CN108287378B - Transparent composite photonic crystal material and its preparation method and application - Google Patents
Transparent composite photonic crystal material and its preparation method and application Download PDFInfo
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- CN108287378B CN108287378B CN201810008537.0A CN201810008537A CN108287378B CN 108287378 B CN108287378 B CN 108287378B CN 201810008537 A CN201810008537 A CN 201810008537A CN 108287378 B CN108287378 B CN 108287378B
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
Abstract
The invention belongs to polymer material technical field, specially transparent photonic material and its preparation method and application.The transparent photonic material of the present invention mainly includes two kinds of materials, and the particle of the first material is arranged in three-dimensional periodic structure in the matrix of second of material, and in the initial state, material is transparent；Under external incentive condition, corresponding change occurs for the refractive index of two kinds of materials, and thus material becomes have color by colorless and transparent；To provide the photon pattern of the encryption with different responses.Such as the image being encrypted on photon crystal structure or character can be shown as universal color pattern by immersing in solvent by these transparent photonic materials.The present invention also proposes application of the transparent photonic material as sensor device in safety and Application in Anti-counterfeiting field, for example it is specifically used for manufacture large-area transparent crystal film with photon, which with completely reversibility can switch between highly transparent and schemochrome state.
Description
Technical field
The invention belongs to polymer material technical fields, and in particular to transparent photonic material and its preparation method and application.
The present invention has specific but non-exclusive applicability for the material for changing color in response to environmental stimuli, such as sensing
In device and safe-guarding and anti-counterfeiting application.
Background technique
Photon crystal material with bright-coloured structure color is widespread in nature, such as the insects such as butterfly, flowers
Even natural albumen stone.On the other hand, there are also some animals, such as chameleon, certain beetles or octopuses to have the ability
The color of oneself skin is adjusted according to the environment of surrounding.
On a microscopic scale, native protein stone is made of the silica spheres that diameter is 150 to 300nm, with closely packed
The arrangement of face-centered cubic (fcc) lattice structure.Because sphere accumulates the distance between plane in the length range of visible light, according to
Bragg's equation, thus can be with the visible light of reflected wavelengths.So if white light impinges upon on opal, all face of rainbow
Color can all be reflected and be can be observed.
The albuminoid stone material of currently reported productive manpower synthesis.For example, US-A-4703020 is disclosed by making
Silica spheres are precipitated out to form this material from aqueous dispersion.Then the sediment is dried and is forged at 800 DEG C
It burns.Then, penetrate into zirconium alkoxide solution in the gap in sediment, zirconium oxide is by hydrolytic precipitation in gap.So
Material is calcined again afterwards, arranges to form three-dimensional lattice, zirconium oxide the filling structure in gap therebetween to leave silica spheres.
Albuminoid stone material is formed in this way to be time-consuming and expensive very much.Thus it is not the suitable of industrial manufacture lot of materials
Use route.
US 2004/0253443(is equal to WO03025035) disclose the molding formed by core-shell particles.Particle by
Monodispersed stone is constituted.Each particle have one around karyomorphism at shell.Core and shell have different refractive index.?
In one embodiment of this document, core is formed by crosslinked polystyrene, and shell is by polyacrylate such as poly-methyl methacrylate
Ester (PMMA) formation.In this case, core has relatively high refractive index, and shell has relatively low refractive index.It can be
Polymer interlayers are provided between core and shell, to adhere to shell on core.The particle of Core-shell Composite Particles is heated and is pressed into
Film.In this heat-press step, shell material is soft, but nuclear material is kept fixed.Karyomorphism is arranged at three-dimensional periodic grid
Column, case material become host material.Obtained material can be with reflecting rainbow color.Can by inorganic nanoparticles (such as gold
Metal nano-particle or semiconductor nanoparticle) it is introduced into the gap between core, to provide the function of enhancing for material.
US 2004/0253443 proposes the mechanism for explaining nuclear particle sequence in matrix, but clear there is no explaining completely
Chu.
US 2005/0142343(is equal to WO03064062) it provides in the disclosure similar with US 2004/0253443
Hold.But in order to improve optical effect, the contrast material of such as pigment joined in matrix.
US 2005/0228072(is equal to WO03106557) it provides in the disclosure similar with US 2004/0253443
Hold.But it is added to a kind of material in addition to control the mechanical performance of composite material.Additional material can be such as thermoplasticity
Rubber polymer etc..
WO2004096894 provides the disclosure similar with US2004/0253443, and in addition proposing will be compound
Material is extruded as sheet material and then rolls material, has obtained the schemochrome uniformly with corner effect.
Academic and industry interest concentrates on the color that surface is parallel to crystal face (<111>plane of fcc lattice), because
These planes provide the structural color most strong from polymer photon crystal.
US 2009/0012207, which is disclosed using nucleocapsid particles, forms one layer of polymeric photonic crystal.The layer is suitable for
Medical treatment or amenities.When strain, due to the variation of spacing of lattice in material, reflection colour can change.This, which thus gives, makes
User indicates when that medical treatment or hygienic articles are tight by La get Tai.A possibility that also disclosing crosslinked matrix material, such as utilize base
Crosslinking agent in matter causes cross-linking reaction by heat or photochemistry.
EP-B-2054241 discloses the manufacturing method for security fields such as banknotes, wherein polymer photon crystal film
Changed by outside stimulus (such as stretching) by security feature, shows structural color.It also proposed polymer photon in file
The localized variation of the mechanical property of crystal film.This leads to the corresponding change of the mechanical response of the different zones of film, causes film not
With the variation of the spacing of lattice between the crystal face at region.So that the office that the structural color of polymer photon crystal film responds
Portion's variation.Mechanical property can significantly be changed by changing the crosslink density in polymer photon crystal film.In EP-B-
In 2054241 alternate embodiment, by changing the local thickness of polymer photon crystal film, similar effect has been obtained
Fruit.
In response to stimulation, the changed material of optical property has related patents report.For example, WO0244728 is disclosed
Crystal colloidal array encapsulating is in the polymer matrix.This material can respond temperature change or ring to the stress of application
Answer and cause the variation of its photon band gap.
US2003122112 proposes the disclosure similar to WO0244728, but concentrates on to polymer substrate packet
The composite material of the colloidal crystal particle buried applies the effect of stress.
WO2009050448, which is disclosed, uses photonic material as security devices, and especially as tool, there are two photonic crystals
The antifalsification label of structure, with different optical characteristics.
WO2008017869 provides the disclosure similar with WO2009050448, and difference is photonic crystal antifake device
Part has different responses to different directions incident light.WO08017864 provides the disclosure similar with WO2009050448,
The difference is that safety device generates two kinds of optically different effects according to outside stimulus.
WO2009042207, which is disclosed, uses photonic crystal as temperature sensor.The photonic crystal is by diblock copolymer
Thin slice formed.Therefore only one dimension of photonic crystal is periodic.Spacing between thin slice is influenced by outside stimulus,
Such as a part can selective absorbing water in diblock copolymer.
US6950584 discloses the formation with One Dimension Periodic material, such as the SiO of suitable thickness2And TiO2Layer can make
Obtain the light that material is not through certain specific wavelengths.
