CN104624125A - Photochromic double-shell microcapsule and preparation method and application thereof - Google Patents
Photochromic double-shell microcapsule and preparation method and application thereof Download PDFInfo
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- CN104624125A CN104624125A CN201310555682.8A CN201310555682A CN104624125A CN 104624125 A CN104624125 A CN 104624125A CN 201310555682 A CN201310555682 A CN 201310555682A CN 104624125 A CN104624125 A CN 104624125A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
The invention discloses a photochromic double-shell microcapsule and a preparation method and an application thereof. The photochromic double-shell microcapsule comprises an internal shell formed by a photochromic material and a shell body coating the internal shell, the shell body comprises an internal layer shell body formed by one or more of a polymer, long-chain saturated hydrocarbon and long chain saturated aliphatic acid, the shell body also comprises an external shell body covering external part of the internal layer shell body, the external shell body is a compact layer formed by one or more of a nonmetallic oxide, a metal oxide or salt of the metal oxide; the preparation method of the photochromic double-shell microcapsule is characterized in that the prepared single-shell microcapsule dispersion liquid is mixed and reacted to a prepared dispersion liquid of alcoxyl nonmetal, alcoxyl metal or a predecessor of metal salt, and the photochromic double-shell microcapsule is prepared by further processing. The photochromic double-shell microcapsule has hear resistance and chemical stability, and especially has stability to acid, alkali and an organic solvent.
Description
Technical field
The present invention relates to a kind of Photochromic double-shell microcapsule and its preparation method and application, belong to functional high molecule material preparing technical field.
Background technology
Photochromicly refer to that the phenomenon of reversible change occurs material color under the light irradiation of suitable wavelength.The change of this color at room temperature can be restored naturally when removing the light irradiation exciting or use instead another kind of different wave length, or also can be restored by heat under the condition of raised temperature.Bacteria rhodopsin is a kind of special photochromic protein matter, there is high photosensitivity and light cycle-index, greatly be superior to photochromic synthetic material, albumen intelligence ink based on bacteria rhodopsin albumen is a kind of antifalse material, photochromic, optical storage and molecule are followed the trail of and are combined together by it, are a kind of new technologies biotechnology, materialogy, optics, printing combined together.
But bacteria rhodopsin is easy to affected by environment and sex change, and its variable color character obviously depends on the pH value of surrounding environment, also detrimental effects can be caused to it when itself and some organic solvent or surfactant fluid.Chinese patent literature CN102413917 A provides a kind of microcapsules containing bacteria rhodopsin, its shell is made up of polymer and/or long-chain saturated hydrocarbons and/or chain saturated fatty acids, and preferably this shell is the paraffin of 45 DEG C to 65 DEG C and/or fusion range by freezing point is further that 70-90 DEG C of Brazil wax is made.Above-mentioned material, to the less stable of part organic solvent, can cause bacteria rhodopsin sex change under part organic solvent environment wherein.When the fusing point of used encapsulating material is lower, when bacteria rhodopsin being used as anti-fake material and joining in ink, in printing dry run, the too high bacteria rhodopsin that may make of wink-dry temperature is exposed among environment, is subject to environment unfavorable factor as organic solvent or H
+, OH
-deng infringement thus sex change.
The microcapsules including active ingredient and metal oxide shell are disclosed in Chinese patent literature CN102596186A and CN102112219A, the physical package coating method joined by the particle of metal oxide in described aqueous phase is adopted in above-mentioned two sections of documents, although select for the particle in clad less, but owing to easily occurring reuniting, be difficult to be dispersed into less particle in dispersion process, and be mutually independently between each metal oxide nanoparticles, and then make clad imperfect, not fine and close.Clad imperfect, not fine and close, is easy to the dissipation of microcapsules use procedure Chinese traditional medicine active ingredient, thus makes the active ingredient in microcapsules play drug effect.But Chinese patent literature CN102596186A and the microcapsules in CN102112219A and the rhodopsin microcapsules recorded in Chinese patent literature CN102413917 A are identical on literal names, its essence is different, completely different to the requirement of outer casing, as mentioned above, the housing of the microcapsules containing active ingredient has the effect of loading active ingredient before the application of these microcapsules, in microcapsules application process, also to ensure that active ingredient can be emitted to external environment from enclosure interior, and the outer casing of the rhodopsin microcapsules recorded in Chinese patent literature CN102413917 A must be stable encapsulating material, for isolated rhodopsin and external environment condition, because once coming off appears in shell encapsulating housing, the phenomenon such as go bad because of reaction, rhodopsin sex change will be caused, thus lose the value and significance of use.
