CN1887941A - Photon crystal film of ultraviolet polymer colloid with photon band gap and its prepn and use - Google Patents
Photon crystal film of ultraviolet polymer colloid with photon band gap and its prepn and use Download PDFInfo
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- CN1887941A CN1887941A CN 200510012021 CN200510012021A CN1887941A CN 1887941 A CN1887941 A CN 1887941A CN 200510012021 CN200510012021 CN 200510012021 CN 200510012021 A CN200510012021 A CN 200510012021A CN 1887941 A CN1887941 A CN 1887941A
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Abstract
The present invention relates to photo crystal film, and is especially one kind of colloidal photon crystal film and its preparation and application in ultraviolet preventing material or cosmetics material. The colloidal photon crystal film is prepared through coating monodispersed polymer latex in hard core-soft shell structure on flat substrate and volatilizing the dispersing liquid; the obtained monodispersed polymer latex particle has shell of 20-50 nm thickness, particle size of 100-160 nm and multiple dispersion index not greater than 0.005; and colloidal photon crystal film has photon band gap in the ultraviolet region of 200-400 nm. The colloidal photon crystal film is used as the ultraviolet preventing material in cosmetics, paint, etc.
Description
Technical field
The invention belongs to the preparing technical field of colloid photonic crystal film, relate in particular to the large size photon band gap at photon crystal membrane of polymer colloid of ultraviolet region and preparation method thereof; And the application of this colloid photonic crystal film in ultraviolet material of prevention or cosmetics material.
Background technology
The colloidal photon crystal material is realized special regulation and control to light with the formed periodic structure of the regular arrangement of single dispersed latex grain to the refraction of light or diffraction.According to the size difference of periodic arrangement, regulate and control the light wavelength difference.The Application Areas difference of corresponding prepared colloidal crystal.In common patent documentation, colloid photonic crystal film is mainly used in wave filter (as CN:01105105.1, CN:98110990.X), optoelectronic switch (CN:02160207.7), optical waveguides (CN:02804125.9, CN:99810798, CN:01132293.4, CN:02811132.X), optical fiber (CN:00803964.X, CN:00803960.7, aspect such as CN:03127694.6), and seldom report crystal film with photon is applied in coating and cosmetic field, especially be applied to pre-antiultraviolet aspect.
The present invention is based on the inventor in the preceding patent application (patent No.: the single dispersed latex grain of CN:200510011219.2) easy manufacture, and big area prepares on the basis of colloidal crystal film fast, prepared the colloidal crystal film of photon band gap at ultraviolet region.And attempt it is applied in aspects such as preventing ultraviolet coating and makeup.Common for the Ultraviolet rays protection majority based on semiconductor property with inorganic nanometer oxide powders such as titanium dioxide, mica, talcum powder and ferric oxide, promptly under UV-irradiation, electronics is excited and is caused the absorption of UV-light by valence band to the conduction band transition, or adopt organic uv absorbers to absorb sunlight, luminous energy is converted into heat energy.As Chinese patent application number: 200410017315.3,03150634.8,200410013397.4,200410021501.4,200410078365.2,95100420.4,96193617.7,97196847.0 disclosed technical scheme is to adopt the optical effect of inorganic nano oxidic particle to realize ultraviolet defence, and Chinese patent application number: 95118640.X, 95120380.0 disclosed technical schemes are to utilize the molecular structure of special organic compound to ultraviolet absorption.There is equilibrium problem (saturability) in inorganic (oxidation nanometer particle) UV light absorber based on the electron excitation under the uv irradiating; And organic uv absorbers generally all contains aromatic hydrocarbon and derivative thereof or carbonyl isopolarity group, human body is had pungency to a certain degree and injures skin, simultaneously action of ultraviolet radiation after for some time organic molecular structure destroy and lose ultraviolet sorption; Inorganic or organic uv absorbers finally can make the luminous energy of absorption change into heat energy, also can produce some side effects to skin or base material.Also have by the ultraviolet selective reflection of metal pair (CN:92102479.7) and realize, but this method needs generally to realize that by the precious metal sputtering technology devices needed is special that cost is very high ultraviolet prevention.Polymer photon crystal film realization ultraviolet protection of the present invention can be avoided as above problem.
Summary of the invention
One of purpose of the present invention provides the photon crystal membrane of polymer colloid of a kind of large size photon band gap at ultraviolet region, and colloid photonic crystal film is with low cost.
Two of purpose of the present invention is neither to need by specific apparatus for assembling, and temperature and humidity to surrounding environment do not have particular requirement, thereby can effectively overcome the defective of the colloid photonic crystal film large size preparation that traditional method is difficult to realize, the simple preparation method of a kind of large size photon band gap at the photon crystal membrane of polymer colloid of ultraviolet region is provided, it is simple that this method has technology, with low cost, equipment there are not advantages such as particular requirement.