US2008095664, which is disclosed, uses colloidal crystal as vapor sensing device.
US6847477 discloses using sequence colloidal crystal the wavelength for changing incident light, and by comparing inputting and defeated
Optical signals obtain temperature or strain signal.
WO0021905 discloses the material being self-assembly of by spheric granules three dimensional periodic structure.Color change
It can be adjusted by the refraction index of material component or the variation of periodic structure lattice parameter is adjusted.
WO0073795 is disclosed for detection such as temperature, electrochemical conditions (including pH and ion concentration), biological antigens,
Radiation level is applied to the sensor of the variation of the conditions such as electric field and the pressure of sensor.Sensor material is scattered by incorporation light
The evenly dispersed matrix of element is formed.But light-scattering component is not periodic arrangement.
WO0126611 discloses a kind of dental composite, and it includes the translucent fillers of dispersed phase and enhancing.About body
The size of the filler particles of fraction 25-80% is range from about 0.2 μm to about 0.6 μm.The composite material has self-optimization
Performance.The refractive index of resin and translucent filler is identical substantially similar, such as in the range of 1.45-1.60.
WO0021905 discloses the material being self-assembly of by spheric granules three dimensional periodic structure.Color change
It can be adjusted by the refraction index of material component or the variation of periodic structure lattice parameter is adjusted.
Summary of the invention
It can be realized the purpose of the present invention is to provide one kind by stimulation and generate from initial high transparency state and schemochrome
The composite photonic crystal material and its preparation method and application of visible change between state.
Composite photonic crystal material provided by the invention includes mainly two kinds of materials, and the particle of the first material is second
It is arranged in three-dimensional periodic structure in the matrix of kind material, in the initial state, the refractive index of first and second kinds of materials is the same
, material is transparent；Under external incentive condition, the refractive index n of the first material1And/or the refractive index n of second of material2Hair
Raw corresponding change, but the refractive index of two kinds of materials is different to the response of stimulation, to possess different refractive index, thus material
Become have color by colorless and transparent.
For example, composite photonic crystal material provided by the invention, when watching under the conditions of natural light, material is in environmental stimuli
Under, the visible change from colorless and transparent to coloured occurs.
Composite photonic crystal material provided by the invention, the typically grain shape of core-shell structure, i.e., each particle packet
Core and the shell around the core are included, also, core three-dimensional periodic in the host material that shell is formed arranges；Nuclear material
The refraction index of (the first material) is n1, the refraction index of shell material (second of material) is n2, the material can be by outer
Portion's stimulation is responded to provide the optical effect of the three-dimensional periodic arrangement based on particle；For example, under external stimulation, n1
And/or n2Generation corresponding change, so that material color be made to change.
First feature of the invention is that photon crystal material is formed by two different Material claddings, and refraction index is
n1Particle in three-dimensional space periodic arrangement refraction index be n2Host material in, in the initial state, first and
The refractive index of two kinds of materials be it is the same, material be it is transparent；
Second feature of the invention is to constitute photon crystal material to have color change effect under extraneous stimulation
It answers, i.e., under environmental stimuli, n1And/or n2Corresponding change occurs, the refractive index of two kinds of materials is not identical, by original colourless
It is bright to become coloured.
In the present invention, the shape of the nuclear particle is spherical or substantially spherical.
In order to obtain ideal optical effect, nuclear particle has the average grain diameter of 5nm to 2000nm, it is desirable that nuclear particle
Average grain diameter with 50-500nm, it is more desirable that nuclear particle has the average grain diameter of 100-500nm.Further it is more desirable that
Nuclear particle has at least average grain diameter of 150nm.Nuclear particle can have at most 400nm, or an at most 300nm, or at most 250nm
Average grain diameter.
In the present invention, nuclear particle (i.e. the first material) is distributed with monodispersed size, for example, standard deviation is 20%
Or hereinafter, more preferably 10% hereinafter, further preferably is 5% or less.
In the present invention, nuclear particle is scattered in host material in a manner of closely packed three-dimensional lattice.Specifically, nuclear particle
It is placed in host material in the form of face-centered cubic lattice.Ideally (111) plane of lattice, which is substantially perpendicular to, is used for
The direction of the power of forming material.
Typically, (111) plane of lattice is basically parallel to the surface of material.
Shell is formed by thermoplasticity or elastomer polymer.Since shell substantially determines the material property of nucleocapsid particles and adds
Work condition, therefore, those skilled in the art can consider selection shell material according to material common in polymer technology, still
It is important to note that will be with the tight fit of nuclear material refractive index.
In the present invention, nuclear material (i.e. the first material) cannot flow, or more than the fusing point of shell material at a temperature of
It will not flow.This can be realized by using the polymer material with corresponding high glass-transition temperature (Tg).
In the present invention, the first described material can be polymetylmethacrylate, refractive index 1.49；It is described
Second of material can be Polyacrylate materials (its refractive index is between 1.30-1.49) and polybenzyl methacrylate
The copolymer of (PBzMA, refractive index 1.51)；Wherein, Polyacrylate materials, can be polyethyl acrylate (n=
1.47) perhaps Vinalac 5920 (n=1.48) perhaps Isobutyl methacrylate (n=1.45) or poly- methyl
Tert-butyl acrylate (n=1.46) or polyethyl methacrylate (n=1.49)；By regulation Polyacrylate materials and
The mass ratio of polybenzyl methacrylate so that the mean refractive index of host material be 1.49, i.e., with the folding of the first material
It is equal to penetrate rate, so that recombination photons material is transparent in original state.For example, shell can be by about 80% PEA's and about 20%
PBzMA is formed.
Preferably, the shell of nucleocapsid particles is by middle layer in conjunction with core.
Preferably, the middle layer is the polymeric layer for being crosslinked or being at least partly crosslinked.The crosslinking of middle layer can pass through
Free radical occurs, such as is caused by ultraviolet light irradiation, or more preferably occurred by two functions or low functional monomer.The reality
Apply the 1%-100% that ideal middle layer mass fraction in scheme is stratum nucleare, it is therefore especially desired to two functions or low of 2.5%-10%
Functional monomer.Two particularly desirable functions or low functional monomer are isoprene and allyl methacrylate (ALMA).It is this
The ideal thickness of crosslinking or the Polymer interlayers being at least partly crosslinked is 10-20nm.As long as the refractive index of middle layer and core material
The refractive index tight fit of material and/or sheathing material, thicker intermediate layer material are also possible.
It, can be suitable for these component selections in order to promote the index matching of core, shell and/or middle layer (if present)
Starting material, and to one or more components add adjustable refractive index agent.
In the present invention, composite photonic crystal material can also include auxiliary agent and/or additive, these components can be used to
Property needed for material is provided.This analog assistant and/or additive may is that antioxidant, UV stabilizer, fungicide, plasticizer,
Coalescing agent, leveling auxiliary agent, filler, melting auxiliary agent, adhesive, release agent, using auxiliary agent, demolding aids and viscosity modifier
(such as thickener).
In the present invention, the outside stimulus can be one of following or a variety of: temperature, pH, fluid, pressure, electromagnetism
Radiation, electric field, magnetic field, chemical reagent, biochemical reagents and biological reagent.
