the present invention provides a method of changing color of a mechanochromatic ink, the method comprising:
a) The structural color of the front-side observation electrochromic ink can see all spectrum single colors from red, green to blue, and the inclined observation can see the color blue shift phenomenon;
b) Under the action of an external force of less than or equal to 0.4 newton, the structural color of the mechanochromatic ink can be red-shifted or blue-shifted, wherein the time required for changing and recovering the structural color is less than 0.1 second; the change in structural color and the restoration to one process can be repeated more than 1000 times.
In another aspect, the invention provides the use of a mechanochromatic ink according to the first aspect of the invention in security labels.
Compared with the prior art, the invention has the beneficial effects that:
the invention obtains the ink with the mechanochromic effect through ultraviolet curing. In the material, the nano microsphere forms a photonic crystal structure through self-assembly, so that the material has structural color, and the elastic polymer endows the material with the characteristic of deformation under the action of external force, so that the structural color is changed. And the structural color change characteristic of the technology does not need to depend on dark background, so that the application range of the technology is widened.
Detailed Description
The following detailed description specifically discloses embodiments of the mechanochromatic ink of the present application, and methods for preparing and using the same.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2,3, 4, 5, 6, 7, 8,9, 10, 11, 12 or the like.
The inventor provides a mechanochromic ink, a preparation method and application thereof through a large number of exploratory experiments. The ink with the mechanochromism effect is obtained by ultraviolet curing by taking the nanometer microsphere as a main component, taking an elastic polymer precursor as a base ink and matching with a photoinitiator. In the material, the nano microsphere forms a photonic crystal structure through self-assembly, so that the material has structural color, and the elastic polymer endows the material with the characteristic of deformation under the action of external force, so that the structural color is changed. And the structural color change characteristic of the technology does not need to depend on dark background, so that the application range of the technology is widened. The present invention has been completed on the basis of this finding.
The first aspect of the invention provides the mechanochromatic ink, which comprises nano microspheres, a polymer precursor and a photoinitiator, wherein the volume ratio of the nano microspheres to the polymer precursor to the photoinitiator is (20-60): (40-80): (2-10). In some embodiments, the mechanochromatic ink comprises a nanoparticle, a polymer precursor and a photoinitiator, wherein the volume ratio of the nanoparticle, the polymer precursor and the photoinitiator can be (20-40): (40-80): (2-10) and (40-60): (40-80): (2-10) and (20-60): (40-60): (2-10) and (20-60): (60-80): (2-10), or (20-60): (40-80): (2-6), or (20-60): (40-80): (6-10), etc.
In the mechanochromatic ink provided by the invention, the nanospheres are selected from one of silicon oxide nanospheres and derivatives thereof, polystyrene nanospheres and derivatives thereof, polymethacrylate nanospheres and derivatives thereof, zinc oxide nanospheres, polyacrylamide nanospheres, zirconium oxide nanospheres, cadmium sulfide nanospheres, iron oxide nanospheres and cerium oxide nanospheres. The invention requires monodisperse nano-microspheres, which are different in types and difficult to control the particle size. And the doping of different nano-microspheres in the ink can be mutually influenced, so that a photonic crystal structure can not be formed. And thus single better. The derivative of the silica nanoparticle may be, for example, an amino-, carboxyl-, or mercapto-modified silica microsphere. The derivative of the polystyrene nano microsphere can be, for example, a nano titanium oxide-polystyrene microsphere compound, a ferroferric oxide@polystyrene microsphere with a core-shell structure, and the like. The derivative of the polymethacrylate nanospheres may be, for example, poly (methyl methacrylate) polyethylene copolymer nanospheres, polymethacrylate polystyrene copolymer nanospheres, and the like.
In the mechanochromatic ink provided by the invention, the particle size of the nano microsphere is 100-900 nm. In a specific embodiment, the particle size of the nanoparticle may be, for example, 100 to 300nm, 300 to 600nm, 600 to 900nm, or the like. The nano-microsphere has monodispersity. The variation coefficient of the nano microsphere is less than 15%.