Three of purpose of the present invention provides a kind of method for preparing single dispersed latex grain by single stage method.Present method adopts the batch method emulsifier-free emulsion polymerization, and by suitable adjustment emulsion polymerization technique, single dispersed latex grain that single stage method is prepared does not need any purification just can realize that single dispersion index is less than or equal to 0.005, and particle size range is 100～160nm.
Four of the object of the invention is that photon band gap is used for suitability for industrialized production at the photon crystal membrane of polymer colloid of ultraviolet region, especially is applied in the ultraviolet coating of prevention, fields such as sun care preparations.
The present invention takes the batch method emulsifier-free emulsion polymerization, and by suitable adjustment emulsion polymerization technique, the emulsion particle that single stage method is prepared does not need any purification just can realize that single dispersion index is less than or equal to 0.005.
By the emulsion particle with nuclear-shell structure that the inventive method is prepared, its particle size range is 100～160nm, and polydispersity index is less than or equal to 0.005.The photon band gap of prepared colloid photonic crystal film is distributed in the ultraviolet region of 200-400nm, and its optimum position is respectively: 253,281,300,319,327,345,380, and can obtain the colloidal photon crystal of more concrete photon band gap as required by adjusting latex particle size.
The colloid photonic crystal film of photon band gap of the present invention in the ultraviolet region is that monodisperse polymer emulsion particle with hard core-soft core structure is piled up and formed; Thick 20～the 50nm of the shell of monodisperse polymer emulsion particle, the latex particle size scope is 100～160nm, polydispersity index is less than or equal to 0.005.
Described photon band gap relates to each wave band of ultraviolet region at the photon band gap of the photon crystal membrane of polymer colloid of ultraviolet region; Along with the descending variation of latex particle size, the peak generation blue shift of the reflection spectrum of resulting colloid photonic crystal film.
The preparation that the present invention has the monodisperse polymer emulsion particle of nucleocapsid structure is to adopt one step of batch method emulsifier-free emulsion polymerization to realize that the typical preparation method who is adopted is:
With the monomer 1 that wetting ability increases successively, monomer 2, monomer 3 blending dispersion are in the aqueous solution that contains pH buffer reagent and emulsifying agent; Is 300～800rpm with resulting emulsion polymerization systems at rotating speed, be preferably under the rotating speed of 500rpm and mix, and be heated to 65～85 ℃ (preferred temperature are 78 ℃), the initiator that adds initiator total amount 1/2 makes reaction begin to carry out, react the initiator that adds initiator total amount 1/4 after 2～4.5 hours again, remaining initiator is continuing reaction adding after 2～4.5 hours, and the 0.2wt%～1wt% of the suitable total monomer weight of the total consumption of described initiator is preferably 0.3wt%.Reaction continues end in 1～3 hour subsequently, obtains single dispersion index and is less than or equal to 0.005, and particle size range is the monodisperse polymer emulsion particle with hard core-soft core structure of 100～160nm.
Wherein, the total consumption of monomer is that (consumption of monomer 1 is 88～94wt% of total monomer weight in the emulsion polymerization systems for 11～17wt% of emulsion polymerization systems gross weight, monomer 2 is 3～6wt%, monomer 3 is 3～6wt%), the concentration of pH buffer reagent in emulsion polymerization systems is 0.02～0.99wt%, the concentration of emulsifying agent in emulsion polymerization systems is that (weight ratio 0.04～0.5wt%) of monomer total amount in emulsifying agent consumption and the polymerization system, the concentration of initiator in emulsion polymerization systems is 0.02～0.99wt% to 0.0068～0.067wt%.
The realization of the nucleocapsid structure of monodisperse polymer emulsion particle does not need special technological process, just according to reaction monomers in the polymerization system and the hydrophilic difference of phase emergencing copolymer, hydrophilic radical progressively moves to the top layer in polymerization process, and lipophilic group partly moves to stratum nucleare, finally realizes hard core-soft core structure.
The reaction times of system is 5～12 hours, and the preferred reaction time is 10～11 hours.
Described reaction monomers is the compound that contains at least one ethylene linkage in the molecule, and its wetting ability increases successively, and monomer 1 is the relatively poor reaction monomers of wetting ability, as vinylbenzene, vinyl toluene or their mixture; And monomer 2 is a wetting ability monomer relatively preferably, as esters of acrylic acid, vinyl acetate or their mixture etc., described esters of acrylic acid is selected from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, isobutyl acrylate or their any mixture; Monomer 3 is the very strong water-soluble reaction monomer of wetting ability, as vinylformic acid, methacrylic acid, acrylamide, propylene cyanogen or their any mixture etc.The introducing of minor amount of water dissolubility reaction monomers 3 is in order to increase the stability of system.And selecting for use of the different successively reaction monomers of wetting ability is for spontaneous formation nuclear-shell structure in polymerization process.
