Background technology
Growing along with commodity economy, the anti-counterfeiting technology of commodity has caused the attention that people are general.Therefore the material that can produce the angular color change effect has obtained to develop rapidly, has obtained widespread use at anti-fake material and decoration material field.
The angular color change effect of material can obtain by the laminate structure at intermittence that forms material, and alternative metal and the coextrusion thin layer that obtains of ceramic plate are just had this effect (Dobrowolski, J.A.; Ho, F.C.and Waldorf, A., Applied Optics, 1989,28, P14).But this material cost is higher, practical inconvenience and should not reclaiming.In addition, a part of cholesteryl liquid crystal also has the performance (GB 1387389) of selective reflection light, but it is less because of molecular weight, is easy to flow, and needs to be clipped in it in glass case or to make microcapsule, and its application is restricted.
Many derivatived celluloses can form a kind of spiral hyperstructure because the chirality of cellulosic molecule makes the derivatived cellulose molecule align by certain method, the certain light of reflection wavelength optionally according to the difference of pitch.This type of derivatived cellulose is dissolved in can gathers in the solvent, fix structural arrangement by thermopolymerization, (Polym.Ed 23,1985, P1043) for Y.Nishio et al., J.Polym.Sci. to obtain the angular color change effect.But in heat polymerization process, can form a kind of inhomogeneous phase, make color developing effect a little less than.
Summary of the invention
One of technical issues that need to address of the present invention are to disclose a kind of angular photochromic material, to overcome the above-mentioned defective that prior art exists.
Two of the technical issues that need to address of the present invention provide the preparation method of above-mentioned materials.
Described material is a kind of composition, and the component and the content of said composition comprise:
Derivatived cellulose 20~60wt%
Polymerisable monomer 40~80wt%
The derivatived cellulose of being addressed is a kind of modified-cellulose derivative, its part or all hydroxyl is substituted, substituting group can be ether, alkyl carbamate etc., chirality because of cellulosic molecule, make the derivatived cellulose chiral molecules align by specific method, form a kind of spiral hyperstructure, optionally reflected light reaches the angular color change effect.
Its general structure is:
Cell-O-R or
In the formula, Cell is a Mierocrystalline cellulose, and R can be C
1~C
20Alkyl, or wherein the part methylene radical has substituting groups such as fluorine, chlorine, nitro, cyano group, or phenyl and derivative thereof.
The polymerisable monomer of being addressed comprises a kind of in acrylate, methacrylic ester, vinyl ether, Resins, epoxy or the maleate.
Coat the transparent film that curing is made on the base material by above-mentioned composition, have the performance of the certain wavelength light of selective reflection, and change, thereby reach the angular color change effect, can be widely used as anti-fake material, finishing material with the variation at visual angle.
Above-mentioned preparation of compositions comprises the steps:
(1) preparation of derivatived cellulose: Mierocrystalline cellulose is dissolved in the solvent, be warming up to backflow, add modified-reaction reagent (as phenyl isocyanide ester or substituted-phenyl isocyanide ester and composition thereof), 20~60hr refluxes, underpressure distillation removes and desolvates, adopt conventional method from reaction product, to collect modified-cellulose, confirm that through IR the hydroxyl in the cellulose crystallite is esterified fully;
The Mierocrystalline cellulose of being addressed comprises a kind of in the hydrocellulose crystallite that obtained by the cellulose acetate hydrolysis, the cellulose crystallite that natural cellulose obtains after special processing;
The solvent of being addressed is general organic solvent, comprises a kind of or its mixture in pyridine, furans, the dimethyl sulfoxide (DMSO);
(2) preparation of compositions: with derivatived cellulose and the polymerisable monomer and the photoinitiator of step (1), be dissolved in the solvent, stir under the room temperature, the acquisition jelly that desolvates is taken out in decompression, jelly is coated on the base material film, by the magnetic field of 0.5~5.0T, then used the ultraviolet lamp radiation curing under the room temperature, promptly obtain the transparent film that composition of the present invention forms, this film has the angular color change performance.