Under outside stimulus, recombination photons material shows opalescence (schemochrome).
The present invention proposes the preparation of composite photonic crystal material (monodispersed core-shell structural polymer beads, unrepeatered transmission)
Method, specific steps are as follows:
(1) being equipped with has stirring, condenses, the 1L reaction kettle of argon inlet mouth and heating mantles, is heated to 65-85 DEG C,
And logical argon gas protection；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized water, 1-5g methyl methacrylate, 1-
5g butanediol diacrylate, is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitoring is mixed
Close object temperature, at 55-75 DEG C, be added three kinds of freshly prepared solution: 0.01-0.1g sodium pyrosulfite be dissolved in 1-5g go from
In sub- water；0.01-0.1g sodium peroxydisulfate is dissolved in 1-10g deionized water；0.1-0.5g sodium pyrosulfite is dissolved in 1-5g and goes
In ionized water；
(2) after reacting 2-30 minutes, lotion composed of the following components: 0.1-1g lauryl sodium sulfate, 0.1-1g hydrogen
Potassium oxide, 0.1-1gDowfax2A1(Dow Chemicals), 10-100g deionized water, 10-100g methyl methacrylate,
Charging is added dropwise with 0.1-10mL/minute rate in 10-100g butanediol diacrylate；
(3) add 10-30 minutes latter, to be made of following component fresh solution: 0.01-1g sodium peroxydisulfate is dissolved in 1-
Charging is added dropwise with 0.1-10mL/minute rate in 10g deionized water；
(4) second of lotion that be 5-30 minutes latter, then being made of following component: 0.1-1g lauryl sodium sulfate is added,
0.1-1g potassium hydroxide, 10-200g deionized water, 10-200g ethyl acrylate, 10-100g benzyl methacrylate, with 0.1-
Charging is added dropwise in 10mL/minute rate；
(5) 10-60 minutes after the completion of adding, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieves
Net filtration, and be added dropwise in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solution under stiring, polymer
Condense and formed after stirring the sediment of sedimentation；Clear supernatant is decanted, by sediment and 0.1-1L deionized water
Mixing then passes through 100 microns of the screen to filtrates；Filter cake dries 1-3 days in 30-60 DEG C of baking oven to get monodispersed core is arrived
Shell structure polymer beads.
The present invention proposes the preparation of composite photonic crystal material (monodispersed core-shell structural polymer beads, there is middle layer)
Addition middle layer lotion is added in method in front between (3) Bu Yu (4) step in the unrepeatered transmission preparation method
Step (3-1), remaining step are identical as abovementioned steps；Specific steps are as follows:
(1) being equipped with has stirring, condenses, the 1L reaction kettle of argon inlet mouth and heating mantles, is heated to 65-85 DEG C,
And logical argon gas protection；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized water, 1-5g methyl methacrylate, 1-
5g butanediol diacrylate, is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitoring is mixed
Close object temperature, at 55-75 DEG C, be added three kinds of freshly prepared solution: 0.01-0.1g sodium pyrosulfite be dissolved in 1-5g go from
In sub- water；0.01-0.1g sodium peroxydisulfate is dissolved in 1-10g deionized water；0.1-0.5g sodium pyrosulfite is dissolved in 1-5g and goes
In ionized water；
(2) after reacting 2-30 minutes, lotion composed of the following components: 0.1-1g lauryl sodium sulfate, 0.1-1g hydrogen
Potassium oxide, 0.1-1gDowfax2A1(Dow Chemicals), 10-100g deionized water, 10-100g methyl methacrylate,
Charging is added dropwise with 0.1-10mL/minute rate in 10-100g butanediol diacrylate；
(3) add 10-30 minutes latter, to be made of following component fresh solution: 0.01-1g sodium peroxydisulfate is dissolved in 1-
Charging is added dropwise with 0.1-10mL/minute rate in 10g deionized water；
5-30 minutes after (3-1) addition, then second of lotion being made of following component: 0.01-0.1g dodecyl sulphur
Sour sodium, 0.1-1gDowfax 2A1,10-100g deionized water, 10-100g methyl methacrylate, 1-10g methacrylic acid benzyl
Charging is added dropwise with 0.1-10mL/minute rate in ester, 1-10g allyl methacrylate；
(4) third that is 5-30 minutes latter, then being made of with 0.1-10mL/minute rate dropwise addition charging following component is added
Kind lotion: 0.1-1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 10-200g deionized water, 10-200g ethyl acrylate,
10-100g benzyl methacrylate；
(5) 10-60 minutes after the completion of adding, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieves
Net filtration, and be added dropwise in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solution under stiring, polymer
Condense and formed after stirring the sediment of sedimentation；Clear supernatant is decanted, by sediment and 0.1-1L deionized water
Mixing then passes through 100 microns of the screen to filtrates；Filter cake dries 1-3 days in 30-60 DEG C of baking oven to get monodispersed core is arrived
Shell structure polymer beads.
The present invention proposes that the preparation method of composite photonic crystal material further includes, for the particle of monodisperse core-shell structure,
Core-shell material is heated to the flowable temperature of shell, makes nuclear particle in the host material that shell is formed under the action of mechanical force
Three-dimensional periodic arrangement.
The heating temperature, it is at least 40 DEG C higher than the glass transition temperature of the shell material of nucleocapsid particles, more preferably up to
It is 60 DEG C few.
The effect of mechanical force can be the effect of the common power in known polymer processing step.For example, mechanical force
Effect can pass through one of the following or multiple progress: single shaft compacting (such as forming film or plate), injection molding translates into
Type squeezes out, and is coextruded, calendering;, it is laminated, blow molding, fiber drawing, embossing and nano impression.
Preferably, crystal film with photon is prepared using single shaft compacting pressure sintering.It is specific the preparation method is as follows:
Equipped with HaakePolyLab OS Rheodrive 7 HaakeRheomix OS laboratory mixing machine in
100-140 DEG C mixes 40-50g polymer with the 1-10% benzophenone that mass fraction is polymer.Then it will obtain
0.1-10g rubber-like polymer particle material is covered with PET film, and is heated to 120-160 between the plate of panel vulcanizing press
℃.By applying the melt flows that cause for pressure 1-10 minutes of 0.1-20MPa, the TPC film of diameter about 1-20cm is formed.In order to hand over
Connection is irradiated 1-5 minutes by industrial mercury lamp in the distance apart from light source 10-15cm.The output power of lamp is 1000 watts.Pass through
The metal plate that corresponding pattern is placed on film carries out the crosslinking of spatial discrimination with the part of protective film from ultraviolet light irradiation.
The present invention also provides the composite photonic crystal material applications.The composite photonic crystal material can be used as a kind of biography
Sensor arrangement, for fields such as anti-fake and sensings.According to These characteristics, sensor device includes at least one composite photonic crystal
Material；The sensor device under external stimulation, by composite photonic crystal material from transparent to it is coloured variation come
Detect the variation of outside stimulus.
Specifically, the composite photonic crystal material (monodispersed polymer beads) of above-mentioned preparation can first be prepared
At film.Film will become have color under extraneous stimulation from clear, colorless, and as different stimulations has differently
Color, thus to the sensing of environmental stimuli.When designing specific pattern on film, pattern can be shown under specific incentive condition
Show and disappear, to realize anti-fake function.