In addition, bacteria rhodopsin microcapsules itself present purple, after receiving visible ray generation variable color, present light yellow.If carry out coated operation of Denging to it, first will ensure the purple itself presented, or the operation done can make it present the higher color of a species saturation.Secondly, coated shell must reach certain requirement to the permeability of visible ray, and such guarantee bacteria rhodopsin in by radiation of visible light, can receive enough photons, thus reach obvious color changeable effect.3rd, the bacteria rhodopsin microcapsules after coated receive the color that presents after illumination must with illumination before distinguish to some extent.In other words, coated shell must ensure that photochromic effect naked eyes can be differentiated, and the color-yellow after the viewed variable color of little impact of will trying one's best.Time several metal oxides disclosed in Chinese patent literature CN102596186A and CN102112219A are powder state, can diffuse reflection be there is in the light be irradiated to above, particle is made to be white, be scattered in emulsion, the process being wrapped in the surface of microcapsules afterwards all can not change its color.Directly carry out coated according to said method, no matter clad thin and thick, all can impact the color of bacteria rhodopsin.When clad relatively thin to ensure the requirement of rhodopsin microcapsules to light transmission reluctantly time, can gap be there is between inorganic particle and inorganic particle in thin outer casing, be difficult the interference of resisting external environment.Otherwise, when the thickness as far as possible increasing clad is to strengthen the resistivity of outer casing to environment, white due to the increase clad of thickness will have a strong impact on bacteria rhodopsin itself color, affect its absorption to visible ray, and then affect its photochromic effect, thus lose its use value.
Summary of the invention
For solving the photochromic material microcapsules in prior art with individual layer clad, individual layer clad poor stability, the problem of covered effect difference, and then a kind of Photochromic double-shell microcapsule is provided, and further provide preparation method and the purposes of described Photochromic double-shell microcapsule.
For this reason, the technical scheme that the present invention takes is:
A kind of Photochromic double-shell microcapsule, comprise the kernel formed by photochromic material, with the housing of coated described kernel, described housing comprises by one or more internal layer shells formed in polymer, long-chain saturated hydrocarbons, chain saturated fatty acids, described housing also comprises the outer casing being coated on described internal layer shell outside, and described outer casing is the compacted zone for stoping penetration by liquid formed by one or more in the salt of nonmetal oxide, metal oxide or metal oxide.
In Photochromic double-shell microcapsule described above, the energy gap of the salt of described nonmetal oxide, described metal oxide or described metal oxide is greater than 3.0eV, and the absorption cutoff wavelength of its correspondence is less than 413nm.
In Photochromic double-shell microcapsule described above, described nonmetal oxide comprises SiO
2; Described metal oxide comprises TiO
2; The salt of described metal oxide is ZnGa
2o
4or SrTiO
3.
In Photochromic double-shell microcapsule described above, described photochromic material is the variant of bacteria rhodopsin and/or described bacteria rhodopsin.
In Photochromic double-shell microcapsule described above, the thickness of described outer casing is not more than 1 micron.
In Photochromic double-shell microcapsule described above, the diameter of described double-shell microcapsule is less than 60 microns.
In Photochromic double-shell microcapsule described above, the diameter of described double-shell microcapsule is less than 10 microns.
