CN108287378A - 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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- CN108287378A CN108287378A CN201810008537.0A CN201810008537A CN108287378A CN 108287378 A CN108287378 A CN 108287378A CN 201810008537 A CN201810008537 A CN 201810008537A CN 108287378 A CN108287378 A CN 108287378A
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- photonic crystal
- crystal material
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- 239000004038 photonic crystal Substances 0.000 title claims description 43
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Integrated Circuits (AREA)
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 includes mainly 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, respective change occurs for the refractive index of two kinds of materials, and thus material is become have color by water white transparency；To provide the encrypted photon pattern with different responses.Such as the image being encrypted on photon crystal structure or character can be shown as universal color pattern by these transparent photonic materials by immersing in solvent.The present invention also proposes application of the transparent photonic material as sensor device in safety and Application in Anti-counterfeiting field, such as specifically 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 technology
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, also some animals, such as chameleon, certain beetles or octopus are had 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 a diameter of 150 to 300nm silica spheres, with closely packed
Face-centered cubic（fcc）Lattice structure arranges.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, zirconium alkoxide solution is made to penetrate into the gap in sediment, zirconium oxide is by hydrolytic precipitation in gap.So
Material is calcined again afterwards, to leave silica spheres arrangement form three-dimensional lattice, zirconium oxide the filling structure in gap therebetween.
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（It is equal to WO03025035）Disclose the molding formed by core-shell particles.Particle by
Monodispersed stone is constituted.Each particle there are 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）It is formed.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
Row, case material become host material.Obtained material can be with reflecting rainbow color.It can be 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 that nuclear particle sorts in matrix, but clear there is no explaining completely
Chu.
US 2005/0142343（It 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 is added in matrix.
US 2005/0228072（It is equal to WO03106557）It provides in the disclosure similar with US 2004/0253443
Hold.But a kind of material is in addition added 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 industrial quarters interest concentrates on surface and is parallel to crystal face（Fcc lattices<111>Plane）Color because
These planes are provided from the most strong structural color of polymer photon crystal.
US 2009/0012207 is disclosed forms one layer of polymeric photonic crystal using nucleocapsid particles.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 is thus made
User indicates when that medical treatment or hygienic articles are tight by La get Tai.The possibility of crosslinked matrix material is also disclosed, such as utilizes 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
By outside stimulus（Such as it stretches）And change by security feature, show structural color.It also proposed polymer photon in file
The localized variation of the mechanical property of crystal film.This leads to the respective 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 of the structural color response of polymer photon crystal film
Portion changes.It can significantly change mechanical property 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 be rung 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 is disclosed using 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 directions incident light different responses.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 is disclosed using photonic crystal as temperature sensor.The photonic crystal is by diblock copolymer
Thin slice formed.Therefore photonic crystal is only periodic there are one dimension.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 is disclosed using colloidal crystal as vapor sensing device.
US6847477 discloses the wavelength for changing incident light using sequence colloidal crystal, 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 detecting 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 by incorporation light scattering
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.
Invention content
It can realize by stimulation and be generated from initial high transparency state and schemochrome the purpose of the present invention is to provide one kind
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 respective 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 water white transparency.
For example, composite photonic crystal material provided by the invention, when being watched under the conditions of natural light, material is in environmental stimuli
Under, occur from water white transparency to coloured visible change.
Composite photonic crystal material provided by the invention, the typically grain shape of nucleocapsid, 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 first material）Refraction index be n1, shell material（Second of material）Refraction index be 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 respective change, to make material color change.
First feature of the present invention is that photon crystal material is formed by two different Material claddings, and refraction index is
n1Particle three dimensions periodically be arranged in refraction index be n2Host material in, in the initial state, first and
The refractive index of two kinds of materials is the same, and material is transparent；
Second feature of the present invention is to constitute photon crystal material to have color change effect under extraneous stimulation,
I.e. under environmental stimuli, n1And/or n2Respective change occurs, the refractive index of two kinds of materials differs, and is become by original water white transparency
At 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 at most 300nm, or at most 250nm
Average grain diameter.