The material is transparent at room temperature, and can show color to heat and/or cooling at ambient temperature
Effect.Alternatively, material (higher or lower) at a temperature of different from room temperature can be it is transparent, and when cooling or be warming up to
It can be with display color effect when room temperature.
Typically, under outside stimulus, the relative index of refraction of nuclear particle and host material changes.Which results in come from
The Fresnel reflection at the interface in composite material.In addition, the spacing between lattice plane in composite material may be with outside
The variation of stimulation and change.Due to bragg reflection peak wavelength in the effect of distance material of plane, so the color seen
May be changed by outside stimulus is influenced.
Preferably, outside stimulus is one or more of: temperature, pH, fluid, pressure (or stress), strain (such as cut
Cut or uniaxial strain), electromagnetic radiation, electric field, magnetic field, chemical reagent, biochemical reagents, biological agent.
In a preferred implementation case, material can be expandable material in the presence of fluid.For example, this material
It can be host material.The material can expand in the presence of the organic solvents such as ethyl alcohol.(there is no ethyl alcohol) in the first scenario,
Material can be transparent.(there are ethyl alcohol) in the latter case, ethyl alcohol may expanded matrix material, influence discrete phase for
The refractive index of nuclear material, and also influence interplanar distance.The result is that there is color effect under a second condition in recombination photons material
On the other hand fruit also indicates that there are ethyl alcohol, illustrate that it senses performance.
Other fluids, chemical reagent (such as the OH in the case of pH sensing-Ion, H+Ion), biological chemical reagent, biology
Reagent etc. can provide similar effect.In order to make material to specific outside stimulus (such as these stimulations) selective sound
It answers, it is preferred that matrix (or in some cases, core) includes for the selectively certain bits in conjunction with outside stimulus
Point.
Under outside stimulus, it is seen that color effects according to material be reflection or transmission from the point of view of be different.
The material can use under up to 150 DEG C of operating temperature.It is desirable that the temperature for reaching this limit it
Before, any colour effect observed all is substantially reversible.
Additionally or alternatively, material can be packaged before the use, and it can be made only to expose when in use.
In this way it is possible to prevent contaminated using preceding material, it is then exposed to interested fluid (or other outside stimulus
Object) to determine whether there is specific analyte.
Material may include image.Image can be graphical representation, such as logo or other shapes.It is highly preferred that image
It is the arrangement of one or more alphanumeric characters.Compared with the non-image portion of material, the image portion in material can be passed through
Image is being formed using heterogeneity respectively.These different ingredients can make the image section table of material in response to outside stimulus
Existing different refractive index or spacing of lattice response.Additionally or alternatively, image can be by making the non-image portion split-phase of material
It is formed than different degrees of crosslinking occurs in the image section of material.Suitable different crosslinking degrees influence the hard of material
Degree, therefore can be with the expansion of local influence material.Compared with the non-image portion of material, this can influence the image portion of material again
Respectively variations in refractive index and/or spacing of lattice variation.It is anti-fake comprising can be used to after specific image.
Detailed description of the invention
Fig. 1 is the representative TEM image for the PMMA@PEA-co-PBzMA core-shell particles that diameter is 225nm.
Fig. 2 is the figure for having transparent photonic crystal (TPC) film of the 225nm particle preparation in the black and white background of Fudan University
Picture discloses the high grade of transparency of the film.
Fig. 3 is the SEM image of TPC film cross section, shows the high-sequential of PEA-co-PBzMA Medium Culture PMMA particle.
Fig. 4 is the afm image on the surface of TPC film, it is shown that orderly (111) plane of the hexagon of photon crystal structure.
Fig. 5 is the schematic diagram that black light sub-pattern is printed on TPC.
Fig. 6 is the schematic diagram for immersing solvent and showing encrypted patterns.
Fig. 7 is that the diameter made of PMMA PEA-co-PBzMA is 187nm(blue), 225nm(green) and 248nm
The photo of the TPC film of (red) display pattern after immersing ethyl alcohol.
Fig. 8 is the reflectance spectrum of the TPC film made of various sizes of PMMA PEA-co-PBzMA.
Fig. 9 is the transmitted spectrum of green TPC film.
Figure 10 is the transmitted spectrum of initial TPC with crosslinking and non-crosslinked diaphragm area after submergence in ethanol.
Figure 11 is the differentiation for immersing the reflectance spectrum of ethyl alcohol post-crosslinking film.
Figure 12 is the submergence differentiation of the reflectance spectrum of non-crosslinked film later in ethanol.
Figure 13 is the differentiation of reflectance spectrum in solution swelling process caused by cross linking membrane regional evapotranspiration.
Figure 14 is to make membrane swelling/knot swelling hysteresis loop with ethyl alcohol.
Figure 15 is the variation that the reflected intensity of the lower crosslinking of 10 circulations of reconciliation swelling and non-crosslinked diaphragm area is swollen with ethyl alcohol.
Figure 16 is the image for being swollen (top) with ethyl alcohol and removing the film after 10 circulations of swelling (bottom).
Figure 17 is to be swollen to pattern with ethyl alcohol under different perspectives (being from left to right 90 °, 80 °, 70 °, 60 °, 50 ° respectively)
The image of film.
Figure 18 is the reflectance spectrum under incidence angles degree.
Figure 19 is reflection wavelength and intensity under different incident light angles.
Figure 20 be immerse different ethanol/water mixtures when film photo (mass fraction is followed successively by 0% from upper left to lower-left,
10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%).
Figure 21 is to immerse in ethanol/water mixture, the reflectance spectrum of different ethanol content lower films.
Figure 22 is the variation in ethanol/water mixture with ethanol content, the reflection wavelength of film and the variation of intensity.
Specific embodiment
Below by preferred implementation case and in conjunction with attached drawing, the present invention is further explained.
The present invention has devised transparent photonic crystal (transparent photonic crystal, TPC) material,
Method using transparent photon crystal material and for manufacturing transparent photon crystal material can to realize large area TPC film
With completely reversibility change between the state that elemental height pellucidity and structure colour.This interesting photon crystal material
It can be made of the nucleocapsid particles of the regularly arranged perfect index match with polymer core and Composite Shell component.This is by a little
Particle can create the photon crystal film of highly transparent, can be irradiated by UV and be spatially crosslinked, with non-crosslinked areas
It compares, the black light sub-pattern with different solvents response is provided.These TPC films can by being simply immersed in solvent,
The image being encrypted on photon crystal structure or character are shown as universal color pattern.This method, which can produce, has storage
The TPC film of secret information, and it is gone back while having fabulous and completely reversibility conversion optical characteristics.Present inventors have proposed
Potential use of the TPC material in safety and sensing application field.
Many security functions of bank money, passport, credit card, brand label and alternative document are all based on special face
Color characteristic (Adv. Mater. 2001,13,980-984；Angew. Chem. Int. Ed. 2010, 49, 3726-
3736；J. Mater. Chem. C 2013,1,2388-2403.).In the most widely used photonic crystal material in security fields
Material is dynamic state material, color with article towards observer eyes direction variation and change.Although many materials can
To realize color change by changing visual angle, but can be by several different modes, such as change environment temperature, selectivity
Chemical wettability, electric field or magnetic field manipulation or mechanical stress cause the material of color change and the reversible hiding security feature of energy,
Still quite rare.
