CN102874002A - Printing method of invisible photonic crystals - Google Patents
Printing method of invisible photonic crystals Download PDFInfo
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- CN102874002A CN102874002A CN2011101923903A CN201110192390A CN102874002A CN 102874002 A CN102874002 A CN 102874002A CN 2011101923903 A CN2011101923903 A CN 2011101923903A CN 201110192390 A CN201110192390 A CN 201110192390A CN 102874002 A CN102874002 A CN 102874002A
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Abstract
The invention relates to a printing method of invisible photonic crystals. The printing method is characterized in that a difference between a pattern and a background is formed on siloxane-contained photonic paper in a planographic printing method through controlling the crosslinking or modifying degree. The photonic crystal structure has the characteristics that the difference between diffraction wavelengths of the pattern and the background of a printed matter is small in a drying state, so that the pattern is invisible. After the printed matter is soaked in the water for minutes, since swelling speeds of the pattern and the background are different, the difference between the diffraction wavelengths after swelling is great, and the pattern is visible. The printed matter is visible or invisible through soaking and drying, and the soaking and drying processes are reversible. Multiple-forbidden-band invisible photonic crystal printing is achieved through controlling the crosslinking or modifying degree step by step. Compared with the prior art, the novel invisible photonic crystal printed matter has a unique optical response, and can be applied in the fields such as antifalsification labels, identification marks and dynamic signals.
Description
Technical field
The invention belongs to colloidal photon crystal application, printing and field of anti-counterfeit technology, especially relate to the stealthy photonic crystal printed article of water identification.
Background technology
Stealthy photonic crystal printed article is a kind of New-type photon crystal material with stealthy ink marks same concept.The latter is usually used in writing and prints invisible characters and pattern, and these stealthy ink markss can be identified under heating, chemical reaction, UV-irradiation or other conditions.Compare with traditional photonic crystal printed article, stealthy photonic crystal printed article requires image identical as far as possible with the diffraction wavelength of background, and both diffraction wavelengths have larger difference when image manifests.This stealthy printed article has wide practical use in fields such as encryption, identification marking and antifalsification labels.For the antifalsification label that uses in the daily life, people wish to identify by convenience, nontoxic means such as heating or immersions.
At present, run into the bottleneck of development based on the printing technique of the stealthy printed article of colloidal photon crystal.Reason is that existing photon printing technology is difficult to make printed article to have following whole speciality: 1, Optical dynamic response changes wavelength when externally condition changes; 2, corresponding feasible printing process makes that information is endurable to be recorded on the photon paper medium; 3, under the stealth mode, the diffraction wavelength of printed patterns and background is very approaching; 4, when manifesting, the pattern of printing causes final wavelength difference larger with background because the speed of diffraction wavelength displacement is different.
What the stealthy photonic crystal printing process of tradition generally utilized is the static difference of diffraction wavelength, and the wavelength difference of background and pattern is fixed in printing process, and is difficult to change in subsequent process.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of nontoxic for the defective that overcomes above-mentioned prior art existence, can be recycled, and, degree of modification crosslinked by progressively controlling can also realize the stealthy photonic crystal printing process of the stealthy photonic crystals printing in many forbidden bands.
Purpose of the present invention can be achieved through the following technical solutions: a kind of stealthy photonic crystal printing process, it is characterized in that, the method be utilize offset printing method on the photon paper of silicone-containing, make the difference of pattern and background by controlling crosslinked or degree of modification.