In the mechanochromatic ink provided by the invention, the polymer precursor is selected from one or a mixture of two of diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate. Preferably, the polymer precursor is selected from the group consisting of a mixture of diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate. The high polymer precursor is selected from diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate with the volume ratio of 1-4: 1 to 4. In some embodiments, the volume ratio of the polymer precursor selected from diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate may be 1-2: 1-4, 2-3: 1 to 4, or 3 to 4:1 to 4, etc. In a specific embodiment, the CAS for diethylene glycol monoethyl ether acrylate is 7328-17-8. The CAS of the polyethylene glycol phenyl ether acrylate is 56641-05-5. Available from reagent companies such as Alatine.
In the mechanochromatic ink provided by the invention, the photoinitiator is selected from one or two of 2-hydroxy-2-methyl-1-phenylpropionic acid and diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide.
The second aspect of the present invention provides a method for preparing a mechanochromatic ink, the method comprising the steps of:
1) Dispersing the nano microspheres in an organic solution to prepare a dispersion liquid A;
2) Mixing a macromolecule precursor and a photoinitiator to prepare a solution B;
3) Mixing the dispersion liquid A and the solution B, and then heating to volatilize the organic solution to obtain a mixed solution C;
4) And (3) standing the mixed solution C, and then irradiating under an ultraviolet lamp to finish curing to obtain the target material.
In the preparation method of the mechanochromatic ink provided by the invention, step 1) is to disperse the nano-microspheres in an organic solution to prepare a dispersion liquid A. Specific:
In the step 1) of the invention, the volume ratio of the nano microsphere to the organic solvent is 1-2: 1 to 2. In a specific embodiment, the volume ratio of the nanoparticle to the organic solvent may be 1 to 1.5:1 to 2, 1.5 to 2: 1-2, etc.
In the step 1) of the invention, the organic solvent is selected from ethanol, propanol and butanol; preferably, the organic solvent is selected from ethanol.
In the step 2), the volume ratio of the polymer precursor to the photoinitiator is 10-15: 1 to 2. In a specific embodiment, the volume ratio of the polymer precursor to the photoinitiator may be 10-15: 1-2, 10-12: 1 to 2, or12 to 15: 1-2, etc.
In the step 3) of the invention, the volume ratio of the dispersion liquid A to the solution B is 3-5: 7-8. In a specific embodiment, the volume ratio of the dispersion liquid a to the solution B may be 3 to 4: 7-8, 4-5: 7 to 8, etc.
In the step 4), the curing condition of the ultraviolet lamp comprises a mercury lamp UV light source with the power of 0.075J/cm 2-0.085J/cm2 and the curing time of 0.05-0.1s. In particular embodiments, the power may be 0.075J/cm 2-0.080J/cm2, or 0.080J/cm 2-0.085J/cm2, etc. The curing time may be 0.05 to 0.08s, or 0.08 to 0.1s, etc.
A third aspect of the present invention provides a method of discolouring a mechanochromatic ink, the method comprising:
a) The structural color of the front-side observation electrochromic ink can see all spectrum single colors from red, green to blue, and the inclined observation can see the color blue shift phenomenon;
b) Under the action of an external force of less than or equal to 0.4 newton, the structural color of the mechanochromic ink can be red-shifted or blue-shifted, wherein the change of the structural color and the time required for recovering are respectively less than 0.1 second; the change in structural color and the restoration to one process can be repeated more than 1000 times.
In the method for changing the color of the mechanochromatic ink, in the step a), the optical characteristics of the mechanochromatic ink can be seen from the front view, all spectrum monocolors from red, green to blue can be seen, and the color blue shift phenomenon can be seen from oblique viewing.
In the method for changing the color of the mechanochromatic ink, in the step b), the optical characteristics of the mechanochromatic ink can be subjected to the action of external force, the structural color of the material can be subjected to red shift or blue shift, and the structural color is recovered immediately after the external force is removed. Wherein the external force comprises pressing, stretching, extruding, bending, scribing, twisting and the like.