In recent years, so-called stimulating responsive colloidal photon crystal because application various outside stimulus (such as ion, pH, solvent,
Reductant-oxidant, electric field or magnetic field) and there is reversible changeable schemochrome, thus cause great concern.Cause crystalline substance
The reversible change of lattice structure and/or refractive index difference, so as to cause reversible change (the Angew. Chem. Int. of structural color
Ed. 2011, 50, 1492-1522； Adv. Funct. Mater. 2010, 20, 2565-2578；J. Mater.
Chem. C 2013,1,6059-6074.).These stimulating responsive photon crystal materials can be applied to sensing device
(Angew. Chem. Int. Ed. 2014,53,3318-3335.), colour display (Adv. Opt. Mater. 2014,
2, 652-662；Adv. Funct. Mater. 2014, 24, 3197-3205；Nat. Photonics 2007, 1,
468-472.), photon print system (Nat. Photonics 2009,3,534-540；Adv. Eng. Mater. 2013,
15, 948-953；J. Mater. Chem. 2012,22,21405-21411.) photon ink and paper (Adv. Mater.
2003, 15, 892-896；Adv. Mater. 2009, 21, 4259-4264；J. Mater. Chem. 2011, 21,
13062-13067.).Although the preparation of stimuli responsive colloidal photon crystal and potential apply are reported extensively in scientific literature
Road, but industrial production or application important so far is realized not yet.
However, such photonic material is highly suitable for the storage of anti counterfeit appts or confidential information.These materials can
It is embedded into banknote or other secure files with for the anti-purpose cheated, therefore the letter of hiding encrypted image or character style
Breath will not be revealed before outside stimulus application.Current sightless photonic crystal pattern is successfully developed, to allow figure
Picture occurs in several of different ways, such as selective chemical soaks (J. Am. Chem. Soc. 2011,133,12430-
12432； J. Mater. Chem. 2012, 22, 367-372；ACS Appl. Mater. Interfaces 2015, 5,
10623-10632.), magnetic field manipulation (Sci. Rep. 2013,3,1-5；J. Mater. Chem. C 2014, 2,
3695；Adv. Funct. Mater. 2014,24,6430-6438.) and mechanical stress (Adv. Opt. Mater.
2014, 2, 652-662；Adv. Funct. Mater. 2014, 24, 3197-3205；ACS Appl. Mater.
Interfaces 2015, 5, 10623-10632；Adv. Funct. Mater. 2014,24,6430-6438).
The major defect for reporting all anti-fake materials based on invisible photonic crystal pattern in the literature is due to it
Resonant light scattering caused by periodic structure makes them with intrinsic with corner effect schemochrome.In general, initial encryption state is
Be it is coloured, this is attributed to pre-existing micro nano structure, this is why these materials always rely upon complete pine
Relaxation returns to original state to ensure the invisibility of encryption information.However, the nuance of these mode different zones cannot be by
It eliminates, and is difficult to inhibit the failure during reversible encryption.
TPC film disclosed herein with significant solvent response characteristic can have particle and surrounding substrate by design
There is equal refractive index to generate, therefore the resonant light scattering of photon crystal structure can be completely inhibited.Importantly, preparation
TPC film can be (transmissivity > 99% at visible wavelengths) of highly transparent in the initial state.Since TPC may quilt
The mixture (refractive index ratio TPC is small) of second alcohol and water is swollen, and causes the refractive index of nuclear particle and host material with different rates
Variation.This may cause further strong resonance Bragg diffraction, this structural color pattern that may cause encryption gradually appears,
Film transmissivity may decrease simultaneously.This solvatochromic mechanism can be by adjusting initial particle size and solvent mixture
The various ways such as composition realize.Reversible transformation between pellucidity and colored state can be in many cycle periods completely
Reversible, this may cause the complete appearing and subsiding of encryption photon pattern, structure and optical perfection without losing film.This
The sightless TPC technology of kind is compared with pervious method, and with being easy to, large area manufacture is (being irradiated by ultraviolet light) and very bright
The particular advantages of true variation (from transparent to colored state).
TPC film is made of the equal nuclear particle of refractive index and adjacent material core-shell particles, specifically includes polymethyl
Sour methyl esters (PMMA) core and 80% polyethyl acrylate of mass fraction and 20% polybenzyl methacrylate (PEA-co-PBzMA)
Shell copolymers.Typically, Fig. 1 illustratively shows that final diameter is the corresponding of the PMMA@PEA-co-PBzMA particle of 225nm
TEM image.The similar product for being respectively provided with 187nm and 248nm can also be obtained by identical step.Then by the material with
The photoinitiator (benzophenone) of mass fraction 5% mixes, and hot pressing 3 minutes under 140 DEG C and 10MPa, thus makes PEA-co-
PBzMA shell material merges to form continuous melting matrix, and PMMA core is assembled under shear action and puts down with (111) crystal face
Row is in the colloid lattice structure (Nat. Commun. 2016,7,1-10) of the high-sequential of sample surfaces.Due to the folding of PMMA
Rate and the perfect index match of PEA-co-PBzMA are penetrated, so composite membrane is in visible light and near-infrared (vis-NIR) range
(400-800nm) is highly transparent, as shown in Figure 2.In fact, due to lacking schemochrome, it is difficult to distinguish the glue of high-sequential
Body crystal structure.In order to confirm this point, more detailed nanostructure characterization (Fig. 3, Fig. 4) is carried out using SEM and AFM.Accordingly
What the PMMA particle in SEM figure (Fig. 3) the display insertion PEA-co-PBzMA material of film sample cross section was ordered into, and hexagonal
The PMMA particle (111 plane) of shape arrangement is high-visible in AFM (Fig. 4), shows that particle is high-sequential in TPC film
's.
As shown in figure 5, selectively irradiate certain parts of TPC by optical mask plate, by Fudan University's mark can not
See that Chinese character is encrypted into TPC.Since the region crosslinking degree of ultraviolet light irradiation is higher, and there is higher rigidity, therefore work as
When immersing in solvent, compared with non-irradiated regions, their expansion is smaller, and structural intergrity is preferable.As a result, being observed in irradiation
To structural color more stronger than non-irradiated region, this leads to color contrast strong between them (Fig. 6).Film be constantly swollen from
And disclose the image of encryption.Its basic prerequisite is to immerse TPC in solvent, and refractive index ratio TPC is high or low, to cause
Refractive index generates difference.In order to prove this point, we have selected ethyl alcohol (nEthanol=1.36) as solvent, with PMMA
Nuclear particle (nPMMA=1.49) has the difference of high index.When by TPC submergence in ethanol, observe that two kinds of optics are existing
As: i) from transparent translation to colored state, and ii) occur uniform white pattern on structure color background.Herein, blue
It is respectively that TPC film made of the particle of 187,225 and 248nm obtains that color, green and red film (Fig. 6), which are by diameter,
's.Due to the colloidal crystal structure of high-sequential, the reflectance spectrum of these three TPC films (Fig. 8) is in 441nm(blue), 561nm
(green) and 636nm(are red) at show very narrow reflection peak.As shown in figure 9, identical green film show it is bright
Transmitted colors wherein observing light source by green TPC film, and can observe uniform purple on all surface.