Described method specifically may further comprise the steps:
1) preparation of blank photon paper;
Be SiO with shell
2, inside is Fe
3O
4Core shell particles be dispersed in the polymer solution that polyethyleneglycol diacrylate (PEGDA), polyethylene glycol methyl methacrylate (PEGMA) and methacrylic acid-3-(trimethoxysilyl) propyl ester (TPM) form, form and ultra-violet curing formation photon paper by the magnetic assembling;
2) printing of NOA protection pattern
Utilize photomask and ultra-violet curing glue on the photon paper, to print out the NOA protective layer with layout;
3) crosslinked, the modification of not protection part
Use NaOH or (3-aminopropyl) trimethoxy silane (APS) solution treatment steps (2) gained paper, make do not protect partial cross-linked, form silica network or hydrocarbon hydrophobic chain, reduce its swelling ability, thereby formed protection zone and the difference of protection zone swelling rate not;
4) removal of protective layer
Remove ultra-violet curing glue mask.After the printed article that obtains was immersed in the water 3～5 minutes, because swelling rate is different, larger wavelength difference (Δ λ t), i.e. color distortion appearred in pattern and background.
The described shell of step (1) is SiO
2, inside is Fe
3O
4Core shell particles make by the following method: with FeCl
3, surfactant 1: 10 in molar ratio mixes, and is dissolved in and is heated to 220 ℃ in the solvent, reaction is 1 hour under nitrogen protection; inject the diethylene glycol solution of NaOH, reacted 1 hour 220 ℃ of lower continuation, leave standstill cooling after the reaction; washing, and be dispersed in the deionized water, make Fe
3O
4The aqueous solution of micelle is with this Fe
3O
4The aqueous solution of micelle and ethanol, ammoniacal liquor mixed in 3: 20: 1 by volume, tetraethyl orthosilicate of injection in per 20 minutes under mechanical agitation, set the number of times that adds according to the micelle design size, the rear ethanol of using that reacts completely separates with water washing, and product is scattered in the ethanol, and obtaining shell is SiO
2, inside is Fe
3O
4Core shell particles;
The described ultra-violet curing glue of step (2) is NOA61;
The described NaOH of step (3) or (3-aminopropyl) trimethoxy silane solution treatment steps (2) gained paper are that step (2) gained paper is immersed in the NaOH solution that concentration is 0.001～0.1mol/L 2 minutes; Perhaps step (2) gained paper is immersed in volume fraction and is in (3-aminopropyl) trimethoxy silane solution of 5% 2～30 minutes;
The method of the described removal ultra-violet curing of step (4) glue mask is to use acetone rinsing.
Described surfactant is polyacrylic acid (PAA); Solvent is diethylene glycol (DEG) (DEG); The concentration of the diethylene glycol solution of NaOH is 2.5mol/L; NaOH and FeCl
3Mol ratio be 10～12: 1; Fe
3O
4Fe in the aqueous solution of micelle
3O
4The concentration of micelle is 0.04～0.05mol/L; The each addition of tetraethyl orthosilicate is 1/10 of ammoniacal liquor.
Action time and concentration, the temperature of the aqueous slkali degree of cross linking and the degree of modification of controlling photon paper of the stealthy photonic crystal printed article that described method makes by regulating silane.
The stealthy photonic crystal printed article that described method makes diffraction wavelength difference between background and the pattern under drying regime is very little, therefore pattern is invisible, after being immersed in the water, because pattern is different from the swelling rate of background parts, cause differing greatly of diffraction wavelength after the swelling, so that image manifests.
Compared with prior art, the present invention utilize simply crosslinked, modify and to realize stealthy photonic crystal printing.The identification printed article is convenient and swift, only needs to soak a few minutes just can manifest secret information in water.The intermediary that manifests that needs is water, is easy to acquisition and nontoxic.Repeat to soak and dry run, stealthy photonic crystal printed article can recycle.Progressively control crosslinked, degree of modification and can also realize the stealthy photonic crystal printing in many forbidden bands.