Prepare a method for above-mentioned Photochromic double-shell microcapsule, comprise the steps,
(1) the monoshell microcapsules of preparation containing photochromic material, described monoshell microcapsules comprise the kernel formed by photochromic material, with the housing of coated described kernel portion, described housing is by one or more housings formed in polymer, long-chain saturated hydrocarbons, chain saturated fatty acids;
(2) described monoshell microcapsules are dissolved in solvent, prepare the dispersion liquid of described monoshell microcapsules;
(3) prepare that described alcoxyl is nonmetal, the predecessor dispersion liquid of alcoxyl metal or slaine;
(4) described predecessor dispersion liquid is mixed with described monoshell micro-capsule dispersion liquid, reaction 2-32 hour;
(5) the product drying described step (4) obtained obtains required photochromic material double-shell microcapsule.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, the predecessor dispersion liquid in described step (3) is SiO
2or TiO
2predecessor dispersion liquid.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, the reaction temperature of described step (4) is 40-60 DEG C.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described SiO
2predecessor dispersion liquid in formed by VTES, ethyl orthosilicate and absolute ethyl alcohol; Described TiO
2predecessor dispersion liquid formed by butyl titanate, absolute ethyl alcohol.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described SiO
2predecessor dispersion liquid comprise silane coupler the aqueous solution formed the first predecessor dispersion liquid and sodium silicate aqueous solution formed the second predecessor dispersion liquid.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, the predecessor dispersion liquid in described step (3) is ZnGa
2o
4or SrTiO
3predecessor dispersion liquid.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described ZnGa
2o
4predecessor dispersion liquid comprise the first predecessor dispersion liquid containing gallium ion and the second predecessor dispersion liquid containing zinc ion;
Described SrTiO
3predecessor dispersion liquid comprise the first predecessor dispersion liquid containing titanium ion and the second predecessor dispersion liquid containing strontium ion.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described ZnGa
2o
4predecessor dispersion liquid comprise the first predecessor dispersion liquid of being formed by gallium nitrate, absolute ethyl alcohol and acetylacetone,2,4-pentanedione and form the second predecessor dispersion liquid by two acetate hydrate zinc, absolute ethyl alcohol and monoethanolamine;
Described SrTiO
3the first predecessor dispersion liquid of being formed of the predecessor dispersion liquid aqueous solution that comprises Strontium dichloride hexahydrate and the second predecessor dispersion liquid of being formed by titanium tetrachloride and absolute ethyl alcohol.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described first predecessor dispersion liquid, described second predecessor dispersion liquid and described monoshell micro-capsule dispersion liquid hybrid reaction at normal temperatures.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, in described step (2) or step (4), also comprise the step regulating solution ph.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, the product obtained in described step (4) washed, filter and dry at 40-80 DEG C and obtain required photochromic material double-shell microcapsule,
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, the product obtained in described step (4) is obtained required photochromic material double-shell microcapsule through spraying dry.
A kind of above-mentioned bacteria rhodopsin double-shell microcapsule is as the application of ink raw materials.
In above-mentioned Photochromic double-shell microcapsule, described photochromic material is bacteria rhodopsin modification D 96N.
Above-mentionedly prepare in the method for Photochromic double-shell microcapsule, described step (4) also comprises the step of vacuum filtration.
Compared with prior art, tool of the present invention has the following advantages:
(1) Photochromic double-shell microcapsule described in the application, not only comprise by a kind of or several middle internal layer shell formed in polymer, long-chain saturated hydrocarbons, chain saturated fatty acids, also comprise the outer casing being coated on described internal layer shell, described outer casing comprises one or more compacted zones for stoping penetration by liquid formed in the salt of nonmetal oxide, metal oxide or metal oxide, as the inorganic material of outer casing, stable chemical nature, water insoluble and most of organic solvent, diluted acid and diluted alkaline is insoluble under normal temperature, the compacted zone compact structure formed by it, space is narrow, interaction force between material molecule is enough to the infiltration keeping out outside liquid, thus make internal layer photochromic material be in relatively-stationary pH value, temperature, humidity, among microenvironment under the conditions such as salinity, not only organic solvent can be resisted, and not by the impact of the pH value outside shell, thus improve described Photochromic double-shell microcapsule heat resistance on the whole, chemical stability, particularly to acid, alkali, the stability of the factors such as organic solvent.
(2) energy gap of the salt of described nonmetal oxide, described metal oxide or described metal oxide is greater than 3.0eV, and the absorption cutoff wavelength of its correspondence is less than 413nm.The demand of described photochromic material to visible ray can not only be met, color and the photochromic properties thereof of photochromic material script can also be kept.
(3) the method for the invention is adopted to prepare Photochromic double-shell microcapsule, abandon in prior art the physical package coating method adding metal oxide nanoparticles and then form metal oxide particle layer shell in aqueous phase, according to photochromic material self-characteristic and to temperature, pH value, the requirement of each side such as photosensitive property, through performing creative labour, adopt specific method at its outside coated inorganic material layer, when adopting the coated outer casing of the method for the invention, formed coated at outer casing by the reaction between presoma, in course of reaction, form nonmetal oxide, the structure be cross-linked with each other between metal oxide or metal oxide salt, the inorganic material layer density adopting the method for the invention to be formed is high, voidage is little, one deck densification " putamina ", instead of the shell that granule is glued together.The outer casing clad adopting the method for the invention to be formed through experimental verification is complete, fine and close, and difficult drop-off can well protect inner layer material.And " putamina " of this continuous state, at least more than 70% is reached to the permeability of visible ray, thus ensures that bacteria rhodopsin is in by radiation of visible light, can receive enough photons, thus reach obvious color changeable effect, and photochromic effect naked eyes can be differentiated.