In the method for changing the color of the mechanochromatic ink, in the step b), the change of the optical characteristics and the structural color can occur under the external force as small as 0.4 newton. Preferably, the external force is 0.6 to 1 newton.
In the method for changing the color of the mechanochromatic ink, in the step b), the optical characteristics, the structural color change and the recovery can all occur rapidly, and the required time is less than 0.1 second.
In the method for changing the color of the mechanochromatic ink, in the step b), the change and recovery of the optical characteristics and the structural color can be repeated for more than 1000 times.
In a third aspect the present invention provides the use of a mechanochromatic ink as described above in an anti-counterfeit label.
The beneficial effects of the invention are as follows:
The ink with the mechanochromic effect is obtained by adding the photoinitiator for ultraviolet curing. In the material, the nano microsphere forms a photonic crystal structure through self-assembly, so that the material has structural color, and the elastic polymer endows the material with the characteristic of deformation under the action of external force, so that the structural color is changed. And the structural color change characteristic of the technology does not need to depend on dark background, so that the application range of the technology is widened.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
Example 1
Preparing a mechanochromic anti-counterfeiting ink, which comprises the following steps:
1. Dispersing silicon oxide nano-microspheres in an ethanol solution, wherein the volume ratio of the silicon oxide nano-microspheres to the ethanol solution is 1:1, preparing a dispersion liquid A; wherein, the particle diameter of the silicon oxide nano microsphere is 100nm, the monodispersity and the variation coefficient is 10 percent.
2. The macromolecule precursor diethylene glycol diethyl ether acrylate (CAS number 7328-17-8), polyethylene glycol phenyl ether acrylate (CAS number 56641-05-5) and initiator 2-hydroxy-2-methyl-1-phenylpropionic acid are mixed according to the volume ratio of 3:9:2, mixing to prepare a solution B;
3. The volume ratio of the dispersion A to the solution B is 6:7, fully mixing, and then placing the mixture in an oven to heat to volatilize ethanol, so as to obtain a mixed solution C;
4. And (3) standing the solution C, and then irradiating the solution C for 0.05s under an ultraviolet lamp to finish curing to obtain the target material.
Optical properties: all spectra from red, green through blue are seen as monochromatic in frontal viewing, while oblique viewing can see the color blue shift phenomenon. Under the action of external force, the structural color of the material can be red-shifted or blue-shifted, and when the external force is removed, the structural color is recovered.
Under an external force of 0.4 newton, both the change and recovery of structural color can occur rapidly, with a required time of 0.1 seconds. The change and restoration of structural color may be repeated 1000 times.
Example 2
Preparing a mechanochromic anti-counterfeiting ink, which comprises the following steps:
1. Dispersing zirconia nano-microspheres in an ethanol solution, wherein the volume ratio of the zirconia nano-microspheres to the ethanol solution is 1:1, preparing a dispersion liquid A; wherein, the particle size of the zirconia nano microsphere is 100nm, the monodispersity and the variation coefficient is 10 percent.
2. The macromolecule precursor diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate and an initiator diphenyl- (2, 4, 6-trimethyl benzoyl) oxygen phosphorus are mixed according to a volume ratio of 4:9:1, mixing to prepare a solution B;
3. The volume ratio of the dispersion A to the solution B is 5:7, fully mixing, and then placing the mixture in an oven to heat to volatilize ethanol, so as to obtain a mixed solution C;
4. and (3) standing the solution C, and then irradiating under an ultraviolet lamp to finish curing to obtain the target material.
Optical properties: all spectra from red, green through blue are seen as monochromatic in frontal viewing, while oblique viewing can see the color blue shift phenomenon. Under the action of external force, the structural color of the material can be red-shifted or blue-shifted, and when the external force is removed, the structural color is recovered.
Under an external force of 0.4 newton, both the change and recovery of structural color can occur rapidly, with a required time of 0.1 seconds. The change and restoration of structural color may be repeated 1000 times.