Description of drawings
The process schematic diagram of the stealthy photonic crystal printing of Fig. 1;
Wherein: the 1) preparation of blank photon paper; 2) printing of NOA protection pattern; 3) crosslinked, the modification of not protection part; 4) removal of protective layer;
The stealthy photonic crystal printing that Fig. 2 the present invention relates to utilizes the crosslinked and APS hydrophobic modification of NaOH to come the swelling in inhibitory reaction zone, forms the difference of swelling rear backdrop and pattern diffraction wavelength;
The pattern that the stealthy photonic crystal printing process that Fig. 3 use the present invention relates to prints;
Wherein: I uses the cross-linking method printing, and II uses the method for modifying printing, is respectively up and down sample among the figure at concealment and display mode;
The infrared spectrogram of the PEGDA-PEGMA-TPM film of four kinds of different proportions of Fig. 4, the numeral abbreviation has represented respectively the ratio of each composition in polymer film;
Fig. 5 identical component, the curve that the diffraction wavelength of the photon paper of different proportion changes with soak time in the water; The ratio of PEGDA, PEGMA, TPM was respectively a) 2: 8: 0, b) 2: 7: 1, c) 2: 6: 2, d) 2: 4: 4, had characterized each sample in the response speed with NaOH solution-treated front and back;
The crosslinked zone of the stealthy photonic crystal printed article of Fig. 6 and uncrosslinked zone are through the diffraction wavelength cyclic curve of 5 continuous immersion-dry runs;
Fig. 7 photon paper (PPT 244) is with NaOH solution-treated two minutes, a) concentration of alkali and b) temperature is on the impact of swelling rate;
The modification time of Fig. 8 APS is on the impact of photon paper (PPT 244) swelling rate.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
A kind of stealthy photonic crystal printing process may further comprise the steps:
(1) colloidal photon crystal is synthetic
Raw material FeCl
3(0.4mmol); surfactant PAA (4mmol) and solvent DEG (16mL) are mixed and heated to 220 degrees centigrade, and reaction is one hour under nitrogen protection, injects an amount of NaOH/DEG (1.7ml; 2.5mol/L) solution, reacted 1 hour 220 ℃ of lower continuation.Leave standstill cooling after the reaction, use second alcohol and water centrifuge washing three times, and be dispersed in the 3ml deionized water.
With the Fe that makes
3O
4The aqueous solution of micelle and 20ml ethanol, 1ml ammoniacal liquor mixes, and injects 0.1mL TEOS in per 20 minutes under mechanical agitation, sets the number of times that adds according to the micelle design size.The rear ethanol of using that reacts completely separates with water washing, and product is scattered in the 3mL ethanol, and obtaining shell is SiO
2, inside is Fe
3O
4Core shell particles (Fe
3O
4@SiO
2).
(2) preparation of blank photon paper
Get an amount of Fe
3O
4@SiO
2Core shell particles, remove solvent, be scattered in the mixed solution of PEGDA, the PEGMA of equal volume and TPM, volume ratio between the three is between 1: 1: 0～1: 4: 4, add simultaneously light trigger DMPA (5wt%), the photonic crystal printed liquid is made in ultrasonic dispersion.Getting this solution 30 μ L places between substrate of glass and the hydrophobic type cover glass, spacing is 90 μ m, and be positioned over above the NdFeB magnet, under the effect of outside magnetic field, Magnetic colloidal particle forms chain 1-D photon crystal structure, lower polymerization 1-2 minute of high intensity ultraviolet lamp (Spectroline SB-100P, 365nm), form the colloidal photon crystal film, namely blank photon paper.At last, this film is fixed in the substrates such as glass, plastics by ultra-violet curing glue NOA61.