(4) Photochromic double-shell microcapsule described in the application is in preparation process, by the factor such as addition of adjustment colloid concentration, monoshell microcapsules, thus make outer casing thickness be not more than 1 micron, and then make described Photochromic double-shell microcapsule have good light transmission, be convenient to observe inner trickle color change, meet the requirement of extraordinary anti-forgery ink, this anti-forgery ink generally can be used as lithographic printing (or coating), silk-screen ink, letterpress printing ink or gravure ink.
figure of description
The TiO that Fig. 1 adopts conventional method of the prior art to prepare
2the microphotograph of film;
The TiO that Fig. 2 adopts method described in the application to prepare
2the microphotograph of film;
The TiO that Fig. 3 adopts method described in the application to prepare
2the electromicroscopic photograph of film.
Detailed description of the invention
Preparation method's referenced patent document CN102413917A containing photochromic monoshell microcapsules of the present invention.The photochromic monoshell microcapsules that contain selected for ease of contrasting following embodiment comprise the kernel formed by bacteria rhodopsin, and the housing of coated described kernel, and described housing parts is the housing formed by paraffin.
embodiment 1
(1) weigh 0.5g containing the monoshell microcapsules of bacteria rhodopsin, be dissolved in 10mL absolute ethyl alcohol and 1mL water mixed solution, stir that within 0.5 hour, to prepare monoshell capsule dispersant liquid for subsequent use;
(2) measure 10mL absolute ethyl alcohol, 0.50mL butyl titanate, add glacial acetic acid and regulate solution ph to be 5, to be mixed in beaker and to stir that within 0.5 hour, to prepare predecessor dispersion liquid for subsequent use;
(3) added in step (1) by the predecessor dispersant liquid drop prepared in step (2) in the dispersion liquid of the described monoshell microcapsules prepared, controlling bath temperature is 40 DEG C, and react after 2 hours, vacuum filtration obtains required product;
(4) to be washed by products therefrom and after filtering, put into baking oven at 60 DEG C dry 3 hours, obtaining outer casing is TiO
2the rhodopsin double-shell microcapsule of clad.
embodiment 2
(1) by the monoshell microcapsules 5g containing bacteria rhodopsin, be dissolved in the mixed solution of 60mL absolute ethyl alcohol and 1mL water, add ammoniacal liquor and regulate pH to 9, and make the monoshell uniform microcapsule of bacteria rhodopsin disperse to obtain in the solution the monoshell micro-capsule dispersion liquid of required bacteria rhodopsin under nitrogen protection;
(2) 3mL VTES (VTES), 2mL ethyl orthosilicate (TEOS) and 10mL absolute ethyl alcohol are mixed to get predecessor dispersion liquid for subsequent use;
(3) under 60 DEG C of conditions, dropwise predecessor dispersant liquid drop is added in the monoshell micro-capsule dispersion liquid of bacteria rhodopsin, dropwises rear insulation 6 hours, be finally cooled to room temperature and precipitation 24 hours filter and obtain required sediment;
(4) by the sediment that obtains in step (5) after washing and filtering, vacuum drying at 60 DEG C, obtaining outer casing is SiO
2the rhodopsin double-shell microcapsule of clad.
embodiment 3
(1) the monoshell microcapsules containing bacteria rhodopsin of 5g are joined in 10mL deionized water, be uniformly mixed, obtain the monoshell micro-capsule dispersion liquid of bacteria rhodopsin;
(2) dose volume concentration is the aqueous solution of the silane coupler KH-560 of 6.0% according to a conventional method, as the first predecessor dispersion liquid;
(3) sodium silicate aqueous solution of 4g/L is prepared according to a conventional method as the second predecessor dispersion liquid;
(4) micro-capsule dispersion liquid is mixed with the first predecessor homogeneous dispersion of 50ml, opening heating water bath and controlling reaction temperature is 60 DEG C, slowly drip the sodium silicate aqueous solution of 4g/L wherein, control the pH value of reaction system about 9.3, along with the increase of reaction system amount constantly increases mixing speed, stop when system pH is 9 dripping sodium silicate aqueous solution, precipitation, after 18 hours, is filtered and is obtained required sediment;
(5), after the sediment obtained from step (3) being spent deionized water, filtration, drying in 60 DEG C of baking ovens and obtaining outer casing is SiO
2the rhodopsin double-shell microcapsule of clad.