In the present invention, nuclear particle（That is the first material）With monodispersed Size Distribution, 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 a manner of closely packed three-dimensional lattice in host material.Specifically, nuclear particle
It is placed in host material in the form of face-centered cubic lattice.Ideally lattice（111）Plane is substantially perpendicular to and is used for
The direction of the power of forming material.
Typically, lattice（111）Plane 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（That is the first material）It cannot flow, or at the temperature more than the fusing point of shell material
It will not flow.This can be by using with corresponding high glass-transition temperature（Tg）Polymer material realize.
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/or polymethylacrylic acid benzyl
Ester（PBzMA, refractive index 1.51）；Wherein, Polyacrylate materials can be polyethyl acrylate（n=1.47）, or
Person's Vinalac 5920（n=1.48）Or Isobutyl methacrylate（n=1.45）Or polymethylacrylic acid uncle
Butyl ester（n=1.46）Or polyethyl methacrylate（n=1.49）；By regulating and controlling Polyacrylate materials and poly- methyl-prop
The mass ratio of olefin(e) acid benzyl ester so that the mean refractive index of host material is 1.49, i.e., equal with the refractive index of the first material,
So that recombination photons material is transparent in original state.For example, shell can be formed by about 80% PEA and about 20% PBzMA.
Preferably, the shell of nucleocapsid particles is combined by middle layer with core.
Preferably, the middle layer is crosslinking or at least partly crosslinked polymeric layer.The crosslinking of middle layer can pass through
Free radical occurs, such as is caused by ultraviolet light irradiation, or is more preferably occurred by two functions or low functional monomer.The reality
Apply the 0.01-100% that ideal middle layer mass fraction in scheme is stratum nucleare, it is therefore especially desired to two functions of 0.25-10% or
Low functional monomer.Two particularly desirable functions or low functional monomer are isoprene and allyl methacrylate (ALMA).This
The ideal thickness of kind crosslinking or at least partly crosslinked Polymer interlayers is 10-20nm.As long as the refractive index and core of middle layer
The refractive index tight fit of material and/or sheathing material, thicker intermediate layer material are also possible.
In order to promote core, shell and/or middle layer（If there is）Index matching, can be these component selections it is suitable
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 for
Property needed for material is provided.This analog assistant and/or additive can be：Antioxidant, UV stabilizer, fungicide, plasticizer,
Coalescents, leveling auxiliary agent, filler, melting auxiliary agent, adhesive, releasing agent, using auxiliary agent, demolding aids and viscosity modifier
（Such as thickener）Deng.
In the present invention, the outside stimulus can be it is following in it is one or more：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 composite photonic crystal material（Monodispersed core-shell structural polymer beads, unrepeatered transmission）Preparation
Method, the specific steps are：
（1）It is equipped with stirring, condenses, the 1L reaction kettles of argon inlet mouth and heating mantles, be heated to 65-85 DEG C, and lead to
Argon gas is protected；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized waters, 1-5g methyl methacrylates, 1-5g fourths
Omega-diol diacrylate is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitors mixture
Three kinds of freshly prepared solution are added at 55-75 DEG C in temperature：0.01-0.1g sodium pyrosulfites are dissolved in 1-5g deionized waters
In；0.01-0.1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；0.1-0.5g sodium pyrosulfites are dissolved in 1-5g deionizations
In water；
（2）After reaction 2-30 minutes, it is added dropwise with 0.1-10mL/minute rate and feeds lotion composed of the following components： 0.1-
1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 0.1-1gDowfax2A1（Dow Chemicals）, 10-100g deionizations
Water, 10-100g methyl methacrylates, 10-100g butanediol diacrylates；
（3）Add 10-30 minutes latter, to be made of following component with 0.1-10mL/minute rate dropwise addition charging fresh solution：
0.01-1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；
（4）Add second of breast that be 5-30 minutes latter, then being made of following component with 0.1-10mL/minute rate dropwise addition charging
Liquid：0.1-1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 10-200g deionized waters, 10-200g ethyl acrylates, 10-
100g benzyl methacrylates；
（5）10-60 minutes after the completion of addition, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieve mistakes
Filter, and be added dropwise under stiring in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solutions, polymer coagulation
And the sediment of sedimentation is formed after stirring；Clear supernatant is decanted, sediment is mixed with 0.1-1L deionized waters,
Then pass through 100 microns of screen filtrations；Filter cake in 30-60 DEG C of baking oven dry 1-3 days to get to monodispersed core-shell structural
Polymer beads.