(3) ratio of TPM is on the impact of speed of expansion
The TPM that introduces in polymeric substrates below 50% can not affect the magnetic assembling of sample, and can obtain by the ratio of adjusting TPM best crosslinked, decorating site.But too much TPM (surpassing 50%) can reduce the stability of ordered structure.In suitable TPM content range, three kinds of monomers form optical clear, meet water-soluble swollen polymeric substrates.Polymer film is named by their component among the present invention, for example contains 20%PEGDA in the PPT244 representation polymer, 40%PEGMA, and 40%TPM.The infrared absorption spectroscopy of the PPT film that 40 μ m are thick (nonmagnetic micelle) has confirmed the existence and relevant proportion of composing of three components.1725cm among Fig. 4
-1The place is the stretching vibration from the carbonyl in the acrylic acid (C=O).3480cm
-1The place wide absworption peak from hydroxyl (OH), with the increase of PEGMA, its strength increase.Along with the increase of TPM, at 2800-2900cm
-1The place divides two peaks 2946 and 2877cm gradually
-1, they are respectively ethyoxyl (CH
2-) asymmetric stretching vibration and methoxyl group silicon (Si-O-CH
3) rocking vibration.Photon paper ratio of swelling speed and TPM in water is closely related.Photon paper before crosslinked as can be seen from Figure 5, along with the increase of TPM amount, its speed of expansion " slowly " reduction in water.Photon paper after crosslinked is increased to 40% with TPM from 10%, and speed of expansion " fast " reduces, because the highly cross-linked intensity that increases substrate of silane, has reduced the swelling ability of paper.Comprehensively both impacts, along with the increase of TPM ratio, the effect that stealthy printed article develops is further obvious.Different based on the swelling rate of crosslinked front and back photon paper, the PPT substrate can be used for realizing the stealthy photonic crystal printing that the present invention relates to.
(4) invertibity crosslinked, that modify is tested
Test stealthy photonic crystal printed article and in water, soak reflectance spectrum in 5 minutes before and after processing, then make it natural drying to initial state and survey it in the reflectance spectrum of dry run.Obtain the cyclic curve of Fig. 6 by immersion-dry continuous 5 circulations.The stealthy photonic crystal printed article of presentation of results has good invertibity and durability.
(5) control of crosslinked, degree of modification
Crosslinked among the present invention, difference that modify front and back photon paper swelling rate has caused the difference of pattern and background diffraction wavelength.Therefore, the swelling rate of control PPT photon paper can be realized stealthy photonic crystal printing.The crosslinking time of control silane and the concentration of aqueous slkali are the most simply to control the method for photon paper swelling rate.
1) concentration of control alkali: identical PPT244 film respectively concentration be 0.001,0.005,0.01,0.05 and the NaOH solution of 0.1mol/L in processed 2 minutes, (Fig. 7 is a) with curve that soak time in the water changes for the diffraction wavelength of surveying respectively them.Along with the increase of NaOH concentration, swelling rate reduces gradually.The temperature of control crosslinked with silicane also is one of feasible method (Fig. 7 b), is effectively replenishing of alkali treatment method.High temperature will speed up the crosslinked of silane, namely reduces swelling rate, thereby reaches the purpose of stealthy photonic crystal printing.
2) the controlled modification time: stealthy photonic crystal printing also can realize by the time of control crosslinked with silicane, and this method is effective and rapid.The dose volume mark is 5% APS alcohol water (V
Ethanol: V
Water=95: 5) solution, identical PPT244 photon paper were processed 2 minutes, 3 minutes, 5 minutes, 20 minutes, 30 minutes in APS solution respectively, and is then dry.Be similar to alkali treatment, survey respectively their diffraction wavelength with the curve (Fig. 8) of soak time variation in the water.Modify the prolongation of time along with APS, can introduce more hydrophobic chain, so the swelling rate of photon paper in water reduces gradually.
