CN105693903B - A kind of preparation method based on photonic crystal structure color security pattern - Google Patents
A kind of preparation method based on photonic crystal structure color security pattern Download PDFInfo
- Publication number
- CN105693903B CN105693903B CN201610074370.9A CN201610074370A CN105693903B CN 105693903 B CN105693903 B CN 105693903B CN 201610074370 A CN201610074370 A CN 201610074370A CN 105693903 B CN105693903 B CN 105693903B
- Authority
- CN
- China
- Prior art keywords
- photonic crystal
- crystal structure
- security pattern
- preparation
- method based
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000011807 nanoball Substances 0.000 claims abstract description 18
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000008859 change Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 10
- 239000002390 adhesive tape Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 trihydroxy methyl Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/14—Esters having no free carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polarising Elements (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The present invention relates to a kind of preparation method based on photonic crystal structure color security pattern, including：At room temperature, acetone, hydrogen peroxide and ferrocene are mixed, the 72h of hydro-thermal reaction 60 at 200 220 DEG C is cooled down, and is centrifuged, washing obtains Fe3O4/ C nano ball；By Fe3O4/ C nano ball is scattered in a solvent, obtains dispersion liquid；Dispersion liquid is mixed with ETPTA, heating removes solvent, add HMPP, obtain mixed liquor；Mixed liquor is filled to slide space, target pattern is placed on slide, solidifies under ultraviolet light, produces.Structure colored pattern prepared by the present invention can change colour under additional magnetic fields and color has dependence of angle, remove after external magnetic field, and pattern color disappears；The security pattern has the characteristics of being difficult imitated, and can realize antiforge function on the premise of without using complex instrument equipment, has important application value in the anti-counterfeit field of product.
Description
Technical field
It is more particularly to a kind of based on photonic crystal structure color security pattern the invention belongs to the preparation field of security pattern
Preparation method.
Background technology
With the rapid development of economy, commodity on the market are a feast for the eyes, some counterfeit and shoddy goods are also following.Its
Real regular brand and personation are distinguishing, but the packaging of commodity is the same on the surface, so consumer is very
Difficulty is distinguished.Although part commodity employ anti-counterfeiting mark, however as the lifting of imitated means, anti-counterfeiting mark increasingly holds
Easily being imitated, therefore how to prepare anti-fake material that is a kind of simple and being difficult to be imitated turns into a very promising problem.
Many materials in the Nature, can show unique gorgeous color, this dependence light and body surface periodicity
The interaction of nanostructured and the color produced, are referred to as " schemochrome ", and this surface texture is referred to as " photonic crystal ".
For example, the gorgeous color of native protein stone is precisely due to there is photon crystal structure in itself.Opal is by many small crystal
Composition, crystal different orientation can reflect the light of different frequency, just generate different colours.Photon crystal structure is one kind by difference
The periodic structure that the dielectric material of dielectric constant is formed in one-dimensional, two and three dimensions space, and the generation of schemochrome be by
In the presence of Light in Photonic Crystal forbidden band.When the scope of band gap falls in visible-range (380-780nm), specific frequency
Visible ray can not pass through the crystal.These light that can not be propagated will be reflected by photonic crystal, in the crystalline substance with periodic structure
Body surface face forms coherent diffraction.The light of these very narrow-bands is perceived by eyes, just produces gorgeous color.This color be by
It is one kind that physics adds lustre in formed by the special structure of photonic crystal.Therefore, if the structure of photonic crystal in itself not by
To destruction, color would not disappear.In addition, this schemochrome also has certain dependence to the angle of observation, from different perspectives
Photonic crystal is observed, we can be appreciated that different colors, and this provides a good application field for photonic crystal, i.e., false proof
Field.There is the characteristics of being difficult to be imitated and have dependence of angle based on photon crystal structure, photon crystal structure system is utilized
Standby anti-fake material undoubtedly turns into a very valuable research direction.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation side based on photonic crystal structure color security pattern
Method, this method is simple and easy to apply, has important value to the preparation of photonic crystal structure color anti-fake material.