The present invention proposes composite photonic crystal material（Monodispersed core-shell structural polymer beads, there is middle layer）Preparation
Method, i.e., in front in the unrepeatered transmission preparation method（3）Step and the（4）Addition middle layer lotion is added between step
Step（3-1）, remaining step is identical as abovementioned steps；The specific steps are：
（1）It is equipped with stirring, condenses, the 1L reaction kettles of argon inlet mouth and heating mantles, be heated to 65-85 DEG C, and lead to
Argon gas is protected；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized waters, 1-5g methyl methacrylates, 1-5g fourths
Omega-diol diacrylate is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitors mixture
Three kinds of freshly prepared solution are added at 55-75 DEG C in temperature：0.01-0.1g sodium pyrosulfites are dissolved in 1-5g deionized waters
In；0.01-0.1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；0.1-0.5g sodium pyrosulfites are dissolved in 1-5g deionizations
In water；
（2）After reaction 2-30 minutes, it is added dropwise with 0.1-10mL/minute rate and feeds lotion composed of the following components： 0.1-
1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 0.1-1gDowfax2A1（Dow Chemicals）, 10-100g deionizations
Water, 10-100g methyl methacrylates, 10-100g butanediol diacrylates；
（3）Add 10-30 minutes latter, to be made of following component with 0.1-10mL/minute rate dropwise addition charging fresh solution：
0.01-1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；
（3-1）5-30 minutes after addition, then be added dropwise that charging is made of following component with 0.1-10mL/minute rate second
Lotion：0.01-0.1g lauryl sodium sulfate, 0.1-1gDowfax 2A1,10-100g deionized waters, 10-100g metering systems
Sour methyl esters, 1-10g benzyl methacrylates, 1-10g allyl methacrylates；
（4）Add the third breast 5-30 minutes latter, then be made of following component with 0.1-10mL/minute rate dropwise addition charging
Liquid：0.1-1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 10-200g deionized waters, 10-200g ethyl acrylates, 10-
100g benzyl methacrylates；
（5）10-60 minutes after the completion of addition, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieve mistakes
Filter, and be added dropwise under stiring in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solutions, polymer coagulation
And the sediment of sedimentation is formed after stirring；Clear supernatant is decanted, sediment is mixed with 0.1-1L deionized waters,
Then pass through 100 microns of screen filtrations；Filter cake in 30-60 DEG C of baking oven dry 1-3 days to get to monodispersed core-shell structural
Polymer beads.
The present invention proposes that the preparation method of composite photonic crystal material further includes, for the particle of monodisperse nucleocapsid,
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 arranges.
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 form 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.Specific preparation method is as follows：
In 100-140 in the HaakeRheomix OS laboratory mixing machines equipped with HaakePolyLab OS Rheodrive 7
DEG C the 1-10% benzophenone that 40-50g polymer and mass fraction are polymer is mixed.Then the 0.1-10g rubbers that will be obtained
Gum polymers granular materials is covered with PET film, and is heated to 120-160 DEG C between the plate of panel vulcanizing press.By applying
Add the pressure of 0.1-20MPa to cause within 1-10 minutes melt flows, forms the TPC films of diameter about 1-20cm.In order to be crosslinked, pass through work
Industry type mercury lamp irradiates 1-5 minutes in the distance apart from light source 10-15cm.The output power of lamp is 1000 watts.By being put on film
It sets the metallic plate of corresponding pattern and the crosslinking of spatial discrimination is carried out from ultraviolet light irradiation with the part of protective film.
