CN116790151A - Photonic crystal intelligent ink capable of being crosslinked at room temperature and preparation method and application thereof - Google Patents
Photonic crystal intelligent ink capable of being crosslinked at room temperature and preparation method and application thereof Download PDFInfo
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- CN116790151A CN116790151A CN202211129864.4A CN202211129864A CN116790151A CN 116790151 A CN116790151 A CN 116790151A CN 202211129864 A CN202211129864 A CN 202211129864A CN 116790151 A CN116790151 A CN 116790151A
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- room temperature
- photonic crystal
- aqueous solution
- particles
- crystal ink
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- 239000004038 photonic crystal Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 12
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 206010063385 Intellectualisation Diseases 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000000059 patterning Methods 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000010382 chemical cross-linking Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract 6
- 239000011248 coating agent Substances 0.000 abstract 3
- 238000000576 coating method Methods 0.000 abstract 3
- 125000000468 ketone group Chemical group 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 150000007857 hydrazones Chemical class 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 35
- 238000001228 spectrum Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229920006275 Ketone-based polymer Polymers 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000001038 titanium pigment 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
- C09D11/02—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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
Landscapes
- 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 provides a preparation method and application of photonic crystal ink capable of being crosslinked at room temperature, which utilizes diacetone acrylamide and styrene to carry out copolymerization so that the surface of colloid particles is provided with rich ketone groups, uses triethylamine to adjust emulsion to be weakly alkaline, uses adipic acid dihydrazide as a curing agent, and carries out crosslinking reaction with the ketone groups to generate hydrazone along with volatilization of the triethylamine in the drying process at room temperature, so that the colloid particles are subjected to chemical crosslinking reaction, and finally the particles are fixed through chemical crosslinking. The obtained coating has bright structural color and good adhesive force on paper, and the structural color of a coating film can be changed by adjusting the water content in the coating, so that a new strategy is provided for the development of novel environment-friendly intelligent ink.
Description
Technical Field
The invention relates to the technical field of photonic crystals, in particular to a method for constructing photonic crystal ink capable of being crosslinked at room temperature based on ketone polymer colloid nano particles and application thereof.
Background
The ink is an important material in the printing process, is a main substance for printing characters, pictures and the like, and generally consists of a film forming substance, carbon black, titanium pigment and various small molecular organic dyes. The photonic crystal has wider color gamut and saturation than the traditional dye due to the unique periodic dielectric structure, and is hopeful to become a substitute of the next generation novel environment-friendly pigment.
However, the weak interfacial forces between conventional organic/inorganic nanoparticles make them extremely challenging to self-assemble into large area structural color supports. The method for improving the interfacial force of colloidal particles is mainly realized by filling elastic polymer matrix in the gaps between particles or adjusting the glass transition temperature of polymer particles to enable partial fusion between particles.
Disclosure of Invention
The invention aims to provide photonic crystal ink capable of being crosslinked at room temperature and application thereof, aiming at the defects that the traditional ink has certain pollution to the environment and is easy to photobleaching to cause the loss of text or pattern information with the passage of time.
Another object of the present invention is to provide a method for preparing the photonic crystal ink.
The aim of the invention is achieved by the following technical scheme.
A photonic crystal ink capable of being crosslinked at room temperature is prepared by adding carbon black and adipic dihydrazide into diacetone acrylamide and styrene copolymer nano particles.
The concentration of the nanoparticle emulsion is 30-40 wt%, preferably 40wt%.
The photonic crystal ink capable of being crosslinked at room temperature, wherein the concentration of the added carbon black is 0.1 weight percent.
The room temperature cross-linkable photonic crystal ink comprises adipic acid dihydrazide and diacetone acrylamide, wherein the molar ratio of the adipic acid dihydrazide to the diacetone acrylamide is 0.5-2, preferably 1.
The preparation method of the photonic crystal ink constructed by the ketone-based polymer colloid nano particles and capable of being crosslinked at room temperature comprises the following steps:
step 1, adding a certain amount of diacetone acrylamide and styrene into a round bottom three-neck flask filled with 100mL of ultrapure water, adding a certain amount of SDS at a stirring speed of 300rpm, and pre-emulsifying for 30min at 50 ℃, and continuously introducing nitrogen in the process to remove oxygen in the system so as to prevent oxygen polymerization inhibition;
step 2: the temperature of the system is raised to 70 ℃ and 10mL of potassium persulfate aqueous solution (the mass fraction is 10 wt%) is added to initiate free radical polymerization, when the system gradually shows blue fluorescence, the timing is started, and the whole polymerization process lasts for 6 hours;
step 3: after polymerization is completed, residual monomers and oligomers are removed by centrifugal washing, and the purified product is prepared into a required concentration for standby;
step 4: adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution, performing ultrasonic dispersion for 30min to uniformly disperse the centrifugally agglomerated nano particles in the aqueous solution again, adding carbon black into the system to uniformly disperse, adding adipic acid dihydrazide, and adjusting the pH value of the system to be alkalescent (7.5) by using ammonia water to prepare the intelligent ink.