A kind of preparation method based on photonic crystal structure color security pattern of the present invention, including：
(1) at room temperature, acetone, hydrogen peroxide and ferrocene are mixed, hydro-thermal reaction 60-72h at 200-220 DEG C, cooling, from
The heart, washing, obtains Fe3O4/ C nano ball；Wherein, the ratio of ferrocene and hydrogen peroxide is 0.10~0.15g：1~2ml；Acetone and
The volume ratio of hydrogen peroxide is 16：1-30：1；
(2) by the Fe in step (1)3O4/ C nano ball is scattered in a solvent, obtains dispersion liquid；By dispersion liquid and ethyoxyl
Change trimethylolpropane trimethacrylate ETPTA mixing, heating removes solvent, adds 2- hydroxy-2-methyl propiophenone HMPP, obtains
To mixed liquor；Wherein, dispersion liquid and ETPTA volume ratio are 1:4-1:1, HMPP and ETPTA volume ratio is 1:200-1:
150；
(3) mixed liquor in step (2) is filled to slide space, target pattern is placed on slide, ultraviolet light
Lower solidification, obtains being based on photonic crystal structure color security pattern.
Reaction is carried out in water heating kettle in the step (1), and the volume of water heating kettle is 50mL, and acetone volume is hydro-thermal kettle
Long-pending 3/5-4/5.
Centrifugation rate is 9000-11000rpm in the step (1)；Wash and washed for ethanol, washing times are 3-5 times.
Fe in the step (1)3O4The particle diameter of/C nano ball is 180-200nm.
Solvent is ethanol in the step (2).
Heating-up temperature is 40-70 DEG C in the step (2).
The concentration of dispersion liquid is 10-20mg/mL in the step (2).
Slide space is the slide space that adhesive tape is separated in the step (3)；Wherein, the thickness of the adhesive tape used for
50-150μm。
The a length of 250-350nm of ultraviolet light wave in the step (3), solidification temperature is 30-40 DEG C.
The present invention is raw material by using ferrocene, acetone, hydrogen peroxide, and four oxygen of carbon coating are prepared by hydro-thermal reaction
Change three-iron (Fe3O4/ C) colloid micro ball, and distribute it to dispersion liquid is formed in ethanol, then by dispersion liquid and ethoxylation three
Hydroxymethyl-propane triacrylate (ETPTA) is sufficiently mixed, at a certain temperature heating remove dispersion liquid, add 2- hydroxyls-
2- methyl phenyl ketones (HMPP) obtain mixed liquor；Mixed liquor is filled into the slide space separated by certain thickness adhesive tape,
Then the pattern being pre-designed is placed on above slide, under ultraviolet light solidified mixed liquor, obtained being based on photonic crystal
Schemochrome security pattern.
The present invention is mixed by preparing the uniform magnetic colloid microballoon of pattern with high polymer monomer and initiator, using ultraviolet
Photocuring technology, changes external magnetic field condition, designs and prepare the security pattern with photon crystal structure.
The preparation method based on photonic crystal structure color security pattern of the present invention, by by photonic crystal structure color angle
The characteristic such as degree dependence, high saturation, will never fade reaches false proof effect.
Structure colored pattern prepared by the present invention can change colour under additional magnetic fields and color has dependence of angle,
Remove after external magnetic field, pattern color disappears；The security pattern has the characteristics of being difficult imitated, and can be without using complexity
Antiforge function is realized on the premise of instrument and equipment, there is important application value in the anti-counterfeit field of product.
Beneficial effect
(1) the inventive method is simple and easy to apply, has important reference value to preparing antifalse material；
(2) security pattern with photonic crystal structure color prepared by the present invention, only needs one block of magnet with regard to that can reach inspection
The purpose of survey, economizes on resources；
(3) security pattern with photonic crystal structure color prepared by the present invention, can be allowed to by changing model shape
With different profiles and pattern；
(4) security pattern with photonic crystal structure color prepared by the present invention, by its internal structure in extraneous magnetic
Special photon crystal structure is formed under field action and is developed the color, with dependence of angle, high saturation, will never fade characteristic；
(5) security pattern with photonic crystal structure color prepared by the present invention, can be by the colour developing of internal structure
False proof purpose is reached, there is important application in the anti-counterfeit field of product.