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.
It specifically, can be by the composite photonic crystal material of above-mentioned preparation（Monodispersed polymer beads）, first prepare
At film.Film will become have color under extraneous stimulation from clear, colorless, and as different stimulations has differently
Color, to the sensing to 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 is at the temperature different from room temperature（It is higher or lower）It can be 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 from
The Fresnel reflection at the interface in composite material.In addition, the spacing between lattice plane in composite material is such as 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 it cuts
It cuts or uniaxial strain）, electromagnetic radiation, electric field, magnetic field, chemical reagent, biochemical reagents, biological agent.
It is preferably implemented in case at one, 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.In the first scenario（There is no ethyl alcohol）,
Material can be transparent.In the latter case（There are ethyl alcohol）, 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 sensings-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）Including the certain bits for selectively being combined 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 from being contaminated using preceding material, it is then exposed to interested fluid（Or other outside stimulus
Object）To determine whether there is specific analyte.
Material can 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
Respectively image is being formed using heterogeneity.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.Including can be used to after specific image anti-fake.
Description of the drawings
Fig. 1 is the representative TEM image of the PMMA@PEA-co-PBzMA core-shell particles of a diameter of 225nm.
Fig. 2 is the transparent photonic crystal for having the 225nm particles in the black and white background of Fudan University to prepare（TPC）The figure of film
Picture discloses the high grade of transparency of the film.
Fig. 3 is the SEM image of TPC films cross section, shows the high-sequential of PEA-co-PBzMA Medium Culture PMMA particles.
Fig. 4 is the afm image on the surface of TPC films, it is shown that the hexagon of photon crystal structure is orderly（111）Plane.
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 a diameter of 187nm made of PMMA PEA-co-PBzMA（Blue）, 225nm（Green）And 248nm
（It is red）TPC films display pattern after immersing ethyl alcohol photo.
Fig. 8 is the reflectance spectrum of the TPC films made of various sizes of PMMA PEA-co-PBzMA.
Fig. 9 is the transmitted spectrum of green TPC films.
Figure 10 is the transmitted spectrum of initial TPC and crosslinking and non-crosslinked diaphragm area after submergence in ethanol.
Figure 11 is the differentiation for the reflectance spectrum for immersing 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 the hysteresis loop for making membrane swelling/knot swelling with ethyl alcohol.
Figure 15 is the variation for the reflected intensity that the lower crosslinking of 10 cycles of reconciliation swelling and non-crosslinked diaphragm area are swollen with ethyl alcohol.
Figure 16 is to be swollen with ethyl alcohol（Top）With go to be swollen（Bottom）The image of film after 10 cycles.
Figure 17 is in different visual angles（It is from left to right 90 °, 80 °, 70 °, 60 °, 50 ° respectively）Lower be swollen with ethyl alcohol patterns
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 is the photo of film when immersing different ethanol/water mixtures（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 with ethanol content, the reflection wavelength of film and the variation of intensity in ethanol/water mixture.
Specific implementation mode
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 films
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 responded with different solvents 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 can be produced with storage
The TPC films 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 materials 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, and color changes with article towards the variation in the direction of the eyes of observer.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 is because applying 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 the reversible change of structural color（Angew. Chem. Int.
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 for the anti-purpose cheated in banknote or other secure files, 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 wetting（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）.
Report that the major defect of all anti-fake materials based on invisible photonic crystal pattern is due to it in the literature
Resonant light scattering caused by periodic structure makes them with intrinsic with corner effect schemochrome.In general, initial encryption state is
Through being 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 pattern different zones cannot be by
It eliminates, and is difficult to inhibit the failure during reversible encryption.