Described initiator is selected from alkali metal sulfates, ammonium persulphate or their mixture.Wherein initiator is that form with the aqueous solution is incorporated in the polymerization system, and its strength of solution is 2～5wt%.
Described basic metal is selected from potassium or sodium.
The emulsifying agent of the size of the final gained emulsion particle of described adjusting is selected from one or more the mixture in sodium laurylsulfonate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate etc.
Described pH buffer reagent is selected from one or more the mixture in bicarbonate of ammonia, sodium bicarbonate, the sodium hydrogen phosphate etc.
For guaranteeing effective realization of emulsion particle monodispersity, strict control stir speed (S.S.) is fed in raw material and heating schedule, to avoid the appearance of secondary nucleation in the polymerization process.
Emulsifying agent consumption difference in the polymerization system of the present invention, the particle diameter difference of gained emulsion particle causes the photon band gap difference of final colloid photonic crystal film; Emulsifying agent is in the mode introducing system by solution among the present invention.For example, the weight ratio of monomer total amount is respectively 0.238%, 0.214% in emulsifying agent consumption and the polymerization system, and 0.19%, 0.119%, 0.095%, 0.071%, 0.048% o'clock, preparation-obtained latex particle size is followed successively by 100,115, and 120,125,130,150,160nm, the photon band gap position of corresponding colloid photonic crystal film is respectively: 253,281,300,319,327,345,380nm.
Photon band gap of the present invention may further comprise the steps in the preparation method of the photon crystal membrane of polymer colloid of ultraviolet region:
(1) earlier the monodisperse polymer emulsion particle is dispersed in the water under the room temperature, then resulting monodisperse polymer emulsion particle emulsion is evenly covered on the flat substrates, wherein the concentration of monodisperse polymer emulsion particle emulsion is 5～30wt%.
(2) make step (1) disperse the aqueous solvent volatilization of monodisperse polymer emulsion particle under the normal temperature and pressure, the monodisperse polymer emulsion particle is piled up with face-centered cubic on base material, behind dried coating film, peel off from base material, can obtain having the colloid photonic crystal film of photon band gap in the ultraviolet region.
Single dispersion index of described monodisperse polymer emulsion particle is less than or equal to 0.005, and particle size range is 100～160nm.Reduce the photon band gap generation blue shift of gained crystal film with photon from 160 to 100nm with latex particle size.
Described base material comprises glass, silicon chip, paper or stainless steel plate etc.
The photon crystal membrane of polymer colloid of the resulting photon band gap of the present invention in the ultraviolet region can be used as the ultraviolet material of prevention or can be used as the material that prevents in the ultraviolet makeup, or with UV light absorber or the membrane-forming agent of latex crystal film with photon as pre-antiultraviolet coating; Or be applied in the association area of other pre-antiultraviolet product.
Become the difference of film base material according to colloidal photon crystal, resulting photon crystal membrane of polymer colloid can be used on the different substrate materials.
Photon band gap of the present invention the photon crystal membrane of polymer colloid of ultraviolet region and other Clear paint mutually the blended application process can be undertaken by following operation:
Colloid photonic crystal film of the present invention is peeled off from base material, be crushed to the micro-size particles size, mix with Clear paint and solvent phase, colloid photonic crystal film can show the Ultraviolet rays protection effect, wherein colloid photonic crystal film is 1～10wt% in the mixed solution, Clear paint is 50～70wt%, and solvent is 20～40wt%.
Described Clear paint is selected from one or more the mixture in acrylic varnish, polyurethane lacquer, 582-2 melamine resin, the zapon varnish.
Described solvent is an ethanol, the mixture of one or more in ethyl acetate or the butylacetate.
Have the crystal film with photon of photon band gap and can be applicable to makeup, especially prevent ultraviolet makeup in the ultraviolet region.Concrete application process is as follows:
Colloid photonic crystal film of the present invention is peeled off from base material, be crushed to the micro-size particles size, mix mutually with the base-material of makeup.Crystal film with photon mainly replaces the pre-antiultraviolet composition in the makeup.
Wherein colloid photonic crystal film is 1～10wt% in the mixed system.The base-material of makeup comprises: pigment extender (4～12wt%), film form agent (0～25wt%), the solvent part (comprise the oiliness part (38～70wt%), water-based part (3～12wt%) and other auxiliary agent (0～5wt%)).
Described pigment extender is TiO
2, one or more the mixture in kaolin or the talcum powder.
Described filming forms agent and is selected from one or more mixture etc. in soluble cotton, Synolac, sulfonamide resin or the acrylic resin etc.