Brief description of the drawings
Fig. 1 is Fe in embodiment 13O4The TEM figures of/C nano ball；
Fig. 2 is Fe in embodiment 23O4The XRD of/C nano ball；
Fig. 3 is the display figure under magnetic field based on photonic crystal structure color security pattern in embodiment 2；A is that pattern exists
There is no the picture under magnetic fields, b is colour developing figure of the pattern under magnetic fields；
Fig. 4 is the preparation flow figure based on photonic crystal structure color security pattern in the present invention；
Fig. 5 is the number of security pattern color change under different viewing angles of photonic crystal structure color in embodiment 3
Photo figure；A, b and c are respectively the design sketch that viewing angle is sequentially reduced.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
At room temperature, 40mL acetone, 2.5mL hydrogen peroxide are measured, 0.30g ferrocene is weighed, is placed in beaker, it is fully mixed
After conjunction, reaction solution is put into reactor, being 220 DEG C in temperature reacts 60 hours, after the completion of reaction, naturally cools to room
Temperature, product is centrifuged under conditions of centrifugation rate is 9000rpm, and is washed 3 times using ethanol, obtains Fe3O4/ C receives
Rice ball.Fig. 1 is the Fe prepared3O4The TEM pictures of/C nano ball.Then by Fe3O4/ C nano ball is scattered in ethanol solution, is made
Its concentration in dispersion liquid is 10mg/mL；Measure the above-mentioned dispersion liquids of 2mL and the propylene of 2mL ethoxylated trimethylolpropanes three
Acid esters (ETPTA) is sufficiently mixed, and is removed ethanol in 70 DEG C of heating evaporations, is obtained Fe3O4The ETPTA mixed liquors of/C nano ball, then
Add 10 μ L 2- hydroxy-2-methyls propiophenones (HMPP), after being sufficiently mixed, by mixed liquor be transferred to by 50 μ m thick adhesive tapes every
In the slide space opened, then the pattern being pre-designed is placed on above slide, is 40 DEG C in solidification temperature, 250nm is purple
Mixed liquor is solidified under outer light, has obtained a kind of based on photonic crystal structure color security pattern.
Embodiment 2
At room temperature, 35mL acetone, 2.0mL hydrogen peroxide are measured, 0.25g ferrocene is weighed, is placed in beaker, it is fully mixed
After conjunction, reaction solution is put into reactor, being 210 DEG C in temperature reacts 66 hours, after the completion of reaction, naturally cools to room
Temperature, product is centrifuged under conditions of centrifugation rate is 10000rpm, and is washed 4 times using ethanol, obtains Fe3O4/C
Nanosphere.Fig. 2 is the Fe prepared3O4The XRD piece of/C nano ball, can be found that obvious C peak from XRD, with reference to
TEM figures in Fig. 1, the composition for illustrating the nanosphere is the Fe coated by C3O4.Then by Fe3O4/ C nano ball is scattered in ethanol
In solution, it is 15mg/mL to make its concentration in dispersion liquid；Measure the above-mentioned dispersion liquids of 1mL and 2mL ethoxylations trihydroxy methyl third
Alkane triacrylate (ETPTA) is sufficiently mixed, and is removed ethanol in 60 DEG C of heating evaporations, is obtained Fe3O4The ETPTA of/C nano ball is mixed
Liquid is closed, 15 μ L 2- hydroxy-2-methyls propiophenones (HMPP) is then added, after being sufficiently mixed, mixed liquor is transferred to by 100 μm
In the slide space that thickness adhesive tape is separated, then the pattern being pre-designed is placed on above slide, is 35 in solidification temperature
DEG C, mixed liquor is solidified under 300nm ultraviolet lights, has obtained a kind of based on photonic crystal structure color security pattern, as shown in figure 3,
The pattern can under magnetic field (0.10~0.50mT) display color；Wherein, a is picture of the pattern under without magnetic field, and b is figure
Colour developing figure of the case under magnetic fields, Fig. 4 is the flow chart for preparing the security pattern.