TPC films 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, prepare
TPC films can be highly transparent in the initial state（Transmissivity at visible wavelengths>99%）.Since TPC may quilt
The mixture of second alcohol and water（Refractive index ratio TPC is small）Swelling, causes the refractive index of nuclear particle and host material with different rates
Variation.This may lead to further strong resonance Bragg diffraction, this may cause encrypted structural color pattern to gradually appear,
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 lead to the complete appearing and subsiding for encrypting photon pattern, structure and optical perfection without losing film.This
The sightless TPC technologies of kind have compared with pervious method and are easy to large area manufacture（It is irradiated by ultraviolet light）It is very bright
True variation（From transparent to colored state）Particular advantages.
TPC films are made of the equal nuclear particle of refractive index and adjacent material core-shell particles, include specifically 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 particles of 225nm
TEM image.Being respectively provided with the similar product of 187nm and 248nm can also be obtained by identical step.Then by the material with
The photoinitiator of mass fraction 5%（Benzophenone）Mixing, and hot pressing 3 minutes under 140 DEG C and 10MPa, thus make PEA-co-
PBzMA shell materials merge to form continuous melting matrix, and PMMA cores are assembled under shear action and have（111）Crystal face is flat
Row is in the colloid lattice structure of the high-sequential of sample surfaces（Nat. Commun. 2016, 7, 1-10）.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）It 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 is carried out using SEM and AFM（Fig. 3, Fig. 4）.Accordingly
The SEM of film sample cross section schemes（Fig. 3）What the PMMA particles in the embedded PEA-co-PBzMA materials of display were ordered into, and hexagonal
The PMMA particles of shape arrangement（111 planes）It is high-visible in AFM（Fig. 4）, show that particle is high-sequential in TPC films
'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 works 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 strong color contrast between them（Fig. 6）.Film be constantly swollen from
And disclose encrypted image.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）Difference with high index.When by TPC submergences in ethanol, observe that two kinds of optics are existing
As：i）From transparent translation to colored state and ii）Occurs uniform white pattern on structure color background.Herein, blue
Color, green and red film（Fig. 6）Be diameter be respectively made of the particle of 187,225 and 248nm TPC films obtain
's.Due to the colloidal crystal structure of high-sequential, these three TPC films（Fig. 8）Reflectance spectrum in 441nm（Blue）, 561nm
（Green）And 636nm（It is red）Place shows 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 films, and can observe uniform purple on all surface.
The typical transmittance spectra of TPC films（Figure 10）Show 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 less 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 films are 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 does not interfere with 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 for recording reflectance spectrum to verify visually observation, and explains the revelation mechanism of invisible photon trace, these
All it is to use TPC as necessary to effective false proof device.In general, it is observed that two different effects in TPC films：
i）Become colored state from pellucidity due to the increase of refractive index in swelling process; ii）Due to the increase of lattice constant,
The structural color in normal incidence direction is with swelling red shift.However, compared with undosed region, UV irradiates selected film
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 strongly increases, 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 of red shift and reflection peak（Figure 12）.
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 located at initial anti-at 561 nm
It penetrates peak and is blue shifted to 475 nm, and the significant reduction of peak intensity, it is completely disappeared after evaporating 5 min（Figure 13）.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 in the reflected intensity of adduction reduction swelling ratio（Figure 14）.But after ethyl alcohol evaporating completely, TPC films
Initial transparent state can restore completely.
TPC can reversibly show its pattern by 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 conciliate 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 cycles, this leads to the complete appearing and subsiding for encrypting photon pattern, without damaging
Lose the structure and optical perfection of film（Figure 15）.
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 TPC film in Fig. 7 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 visual angles, we use red TPC films 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.
Availability about its solvation behavior and its in optical sensing application, has studied the optics of the TPC films of preparation
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 best 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 more than 100nm
（Figure 22）, i.e., from the 538nm of bragg peak（It is green）To 640nm（It is red）Variation.Along with red caused by being significantly swollen
It moves, reflected intensity increases therewith（Figure 22）With the visual color brightness of enhancing, therefore in host material have relatively low refraction
The volume fraction of the ethanol/water of rate increases.The significant change of this color shows that TPC films are that naked eyes can to the response of ethanol/water
See（Figure 20）.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 with the refractive index exactly matched
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 by being simply immersed in solvent on photon crystal structure
Universal color pattern.The method of this simplicity can generate the TPC films 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 kettles of argon inlet mouth and heating mantles are 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,
Three kinds of freshly prepd solution are then added：Dissolving 0.050g sodium pyrosulfites in 2.5g deionized waters；In 5g deionized waters
In dissolving 0.150g sodium peroxydisulfates；Dissolving 0.360g sodium pyrosulfites in 2.5g deionized waters；
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：0.050g is dissolved in 5g deionized waters
Sodium peroxydisulfate；
After being added 15 minutes, second of lotion group becomes：
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.Last time addition is completed synthesis after sixty minutes and is terminated.Latex is passed through into 100 μm of sieve mistakes
Filter, and be added drop-wise under stiring in the mixture of 1.7L methanol and 4mL concentrated sodium chloride aqueous solutions.Polymer coagulation is simultaneously tied in stirring
The sediment of sedimentation is formed after beam.Clear supernatant is decanted, sediment is mixed with 0.3L deionized waters, then passes through 100
Micron screen filtration.Filter cake is three days dry in 45 DEG C of convection oven.
2. preparing monodispersed core-middle layer-core-shell polymeric particles
It is equipped with stirring, is condensed, the 1L reaction kettles of argon inlet mouth and heating mantles are 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,
Three kinds of freshly prepd solution are then added：Dissolving 0.050g sodium pyrosulfites in 2.5g deionized waters；In 5g deionized waters
In dissolving 0.150g sodium peroxydisulfates；Dissolving 0.360g sodium pyrosulfites in 2.5g deionized waters；
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：It is dissolved in 5g deionized waters
0.050g sodium peroxydisulfates；
After being added 15 minutes, second of lotion group becomes：
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.Last time addition is completed synthesis after sixty minutes and is terminated.Latex is passed through into 100 μm of sieve mistakes
Filter, and be added drop-wise under stiring in the mixture of 1.7L methanol and 4mL concentrated sodium chloride aqueous solutions.Polymer coagulation is simultaneously tied in stirring
The sediment of sedimentation is formed after beam.Clear supernatant is decanted, sediment is mixed with 0.3L deionized waters, then passes through 100
Micron screen filtration.Filter cake is three days dry in 45 DEG C of convection oven.
It is processed 3. preparing the photoinitiator that addition can be additional photocuring and being used for melt molding in the composite
It will in 120 DEG C in the HaakeRheomix OS laboratory mixing machines equipped with HaakePolyLab OS Rheodrive 7
50g polymer and 5% benzophenone（Aladdin）Mixing.
4. hot pressing is for crystal film with photon
A part for 1 gram of rubber-like polymer is covered with PET film, and is heated to 140 DEG C between the plate of panel vulcanizing press.
Pressure by applying 100MPa causes melt flows for 3 minutes, forms the TPC films of diameter about 10cm.
5. ultraviolet radiation is crosslinked and patterning crystal film with photon
In order to be crosslinked, pass through industrial mercury lamp（Dongguan Er Gu photoelectricity technology corporation, Ltd.s）In the distance irradiation apart from light source 15cm
1 minute.The output power of lamp is 1000 watts.Exempted from the part of protective film by placing the metallic plate of corresponding pattern on film
It is crosslinked by ultraviolet light irradiation to carry out spatial discrimination.