(6) the stealthy photonic crystal printing of monochromatic pattern
1) cross-linking method: magnetic ink is placed between substrate of glass and the hydrophobic type cover glass, it is spaced apart 90 μ m, and be positioned over 1 centimetre of NdFeB magnet top, under the effect of outside magnetic field, Magnetic colloidal particle forms chain 1-D photon crystal structure, utilize the high intensity ultraviolet lamp above sample, to shine 1～2 minute, form photon paper (step 1).On paper, cover the liquid NOA61 (optical adhesive) of skim; utilize photomask (the pattern printing opacity on the mask; remainder is light tight) under uviol lamp, shone 2 minutes, the NOA61 curing of pattern part under the mask is bonded in above the photon paper, form protective layer.With the uncured NOA61 (step 2) of ethanol flush away.The volume ratio that the photon paper immerses the second alcohol and water is to process 2 minutes in 95: 5 NaOH (0.1mol/L) solution, makes unprotected partial cross-linked (step 3) on the photon paper.At last, fall NOA61 protective layer (step 4) with acetone rinsing.Just formed simple stealthy photonic crystal printed article (Fig. 3, I).This printed article shows at the drying regime pattern-free, in water, soak a few minutes after pattern manifest.
2) modification method: be similar to cross-linking method, but this method needs twice modification at least.In step 1, the photon paper at first is the pure water (V of 5%APS in volume fraction
Ethanol: V
Water=95: 5) processed 2 minutes in the solution, and then the printing of beginning step 2.In the step 3, the photon paper is processed 5 minutes (setting on demand the processing time) in identical APS solution.Last acetone flush away protective layer obtains stealthy photonic crystal printed article (Fig. 3, II).Effect is similar to the printed article that cross-linking method obtains.
The stealthy photonic crystal printing in many forbidden bands
The multistage distribution that repeats the degree of cross linking and degree of modification can realize the stealthy photonic crystal printing in many forbidden bands.Take cross-linking method as example, on the photon paper, print out the protection pattern, the NOA61 that the ethanol flush away is uncured.The volume ratio that the photon paper immerses the second alcohol and water is 95: 5 NaOH (0.005mol/L) solution 2 minutes, makes on the photon paper unprotected partial cross-linkedly, recycles the corresponding photomask process of repeating print.Same, unpolymerized NOA61 falls with alcohol flushing, then uses the sodium hydroxide solution (0.1mol/L) of higher concentration to process, and makes unprotected zone crosslinked (repeating step 2 and step 3).At last, the protective layer used acetone rinsing of the NOA61 in all processes falls, and has just obtained the stealthy photonic crystal printed article in many forbidden bands.The pattern that prints is not seen clue in drying regime, in water, soak a few minutes after, demonstrate multiple color.For method of modifying, the processing time of control APS is equivalent to control the concentration of NaOH, and the modification time is longer than for the first time for the second time, and effect and above-mentioned cross-linking method are similar.
As shown in Figure 1, the process of stealthy photonic crystal printing comprises: the 1) preparation of blank photon paper; 2) printing of NOA protection pattern; 3) crosslinked, the modification of not protection part; 4) removal of protective layer.This hidden pattern is met water and is manifested, dry rear concealment.
Concrete steps are as follows:
1) preparation of blank photon paper;
With FeCl
3, surfactant PAA 1: 10 in molar ratio mixes, and is dissolved in and is heated to 220 ℃ among the diethylene glycol (DEG) DEG, reaction is 1 hour under nitrogen protection, implantation concentration is the DEG solution of the NaOH of 2.5mol/L, NaOH and FeCl
3Mol ratio be 10: 1, lower continue reaction 1 hour at 220 ℃, leave standstill cooling after the reaction, washing, and being dispersed in the deionized water makes Fe
3O
4The aqueous solution of micelle, Fe in this solution
3O
4The concentration of micelle is 0.04mol/L, with this Fe
3O
4The aqueous solution of micelle and ethanol, ammoniacal liquor mixed in 3: 20: 1 by volume, tetraethyl orthosilicate of injection in per 20 minutes under mechanical agitation, the each addition of tetraethyl orthosilicate is 1/10 of ammoniacal liquor, set the number of times that adds according to the micelle design size, the rear ethanol of using that reacts completely separates with water washing, and product is scattered in the ethanol, and obtaining shell is SiO
2, inside is Fe
3O
4Core shell particles;
Be SiO with shell
2, inside is Fe
3O
4Core shell particles be dispersed in polyethyleneglycol diacrylate, polyethylene glycol methyl methacrylate and methacrylic acid-3-(trimethoxysilyl) propyl ester (PEGDA/PEGMA/TPM, abbreviation PPT) in the three-component polymer that forms, form magnetic ink, then getting 30 μ L places between substrate of glass and the hydrophobic type cover glass, it is spaced apart 90 μ m, and be positioned over 1 centimetre of NdFeB magnet top, under the effect of outside magnetic field, Magnetic colloidal particle forms chain 1-D photon crystal structure, utilize the high intensity ultraviolet lamp above sample, to shine 1～2 minute, form the photon paper; When water is penetrated in the photon paper, polymer absorbs the moisture swelling, thereby has increased intergranular spacing in the chain, so that the diffraction wavelength red shift of photon paper.Alkoxyl silicone-Si (OCH has been introduced in the copolymerization of TPM and PEG acrylate
3)
3, so that the swelling rate of polymeric matrix, i.e. the speed of photon paper diffraction wavelength red shift can and be modified and regulate by crosslinked with silicane.