Embodiment 3
At room temperature, 30mL acetone, 1.5mL hydrogen peroxide are measured, 0.20g ferrocene is weighed, is placed in beaker, it is fully mixed
After conjunction, reaction solution is put into reactor, being 200 DEG C in temperature reacts 72 hours, after the completion of reaction, naturally cools to room
Temperature, product is centrifuged under conditions of centrifugation rate is 11000rpm, and is washed 5 times using ethanol, obtains Fe3O4/C
Nanosphere.Then by Fe3O4/ C nano ball is scattered in ethanol solution, and it is 20mg/mL to make its concentration in dispersion liquid；Measure
The above-mentioned dispersion liquids of 1mL are sufficiently mixed with 3mL ethoxylated trimethylolpropane triacrylates (ETPTA), are steamed in 50 DEG C of heating
Hair removes ethanol, obtains Fe3O4The ETPTA mixed liquors of/C nano ball, then add 20 μ L 2- hydroxy-2-methyl propiophenones
(HMPP) after, being sufficiently mixed, mixed liquor is transferred in the slide space separated by 150 μ m thick adhesive tapes, then will be advance
The pattern of design is placed on above slide, is solidified mixed liquor in the case where solidification temperature is 30 DEG C, 350nm ultraviolet lights, has been obtained one
Plant and be based on photonic crystal structure color security pattern.Fig. 5 (a, b and c are respectively the design sketch that viewing angle is sequentially reduced) is the figure
Digital photograph when case is observed under different angles, it is found that with the reduction of viewing angle, the color of picture there occurs indigo plant
Move.
Claims (7)
1. a kind of preparation method based on photonic crystal structure color security pattern, including：
(1) at room temperature, acetone, hydrogen peroxide and ferrocene are mixed, hydro-thermal reaction 60-72h at 200-220 DEG C is cooled down, centrifugation,
Washing, obtains Fe3O4/ C nano ball；Wherein, the ratio of ferrocene and hydrogen peroxide is 0.10~0.15g：1~2ml；Acetone and double
The volume ratio of oxygen water is 16：1-30：1；Centrifugation rate is 9000-11000rpm wherein in step (1)；Wash and washed for ethanol,
Washing times are 3-5 times；
(2) by the Fe in step (1)3O4/ C nano ball is scattered in a solvent, obtains dispersion liquid；By dispersion liquid and ethoxylation three
Hydroxymethyl-propane triacrylate ETPTA is mixed, and heating removes solvent, is added 2- hydroxy-2-methyl propiophenone HMPP, is mixed
Close liquid；Wherein, dispersion liquid and ETPTA volume ratio are 1:4-1:1, HMPP and ETPTA volume ratio is 1:200-1:150；
(3) mixed liquor in step (2) is filled to slide space, target pattern is placed on slide, it is solid under ultraviolet light
Change, obtain being based on photonic crystal structure color security pattern.
2. a kind of preparation method based on photonic crystal structure color security pattern according to claim 1, it is characterised in that
Fe in the step (1)3O4The particle diameter of/C nano ball is 180-200nm.
3. a kind of preparation method based on photonic crystal structure color security pattern according to claim 1, it is characterised in that
Solvent is ethanol in the step (2).
4. a kind of preparation method based on photonic crystal structure color security pattern according to claim 1, it is characterised in that
The concentration of dispersion liquid is 10-20mg/mL in the step (2).
5. a kind of preparation method based on photonic crystal structure color security pattern according to claim 1, it is characterised in that
Heating-up temperature is 40-70 DEG C in the step (2).
6. a kind of preparation method based on photonic crystal structure color security pattern according to claim 1, it is characterised in that
Slide space is the slide space that adhesive tape is separated in the step (3).
7. a kind of preparation method based on Opto-Electronics Crystals schemochrome security pattern according to claim 1, its feature exists
In a length of 250-350nm of ultraviolet light wave in the step (3), solidification temperature is 30-40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610074370.9A CN105693903B (en) | 2016-02-02 | 2016-02-02 | A kind of preparation method based on photonic crystal structure color security pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610074370.9A CN105693903B (en) | 2016-02-02 | 2016-02-02 | A kind of preparation method based on photonic crystal structure color security pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105693903A CN105693903A (en) | 2016-06-22 |
| CN105693903B true CN105693903B (en) | 2017-10-24 |
Family
ID=56230253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610074370.9A Active CN105693903B (en) | 2016-02-02 | 2016-02-02 | A kind of preparation method based on photonic crystal structure color security pattern |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693903B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106244076B (en) * | 2016-07-28 | 2019-03-01 | 北京化工大学 | The fixing means of pattern in a kind of magnetic field |