The typical transmittance spectra (Figure 10) of TPC film shows that initial film has in almost entire visible-near-infrared spectral region
100% transmissivity and the crosslinking diaphragm area after being swollen with ethyl alcohol also have very high transmissivity, are 99% in long wavelength region,
In wavelength lower than the transmissivity that the short wavelength region of Bragg peak is 88%.On the contrary, as shown in Figure 10, non-crosslinked areas it is saturating
It penetrates rate and is reduced to 98% long wavelength region is significant, be reduced to 84% short wavelength region is significant.However, TPC film is shown
Significant reflectivity, the Bragg peak and the high-transmission rate outside bragg peak of cross-linked areas clearly may be used in transmissivity measurement
See.However, non-crosslinked areas shows continuous spectrum band, show the forfeiture of the colloid sequence of crystallization during swelling.It was noticed that
Since initial transparent state is independent of nanostructure, the order loss of non-crosslinked part will not influence encryption information
Invisibility and announcement process.Although the difference very little of refractive index after swelling, due to a large amount of orderly TPC film layers and not
Same structural intergrity is along with the different swelling ratios irradiated with non-irradiated thin membrane regions, it is possible to obtain high contrast
Encrypted image.
The differentiation of reflectance spectrum is recorded, to verify visually observation, and explains the revelation mechanism of invisible photon trace, these
It is all to use TPC as necessary to effective false proof device.In general, it can be observed that two different effects in TPC film:
I) become colored state from pellucidity due to the increase of refractive index in swelling process;Ii) due to lattice constant increase,
The structural color in normal incidence direction is with swelling red shift.However, UV irradiates selected film compared with undosed region
Crosslinking in region generates different expansion characteristics, and two regions all show different optic responses.Thus, it is found that handing over
The strong variations of reflectance spectrum between connection and non-crosslinked areas.The reflectance spectrum of crosslinking and non-crosslinked areas is all shown jointly
Feature comprising the reflection peaks of two superpositions, until membrane swelling after five minutes is completed, they merge (Figure 11, Figure 12).However,
Due to structural intergrity (Figure 11), the reflected intensity in the crosslink part of film is strongly increased, this is derived from the increase of refractive index difference,
And peak wavelength only slightly moves.On the contrary, the reflectance spectrum in non-crosslinked film region only shows the slight change of reflected intensity,
Reflected intensity slightly rises and then declines again, along with the strong extension (Figure 12) of red shift and reflection peak.
In order to further appreciate that the structure change and optical characteristics of TPC, and practical application is obtained, has also carried out reflectance spectrum and existed
Solve the differentiation in swelling process., it is surprising that in the solution swelling process of evaporation induction, it is initial anti-at 561 nm
It penetrates peak and is blue shifted to 475 nm, and the significant reduction of peak intensity, (Figure 13) is completely disappeared after evaporating 5 min.Between swelling reconciliation swelling
This big difference of optic response is attributable to ethyl alcohol being uniformly evaporated from the equilibrium swelling state of TPC.It is interesting that increasing
There are apparent hysteresis (Figure 14) in the reflected intensity of adduction reduction swelling ratio.But after ethyl alcohol evaporating completely, TPC film
Initial transparent state can restore completely.
TPC can reversibly show its pattern and being swollen with ethyl alcohol, and by solution swelling caused by repeatedly evaporating come
Hide itself pattern.The peak strength for the different diaphragm areas summarized in Fig. 3 e this expansion reconciliation expansion cycles in repeatability very
It is good.In each cyclic process, entire TPC is switched to its structure colored state by immersing ethyl alcohol, is then steamed by solvent
Hair is discharged into its initial transparent state.The peak strength in irradiation area and non-irradiated region reversibly moves up and down, and has good
Reproducibility.Although the structurally ordered partial loss in the non-crosslinked areas of film, between pellucidity and colored state
Reversible transformation is completely reversibility in many circulations, this leads to the complete appearing and subsiding for encrypting photon pattern, without damaging
Lose the structure and optical perfection (Figure 15) of film.
About the practical application as security feature, it is necessary to ensure that the visibility of the pattern in extensive angular field of view.
Each of Fig. 7 TPC film all shows bright reflection colour, and the pattern shown under normal light incidence has
Good optical contrast.In order to show the visibility of the pattern under different perspectives, we use red TPC film as anti-fake
The example of pattern.As shown in the master map in Figure 17, which shows bright reflection colour.When incidence angle and angle of reflection reduce
When, the angle of incident light is from when being reduced to 50 ° for 90 °, and blue shift occurs for the color of cross-linked areas, and at all visual angles observed
On, multicolour pattern keeps fully visible.With the reduction of angle, the displacement of bragg peak is high-visible in reflectance spectrum, and
The maximum value of intensity of reflected light slightly declines (Figure 18).Bragg peak is in the significant blue shift of smaller angle and according to Prague side
The expection of journey is consistent (Figure 19), and the maximum value reflected reduces simultaneously.It is worth noting that, the reduction of reflected intensity be due to
Caused by the Fresnel reflection of the non-polarized light of measurement, it is not due to the knot that following photon crystal structure lacks order
Fruit.
About its solvation behavior and its availability in optical sensing application, the optics of the TPC film of preparation is had studied
Response.Therefore, they are by specific wet with solvent and swelling.Therefore, it can be obtained according to the osmotic pressure of the solvent of Fig. 6 different
Solvent response.For this purpose, being swollen TPC using the different mixtures of ethanol/water, different effects is shown, disclose invisible on TPC
Pattern (Figure 20).With the increase of ethanol content, the pattern in irradiation area and non-irradiated region becomes to be more and more obvious, pattern
Color occur red shift (Figure 20).Increased contrast and red shift are due to the increase of refractive index difference and by solvent swell tune
Lattice constant is saved, straight alcohol provides optimal picture contrast.Figure 21 is shown when TPC immerses different solvent mixtures
Corresponding reflectance spectrum.With the increase of ethanol content, under normal incident light, bragg peak consumingly red shift is greater than 100nm
It is (Figure 22), i.e., green from the 538nm(of bragg peak) it is red to 640nm() variation.Along with due to red caused by being significantly swollen
It moves, reflected intensity increases the visual color brightness of (Figure 22) and enhancing therewith, therefore has relatively low refraction in host material
The volume fraction of the ethanol/water of rate increases.The significant change of this color shows that TPC film is that naked eyes can to the response of ethanol/water
(Figure 20) seen.Therefore such response color change can be not only used for false proof device, and may be used as the colorimetric of ethyl alcohol
Sensor.
It summarizes, present inventors have demonstrated that the side from the polymer core shell particles of the refractive index with exact matching
Just it is prepared for transparent crystal film with photon, with completely reversibility can be switched to structure colored state from highly transparent state.And
And this TPC can be irradiated by ultraviolet light and is spatially crosslinked, and compared with non-crosslinked areas, provided and rung with different solvents
The black light sub-pattern answered.Corresponding encrypted image is rendered as on photon crystal structure and being simply immersed in solvent
Universal color pattern.The method of this simplicity can generate the TPC film of the secret information with storage, along with fabulous sum
The tuneable optical properties of completely reversibility.The TPC studied herein is considered as promising photonic material by the present inventor, is possibly used for
Sensor stores secret information and is used for banknote, passport, the false proof device on credit card and brand label.