embodiment 4
(1) the monoshell microcapsules containing bacteria rhodopsin of 1g are joined in 10mL absolute ethyl alcohol, be uniformly mixed, obtain the monoshell micro-capsule dispersion liquid of bacteria rhodopsin;
(2) by the gallium nitrate (Ga (NO of 2.56g
3)
3) join in the absolute ethyl alcohol of 20mL, add the acetylacetone,2,4-pentanedione of 3mL, stirring and dissolving under the water-bath of 50 DEG C, obtain the first predecessor dispersion liquid for subsequent use;
(3) by the two acetate hydrate zinc (Zn (CH of 1.09g
3cOOH)
22H
2o) join in 10mL absolute ethyl alcohol, stir under the water-bath of 50 DEG C, and add the monoethanolamine of 0.5mL gradually, slaine is fully dissolved, obtain the second predecessor dispersion liquid for subsequent use;
(4) the dispersion liquid normal temperature prepared in step (1), (2) and (3) to be mixed and after stirring two hours, sediment is required product;
(5) washed by products therefrom and filter and to put at 60 DEG C, baking oven dry 3 hours, obtaining outer casing is ZnGa
2o
4the rhodopsin double-shell microcapsule of clad.
embodiment 5
(1) weigh 1g monoshell bacteria rhodopsin, be distributed in 10ml absolute ethyl alcohol, obtain monoshell capsule dispersant liquid for subsequent use;
(2) be dissolved in 40mL absolute ethyl alcohol by titanium tetrachloride 1.90g, adding citric acid adjust ph is 5, and stirring, it is for subsequent use to obtain the first predecessor dispersion liquid;
(3) weigh 2.66g Strontium dichloride hexahydrate to be dissolved in 10mL water, stir and obtain the second predecessor dispersion liquid;
(4) the dispersion liquid normal temperature mixing will prepared in step (1), (2), (3), add 0.62g ethylene glycol, continue stirring more than 2 hours, sediment is required product;
(5) by products therefrom in step (4) through spraying dry, obtaining outer casing is SrTiO
4the rhodopsin double-shell microcapsule of clad.
comparative example 1
(1) the monoshell microcapsules containing bacteria rhodopsin are obtained by method of the prior art, described monoshell microcapsules comprise the kernel portion formed by bacteria rhodopsin, with the housing parts of coated described kernel portion, described housing parts is the housing formed by paraffin; Monoshell microcapsules containing bacteria rhodopsin described in this comparative example are identical with the monoshell microcapsules containing bacteria rhodopsin adopted in above-described embodiment.
(2) by 6g fragrance 200(Exxon Mobil ExxonMobil, the U.S., No. CAS: 64742-94-5), after the epoxidized soybean oil mixing of 5.2g tetramethoxy-silicane, 1.0g, adding 90g mass fraction is 5%Na
2sO
4dispersion liquid A is obtained in the aqueous solution;
(3) the bacteria rhodopsin monoshell microcapsules of 6g are joined in solution A, after stirring, add 15g TiO
2(p25) powder, stirs and obtains dispersion liquid B;
(4) with watery hydrochloric acid, the pH value of solution B is adjusted to 5, Keep agitation added saturated NaHCO after 24 hours
3the aqueous solution, regulates pH to 7.Sediment is filtered and obtains by nano-TiO
2the rhodopsin double-shell microcapsule of particles coat.
comparative example 2
(1) obtain the monoshell microcapsules containing bacteria rhodopsin by method of the prior art, described microcapsules comprise the kernel portion formed by bacteria rhodopsin, and described in the housing parts of coated described kernel portion, housing parts is the housing formed by paraffin; Monoshell microcapsules containing bacteria rhodopsin described in this comparative example are identical with the monoshell microcapsules containing bacteria rhodopsin adopted in above-described embodiment.
(2) the 1-butylene vinyl pyrrolidone polymer of 7.5g deionized water and 2.5g is dissolved in 100mL water, obtains solution A.