| CN109370263B (en) * | 2018-11-13 | 2021-03-23 | 天津科技大学 | Preparation method of full-color structure-changeable chromogenic material |
| CN113105769B (en) * | 2021-04-09 | 2022-07-22 | 哈尔滨工业大学（深圳） | Coatable structural color slurry and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050124712A1 (en) * | 2003-12-05 | 2005-06-09 | 3M Innovative Properties Company | Process for producing photonic crystals |
| CN101794652B (en) * | 2010-03-10 | 2012-05-09 | 中国科学技术大学 | Method for preparing carbon-coated superparamagnetic ferroferric colloidal spheres |
| CN102304263B (en) * | 2011-07-14 | 2013-05-29 | 中国科学技术大学 | Photonic crystal paper and preparation method thereof |
| CN102708773A (en) * | 2012-06-26 | 2012-10-03 | 中国科学技术大学 | Magnetic response photonic crystal anti-fake label and manufacturing method thereof |
| CN103303013B (en) * | 2013-06-06 | 2016-03-02 | 中国科学技术大学 | A kind of invisible photonic crystal Method of printing |
| CN103802315B (en) * | 2013-12-31 | 2017-04-26 | 中国科学院深圳先进技术研究院 | Method for preparing photonic crystals through 3D (Three-Dimensional) printing |
| CN105017863B (en) * | 2015-07-01 | 2017-08-11 | 苏州中科纳福材料科技有限公司 | Water-based ink, its preparation method and printed matter |
| CN104961906B (en) * | 2015-07-03 | 2017-11-10 | 华中科技大学 | A kind of photonic crystal hydrogel thin film, its preparation method and application for having pH value and ionic strength response concurrently |
-
2016
- 2016-02-02 CN CN201610074370.9A patent/CN105693903B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105693903A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Self-assembly of silica colloidal crystal thin films with tuneable structural colours over a wide visible spectrum | |
| JP6739071B2 (en) | Membranes and articles containing core-shell particles | |
| Shang et al. | Fabrication of magnetic field induced structural colored films with tunable colors and its application on security materials | |
| Chu et al. | Hollow silica opals/cellulose acetate nanocomposite films with structural colors for anti-counterfeiting of banknotes | |
| CN105693903B (en) | A kind of preparation method based on photonic crystal structure color security pattern | |
| Shang et al. | Facile fabrication of a magnetically induced structurally colored fiber and its strain-responsive properties | |
| Cong et al. | Preparation of iridescent colloidal crystal coatings with variable structural colors | |
| Zhou et al. | Fast water-response double-inverse opal films with brilliant structural color | |
| CN103173039B (en) | Method for preparing structural color material without angle dependency | |
| Li et al. | Synthesis of strawberry-like Fe3O4@ SiO2@ Ag composite colloidal particles for constructing responsive photonic crystals | |
| Tang et al. | Heat-resistant PMMA photonic crystal films with bright structural color | |
| Dong et al. | Bio-inspired non-iridescent structural coloration enabled by self-assembled cellulose nanocrystal composite films with balanced ordered/disordered arrays | |
| CN105177714A (en) | Morphology-controllable and color angle-independent photonic crystal particle and preparation method thereof | |
| Li et al. | Noniridescent structural color from enhanced electromagnetic resonances of particle aggregations and its applications for reconfigurable patterns | |
| Li et al. | A facile two-step approach to synthesize monodisperse and high-magnetization Fe3O4@ PS composite colloidal particles for constructing dual-response photonic crystals | |
| CN104698536B (en) | A kind of optical functional materialses and its preparation and application with gloss and form and aspect | |
| Liu et al. | Preparation of carbon fiber substrates with structural colors based on photonic crystals | |
| Liu et al. | Controllable in situ generated carbon black hollow silica (C@ h-SiO2) photonic crystal inks with highly saturated structural colors | |
| Chai et al. | Preparation of disperse dye@ P (St-BA-MAA) microsphere inks and their application on white textile substrates with high color saturation | |
| Zhu et al. | Bioinspired fabrication of noniridescent structurally colored cotton fabric based on polystyrene@ polycaffeic acid particles | |
| Zhou et al. | Hollow mesoporous cubic silica self-assembling into photonic crystals with rhombohedral lattices and vivid structural colors for anti-counterfeiting | |
| Lu et al. | Highly charged, magnetically sensitive magnetite/polystyrene colloids: synthesis and tunable optical properties | |
| Xinyang et al. | Efficient preparation of liquid photonic crystals and their application in bionic structural coloration of textiles | |
| Li et al. | Preparation of robust fully encapsulated structural color fabrics and their application to display | |
| Ma et al. | Eccentric 1-D magnetic core–shell photonic crystal balls: ingenious fabrication and distinctive optical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |