CN102708773A - Magnetic response photonic crystal anti-fake label and manufacturing method thereof - Google Patents
Magnetic response photonic crystal anti-fake label and manufacturing method thereof Download PDFInfo
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- CN102708773A CN102708773A CN2012102130142A CN201210213014A CN102708773A CN 102708773 A CN102708773 A CN 102708773A CN 2012102130142 A CN2012102130142 A CN 2012102130142A CN 201210213014 A CN201210213014 A CN 201210213014A CN 102708773 A CN102708773 A CN 102708773A
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Abstract
The invention provides a magnetic response photonic crystal anti-fake label and a manufacturing method thereof. The magnetic response photonic crystal anti-fake label provided by the invention comprises a plurality of patterns, wherein the patterns comprise polymer substrates and ethylene glycol micro droplets which contain carbon-coated superparamagnetism ferroferric oxide colloidal nanometer particles and are encapsulated in the polymer substrates; single pattern among the patterns at least comprises two kinds of carbon-coated superparamagnetism ferroferric oxide colloidal nanometer particles of different particle diameters. In the magnetic response photonic crystal anti-fake label provided by the invention, the carbon-coated superparamagnetism ferroferric oxide colloidal nanometer particles of different particle diameters are self-assembled respectively to acquire a multi-photon band gap structure under the action of magnetic fields, so that visible light of different wavelengths can be reflected and is superposed to acquire a new colour; and the color can not be copied by common pigment or dye color, has a good anti-fake effect and good color adjustability, and is beneficial to application.
Description
Technical field
The present invention relates to functional form photonic crystal technical field, relate in particular to a kind of magnetic response photonic crystal anti-counterfeiting mark and preparation method thereof.
Background technology
Photonic crystal is a kind of periodic dielectric material with photonic band gap structure, can regulate and control effectively the direction of propagation of light, has the character that is similar to electronic semi-conductor.From 1987 by Yablonovitch (Yablonovitch E.Phys.Rev.Lett.; 1987; 58:2059 ~ 2061.) and John (John S.Phys.Rev.Lett., 1987,58:2486 ~ 2488.) etc. propose after the photonic crystal notion; Great concern has been received in the research of photonic crystal, and has obtained development rapidly.The photonic crystal optical semiconductor that is otherwise known as, material contact that it is considered to following photon industry has broad application prospects in fields such as all kinds of optical device, fiber optics communications and photon calculating.
Band gap can be modulated photon crystal material and is one type and through regulating self photonic band gap structure the outfield stimulated the photon crystal material of making response, is called functional photon crystal material or response photon crystal material again.The response photonic crystal is the bandgap structure photonic crystal of the variation of environment with response to external world; Since Asher in 1997 etc. had developed novel photonic crystal chemistry intelligent sensing material, the research work that responds the photon crystal material of different external environments was little by little carried out.Different according to external environment, the response photonic crystal can be divided into chemical response, physical responses property (like temperature, mechanical force, electric field and magnetic responsiveness etc.) and biological responding photonic crystal (like organic phosphide, creatinine response etc.) simply on macroscopic view.The response evaluation of most of response photonic crystal all uses the displacement of diffraction peak to characterize; If the diffraction peak of response photonic crystal drops in visible or the near infrared spectral range; Material can show change in color on macroscopic view, this is a kind of expression way of response the most intuitively.At present; The response photon crystal material is applied in temperature sensor, humidity sensor, pressure transducer, biological monitoring, chemical reagent monitoring, fingerprint recognition, color monitor, colored printing, military field such as false proof widely, can be used for colour print, camouflage and color monitor like the liquid photonic crystal of magnetic response; But the monitoring of response photonic crystal gel using glucose, ion monitoring and fingerprint monitoring etc.
Based on the excellent character of response photon crystal material, multiple response photon crystal material, its preparation method and application thereof are disclosed in the prior art.For example; Germany's advanced material magazine has been reported a kind of preparation method (Adv.Mater. of the photonic crystal paper based on the magnetic response photonic crystal; 2009,21:4259 ~ 4264.), at first the ferroferric oxide magnetic nano-particles with the silicon dioxide parcel forms the 1-D photon crystal structure under induced by magnetic field; Utilize polyglycol acrylic acid and light trigger 2 then; 2-dimethoxy-2-phenyl acetophenone carries out polyreaction under the ultraviolet ray irradiation, make this 1-D photon crystal structure solidify, and obtains photonic crystal paper.The experiment proof; This kind photonic crystal paper acceptable salts WS carries out writing above that reversiblely; And the font color that obtains is bright-coloured, and this photonic crystal paper shows good stable property and environment friendly, is a kind of novel writing material with potential application foreground.In addition; The son periodical magazine Nature Photonics of Britain Nature Journal society has been reported a kind of colour print technology (Nature Photonics based on the magnetic response photonic crystal; 2009,3:534 ~ 540.), it solidifies light-cured resin through ultraviolet light beam; And then solidify and to be blended in photon crystal structure wherein, thereby realized the curing of bright-coloured schemochrome.In addition, it can also realize the adjusting to photonic band gap through magnetic field, and then realizes the adjusting of color, thereby has realized colour print.This colour print technology based on the magnetic responsiveness photonic crystal can realize bright-coloured colour print true to nature, and technology is simple ripe, is a kind of colour print technology with very big application prospect.
The character that manifests bright-colored based on the response photonic crystal; The disclosed response photonic crystal of prior art has character and wide application space preferably; Yet when being applied to the commodity counterfeit prevention field; Because its glow color is easy to by common pigments or dyestuff look imitated, makes its antifalse effect lower, is unfavorable for its application.
Summary of the invention
The object of the present invention is to provide a kind of magnetic response photonic crystal anti-counterfeiting mark and preparation method thereof, the color that magnetic response photonic crystal anti-counterfeiting mark provided by the invention manifests is difficult for by common pigments or dyestuff look imitated, has good antifalse effect.
The invention provides a kind of magnetic response photonic crystal anti-counterfeiting mark, comprising:
A plurality of patterns, said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate;
At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.
Preferably, the particle diameter of said carbon coating superparamagnetism tri-iron tetroxide colloid nano particle is 110nm ~ 130nm, 140nm ~ 160nm or 190nm ~ 210nm.
Preferably, said polymkeric substance is polysiloxane condensate, polyglycol double methacrylate condensate, polyvinyl alcohol (PVA) condensate or polyacrylamide polymerization body.
Preferably, said polymkeric substance is the polysiloxane condensate.
The invention provides a kind of preparation method of magnetic response photonic crystal anti-counterfeiting mark, may further comprise the steps:
The ethylene glycol solution that polymerization single polymerization monomer, hardening agent and the carbon that contains different-grain diameter is coated superparamagnetism tri-iron tetroxide colloid nano particle mixes, and obtains jelly;
Said jelly is placed a plurality of patterns of anti-counterfeiting mark pattern template; Carry out obtaining magnetic response photonic crystal anti-counterfeiting mark after the polyreaction, comprise at least in the single pattern in the said pattern that the carbon of two kinds of different-grain diameters coats superparamagnetism four iron oxide colloid nano particles.
Preferably, the said carbon that contains different-grain diameter coats the mass concentration that carbon in the ethylene glycol solution of superparamagnetism tri-iron tetroxide colloid nano particle coats superparamagnetism tri-iron tetroxide colloid nano particle and is (0.005-0.020) g/mL.
Preferably, the quality of the quality of said polymerization single polymerization monomer, hardening agent and the said mass ratio that contains the ethylene glycol solution of carbon coating superparamagnetism tri-iron tetroxide colloid nano particle are 10: (1 ~ 2): (1 ~ 10).
Preferably, said polymerization single polymerization monomer is siloxanyl monomers, ethylene glycol diacrylate monomer, vinyl alcohol monomer or acrylamide monomer.
Preferably, said polymerization single polymerization monomer is a siloxanyl monomers.
Preferably, the temperature of said polyreaction is 50 ℃ ~ 80 ℃;
The time of said polyreaction is 1 h ~ 5 hours.
The present invention provides a kind of magnetic response photonic crystal anti-counterfeiting mark, comprises a plurality of patterns, and said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate; At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.The present invention places magnetic field with the magnetic response photonic crystal anti-counterfeiting mark that provides, and said magnetic response photonic crystal anti-counterfeiting mark can reach false proof effect by colourless to colored transformation.At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the pattern of magnetic response photonic crystal anti-counterfeiting mark provided by the invention coats superparamagnetism tri-iron tetroxide colloid nano particle; Under the effect of externally-applied magnetic field; Wherein the particle of greater particle size has bigger induced magnetic moment; Can at first have bigger enough magnetic aggregation force, at first carry out self assembly; And than the particle of small particle diameter, because the induced magnetic moment that has is less, under the situation that applies same magnetic field intensity, the magnetic aggregation force is less, so the bigger particle of self assembly behavior relative grain size is comparatively slow.The final so different particle of particle diameter that caused carries out self assembly respectively; And the particle than small particle diameter carries out self assembly on the aggregate of the particle self assembly formation of greater particle size, finally obtain the uniform composite particle of distribution of particles, forms multi-photon band gap heterojunction structure; Make the single pattern of magnetic response photonic crystal anti-counterfeiting mark provided by the invention all can reflect the visible light of different wave length; The visible light of this different wave length obtains new color after space stack, along with the withdrawing and applying of magnetic field, its can take place colourless-coloured stablize reversible transformation; And manifest this bright-colored; Colour developing mechanism is different fully with the colour developing mechanism of common dye and pigment, can be not imitated by common pigments or dyestuff look, have good antifalse effect.
After the ethylene glycol solution that the present invention coats superparamagnetism tri-iron tetroxide colloid nano particle with polymerization single polymerization monomer, hardening agent and the carbon that contains different-grain diameter mixes; Place the anti-counterfeiting mark pattern template to carry out polyreaction the jelly that obtains, can obtain magnetic response photonic crystal anti-counterfeiting mark.Method provided by the invention is simple, easy operating, and old of starting material are cheap, are easy to large-scale industrialization production.In addition, magnetic response photonic crystal anti-counterfeiting mark provided by the invention places magnetic field can have antifalse effect, and is simple and practical, is beneficial to its large-scale promotion and uses.
Description of drawings
The carbon that Fig. 1 obtains for the embodiment of the invention 1 coats the XRD figure spectrum of superparamagnetism tri-iron tetroxide colloid nano particle;
The carbon that Fig. 2 obtains for the embodiment of the invention 1 coats the TEM image of superparamagnetism tri-iron tetroxide colloid nano particle;
The carbon that Fig. 3 obtains for the embodiment of the invention 1 coats the Raman spectrum of superparamagnetism tri-iron tetroxide colloid nano particle;
The carbon that Fig. 4 obtains for the embodiment of the invention 1 coats the infrared spectrogram of superparamagnetism tri-iron tetroxide colloid nano particle;
The carbon that Fig. 5 obtains for the embodiment of the invention 1 coats the magnetic hysteresis loop of superparamagnetism tri-iron tetroxide colloid nano particle;
The reflectance spectrum of the superparamagnetism tri-iron tetroxide colloid nano particle that the carbon that Fig. 6 obtains for the embodiment of the invention 1 coats;
The carbon of two kinds of different-grain diameters that Fig. 7 obtains for the embodiment of the invention 2 ~ 4 coats the reflectance spectrum of superparamagnetism tri-iron tetroxide colloid nano mix particles solution.
Embodiment
The present invention provides a kind of magnetic response photonic crystal anti-counterfeiting mark, comprising:
A plurality of patterns, said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate;
Single pattern in the said pattern comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle.
Magnetic response photonic crystal anti-counterfeiting mark provided by the invention comprises a plurality of patterns, and said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate; At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.When magnetic response photonic crystal anti-counterfeiting mark provided by the invention is placed magnetic field; Wherein the carbon of different-grain diameter coats superparamagnetism tri-iron tetroxide colloid nano particle and under the effect in magnetic field, carries out self assembly respectively and obtain multi-photon band gap heterojunction structure; Particle in each pattern can reflect the visible light of different wave length simultaneously, after the stack of space, can show gorgeous color, and the color that manifests is a tertiary colour; Have variation and good controllability; Colour developing mechanism is different fully with the colour developing mechanism of common dye and pigment, can be not imitated by common pigment or dyestuff look, have anti-fake effect preferably.
Magnetic response photonic crystal anti-counterfeiting mark provided by the invention comprises a plurality of patterns; Said pattern comprises polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate, and comprises at least in the single pattern in the said pattern that the carbon of two kinds of different-grain diameters coats the superparamagnetism ferriferrous oxide nano-particle;
The present invention does not have special limitation to the shape of said pattern, adopts the shape of security pattern well known to those skilled in the art to get final product.In the present invention, said pattern can be a letter; It can be Chinese character; It can be numeral; Can be the figure of different shape, like circle, triangle, pentagon, rectangle, rhombus etc.; It can be the combination of the figure of above-mentioned letter, Chinese character, numeral or different shape.
In the present invention, said pattern comprises polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate.Said gel-type vehicle is realized carbon is coated the fixing of superparamagnetism tri-iron tetroxide colloid nano particle; The present invention does not have special limitation to the kind of said gel; Can realize getting final product to containing the encapsulation that carbon coats the little drop of monoethylene glycol of superparamagnetism tri-iron tetroxide colloid nano particle; Make it can in mould, present certain shape, obtain difform magnetic response photonic crystal anti-counterfeiting mark.In the present invention, said polymkeric substance is preferably polysiloxane condensate, polyglycol double methacrylate condensate, polyvinyl alcohol (PVA) condensate or polyacrylamide polymerization body, more preferably polysiloxane condensate; Most preferably be the dimethyl silicone polymer condensate, gather methyl cyclosiloxane condensate, gather the amino silicone condensate, PSI condensate or polyethers polysiloxane condensate, the most be preferably the dimethyl silicone polymer condensate or gather methyl cyclosiloxane condensate.
Magnetic response photonic crystal anti-counterfeiting mark provided by the invention comprises the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the described polymer substrate of technique scheme; At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle, and the particle diameter that said carbon coats superparamagnetism tri-iron tetroxide colloid nano particle is preferably 110nm ~ 130nm, 140nm ~ 160nm or 190nm ~ 210nm.Single pattern in the pattern of magnetic response photonic crystal anti-counterfeiting mark provided by the invention comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle; When being placed in the magnetic field; The carbon of the different-grain diameter in single pattern coats superparamagnetism tri-iron tetroxide colloid nano particle under the effect of same magnetic field, can produce different magnetic aggregation force, obtains the multi-photon bandgap structure thereby make it carry out self assembly separately; It can reflect the natural light of two kinds or two kinds different wave lengths; The natural light of these two kinds or two kinds different wave lengths obtains new color after in the space, superposeing, and along with the withdrawing and applying of magnetic field, magnetic response photonic crystal anti-counterfeiting mark provided by the invention can have colourless to coloured reversible transformation of stablizing; And manifest bright-colored; Its colour developing mechanism is different fully with the colour developing matrix of common dye and pigment, can be not imitated by common pigments or dyestuff look, have good antifalse effect.
In the present invention, said carbon coats superparamagnetism tri-iron tetroxide colloid nano particle preferably according to following method preparation:
Ferrocene and hydrogen peroxide are dissolved in acetone, and sealing, 200 ℃ ~ 230 ℃ reactions down obtain carbon and coat superparamagnetism tri-iron tetroxide colloid nano particle.
The present invention preferably at first is dissolved in ferrocene in the acetone, obtains the solution of ferrocene, to the WS that wherein adds hydrogen peroxide, obtains mixed solution then.The present invention preferably carries out ultrasonic dispersion with it after being dissolved in ferrocene in the acetone, obtain the solution of ferrocene; In the solution of said ferrocene, dropwise add the WS of hydrogen peroxide then, carry out obtaining mixed solution after the magnetic agitation.The present invention does not have special limitation to the condition of said ultrasonic dispersion like ultrasonic temperature, ultrasonic time etc., adopts the technical scheme of ultrasonic dispersion well known to those skilled in the art to get final product; The condition of magnetic agitation according to the invention; Do not have special limitation like stirring rate, mixing time etc., adopt the technical scheme of magnetic agitation well known to those skilled in the art to get final product, in the present invention; The speed of said magnetic agitation is preferably 800r/min ~ 2000r/min; 1000r/min ~ 1500r/min more preferably, the time of said stirring is preferably 20min ~ 60min, more preferably 30min ~ 50min.
In the present invention, the quality of said ferrocene and the volume ratio of said acetone are preferably (0.1g ~ 0.5g): 30mL, more preferably (0.2g ~ 0.3g): 30; The mass concentration of said aqueous hydrogen peroxide solution is preferably 20% ~ 50%, and more preferably 25% ~ 40%; The quality of said ferrocene and the volume ratio of said aqueous hydrogen peroxide solution are preferably (0.1g ~ 0.5g): (1.0mL ~ 2.0L), more preferably (0.2g ~ 0.3g): (1.0mL ~ 2.0L).
After obtaining the mixed solution of ferrocene and hydrogen peroxide, the present invention carries out reacting by heating after said mixed solution is sealed, and obtains carbon and coats superparamagnetism tri-iron tetroxide colloid nano particle.The present invention is the said mixed solution of heating under the condition of sealing; The temperature of said heating is preferably 200 ℃ ~ 230 ℃, more preferably 205 ℃ ~ 220 ℃; The time of said heating is preferably 48 h ~ 96 hours, and more preferably 60 h ~ are 72 hours.
After heating was accomplished, the present invention preferably was cooled to room temperature with reaction system, obtained carbon and coated superparamagnetism tri-iron tetroxide colloid nano particle.
After the present invention is cooled to room temperature with reaction system, preferably the product that obtains is washed and drying, obtain carbon and coat superparamagnetism tri-iron tetroxide colloid nano particle.The present invention does not have special limitation to said washing and dry method, adopts washing well known to those skilled in the art and dry technical scheme to get final product.The present invention preferably respectively cleans product 2 times ~ 5 times with acetone and ethanol respectively; After cleaning completion; Product after the cleaning that the present invention preferably will obtain carries out vacuum drying, and said vacuum drying is worked as temperature and is preferably 30 ℃ ~ 50 ℃, more preferably 35 ℃ ~ 45 ℃; The said vacuum drying time is preferably 4 h ~ 10 hours, and more preferably 5 h ~ are 8 hours.
After the preparation process was accomplished, the present invention carried out the X-ray diffraction analysis with the product that obtains, and the result shows in the product that obtains tri-iron tetroxide is arranged; The present invention carries out the raman spectroscopy scans analysis with the product that obtains, and the result shows, in the Raman spectrum at 1585cm
-1And 1378cm
-1There is the peak at the place, and the carbon of this corresponding sp2 hydridization has confirmed that the component on product surface is a carbon; The present invention carries out the transmission electron microscope scanning analysis with the product that obtains; The result shows; Said product is the even spheroid with nucleocapsid structure; Particle diameter is respectively 110nm ~ 130nm, 140nm ~ 160nm and 190nm ~ 210nm, and inner core is a plurality of particle diameters less than the molecular group of the nanoparticle of 20nm bunch; The present invention detects the magnetic hysteresis loop of the product that obtains, and the result shows that the product that the present invention obtains does not at room temperature have coercive force, presents superparamagnetism.Can find out that by above test result the product that above-mentioned preparation method obtains is that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle.
In magnetic response photonic crystal anti-counterfeiting mark provided by the invention; Single pattern in its pattern comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle; When it is applied magnetic field; The carbon of different-grain diameter coats superparamagnetism tri-iron tetroxide colloid nano particle under the effect of externally-applied magnetic field; Can produce different magnetic aggregation force, the magnetic aggregation force of generation can be assembled towards local maximum field gradient by charmed particle, greatly influences the self assembly behavior of superparamagnetism colloid nano particle.In magnetic response photonic crystal anti-counterfeiting mark provided by the invention, the particle of greater particle size has bigger induced magnetic moment, therefore when applying same magnetic field intensity, understands because at first have bigger enough magnetic aggregation force, and carries out self assembly earlier.And than the particle of particle diameter, because its induced magnetic moment is less, when applying same magnetic field intensity, because have less magnetic aggregation force, the particle that self assembly behavior relative grain size is bigger is comparatively slow.Final like this having caused; The particle that size is different carries out self assembly respectively, and finally formation has multi-photon band gap heterojunction structure, and it can reflect the visible light of different wave length simultaneously; The visible light of this different wave length has just formed new color after the stack of space.Because the colour developing of magnetic response photonic crystal anti-counterfeiting mark provided by the invention mechanism is different with the colour developing mechanism of common dye or pigment, can be not imitated by common dye or pigment, have good antifalse effect.And; The color of magnetic response photonic crystal anti-counterfeiting mark provided by the invention has diversity; Can change the color of magnetic response photonic crystal through the particle diameter that changes carbon coating superparamagnetism tri-iron tetroxide colloid nano particle, make it have good tunable performance, be beneficial to its application.
The present invention provides a kind of preparation method of magnetic response photonic crystal anti-counterfeiting mark, may further comprise the steps:
The ethylene glycol solution that polymerization single polymerization monomer, hardening agent and the carbon that contains different-grain diameter is coated superparamagnetism tri-iron tetroxide colloid nano particle mixes, and obtains jelly;
Said jelly is placed a plurality of patterns of anti-counterfeiting mark pattern template; Carry out obtaining magnetic response photonic crystal anti-counterfeiting mark after the polyreaction, comprise at least in the single pattern in the said pattern that the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle.
Ethylene glycol solution, polymerization single polymerization monomer and hardening agent that the present invention at first will contain the carbon coating superparamagnetism tri-iron tetroxide colloid nano particle of different-grain diameter mix, and obtain jelly.The present invention does not have special limitation to the mode of said mixing, adopts the hybrid mode of each raw material in the polyreaction well known to those skilled in the art to get final product.The present invention is dissolved in the carbon coating superparamagnetism tri-iron tetroxide colloid nano particle of different-grain diameter in the monoethylene glycol earlier, obtains mixed solution, then the mixed solution that obtains, polymerization single polymerization monomer and hardening agent is mixed, and obtains jelly.The present invention coats the mass concentration that carbon in the ethylene glycol solution of superparamagnetism tri-iron tetroxide colloid nano particle coats superparamagnetism tri-iron tetroxide colloid nano particle to the said carbon that contains different-grain diameter do not have special limitation; The mass concentration that adopts carbon well known to those skilled in the art to coat superparamagnetism tri-iron tetroxide colloid nano particle ethylene glycol solution gets final product; In the present invention; The said carbon that contains different-grain diameter coats the mass concentration that carbon in the ethylene glycol solution of superparamagnetism tri-iron tetroxide colloid nano particle coats superparamagnetism tri-iron tetroxide colloid nano particle and is preferably (0.005 ~ 0.020) g/mL, more preferably (0.01 ~ 0.015) g/mL.
The present invention does not have special limitation to said polymerization single polymerization monomer; Can obtain polymer substrate through polyreaction; Said polymer substrate can realize that the encapsulation that the carbon that contains different-grain diameter is coated the little drop of monoethylene glycol of superparamagnetism tri-iron tetroxide colloid nano particle gets final product; Make it in a plurality of patterns of mould, present different shapes, thereby obtain difform magnetic response photonic crystal anti-counterfeiting mark.In the present invention; Said polymerization single polymerization monomer is preferably siloxanyl monomers, ethylene glycol diacrylate monomer, vinyl alcohol monomer or acrylamide monomer; Siloxanyl monomers more preferably; Most preferably be dimethyl siloxane, methyl cyclosiloxane, amino silicone, methyl phenyl siloxane or ethers siloxane, the most be preferably dimethyl siloxane or methyl cyclosiloxane.The present invention preferably stirs after the said carbon that contains different-grain diameter is coated ethylene glycol solution, polymerization single polymerization monomer and the hardening agent mixing of superparamagnetism tri-iron tetroxide colloid nano particle, forms jelly equably respectively.The present invention does not have special limitation to stirring method, adopts the technical scheme of stirring well known to those skilled in the art to get final product, and can be mechanical raking, can be manual stirring yet, obtains uniform jelly until stirring and gets final product.The present invention does not have special limitation to said hardening agent, adopts hardening agent well known to those skilled in the art to get final product, and can be fatty amine class hardening agent like said hardening agent, can be the aromatic amines hardening agent yet, can also be amide group amine hardening agent.
After obtaining jelly; The present invention places said jelly a plurality of patterns of anti-counterfeiting mark pattern template respectively; Carry out obtaining magnetic response photonic crystal anti-counterfeiting mark after the polyreaction, the single pattern in the said pattern comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle.In order to obtain difform magnetic response photonic crystal anti-counterfeiting mark; After the present invention obtains jelly; Preferably said jelly is placed a plurality of patterns of template respectively, the shape of the magnetic response photonic crystal anti-counterfeiting mark that obtains according to the shape adjustment of die plate pattern, and then carry out polyreaction; Obtain magnetic response photonic crystal anti-counterfeiting mark, the single pattern in the said pattern comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle.The present invention does not have special limitation to the pattern of said template, adopts anti-counterfeiting mark pattern template well known to those skilled in the art to get final product.In the present invention, the pattern of said template can be the combination of a plurality of letters, also can be the combination of a plurality of numerals, also can be the combination of Chinese character, can also be the combination of the figure of different shape, like circle, triangle, pentagon, rectangle, rhombus etc.; It can be the combination of above-mentioned letter, Chinese character, numeral or various patterns; The anti-counterfeiting mark template that jelly is arranged that the present invention preferably will obtain places baking oven to carry out polyreaction, and the temperature of said polyreaction is preferably 50 ℃ ~ 80 ℃, more preferably 55 ℃ ~ 70 ℃; The time of said polyreaction is preferably 1 h ~ 5 hours, and more preferably 1.5 h ~ are 3 hours.
After the ethylene glycol solution that the present invention coats superparamagnetism tri-iron tetroxide colloid nano particle with polymerization single polymerization monomer, hardening agent and the carbon that contains different-grain diameter mixes; Respectively the jelly that obtains is placed a plurality of patterns of anti-counterfeiting mark pattern template; The carbon that in the single pattern of said pattern, comprises two kinds of different-grain diameters at least coats superparamagnetism tri-iron tetroxide colloid nano particle; Carry out polyreaction, can obtain magnetic response photonic crystal anti-counterfeiting mark.Method provided by the invention is simple, easy operating, and old of starting material are cheap, are easy to large-scale industrialization production.
Magnetic response photonic crystal anti-counterfeiting mark provided by the invention preferably adopts following method of application, may further comprise the steps:
The magnetic response photonic crystal anti-counterfeiting mark that technique scheme described magnetic response photonic crystal anti-counterfeiting mark or the said preparation method of technique scheme are obtained places magnetic field, and said magnetic response photonic crystal anti-counterfeiting mark is from the colourless colour that becomes.
The magnetic response photonic crystal anti-counterfeiting mark that the present invention obtains; Along with the applying and cancelling of magnetic field, can stablize realize reversiblely coloured to colourless transformation, and because its color is multiple monochromatic stack; Use common pigment or dyestuff look to copy, have antifalse effect preferably.The present invention does not have special limitation to the intensity in the magnetic field that applies; Adopt the magnetic field intensity as the response of magnetic response photonic crystal well known to those skilled in the art to get final product; In the present invention, the intensity in said magnetic field is preferably 0.01T ~ 0.2T, more preferably 0.05T ~ 0.1T.
To being dispersed in the colloid nano particle that has superparamagnetism in the solution, when applying an externally-applied magnetic field, can produce a magnetic aggregation force (magnetic packing forces) F, F=Δ (μ B), wherein B is the magnetic field intensity that applies, μ is the induced magnetic moment of particle.The magnetic aggregation force that produces can be assembled towards local maximum field gradient by charmed particle, greatly affects the self assembly behavior of superparamagnetism colloid nano particle.In magnetic response photonic crystal anti-counterfeiting mark provided by the invention, the particle that particle diameter is bigger has bigger induced magnetic moment μ, and therefore when applying identical magnetic field intensity, it is understood because at first have bigger enough magnetic aggregation force, and carries out self assembly earlier.And the less particle of particle diameter, because induced magnetic moment μ is less, when applying identical magnetic field intensity, the magnetic aggregation force that has is also less, the particle of the relatively large particle diameter of its self assembly behavior is comparatively slow.Final like this having caused, the difference self assembly of the particle of different-grain diameter, and final formation has multi-photon band gap heterostructure;
A kind of particle of homogeneous particle diameter is after self assembly forms photon crystal structure, according to bragg's formula λ=2ndsin θ; Wherein n is the material refractive index; D is the lattice plane distance, and θ is an incident angle of light, after refractive index and incident angle of light are fixing; A kind of d value can only produce a kind of reflected light of wavelength, that is to say that a kind of particle of homogeneous particle diameter can only reflect a kind of visible light of wavelength.In the present invention, this magnetic response photonic crystal is owing to have the particle of different-grain diameter, the photonic crystal that under induced by magnetic field, generates; Have different d values simultaneously; Therefore can reflect the visible light of different wave length simultaneously, the visible light of this different wave length has just formed new color after mix in the space.Therefore, the variation of the color of magnetic response photonic crystal anti-counterfeiting mark provided by the invention can realize the adjusting to its colour switching through changing the particle diameter of forming its particle, has good color tunable property, is beneficial to its application.
The present invention provides a kind of magnetic response photonic crystal anti-counterfeiting mark, comprises a plurality of patterns, and said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate; At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.Magnetic response photonic crystal anti-counterfeiting mark provided by the invention can show chromatic colour under the effect in magnetic field, its color has diversity, and its color that manifests can be not imitated by common dyestuff and pigment, has antifalse effect preferably.Single pattern in the pattern of magnetic response photonic crystal anti-counterfeiting mark provided by the invention comprises that at least the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle; Under the effect of externally-applied magnetic field; The particle of greater particle size is owing to have bigger induced magnetic moment; Can at first have bigger enough magnetic aggregation force, at first carry out self assembly; And than the particle of small particle diameter, because the induced magnetic moment that has is less, under the situation that applies same magnetic field intensity, its magnetic aggregation force is less, so the self assembly behavior is comparatively slow with respect to the bigger particle of particle diameter.The final like this particle of different-grain diameter that caused carries out self assembly respectively; Formation has the photonic crystal of multi-photon band gap heterojunction structure, can reflect the visible light of different wave length simultaneously, after the visible light of this different wave length superposes in the space; Formed new color, its color has diversity; The present invention can obtain the magnetic response photonic crystal of different colours, thereby make magnetic response photonic crystal provided by the invention have good color tunable property through regulating the particle diameter that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle, is beneficial to its application.In order to further specify the present invention, below in conjunction with embodiment magnetic response photonic crystal provided by the invention and preparation method thereof is described in detail, but can not they be interpreted as the qualification to protection domain of the present invention.
The 0.2g ferrocene is dissolved in the 30mL acetone, and the ultrasonic back that disperses is 30% aqueous hydrogen peroxide solution to wherein dropwise adding the 1.0mL mass concentration, after carrying out magnetic agitation 30min under the rotating speed of 1000r/min, obtains mixed solution; Said mixed solution is transferred in the 40mL autoclave, and heated sealed to 210 ℃ is cooled to room temperature with reaction system behind the insulation 72h, obtains black powder; Said black powder is respectively cleaned three times with acetone and ethanol respectively, in 40 ℃ of vacuum drying ovens dry 6 hours then, obtain product.
The present invention carries out the transmission electron microscope scanning analysis with the product that obtains; The result is as shown in Figure 1; The carbon that Fig. 1 obtains for the embodiment of the invention 1 coats the TEM image of superparamagnetism tri-iron tetroxide colloid nano particle, can be found out that by Fig. 1 the product that present embodiment obtains is the even spheroid with nucleocapsid structure; Particle diameter is respectively 125nm (Fig. 1 c), 140nm (Fig. 1 b) and 200nm, and (Fig. 1 a), inner core is a plurality of particle diameters less than the molecular group of the nanoparticle of 20nm bunch;
The present invention carries out the X-ray diffraction analysis with the product that obtains, and the result is as shown in Figure 2, and the carbon that Fig. 2 obtains for the embodiment of the invention 1 coats the XRD figure spectrum of superparamagnetism tri-iron tetroxide colloid nano particle, wherein; Curve a is that particle diameter is the XRD figure spectrum of the product of 200nm, and curve b is that particle diameter is the XRD figure spectrum of the product of 140nm, and curve c is that particle diameter is the XRD figure spectrum of the product of 125nm, by finding out among Fig. 2; All diffraction peak positions correspond respectively to (220) of tri-iron tetroxide, (311), (400) among curve a, curve b and the curve c; (422), (511), (440); (622) face, this explanation contains tri-iron tetroxide in the product that obtains;
The present invention carries out the raman spectroscopy scans analysis with the product that obtains, and the result is as shown in Figure 3, and the carbon that Fig. 3 obtains for the embodiment of the invention 1 coats the Raman spectrum of superparamagnetism tri-iron tetroxide colloid nano particle; Wherein, curve a be particle diameter be 125nm be the Raman spectrum of product, curve b is that particle diameter is the Raman spectrum of the product of 140nm; Curve c is that particle diameter is the Raman spectrum of the product of 200nm; Can find out curve a, the 1585cm of curve b and curve c by Fig. 3
-1And 1378cm
-1There is a peak at the place, and the corresponding carbon of sp2 hydridization has confirmed that the component on product surface is a carbon;
The present invention carries out the magnetic hysteresis loop analysis with the product that obtains; The result is as shown in Figure 4, and the carbon that Fig. 4 obtains for the embodiment of the invention 1 coats the magnetic hysteresis loop of superparamagnetism tri-iron tetroxide colloid nano particle, and wherein curve a is that particle diameter is the magnetic hysteresis loop of the product of 125nm; Curve b is that particle diameter is the magnetic hysteresis loop of the product of 140nm; Curve c is that particle diameter is the magnetic hysteresis loop of the product of 200nm, can be found out that by Fig. 4 the product that present embodiment obtains does not at room temperature have coercive force; This explanation, the product of present embodiment preparation manifests superparamagnetism.Can find out that by above experimental result the product that present embodiment obtains is the superparamagnetism ferriferrous oxide nano-particle that carbon coats.
The present invention carries out the IR spectrum scanning analysis with the product that obtains, and the result is as shown in Figure 5, and the carbon that Fig. 5 obtains for the embodiment of the invention 1 coats the infrared spectrogram of superparamagnetism tri-iron tetroxide colloid nano particle; Wherein, Curve a is that particle diameter is the infrared spectrum of the product of 125nm, and curve b is that particle diameter is the infrared spectrum of the product of 140nm, and curve c is that particle diameter is the infrared spectrum of the product of 200nm; Can find out that by Fig. 5 curve a, curve b and curve c are at 3400cm
-1And 1675cm
-1The peak at place shows that possibly there is carboxyl in the surface of the product that obtains;
In the dispersion of superparamagnetism ferriferrous oxide nano-particle and 10mL ethylene glycol solution that the carbon that present embodiment is obtained coats, obtain the superparamagnetism tri-iron tetroxide colloid nano particle that carbon coats.When no the action of a magnetic field, it diffraction phenomena do not occur; Under the effect in magnetic field, diffraction phenomena appears immediately, demonstrate chromatic colour.The superparamagnetism tri-iron tetroxide colloid nano particle that the present invention coats the carbon that obtains carries out reflectance spectrum and measures; The result is as shown in Figure 6; The reflectance spectrum of the superparamagnetism tri-iron tetroxide colloid nano particle that the carbon that Fig. 6 obtains for the embodiment of the invention 1 coats; Wherein curve a is that particle diameter is the reflectance spectrum of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 200nm; Curve b is that particle diameter is the reflectance spectrum of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 140nm; Curve c is that particle diameter is the reflectance spectrum of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 125nm; Can find out by Fig. 6; The particle diameter of present embodiment preparation be the reflection wavelength of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 125nm at the 440nm place, particle diameter be the reflection wavelength of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 140nm at the 549nm place, particle diameter is that the reflection wavelength of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 200nm is at the 696nm place.This shows that the different carbon of three kinds of particle diameters that present embodiment makes coats superparamagnetism tri-iron tetroxide colloid nano particle and has distinct transmit spectrum, thereby manifests various colors.
Embodiment 2
With particle diameter among the embodiment 1 is that 125nm and particle diameter are that the ethylene glycol solution equal-volume of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 140nm mixes, and obtains mixed solution.Under the action of a magnetic field, diffraction phenomena appears in mixed solution immediately that obtain, and demonstrates the bright-colored that is different from before mixing.
The mixed solution 0.5mL that obtains is mixed with 2.0g dimethyl silicone polymer monomer and 0.4g hardening agent respectively, and the powerful 5min that stirs is until forming even jelly.Then the jelly that obtains is poured into to the template of preparation in advance, template is placed 60 ℃ of baking oven polyreaction 2h, after the curing, obtain magnetic response photonic crystal anti-counterfeiting mark.
The present invention detects the reflectance spectrum that obtains mixed solution, and the result is as shown in Figure 7, the reflectance spectrum of the mixed solution that Fig. 7 obtains for the embodiment of the invention 2 ~ 4; The reflectance spectrum of the mixed solution that obtains for embodiment 2 of curve a wherein; Can find out that by curve a among Fig. 7 the mixed solution that obtains reflects the light of two kinds of wavelength simultaneously, and wavelength is corresponding to the wavelength of sample institute diffraction before mixing; This explanation; Mixed colloid has formed the photonic crystal with two-photon band gap heterojunction structure under induced by magnetic field, this photonic crystal with two-photon band gap can reflect the light wave of two kinds of wavelength simultaneously, just presents the color mixture that makes new advances after the stack.
Embodiment 3
With particle diameter among the embodiment 1 is that 140nm and particle diameter are that the ethylene glycol solution equal-volume of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 200nm mixes, and obtains mixed solution.Under the action of a magnetic field, diffraction phenomena appears in mixed solution immediately that obtain, and demonstrates the bright-colored that is different from before mixing.
The mixed solution 0.5mL that obtains is mixed with 2.0g dimethyl silicone polymer monomer and 0.4g hardening agent respectively, and the powerful 5min that stirs is until forming even jelly.Then the jelly that obtains is poured into to the template of preparation in advance, template is placed 60 ℃ of baking oven polyreaction 2h, after the curing, obtain magnetic response photonic crystal anti-counterfeiting mark.
The magnetic response photonic crystal anti-counterfeiting mark that obtains is placed the magnetic field of 0.05T; Can observe; Along with the applying and cancelling of magnetic field, the magnetic response photonic crystal anti-counterfeiting mark that present embodiment obtains can be stablized reversible realization " coloured-colourless " and change, and obtains after the visible light stack that this color that shows is two kinds of different wave lengths; Can be not imitated by common pigment or dyestuff look, have good antifalse effect.
The present invention detects the reflectance spectrum that obtains mixed solution, and the result is as shown in Figure 7, the reflectance spectrum of the mixed solution that Fig. 7 obtains for the embodiment of the invention 2 ~ 4; The reflectance spectrum of the mixed solution that obtains for embodiment 3 of curve b wherein; Can find out that by curve b among Fig. 7 the mixed solution that obtains reflects the light of two kinds of wavelength simultaneously, and wavelength is corresponding to the wavelength of sample institute diffraction before mixing; This explanation; Mixed colloid has formed the photonic crystal with two-photon band gap heterojunction structure under induced by magnetic field, this photonic crystal with two-photon band gap can reflect the light wave of two kinds of wavelength simultaneously, just presents the color mixture that makes new advances after the stack.
Embodiment 4
With particle diameter among the embodiment 1 is that 125nm and particle diameter are that the ethylene glycol solution equal-volume of the superparamagnetism tri-iron tetroxide colloid nano particle that coats of the carbon of 200nm mixes, and obtains mixed solution.Under the action of a magnetic field, diffraction phenomena appears in mixed solution immediately that obtain, and demonstrates the bright-colored that is different from before mixing.