The photoinitiator of being addressed can be general commercial photoinitiator, comprises the isobutyl-benzoin ether, 2,4, and 6-Three methyl Benzene formyl hexichol phosphine oxide, 1-hydroxy cyclohexyl phenylketone, 2,2-dimethyl-2-phenyl acetophenone etc.Consumption is decided according to its performance, as excessive quality and the color changeable effect that then influences film of consumption.The add-on of photoinitiator is counted 0.05~0.5wt% with the total amount of derivatived cellulose and polymerisable monomer.
The base material film that is adopted can be selected polyester film for use, polyethylene film, a kind of in the polycarbonate film etc.
According to the present invention, preferred magneticstrength is 0.5~5.0T.
The ratio of magneticstrength when adjusting aligns and derivatived cellulose and polymerisable monomer will obtain to have the film of different reflection wavelength light.
Material of the present invention can be used for preparing anti-counterfeiting product, as the protective sleeve of anti-counterfeiting mark, certificate and card card and anti-forge cigarette wire drawing etc.
By above-mentioned disclosed technical scheme as seen, angular photochromic material of the present invention aligns it by magnetic field, by uv-radiation it is solidified, and the color of material is durable, bright-coloured, and tone is not subjected to Temperature Influence, solidification process rapidly and efficiently, undergoing phase transition not.Because the color of selective reflection light depends on the magneticstrength when aligning and the composition of mixture, it is very easy to regulate color.Angular photochromic material preparation process of the present invention is simple, processing ease, and can regulate color as required, can be widely used in anti-fake material and finishing material.
Embodiment
Embodiment 1
10g Mierocrystalline cellulose (being obtained by the cellulose acetate hydrolysis) is dissolved in the 210ml pyridine, is warming up to backflow, add the 50ml phenylcarbimide, backflow 48hr, most of pyridine is removed in underpressure distillation, adds 0.8l methyl alcohol, separates out solid, filter, filter cake is dissolved in the 600ml acetone, adds 0.8L methyl alcohol again the product precipitation is separated out, filter, washing, vacuum-drying.Get the 20g product.Confirm that through IR the hydroxyl in the cellulose crystallite is esterified fully basically.
With the above-mentioned derivatived cellulose of 3.0g, 5.5g trimethylolpropane trimethacrylate and 60mg 2,2-methyl-2-phenyl acetophenone is dissolved in the 100ml acetone, vigorous stirring 2hr, acetone is taken out in decompression, and it is gluey that resistates is, this jelly is applied on the PET polyester film, the about 30 μ m of thickness place the magnetic field 1.0min of 1.0T, then use the ultraviolet lamp radiation curing, obtain the layer of transparent film, this film has the angular color change performance, and 90 ° of visual angles take on a red color when seeing, side is seen and is green.Reflection spectrum under 90 ° of visual angles of spectrophotometric instrumentation has the intensive absorption peak at the 628nm place.
Embodiment 2~5
With the above-mentioned derivatived cellulose of 6.0g, 11.0g trimethylolpropane trimethacrylate and 120mg 2,2-methyl-2-phenyl acetophenone is dissolved in the 200ml acetone, vigorous stirring 2hr, and acetone is taken out in decompression, mixture with five equilibrium is applied on the PET film respectively, the about 30 μ m of thickness place the magnetic field 1.0min of varying strength, radiation curing under identical ultraviolet lamp, obtain selecting to reflect the film of different wavelengths of light, as following table:
Magneticstrength film color (90 ° of visual angles) reflection spectrum absorption peak (90 ° of visual angles)
The red 652nm of embodiment 2 1.0T
The orange 580nm of embodiment 3 1.5T
The green 533nm of embodiment 4 2.0T
The blue 488nm of embodiment 5 2.5T
Embodiment 6~8
Embodiment 1 gained derivatived cellulose and trimethylolpropane trimethacrylate are prepared burden by the different mass ratio, place 1.0min under the magnetic field of 1.0T, then carry out radiation curing, also obtain selecting to reflect the film of different wavelengths of light, as following table:
Derivatived cellulose ratio (wt%) film color (90 ° of visual angles) reflection spectrum absorption peak (90 ° of visual angles)
Embodiment 6 35 red 655nm
Embodiment 7 45 orange 575nm
Embodiment 8 55 green 550nm