2) printing of NOA protection pattern
Utilize photomask and ultra-violet curing glue NOA61 on the photon paper, to print out the NOA protective layer with layout;
3) crosslinked, the modification of not protection part
Step (2) gained paper is immersed in the NaOH solution that concentration is 0.001mol/L 2 minutes; Perhaps step (2) gained paper is immersed in volume fraction and is in (3-aminopropyl) trimethoxy silane solution of 5% 2 minutes, make do not protect partial cross-linked, form silica network or hydrocarbon hydrophobic chain, reduce its swelling ability, thereby formed protection zone and the difference of protection zone swelling rate not; Be illustrated in figure 2 as stealthy photonic crystal printing and utilize the crosslinked and APS hydrophobic modification of NaOH to come the swelling in inhibitory reaction zone, form the difference of swelling rear backdrop and pattern diffraction wavelength;
4) removal of protective layer
Adopt acetone rinsing to remove ultra-violet curing glue mask, after the printed article that obtains was immersed in the water 3～5 minutes, because swelling rate is different, larger wavelength difference (Δ λ t), i.e. color distortion appearred in pattern and background.
The process of stealthy photonic crystal printing comprises: step is as follows:
1) preparation of blank photon paper;
With FeCl
3, surfactant PAA 1: 10 in molar ratio mixes, and is dissolved in and is heated to 220 ℃ among the diethylene glycol (DEG) DEG, reaction is 1 hour under nitrogen protection, implantation concentration is the DEG solution of the NaOH of 2.5mol/L, NaOH and FeCl
3Mol ratio be 12: 1, lower continue reaction 1 hour at 220 ℃, leave standstill cooling after the reaction, washing, and being dispersed in the deionized water makes Fe
3O
4The aqueous solution of micelle, Fe in this solution
3O
4The concentration of micelle is 0.05mol/L, with this Fe
3O
4The aqueous solution of micelle and ethanol, ammoniacal liquor mixed in 3: 20: 1 by volume, tetraethyl orthosilicate of injection in per 20 minutes under mechanical agitation, the each addition of tetraethyl orthosilicate is 1/10 of ammoniacal liquor, set the number of times that adds according to the micelle design size, the rear washing with ethanol that react completely separated, and product is scattered in the ethanol, and obtaining shell is SiO
2, inside is Fe
3O
4Core shell particles;
Be SiO with shell
2, inside is Fe
3O
4Core shell particles be dispersed in polyethyleneglycol diacrylate, polyethylene glycol methyl methacrylate and methacrylic acid-3-(trimethoxysilyl) propyl ester (PEGDA/PEGMA/TPM, abbreviation PPT) in the three-component polymer that forms, form magnetic ink, then getting 30 μ L places between substrate of glass and the hydrophobic type cover glass, it is spaced apart 90 μ m, and be positioned over 1 centimetre of NdFeB magnet top, under the effect of outside magnetic field, Magnetic colloidal particle forms chain 1-D photon crystal structure, utilize the high intensity ultraviolet lamp above sample, to shine 1～2 minute, form the photon paper; When water is penetrated in the photon paper, polymer absorbs the moisture swelling, thereby has increased intergranular spacing in the chain, so that the diffraction wavelength red shift of photon paper.Alkoxyl silicone-Si (OCH has been introduced in the copolymerization of TPM and PEG acrylate
3)
3, it is so that the swelling rate of polymeric matrix, i.e. and the speed of photon paper diffraction wavelength red shift can and be modified and regulate by crosslinked with silicane.
2) printing of NOA protection pattern
Utilize photomask and ultra-violet curing glue NOA61 on the photon paper, to print out the NOA protective layer with layout;
3) crosslinked, the modification of not protection part
Step (2) gained paper is immersed in the NaOH solution that concentration is 0.1mol/L 2 minutes; Perhaps step (2) gained paper is immersed in volume fraction and is in (3-aminopropyl) trimethoxy silane solution of 5% 30 minutes, make do not protect partial cross-linked, form silica network or hydrocarbon hydrophobic chain, reduce its swelling ability, thereby formed protection zone and the difference of protection zone swelling rate not;
4) removal of protective layer
Adopt acetone rinsing to remove ultra-violet curing glue mask, after the printed article that obtains was immersed in the water 3～5 minutes, because swelling rate is different, larger wavelength difference (Δ λ t), i.e. color distortion appearred in pattern and background.
Claims (6)
1. a stealthy photonic crystal printing process is characterized in that, the method be utilize offset printing method on the photon paper of silicone-containing, make the difference of the diffraction wavelength of pattern and background by controlling crosslinked or degree of modification.
2. a kind of stealthy photonic crystal printing process according to claim 1 is characterized in that, described method specifically may further comprise the steps:
1) preparation of blank photon paper;
Be SiO with shell
2, inside is Fe
3O
4Core shell particles be dispersed in the polymer solution that polyethyleneglycol diacrylate, polyethylene glycol methyl methacrylate and methacrylic acid-3-(trimethoxysilyl) propyl ester form, by magnetic assembling and ultra-violet curing formation photon paper;
2) printing of NOA protection pattern
Utilize photomask and ultra-violet curing glue on the photon paper, to print out the NOA protective layer with layout;
3) crosslinked, the modification of not protection part
Use NaOH or (3-aminopropyl) trimethoxy silane solution treatment steps (2) gained paper, make do not protect partial cross-linked, form silica network or hydrocarbon hydrophobic chain, reduce its swelling ability, thereby formed protection zone and the difference of protection zone swelling rate not;
4) removal of protective layer
Remove ultra-violet curing glue mask, after the printed article that obtains was immersed in the water 3～5 minutes, because swelling rate is different, larger wavelength difference (Δ λ t), i.e. color distortion appearred in pattern and background.
3. a kind of stealthy photonic crystal printing process according to claim 2 is characterized in that, the described shell of step (1) is SiO
2, inside is Fe
3O
4Core shell particles make by the following method: with FeCl
3, surfactant 1: 10 in molar ratio mixes, and is dissolved in and is heated to 220 ℃ in the solvent, reaction is 1 hour under nitrogen protection; inject the diethylene glycol solution of NaOH, reacted 1 hour 220 ℃ of lower continuation, leave standstill cooling after the reaction; washing, and be dispersed in the deionized water, make Fe
3O
4The aqueous solution of micelle, with itself and ethanol, ammoniacal liquor mixed in 3: 20: 1 by volume, tetraethyl orthosilicate of injection in per 20 minutes under mechanical agitation, set the number of times that adds according to the micelle design size, the rear ethanol of using that reacts completely separates with water washing, and product is scattered in the ethanol, and obtaining shell is SiO
2, inside is Fe
3O
4Core shell particles;
The described ultra-violet curing glue of step (2) is NOA61;
The described paper of step (3) is that the blank photonic crystal paper with step (2) gained is immersed in the NaOH solution that concentration is 0.001～0.1mol/L 2 minutes, perhaps it is immersed in volume fraction and is in (3-aminopropyl) trimethoxy silane solution of 5% 2～30 minutes;
The method of the described removal ultra-violet curing of step (4) glue mask is to use acetone rinsing.