The mixed solution 0.5mL that obtains is mixed with 2.0g dimethyl silicone polymer monomer and 0.4g hardening agent respectively, and the powerful 5min that stirs is until forming even jelly.Then the jelly that obtains is poured into to the template of preparation in advance, template is placed 60 ℃ of baking oven polyreaction 2h, after the curing, obtain magnetic response photonic crystal anti-counterfeiting mark.
The magnetic response photonic crystal anti-counterfeiting mark that obtains is placed the magnetic field of 0.05T; Can observe; Along with the applying and cancelling of magnetic field, the magnetic response photonic crystal anti-counterfeiting mark that present embodiment obtains can be stablized reversible realization " coloured-colourless " and change, and obtains after the visible light stack that this color that shows is two kinds of different wave lengths; Can be not imitated by common pigment or dyestuff look, have good antifalse effect.
The present invention detects the reflectance spectrum that obtains mixed solution, and the result is as shown in Figure 7, the reflectance spectrum of the mixed solution that Fig. 7 obtains for the embodiment of the invention 2 ~ 4; The reflectance spectrum of the mixed solution that obtains for embodiment 4 of curve c wherein; Can find out that by curve c among Fig. 7 the mixed solution that obtains reflects the light of two kinds of wavelength simultaneously, and wavelength is corresponding to the wavelength of sample institute diffraction before mixing; This explanation; Mixed colloid has formed the photonic crystal with two-photon band gap heterojunction structure under induced by magnetic field, this photonic crystal with two-photon band gap can reflect the light wave of two kinds of wavelength simultaneously, just presents the color mixture that makes new advances after the stack.
Can know by above embodiment; The present invention provides a kind of magnetic response photonic crystal anti-counterfeiting mark; Comprise a plurality of patterns, said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate; At least the carbon that comprises two kinds of different-grain diameters in the single pattern of said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.Magnetic response photonic crystal anti-counterfeiting mark provided by the invention has good antifalse effect; This be because; The carbon of different-grain diameter coats superparamagnetism tri-iron tetroxide colloid nano particle and under the effect in magnetic field, has different induced magnetic moments; The particle of greater particle size has bigger induced magnetic moment, and it can at first have bigger enough thick aggregation force, at first carries out self assembly; And than the particle of small particle diameter, because its induced magnetic moment that has is less, under the situation that applies same magnetic field intensity, its magnetic aggregation force underfooting, so the self assembly behavior is comparatively slow with regard to the bigger particle of relative grain size.The final like this particle of different-grain diameter that caused carries out self assembly respectively, and the final photonic crystal with multi-photon band gap heterojunction structure that forms.The single pattern of magnetic response photonic crystal anti-counterfeiting mark provided by the invention can reflect the visible light of different wave length; Form new color after the visible light of this different wave length superposes in the space, thereby make the color of magnetic response photonic crystal provided by the invention have diversity; And the present invention can make magnetic response photonic crystal provided by the invention have good color tunable property through changing the color that carbon coats the particle diameter change magnetic response photonic crystal of superparamagnetism tri-iron tetroxide colloid nano particle, helps its application.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. magnetic response photonic crystal anti-counterfeiting mark comprises:
A plurality of patterns, said pattern comprises: polymer substrate and the little drop of monoethylene glycol that carbon coats superparamagnetism tri-iron tetroxide colloid nano particle that contains that is encapsulated in the said polymer substrate;
At least the carbon that comprises two kinds of different-grain diameters in the single pattern in the said pattern coats superparamagnetism tri-iron tetroxide colloid nano particle.
2. magnetic response photonic crystal anti-counterfeiting mark according to claim 1 is characterized in that, the particle diameter that said carbon coats superparamagnetism tri-iron tetroxide colloid nano particle is 110nm ~ 130nm, 140nm ~ 160nm or 190nm ~ 210nm.
3. magnetic response photonic crystal anti-counterfeiting mark according to claim 1 is characterized in that, said polymkeric substance is polysiloxane condensate, polyglycol double methacrylate condensate, polyvinyl alcohol (PVA) condensate or polyacrylamide polymerization body condensate.
4. magnetic response photonic crystal anti-counterfeiting mark according to claim 1 is characterized in that said polymkeric substance is the polysiloxane condensate.
5. the preparation method of a magnetic response photonic crystal anti-counterfeiting mark may further comprise the steps:
The ethylene glycol solution that polymerization single polymerization monomer, hardening agent and the carbon that contains different-grain diameter is coated superparamagnetism tri-iron tetroxide colloid nano particle mixes, and obtains jelly;
Said jelly is placed a plurality of patterns of anti-counterfeiting mark pattern template; Carry out obtaining magnetic response photonic crystal anti-counterfeiting mark after the polyreaction, comprise at least in the single pattern in the said pattern that the carbon of two kinds of different-grain diameters coats superparamagnetism tri-iron tetroxide colloid nano particle.
6. preparation method according to claim 5; It is characterized in that the said carbon that contains different-grain diameter coats the mass concentration that carbon in the ethylene glycol solution of superparamagnetism tri-iron tetroxide colloid nano particle coats superparamagnetism tri-iron tetroxide colloid nano particle and is (0.005-0.020) g/mL.
7. preparation method according to claim 6; It is characterized in that the quality of said polymerization single polymerization monomer, the quality of hardening agent and the said ethylene glycol solution mass ratio that contains carbon coating superparamagnetism tri-iron tetroxide colloid nano particle are 10: (1 ~ 2): (1 ~ 10).
8. preparation method according to claim 5 is characterized in that, said polymerization single polymerization monomer is siloxanyl monomers, ethylene glycol diacrylate monomer, vinyl alcohol monomer or acrylamide monomer.
9. preparation method according to claim 8 is characterized in that, said polymerization single polymerization monomer is a siloxanyl monomers.
10. preparation method according to claim 5 is characterized in that, the temperature of said polyreaction is 50 ℃ ~ 80 ℃;
The time of said polyreaction is 1 h ~ 5 hours.
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Application publication date: 20121003 |