Case study on implementation listed above is described by way of example.When reading this patent, to these
The modification of case study on implementation, further case study on implementation and its modification are it will become apparent to those skilled in the art that simultaneously
And therefore within the scope of the invention.The further experimental detail of the example is given below.
Prepare transparent photon crystal material citing
1. preparing monodispersed core-shell polymer particles
It is equipped with stirring, is condensed, the 1L reaction kettle of argon inlet mouth and heating mantles is heated to 75 DEG C and logical argon gas protection.
0.150 gram of lauryl sodium sulfate,
280.000 gram deionized water,
2.800 gram methyl methacrylate,
1.200 gram butanediol diacrylate,
It is pre-mixed and is fed in reactor.Blender is adjusted to 250rpm.Monitor the temperature of mixture.At 65 DEG C
Under, three kinds of freshly prepd solution: the dissolution 0.050g sodium pyrosulfite in 2.5g deionized water are then added；In 5g deionization
Dissolution 0.150g sodium peroxydisulfate in water；Dissolution 0.360g sodium pyrosulfite in 2.5g deionized water；
After after ten minutes, by lotion composed of the following components:
0.230 gram of lauryl sodium sulfate,
0.400 gram of potassium hydroxide,
0.220 gram of Dowfax2A1(Dow Chemicals),
90.000 gram deionized water,
53.900 gram methyl methacrylate,
23.100 gram butanediol diacrylate,
Charging is added dropwise with 1mL/minute.30 minutes after adding, freshly prepared solution is added: molten in 5g deionized water
Solve 0.050g sodium peroxydisulfate；
After being added 15 minutes, second of lotion composition is added dropwise are as follows:
0.400 gram of lauryl sodium sulfate,
0.200 gram of potassium hydroxide,
160.000 gram deionized water,
112.600 gram ethyl acrylate,
27.400 gram benzyl methacrylate；
It is added dropwise with 1.35mL/minute.Synthesis after sixty minutes is completed in last time addition to be terminated, and polymer latex is obtained.It will
Latex is added drop-wise in the mixture of 1.7L methanol and 4mL concentrated sodium chloride aqueous solution under stiring by 100 μm of the screen to filtrates.
Polymer coagulation and the sediment that sedimentation is formed after stirring.Clear supernatant is decanted, by sediment and 0.3L go from
Sub- water mixing, then passes through 100 microns of the screen to filtrates.Filter cake is three days dry in 45 DEG C of convection oven.
Prepare monodispersed core-middle layer-core-shell polymeric particles
It is equipped with stirring, is condensed, the 1L reaction kettle of argon inlet mouth and heating mantles is heated to 75 DEG C and logical argon gas protection.
0.150 gram of lauryl sodium sulfate,
280.000 gram deionized water,
2.800 gram methyl methacrylate,
1.200 gram butanediol diacrylate,
It is pre-mixed and is fed in reactor.Blender is adjusted to 250rpm.Monitor the temperature of mixture.At 70 DEG C
Under, three kinds of freshly prepd solution: the dissolution 0.050g sodium pyrosulfite in 2.5g deionized water are then added；In 5g deionization
Dissolution 0.150g sodium peroxydisulfate in water；Dissolution 0.360g sodium pyrosulfite in 2.5g deionized water；
After after ten minutes, by lotion composed of the following components:
0.230 gram of lauryl sodium sulfate,
0.400 gram of potassium hydroxide,
0.220 gram of Dowfax2A1(Dow Chemicals),
90.000 gram deionized water,
53.900 gram methyl methacrylate,
23.100 gram butanediol diacrylate,
Charging is added dropwise with 1.4mL/minute.30 minutes after adding, freshly prepared solution is added: in 5g deionized water
Dissolve 0.050g sodium peroxydisulfate；
After being added 15 minutes, second of lotion composition is added dropwise are as follows:
0.050 gram of lauryl sodium sulfate,
0.210 gram of Dowfax 2A1,
32.000g deionized water,
21.000 gram methyl methacrylate,
4.000 gram benzyl methacrylate,
3.000 gram allyl methacrylate,
Charging is added dropwise with 1.35mL/minute.It adds after twenty minutes, the third lotion is added:
0.400 gram of lauryl sodium sulfate,
0.200 gram of potassium hydroxide,
160.000 gram deionized water,
112.600 gram ethyl acrylate,
27.400 gram benzyl methacrylate；
It is added dropwise with 1.35mL/minute.Synthesis after sixty minutes is completed in last time addition to be terminated, and polymer latex is obtained.It will
Latex is added drop-wise in the mixture of 1.7L methanol and 4mL concentrated sodium chloride aqueous solution under stiring by 100 μm of the screen to filtrates.
Polymer coagulation and the sediment that sedimentation is formed after stirring.Clear supernatant is decanted, by sediment and 0.3L go from
Sub- water mixing, then passes through 100 microns of the screen to filtrates.Filter cake is three days dry in 45 DEG C of convection oven.
3. the photoinitiator that preparation addition can be additional photocuring is used for melt molding processing in the composite
In 120 in the HaakeRheomix OS laboratory mixing machine equipped with HaakePolyLab OS Rheodrive 7
DEG C 50g polymer is mixed with 5% benzophenone (Aladdin).
4. hot pressing is for crystal film with photon
A part of 1 gram of rubber-like polymer is covered with PET film, and is heated between the plate of panel vulcanizing press
140℃.By applying the melt flows that cause for pressure 3 minutes of 100MPa, the TPC film of diameter about 10cm is formed.
5. ultraviolet radiation crosslinking and patterning crystal film with photon
In order to be crosslinked, by industrial mercury lamp (Dongguan Er Gu photoelectricity technology corporation, Ltd.) in the distance apart from light source 15cm
Irradiation 1 minute.The output power of lamp is 1000 watts.By placing the metal plate of corresponding pattern on film with the portion of protective film
Divide the crosslinking that spatial discrimination is carried out from ultraviolet light irradiation.
The material citing used
Methyl methacrylate (MMA), ethyl acrylate (EA) and butanediol diacrylate (BDDA) derive from Shanghai state
Medicine chemical reagent Co., Ltd (China), allyl methacrylate (ALMA) and benzyl methacrylate (BzMA) derive from me
The Dowfax 2A1 of fourth Chemical Co., Ltd. (China) and Dow Chemical (China).Every other chemicals is all from Shanghai
Traditional Chinese medicines chemical reagent Co., Ltd (China) and Aladdin Chemical Co., Ltd. (China) purchase, and use as it is.It is being used for
Before emulsion polymerization, destabilizing agent is removed from monomer.For this purpose, using alumina column, (alkalinity, 50-200 mesh, Aladdin chemistry have
Limit company), remove MMA, EA, BzMA, the stabilizer in ALMA and BDDA.