4. a kind of stealthy photonic crystal printing process according to claim 3 is characterized in that, described surfactant is polyacrylic acid (PAA); Solvent is diethylene glycol (DEG) (DEG); The concentration of the diethylene glycol solution of NaOH is 2.5mol/L; NaOH and FeCl
3Mol ratio be 10～12: 1; Fe
3O
4Fe in the aqueous solution of micelle
3O
4The concentration of micelle is 0.04～0.05mol/L; The each addition of tetraethyl orthosilicate is 1/10 of ammoniacal liquor.
5. a kind of stealthy photonic crystal printing process according to claim 1, it is characterized in that action time and concentration, the temperature of the aqueous slkali degree of cross linking and the degree of modification of controlling photon paper of the stealthy photonic crystal printed article that described method makes by regulating silane.
6. a kind of stealthy photonic crystal printing process according to claim 1, it is characterized in that, the stealthy photonic crystal printed article that described method makes diffraction wavelength difference between background and the pattern under drying regime is very little, therefore pattern is invisible, after being immersed in the water, because pattern is different from the swelling rate of background parts, cause differing greatly of diffraction wavelength after the swelling, so that image manifests.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303013A (en) * | 2013-06-06 | 2013-09-18 | 中国科学技术大学 | Invisible photonic crystal printing method |
| CN104464506A (en) * | 2014-11-28 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Anti-counterfeiting mark used for information storage and preparing method thereof |
| CN106990456A (en) * | 2017-04-25 | 2017-07-28 | 东南大学 | One kind immersion shows hidden photon crystal surface and preparation method thereof |
| CN108535954A (en) * | 2018-02-23 | 2018-09-14 | 中山大学 | A kind of preparation method of the dynamic photon crystal pattern of infiltration control film refractive index |
| CN113062142A (en) * | 2021-02-24 | 2021-07-02 | 中山大学 | Photonic crystal paper for multicolor printing and application thereof |
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| CN101259464A (en) * | 2007-12-19 | 2008-09-10 | 中国科学院化学研究所 | Method for using printing method to prepare patterned polymer colloid photon crystal film |
| WO2011004190A2 (en) * | 2009-07-07 | 2011-01-13 | De La Rue International Limited | Method of forming a photonic crystal material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303013A (en) * | 2013-06-06 | 2013-09-18 | 中国科学技术大学 | Invisible photonic crystal printing method |
| CN104464506A (en) * | 2014-11-28 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Anti-counterfeiting mark used for information storage and preparing method thereof |
| CN104464506B (en) * | 2014-11-28 | 2017-09-29 | 深圳先进技术研究院 | A kind of anti-counterfeiting mark stored available for information and preparation method thereof |
| CN106990456A (en) * | 2017-04-25 | 2017-07-28 | 东南大学 | One kind immersion shows hidden photon crystal surface and preparation method thereof |
| CN106990456B (en) * | 2017-04-25 | 2019-04-30 | 东南大学 | A kind of immersion shows hidden photon crystal surface and preparation method thereof |
| CN108535954A (en) * | 2018-02-23 | 2018-09-14 | 中山大学 | A kind of preparation method of the dynamic photon crystal pattern of infiltration control film refractive index |
| CN113062142A (en) * | 2021-02-24 | 2021-07-02 | 中山大学 | Photonic crystal paper for multicolor printing and application thereof |
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Application publication date: 20130116 |