The material citing used
Methyl methacrylate（MMA）, ethyl acrylate（EA）And butanediol diacrylate（BDDA）Derived from Shanghai traditional Chinese medicines
Learn reagent Co., Ltd（China）, allyl methacrylate（ALMA）And benzyl methacrylate（BzMA）Derived from Aladdin
Learn Co., Ltd（China）And Dow Chemical（China）Dowfax 2A1.Every other chemicals is all from Shanghai traditional Chinese medicines
Chemical reagent Co., Ltd（China）With Aladdin Chemical Co., Ltd.（China）Purchase, and use as it is.For lotion
Before polymerization, destabilizing agent is removed from monomer.For this purpose, using alumina column（Alkalinity, 50-200 mesh, the limited public affairs of Aladdin chemistry
Department）, remove MMA, EA, BzMA, the stabilizer in ALMA and BDDA.
Claims (16)
1. a kind of composite photonic crystal material, which is characterized in that include mainly two kinds of materials, 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 respective 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 water white transparency；
The form of the material is the grain shape of nucleocapsid, i.e., each particle includes core and the shell around the core, also,
The core i.e. the first material three-dimensional periodic in the host material that shell is formed i.e. second of material arranges.
2. composite photonic crystal material according to claim 1, which is characterized in that the nuclear particle average grain diameter is 5nm
To 2000nm；And nuclear particle has monodispersed Size Distribution.
3. composite photonic crystal material according to claim 1, which is characterized in that the nuclear particle is with closely packed three-dimensional
Lattice mode is scattered in host material, i.e., nuclear particle is placed in the form of face-centered cubic lattice in host material；And the core
Particle lattice（111）Plane is basically parallel to the surface of material.
4. composite photonic crystal material according to claim 1, which is characterized in that nuclear material i.e. the first material cannot flow
It moves, or will not be flowed at the temperature more than the fusing point of shell material, this is by using with corresponding high glass-transition temperature
The polymer material of Tg is realized.
5. composite photonic crystal material according to claim 4, which is characterized in that the poly- methyl of the first material selection
Methyl acrylate PMMA；Second of material selection Polyacrylate materials and/or polybenzyl methacrylate PBzMA；
Wherein, Polyacrylate materials are selected from polyethyl acrylate, Vinalac 5920, and Isobutyl methacrylate gathers
Tert-butyl Methacrylate, polyethyl methacrylate；And by regulating and controlling Polyacrylate materials and polymethylacrylic acid benzyl
The mass ratio of ester so that the mean refractive index of host material is equal with the refractive index of the first material, so that complex light
Sub- material is transparent in original state.
6. the composite photonic crystal material according to one of claim 1-5, which is characterized in that the nucleocapsid particles further include
Middle layer, i.e. shell are combined by middle layer with core；The middle layer is crosslinking or at least partly crosslinked polymeric layer.
7. composite photonic crystal material according to claim 6, which is characterized in that the middle layer quality is stratum nucleare
0.01-99%；The thickness of Polymer interlayers is 10-20nm.
8. composite photonic crystal material according to claim 7, which is characterized in that the intermediate layer material be two functions or
Low functional monomer.
9. the composite photonic crystal material according to one of claim 1-5,7-8, which is characterized in that also include auxiliary agent and/
Or additive, these components are used for providing the property needed for material；This analog assistant and/or additive are：Antioxidant, UV stablize
Agent, fungicide, plasticizer, coalescents, leveling auxiliary agent, filler melt auxiliary agent, adhesive, releasing agent, using auxiliary agent, demoulding
Auxiliary agent and viscosity modifier.