(3) 0.6g tetramethoxy-silicane is mixed with the bacteria rhodopsin monoshell uniform microcapsule of 7g, obtain dispersion liquid B;
(4) above-mentioned solution A and dispersion liquid B are mixed, and be fully uniformly mixed, add the colloidal silica silicon suspension of 4g, and fully stirring obtains suspension C;
(5) with watery hydrochloric acid, the pH value of suspension C is adjusted to 5, Keep agitation added saturated NaHCO after 24 hours
3the aqueous solution, regulates pH to 7.Sediment is filtered and obtains nano particle SiO
2coated rhodopsin double-shell microcapsule.
evaluation Example 1
The double-shell microcapsule prepared in above-described embodiment and comparative example is dipped in oxolane A respectively, in the sulfuric acid solution B of the mass fraction 2% and sodium hydroxide solution C of mass fraction 2%, observe its stability, wherein, the bacteria rhodopsin double-shell microcapsule that described in embodiment 1-3, method prepares is adopted to be dipped in oxolane A respectively, in the sulfuric acid solution B of the mass fraction 2% and sodium hydroxide solution C of mass fraction 2% after 1 hour, not change, and the bacteria rhodopsin double-shell microcapsule in comparative example 1 and 2 is all dipped in the sulfuric acid solution B of oxolane A and mass fraction 2%, after 5 minutes, sample part dissolves, purple capsule becomes yellow, irreversible yellow is all changed into after 8 minutes, be dipped in the bacteria rhodopsin double-shell microcapsule sample part dissolving after 8 minutes in two comparative examples in the sodium hydroxide solution C of mass fraction 2%, part purple capsule changes yellow into, irreversible yellow is all changed into after 12 minutes.
evaluation Example 2
By a certain amount of TiO
2(p25, white nanometer grade powder) ultrasonic disperse is in absolute ethyl alcohol, and ultrasonic disperse obtains the TiO of 0.1mol/L
2alcohol dispersion liquid.The method of Best-Effort request is adopted to make TiO
2be deposited on substrate, be placed in baking oven and dry.Obtain the microphoto of sample as shown in Figure 1.
Be dissolved in by 0.50mL butyl titanate in the mixed solution of 20mL absolute ethyl alcohol and 1mL water, add glacial acetic acid and regulate solution ph to be 5, controlling bath temperature is 40 DEG C, reacts after 2 hours, obtains settled solution.Adopt the method for Best-Effort request to obtain film after standing sedimentation 24h, be placed in baking oven and fully dry, the microphotograph obtaining sample as shown in Figure 2 with stereoscan photograph as shown in Figure 3.
Although TiO as can be seen from Figure 1
2for nano particle, but there is agglomeration, TiO
2occur with bulk, in ethanol can not bunch the scattering of agglomerated even if disperse, and the TiO of reunion
2between separate, space is very large, and whole film is not fine and close.As can be seen from Figure 2, the TiO adopting this method obtained
2film is a fine and close film, further as can be seen from Figure 3 TiO
2particle only has tens nanometers, and very fine and close between particle.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among the protection domain of the invention.
Claims (20)
1. a Photochromic double-shell microcapsule, comprise the kernel formed by photochromic material, and the housing of coated described kernel, described housing comprises by one or more internal layer shells formed in polymer, long-chain saturated hydrocarbons, chain saturated fatty acids, it is characterized in that
Described housing also comprises the outer casing being coated on described internal layer shell outside, and described outer casing is the compacted zone for stoping penetration by liquid formed by one or more in the salt of nonmetal oxide, metal oxide or metal oxide.
2. Photochromic double-shell microcapsule according to claim 1, is characterized in that,
The energy gap of the salt of described nonmetal oxide, described metal oxide or described metal oxide is greater than 3.0eV, and the absorption cutoff wavelength of its correspondence is less than 413nm.
3. Photochromic double-shell microcapsule according to claim 2, is characterized in that,
Described nonmetal oxide comprises SiO
2;
Described metal oxide comprises TiO
2;
The salt of described metal oxide is ZnGa
2o
4or SrTiO
3.
4. Photochromic double-shell microcapsule according to claim 1, is characterized in that, described photochromic material is the variant of bacteria rhodopsin and/or described bacteria rhodopsin.
5., according to the arbitrary described Photochromic double-shell microcapsule of claim 1-4, it is characterized in that, the thickness of described outer casing is not more than 1 micron.