The foregoing description is only of the preferred embodiment of the invention, and is not intended to limit the scope of the invention, but the embodiment of the invention can be variously modified in terms of material composition. All simple, equivalent changes and modifications made in accordance with the content of the claims of the present application fall within the scope of the claims of this patent. The present invention is not described in detail in the conventional art.
Claims (7)
1. The mechanochromic ink comprises a nano microsphere, a polymer precursor and a photoinitiator, wherein the volume ratio of the nano microsphere to the polymer precursor to the photoinitiator is (20-60): (40-80): (2-10);
The polymer precursor is selected from a mixture of diethylene glycol diethyl ether acrylate and polyethylene glycol phenyl ether acrylate; the volume ratio of the diethylene glycol diethyl ether acrylate to the polyethylene glycol phenyl ether acrylate is 1-4: 1 to 4;
The particle size of the nano microsphere is 100-900 nm;
the nano microsphere has monodispersity; the variation coefficient of the nano microsphere is less than 15%.
2. The mechanochromatic ink of claim 1 wherein the nanospheres are selected from one of silicon oxide nanospheres and derivatives thereof, polystyrene nanospheres and derivatives thereof, polymethacrylate nanospheres and derivatives thereof, polyacrylamide nanospheres, zinc oxide nanospheres, zirconium oxide nanospheres, cadmium sulfide nanospheres, iron oxide nanospheres, cerium oxide nanospheres.
3. The mechanochromatic ink of claim 1 wherein said photoinitiator is selected from one of 2-hydroxy-2-methyl-1-phenylpropion and diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphine.
4. A method of preparing a mechanochromatic ink according to any one of claims 1 to 3, said method comprising the steps of:
1) Dispersing the nano microspheres in an organic solution to prepare a dispersion liquid A;
2) Mixing a macromolecule precursor and a photoinitiator to prepare a solution B;
3) Mixing the dispersion liquid A and the solution B, and then heating to volatilize the organic solution to obtain a mixed solution C;
4) Standing the mixed solution C, and then irradiating under an ultraviolet lamp to finish solidification to obtain a target material;
In step 4), the conditions of the ultraviolet lamp curing: the power of the UV light source of the mercury lamp is 0.075J/cm 2-0.085J/cm2, and the curing time is 0.05-0.1s.
5. The method for preparing a mechanochromatic ink of claim 4 wherein in step 1), the volume ratio of said nanomicrospheres to organic solvent is 1-2: 1, a step of;
In step 1), the organic solvent is selected from ethanol, propanol and butanol;
in the step 3), the volume ratio of the dispersion liquid A to the solution B is 3-5: 7-8.
6. A method of changing colour of a mechanochromatic ink according to any one of claims 1 to 3, said method comprising: a) The structural color of the front-side observation electrochromic ink can see all spectrum single colors from red, green to blue, and the inclined observation can see the color blue shift phenomenon;
b) Under the action of an external force of less than or equal to 0.4 newton, the structural color of the mechanochromatic ink can be red-shifted or blue-shifted, wherein the time required for changing and recovering the structural color is less than 0.1 second; the change in structural color and the restoration to one process can be repeated more than 1000 times.
7. Use of a mechanochromatic ink according to any one of claims 1 to 3 in security labels.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101627339A (en) * | 2007-06-18 | 2010-01-13 | 旭化成电子材料株式会社 | Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate |
| KR20230033409A (en) * | 2021-09-01 | 2023-03-08 | 한국과학기술원 | Ink composition for direct writing of structure color structure and method for manufacturing structure color structure using same |
| CN115926774A (en) * | 2022-11-03 | 2023-04-07 | 广东工业大学 | Force-induced color-changing photonic crystal and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101627339A (en) * | 2007-06-18 | 2010-01-13 | 旭化成电子材料株式会社 | Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate |
| KR20230033409A (en) * | 2021-09-01 | 2023-03-08 | 한국과학기술원 | Ink composition for direct writing of structure color structure and method for manufacturing structure color structure using same |
| CN115926774A (en) * | 2022-11-03 | 2023-04-07 | 广东工业大学 | Force-induced color-changing photonic crystal and preparation method and application thereof |
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