The room temperature cross-linkable photonic crystal ink constructed by the ketone-based polymer colloid nano particles is applied to patterning, intellectualization and anti-counterfeiting.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the photonic crystal ink capable of being crosslinked at room temperature has the characteristic of photonic crystals, does not have the bleaching phenomenon compared with the traditional ink, and is environment-friendly because the dispersion medium is water.
2. According to the photonic crystal ink capable of being crosslinked at room temperature, the particles are fixed by utilizing chemical crosslinking reaction among the colloid particles, and the obtained ink has a bright structural color and has good adhesive force on paper.
3. The photonic crystal ink capable of being crosslinked at room temperature has long-range order microstructure after being dried and cured into a film, has angle dependence on structural color, has certain absorption and swelling characteristics on water due to the hydrophilicity of the prepared colloid nano particles, and has wide application prospect in the fields of anti-counterfeiting and intelligent ink based on the performances of the two aspects.
Drawings
FIG. 1 is an optical photograph of a smart ink configured with nanoparticles of different particle sizes and a corresponding reflectance spectrum;
wherein a is an optical photograph of the ink and b is a reflection spectrum of the ink
FIG. 2 is an SEM image of an array of colloidal particles before and after cross-linking;
wherein a is an SEM image of the colloidal particle array before crosslinking, and b is an SEM image of the colloidal particle array after crosslinking.
FIG. 3 is a graph of patterns drawn by inks constructed with different particle sizes and reflection spectra corresponding to each part;
wherein the graph a is a pattern drawn by ink, and the graph b is a reflection spectrum corresponding to each part.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Preparing precursor colloid particles: 1g of diacetone acrylamide and 6g of styrene were charged into a round-bottom three-necked flask equipped with 100mL of ultrapure water, 0.02g of sodium dodecyl sulfate was added at a stirring rate of 300rpm and pre-emulsified at 50℃for 30 minutes, during which nitrogen was continuously introduced to exclude oxygen in the system to prevent oxygen from blocking polymerization, then the temperature of the system was raised to 70℃and 10mL of aqueous potassium persulfate solution (mass fraction: 10 wt%) was added to initiate radical polymerization, and when the system gradually developed blue fluorescence, the whole polymerization process was continued for 6 hours. The particle size was 217nm after completion of the polymerization, followed by three centrifugal washes to remove the remaining monomers and oligomers.
(2) Adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution with the mass fraction of 40%, dispersing the centrifugally agglomerated nano particles in the aqueous solution again by ultrasonic dispersion for 30min, adding 0.1wt% of carbon black into the system to disperse uniformly, adding 1g of adipic dihydrazide, and regulating the pH value of the system to be alkalescent (7.5) by ammonia water to obtain the intelligent ink.
(3) FIG. 1 is an optical photograph of the obtained smart ink and a reflection spectrum thereof. As can be seen from the figure, the ink made of 217nm colloidal particles had a reflection peak at 483nm and exhibited a blue-green color.
Example 2
(1) Preparing precursor colloid particles: 1g of diacetone acrylamide and 6g of styrene were charged into a round-bottom three-necked flask equipped with 100mL of ultrapure water, 0.015g of sodium dodecyl sulfate was added at a stirring rate of 300rpm and pre-emulsified at 50℃for 30 minutes, during which nitrogen was continuously introduced to exclude oxygen in the system to prevent oxygen from blocking polymerization, then the temperature of the system was raised to 70℃and 10mL of aqueous potassium persulfate solution (mass fraction: 10 wt%) was added to initiate radical polymerization, and when the system gradually developed blue fluorescence, the whole polymerization process was continued for 6 hours. The particle size was 238nm after completion of the polymerization, followed by three centrifugal washes to remove the remaining monomers and oligomers.
(2) Adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution with the mass fraction of 40%, dispersing the centrifugally agglomerated nano particles in the aqueous solution again by ultrasonic dispersion for 30min, adding 0.1wt% of carbon black into the system to disperse uniformly, adding 1g of adipic dihydrazide, and regulating the pH value of the system to be alkalescent (7.5) by ammonia water to obtain the intelligent ink.
(3) FIG. 1 is an optical photograph of the obtained smart ink and a reflection spectrum thereof. As can be seen from the figure, the ink made of 238nm colloidal particles has a reflection peak at 531nm and exhibits a green color.
Example 3
(1) Preparing precursor colloid particles: 1g of diacetone acrylamide and 6g of styrene were charged into a round-bottom three-necked flask equipped with 100mL of ultrapure water, 0.007g of sodium dodecyl sulfate was added at a stirring rate of 300rpm and pre-emulsified at 50℃for 30 minutes, during which nitrogen was continuously introduced to exclude oxygen in the system to prevent oxygen inhibition, then the temperature of the system was raised to 70℃and 10mL of aqueous potassium persulfate solution (mass fraction: 10 wt%) was added to initiate radical polymerization, and when the system gradually developed blue fluorescence, the whole polymerization process was continued for 6 hours. The particle size was 250nm after completion of the polymerization, followed by three centrifugal washes to remove the remaining monomers and oligomers.