10. a kind of preparation method of composite photonic crystal material as described in one of claim 1-9, which is characterized in that specific
Step is：
（1）It is equipped with stirring, condenses, the 1L reaction kettles of argon inlet mouth and heating mantles, be heated to 65-85 DEG C, and lead to
Argon gas is protected；By 0.1-0.5g lauryl sodium sulfate, 100-300g deionized waters, 1-5g methyl methacrylates, 1-5g fourths
Omega-diol diacrylate is pre-mixed, and is fed in reactor；Agitator speed is adjusted to 200-500rpm, monitors mixture
Three kinds of freshly prepared solution are added at 55-75 DEG C in temperature：0.01-0.1g sodium pyrosulfites are dissolved in 1-5g deionized waters
In；0.01-0.1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；0.1-0.5g sodium pyrosulfites are dissolved in 1-5g deionizations
In water；
（2）After reaction 2-30 minutes, it is added dropwise with 0.1-10mL/minute rate and feeds lotion composed of the following components： 0.1-
1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 0.1-1gDowfax2A1（Dow Chemicals）, 10-100g deionizations
Water, 10-100g methyl methacrylates, 10-100g butanediol diacrylates；
（3）Add 10-30 minutes latter, to be made of following component with 0.1-10mL/minute rate dropwise addition charging fresh solution：
0.01-1g sodium peroxydisulfates are dissolved in 1-10g deionized waters；
（4）Add second of breast that be 5-30 minutes latter, then being made of following component with 0.1-10mL/minute rate dropwise addition charging
Liquid：0.1-1g lauryl sodium sulfate, 0.1-1g potassium hydroxide, 10-200g deionized waters, 10-200g ethyl acrylates, 10-
100g benzyl methacrylates；
（5）10-60 minutes after the completion of addition, synthetic reaction terminates, and obtains polymer emulsion；Latex is passed through into 100 μm of sieve mistakes
Filter, and be added dropwise under stiring in the mixture of 1-10L methanol and 1-10mL saturated sodium-chloride water solutions, polymer coagulation
And the sediment of sedimentation is formed after stirring；Clear supernatant is decanted, sediment is mixed with 0.1-1L deionized waters,
Then pass through 100 microns of screen filtrations；Filter cake in 30-60 DEG C of baking oven dry 1-3 days to get to monodispersed core-shell structural
Polymer beads.
11. the preparation method of composite photonic crystal material according to claim 10, which is characterized in that in step（3）With
Step（4）Between further include：
Step（3-1）, 5-30 minutes after addition, then be added dropwise that charging is made of following component with 0.1-10mL/minute rate the
Two kinds of lotions：0.01-0.1g lauryl sodium sulfate, 0.1-1gDowfax 2A1,10-100g deionized waters, 10-100g methyl
Methyl acrylate, 1-10g benzyl methacrylates, 1-10g allyl methacrylates.
12. the preparation method of composite photonic crystal material according to claim 10, which is characterized in that further include, for
The particle of monodisperse nucleocapsid, heating core-shell material make nuclear particle to the flowable temperature of shell under the action of mechanical force
Three-dimensional periodic arranges in the host material that shell is formed；
The heating temperature is at least 40 DEG C higher than the glass transition temperature of the shell material of nucleocapsid particles.
13. the preparation method of composite photonic crystal material according to claim 12, 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;,
Lamination, blow molding, fiber drawing, embossing and nano impression.
14. the application as sensor device of the composite photonic crystal material as described in one of claim 1-9, the sensing
Device device includes at least one composite photonic crystal material；The sensor device passes through recombination photons under external stimulation
Crystalline material detects the variation of outside stimulus from transparent to coloured variation.
15. application according to claim 14, which is characterized in that by by the composite photonic crystal material preparation at thin
Film, the film become have color under extraneous stimulation from clear, colorless, and as different stimulations has differently color,
To the sensing to environmental stimuli；The outside stimulus is one or more of：Temperature, pH, fluid, pressure or stress, are answered
Become, electromagnetic radiation, electric field, magnetic field, chemical reagent, biochemical reagents, biological agent.
16. application according to claim 15, which is characterized in that be designed with specific pattern on film, pattern is in spy
It shows and disappears under fixed incentive condition, to realize anti-fake function.
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