Claims (15)
1. a kind of composite photonic crystal material, which is characterized in that mainly include the first material and second of material, the first material
The particle that material is formed is arranged in three-dimensional periodic structure, in the initial state, first in the host material that second of material is formed
As refractive index with second of material is, composite photonic crystal material is transparent at this time；When being watched under the conditions of natural light,
Under external incentive condition, the refractive index n of the first material1And/or the refractive index n of second of material2Corresponding change occurs, but
Be the first material and second of material refractive index it is different to the response of outside stimulus, to possess different refractive index, by
This composite photonic crystal material becomes have color by colorless and transparent；
The form of the composite photonic crystal material is the particle of core-shell structure, i.e., the particle of each core-shell structure includes core and encloses
Around the shell of the core, also, the karyomorphism at the particle that is formed of particle i.e. the first material outer hull shape at host material
That is three-dimensional periodic arranges in second of material；
The karyomorphism at mean particle size be 5nm to 2000nm；And karyomorphism at particle with monodispersed size be distributed.
2. composite photonic crystal material according to claim 1, which is characterized in that the karyomorphism at particle with closs packing
Three-dimensional lattice mode be scattered in host material, i.e., karyomorphism at particle host material is placed in the form of face-centered cubic lattice
In；And the karyomorphism at the plane of lattice of particle be parallel to the surface of composite photonic crystal material.
3. composite photonic crystal material according to claim 1, which is characterized in that the first material for forming core cannot flow
Dynamic, this is realized by using the polymer material with corresponding high glass-transition temperature Tg.
4. composite photonic crystal material according to claim 3, which is characterized in that the poly- methyl of the first material selection
Methyl acrylate PMMA；Second of material selection Polyacrylate materials and polybenzyl methacrylate PBzMA's is total to
Polymers；Wherein, Polyacrylate materials are polyethyl acrylate, Vinalac 5920, Isobutyl methacrylate,
Polymethyl tert-butyl acrylate or polyethyl methacrylate；And pass through regulation Polyacrylate materials and polymethylacrylic acid
The mass ratio of benzyl ester, so that the mean refractive index of host material is equal with the refractive index of the first material, so that compound
Photon crystal material is transparent in original state.
5. composite photonic crystal material described in one of -4 according to claim 1, which is characterized in that the particle of the core-shell structure
It further include middle layer, i.e., shell is by middle layer in conjunction with core；The middle layer is the polymeric layer of crosslinking.
6. composite photonic crystal material according to claim 5, which is characterized in that the quality of the middle layer is the matter of core
The 1%-99% of amount；Middle layer with a thickness of 10-20nm.
7. composite photonic crystal material according to claim 6, which is characterized in that the material for forming the middle layer is two
Function or low functional monomer.
8. according to claim 1-4, composite photonic crystal material described in any one of 6-7, which is characterized in that also include auxiliary agent
And/or additive, property needed for these components are used to provide composite photonic crystal material；The auxiliary agent is: antioxidant, UV are steady
Determine agent, fungicide, plasticizer, at least one of leveling auxiliary agent and melting auxiliary agent；The additive is: adhesive, demolding aids
At least one of with viscosity modifier.
9. a kind of preparation method of such as composite photonic crystal material of any of claims 1-8, which is characterized in that tool
Body step are as follows:
(1) being equipped with has stirring, condenses, the 1L reaction kettle of argon inlet mouth and heating mantles, is heated to 65-85 DEG C, and lead to
Argon gas protection；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized water, 1-5g methyl methacrylate, 1-5g fourth
Omega-diol diacrylate is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitors mixture
Temperature, at 55-75 DEG C, three kinds of freshly prepared solution are added: 0.01-0.1g sodium pyrosulfite is dissolved in 1-5g deionized water
In；0.01-0.1g sodium peroxydisulfate is dissolved in 1-10g deionized water；0.1-0.5g sodium pyrosulfite is dissolved in 1-5g deionization
In water；
(2) after reacting 2-30 minutes, lotion composed of the following components: 0.1-1g lauryl sodium sulfate, 0.1-1g hydroxide
Potassium, 0.1-1gDowfax2A1(Dow Chemicals), 10-100g deionized water, 10-100g methyl methacrylate, 10-
Charging is added dropwise with 0.1-10mL/minute rate in 100g butanediol diacrylate；
(3) add 10-30 minutes latter, to be made of following component fresh solution: 0.01-1g sodium peroxydisulfate is dissolved in 1-10g and goes
Charging is added dropwise with 0.1-10mL/minute rate in ionized water；
(4) second of lotion that be 5-30 minutes latter, then being made of following component: 0.1-1g lauryl sodium sulfate, 0.1- is added
1g potassium hydroxide, 10-200g deionized water, 10-200g ethyl acrylate, 10-100g benzyl methacrylate, with 0.1-10mL
Charging is added dropwise in/minute rate；
(5) 10-60 minutes after the completion of adding, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieve mistakes
Filter, and be added dropwise in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solution under stiring, polymer coagulation
And the sediment of sedimentation is formed after stirring；Clear supernatant is decanted, sediment is mixed with 0.1-1L deionized water,
Then pass through 100 microns of the screen to filtrates；Filter cake dries 1-3 days in 30-60 DEG C of baking oven to get monodispersed core-shell structural is arrived
Particle.
10. the preparation method of composite photonic crystal material according to claim 9, which is characterized in that in step (3) and step
Suddenly between (4) further include:
5-30 minutes after addition, then with 0.1-10mL/minute rate that charging is made of following component is added dropwise in step (3-1)
Three kinds of lotions: 0.01-0.1g lauryl sodium sulfate, 0.1-1gDowfax 2A1,10-100g deionized water, 10-100g methyl
Methyl acrylate, 1-10g benzyl methacrylate, 1-10g allyl methacrylate.
11. the preparation method of composite photonic crystal material according to claim 9, which is characterized in that further include, for list
The particle of the core-shell structure of dispersion heats the particle of core-shell structure to the flowable temperature of shell, makes under the action of mechanical force
Karyomorphism at particle outer hull shape at host material in three-dimensional periodic arrange；
Vitrifying of the particle of the heating core-shell structure to the flowable temperature of shell than the shell of the particle of core-shell structure turns
At least 40 DEG C of temperature height.
12. the preparation method of composite photonic crystal material according to claim 11, which is characterized in that the mechanical force
Act through one of the following or multiple progress: single shaft compacting, injection molding, transfer formation squeeze out, and are coextruded, calendering, layer
Pressure, blow molding, fiber drawing, embossing and nano impression.
13. a kind of sensor device, which includes such as composite photonic crystal of any of claims 1-8
Material；The sensor device under external stimulation, by composite photonic crystal material from transparent to it is coloured variation come
Detect the variation of outside stimulus.
14. sensor device according to claim 13, which is characterized in that prepare the composite photonic crystal material
At film, which becomes have color under external stimulation from clear, colorless, and as different outside stimulus has not
With ground color, thus to the sensing of outside stimulus；The outside stimulus is one or more of: temperature, pH, fluid, pressure,
Electromagnetic radiation, chemical reagent and biological agent.
15. sensor device according to claim 14, which is characterized in that design has specific pattern on film, schemes
Case shows and disappears under the conditions of specific outside stimulus, to realize anti-fake function.
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