(2) Adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution with the mass fraction of 40%, dispersing the centrifugally agglomerated nano particles in the aqueous solution again by ultrasonic dispersion for 30min, adding 0.1wt% of carbon black into the system to disperse uniformly, adding 1g of adipic dihydrazide, and regulating the pH value of the system to be alkalescent (7.5) by ammonia water to obtain the intelligent ink.
(3) FIG. 1 is an optical photograph of the obtained smart ink and a reflection spectrum thereof. As can be seen from the figure, the ink made of 250nm colloidal particles has a reflection peak at 579nm and exhibits a yellow color.
Example 4
(1) Preparing precursor colloid particles: 1g of diacetone acrylamide and 6g of styrene were charged into a round-bottom three-necked flask equipped with 100mL of ultrapure water, 0.006g of sodium dodecyl sulfate was added at a stirring rate of 300rpm, and pre-emulsified at 50℃for 30 minutes, during which nitrogen was continuously introduced to exclude oxygen in the system to prevent oxygen from blocking polymerization, then the temperature of the system was raised to 70℃and 10mL of aqueous potassium persulfate solution (mass fraction: 10 wt%) was added to initiate radical polymerization, and when the system gradually developed blue fluorescence, the whole polymerization process was continued for 6 hours. The particle size was 256nm after completion of the polymerization, followed by three centrifugal washes to remove the remaining monomers and oligomers.
(2) Adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution with the mass fraction of 40%, dispersing the centrifugally agglomerated nano particles in the aqueous solution again by ultrasonic dispersion for 30min, adding 0.1wt% of carbon black into the system to disperse uniformly, adding 1g of adipic dihydrazide, and regulating the pH value of the system to be alkalescent (7.5) by ammonia water to obtain the intelligent ink.
(3) FIG. 1 is an optical photograph of the obtained smart ink and a reflection spectrum thereof. As can be seen from the figure, the ink made of 256nm colloidal particles has a reflection peak at 645nm and exhibits a red color.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, but other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent in scope.
Claims (5)
1. The photonic crystal ink capable of being crosslinked at room temperature is characterized by being prepared from polymer nano particles synthesized by a free radical emulsion polymerization method of diacetone acrylamide and styrene in an aqueous solution.
The preparation method of the photonic crystal ink comprises the following steps:
step 1: adding a certain amount of diacetone acrylamide and styrene into a round bottom three-neck flask filled with 100mL of ultrapure water, adding a certain amount of SDS at a stirring speed of 300rpm, and pre-emulsifying for 30min at 50 ℃, wherein nitrogen is continuously introduced in the process to remove oxygen in the system so as to prevent oxygen polymerization inhibition;
step 2: the temperature of the system is raised to 70 ℃ and 10mL of potassium persulfate aqueous solution (the mass fraction is 10 wt%) is added to initiate free radical polymerization, when the system gradually shows blue fluorescence, the timing is started, and the whole polymerization process lasts for 6 hours;
step 3: after polymerization is completed, residual monomers and oligomers are removed by centrifugal washing, and the purified product is prepared into a required concentration for standby;
step 4: adding ultrapure water into the purified solid polymer particles to prepare an aqueous solution, performing ultrasonic dispersion for 30min to uniformly disperse the centrifugally agglomerated nano particles in the aqueous solution again, adding carbon black into the system to uniformly disperse, finally adding adipic acid dihydrazide to crosslink, and adjusting the pH value of the system to be alkalescent (7.5) by ammonia water to prepare the intelligent ink.
2. A room temperature cross-linkable photonic crystal ink according to claim 1, wherein said aqueous solution of solid polymer particles has a mass fraction of 40%.
3. A room temperature cross-linkable photonic crystal ink according to claim 1, wherein said carbon black is present in an amount of 0.1wt%.
4. A room temperature cross-linkable photonic crystal ink according to claim 1, wherein the molar ratio of adipic acid dihydrazide to diacetone acrylamide added is 1:1.
5. The use of a room temperature cross-linkable photonic crystal ink as defined in claim 1 for patterning, intellectualization and security.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211129864.4A CN116790151A (en) | 2022-09-15 | 2022-09-15 | Photonic crystal intelligent ink capable of being crosslinked at room temperature and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211129864.4A CN116790151A (en) | 2022-09-15 | 2022-09-15 | Photonic crystal intelligent ink capable of being crosslinked at room temperature and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116790151A true CN116790151A (en) | 2023-09-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211129864.4A Pending CN116790151A (en) | 2022-09-15 | 2022-09-15 | Photonic crystal intelligent ink capable of being crosslinked at room temperature and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116790151A (en) |
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2022
- 2022-09-15 CN CN202211129864.4A patent/CN116790151A/en active Pending
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