6. Photochromic double-shell microcapsule according to claim 5, is characterized in that, the diameter of described double-shell microcapsule is less than 60 microns.
7. Photochromic double-shell microcapsule according to claim 6, is characterized in that, the diameter of described double-shell microcapsule is less than 10 microns.
8. prepare a method for the arbitrary described Photochromic double-shell microcapsule of claim 1-7, comprise the steps,
(1) the monoshell microcapsules of preparation containing photochromic material, described monoshell microcapsules comprise the kernel formed by photochromic material, with the housing of coated described kernel portion, described housing is by one or more housings formed in polymer, long-chain saturated hydrocarbons, chain saturated fatty acids;
(2) described monoshell microcapsules are dissolved in solvent, prepare the dispersion liquid of described monoshell microcapsules;
(3) prepare that described alcoxyl is nonmetal, the predecessor dispersion liquid of alcoxyl metal or slaine;
(4) described predecessor dispersion liquid is mixed with described monoshell micro-capsule dispersion liquid, reaction 2-32 hour;
(5) the product drying described step (4) obtained obtains required photochromic material double-shell microcapsule.
9. the method preparing Photochromic double-shell microcapsule according to claim 8, is characterized in that,
Predecessor dispersion liquid in described step (3) is SiO
2or TiO
2predecessor dispersion liquid.
10. the method preparing Photochromic double-shell microcapsule according to claim 9, is characterized in that, the reaction temperature of described step (4) is 40-60 DEG C.
11. methods preparing Photochromic double-shell microcapsule according to claim 10, is characterized in that, described SiO
2predecessor dispersion liquid in formed by VTES, ethyl orthosilicate and absolute ethyl alcohol; Described TiO
2predecessor dispersion liquid formed by butyl titanate, absolute ethyl alcohol.
12. methods preparing Photochromic double-shell microcapsule according to claim 10, is characterized in that, described SiO
2predecessor dispersion liquid comprise silane coupler the aqueous solution formed the first predecessor dispersion liquid and sodium silicate aqueous solution formed the second predecessor dispersion liquid.
13. methods preparing Photochromic double-shell microcapsule according to claim 8, is characterized in that,
Predecessor dispersion liquid in described step (3) is ZnGa
2o
4or SrTiO
3predecessor dispersion liquid.
14. methods preparing Photochromic double-shell microcapsule according to claim 13, is characterized in that,
Described ZnGa
2o
4predecessor dispersion liquid comprise the first predecessor dispersion liquid containing gallium ion and the second predecessor dispersion liquid containing zinc ion;
Described SrTiO
3predecessor dispersion liquid comprise the first predecessor dispersion liquid containing titanium ion and the second predecessor dispersion liquid containing strontium ion.
15. methods preparing Photochromic double-shell microcapsule according to claim 14, is characterized in that,
Described ZnGa
2o
4predecessor dispersion liquid comprise the first predecessor dispersion liquid of being formed by gallium nitrate, absolute ethyl alcohol and acetylacetone,2,4-pentanedione and form the second predecessor dispersion liquid by two acetate hydrate zinc, absolute ethyl alcohol and monoethanolamine;
Described SrTiO
3the first predecessor dispersion liquid of being formed of the predecessor dispersion liquid aqueous solution that comprises Strontium dichloride hexahydrate and the second predecessor dispersion liquid of being formed by titanium tetrachloride and absolute ethyl alcohol.
16. methods preparing Photochromic double-shell microcapsule according to claim 15, is characterized in that,
Described first predecessor dispersion liquid, described second predecessor dispersion liquid and described monoshell micro-capsule dispersion liquid hybrid reaction at normal temperatures.
17.-16 arbitrary described methods preparing Photochromic double-shell microcapsule according to Claim 8, is characterized in that, also comprise the step regulating solution ph in described step (2) or step (4).
18. methods preparing Photochromic double-shell microcapsule according to claim 17, is characterized in that,
By the product obtained in described step (4) wash, filter and at 40-80 DEG C dry obtain required photochromic material double-shell microcapsule.
19. methods preparing Photochromic double-shell microcapsule according to claim 17, is characterized in that,
The product obtained in described step (4) is obtained required photochromic material double-shell microcapsule through spraying dry.
Bacteria rhodopsin double-shell microcapsule described in 20. 1 kinds of claim 1-8 are arbitrary is as the application of ink raw materials.
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