Described oiliness partly comprises wax component, synthetic oil and oil-based solvent.Wherein wax component is one or more mixing of gama wax, solid paraffin, beeswax or carnauba wax; Synthetic oil mostly is glyceryl ester, particularly one or more mixing of tri-glyceride or ricinoleic acid octyl group dodecane ester; Oil-based solvent is Viscotrol C and some solubility promoters, resembles Unimac 5680 two glyceryl ester, ethyl sebacate, tetrahydrofurfuryl alcohol and acetic ester thereof.
Described water-based partly comprises one or more mixing in deionized water, glycerine, propylene glycol, glycol or the polyoxyethylene glycol etc.
Described other auxiliary agent comprises nonionogenic tenside, softening agent etc.Wherein nonionogenic tenside mostly is the epoxy ethane-epoxy propane embedding and forges multipolymer, as polyoxyethylene (25) polyoxypropylene (202) tetradecane ether; Softening agent is one or more mixing in citric acid acetyl tri-n-butyl, the camphor etc.
The monodisperse polymer emulsion particle that has nucleocapsid structure among the present invention is by the preparation of emulsifier-free emulsion polymerization single stage method, its preparation technology is simple, the size and the form of emulsion particle are controlled easily, and preparation-obtained emulsion particle does not need to carry out any purification just can realize that single dispersion index is less than or equal to 0.005.The self-assembly preparation of colloid photonic crystal film of the present invention, adopt a kind of simple method to realize: evenly to cover certain density single dispersed latex grain on the flat substrates, after treating that wherein dispersion liquid volatilization is done, just form the orderly three-D photon crystal film of periodic arrangement, the photonic crystal order degree is good.The inventive method is simple, and required equipment is simple, helps realizing the mass preparation of crystal film with photon.According to the difference of used single dispersed latex grain particle diameter, the photon band gap of gained colloid photonic crystal film of the present invention changes in the ultraviolet region.
The single dispersed latex grain shell in self assembling process with hard core-soft core structure that aforementioned one step of employing emulsion polymerization prepared obtains deforms, and forms fine and close structure, helps improving the mechanical stability of film.
The present invention is by utilizing photon band gap at the photonic crystal of ultraviolet region the regulating and controlling effect of light to be realized Ultraviolet rays protection, also is simultaneously to have proposed a new way to solving ultraviolet protection to human body radiation, and this method cost is low, realizes easily.
The newborn epitaxial that the inventive method prepares is because for polymeric film, in the ultraviolet while of prevention, to the human body toxicological harmless, and can avoid the saturability problem of conventional uv-absorbing agent again, can be widely used in the ultraviolet coating of prevention, fields such as sun care preparations.
Because photon band gap is functional adjustable polymkeric substance at the used material of the photon crystal membrane of polymer colloid of ultraviolet region, makes to have good agglutinating value(of coal) between colloidal crystal film and the various base material like this.
The invention will be further described below in conjunction with accompanying drawing and by embodiment.
Description of drawings
The three-dimensional periodic of Fig. 1 a. embodiment of the invention 4 is arranged the SEM photo (particle diameter is 160nm) of long-range order latex crystal film with photon.
The reflected light spectrogram of the colloid photonic crystal film of Fig. 1 b. embodiment of the invention 4 changes from small to large according to latex particle, and the photon band gap position is respectively: 253,281,300,319,327,345, and 380nm
Fig. 2 a. is the molecular structural formula of the DTM in the embodiment of the invention 5, a base pair in this molecule similar DNA.
Fig. 2 b. is the uv irradiation synoptic diagram in the embodiment of the invention 5.
Fig. 2 c. is the irradiation figure as a result that the DTM molecule detects in UV-VIS after 6 hours under the different condition in the embodiment of the invention 5.
Fig. 2 d. is the irradiation figure as a result that the DTM molecule detects at UV-VIS after 18 hours under the different condition in the embodiment of the invention 5
Embodiment
The preparation of embodiment 1:(monodisperse polymer emulsion particle)
With monomer mixture methyl methacrylate (0.5 gram), vinylbenzene (7 gram), vinyl toluene (8 gram) and vinylformic acid (0.5 gram), the pH buffer reagent bicarbonate of ammonia (0.5 gram) and the mixture (weight percent 1: 1) of emulsifying agent Sodium dodecylbenzene sulfonate and sodium laurylsulfonate (0.038g) are dispersed in the water (100mL), resulting mixed system is mixed at 500rpm, and be heated to 65 ℃.Ammonium persulphate (0.5 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the ammonium persulfate aqueous solution that adds 5 milliliters after 4.5 hours again, remaining ammonium persulfate aqueous solution is continuing reaction adding after 4.5 hours, and reaction finished in lasting 3 hours subsequently.Finally obtain single dispersion index and be less than or equal to 0.005, particle size range is the monodisperse polymer emulsion particle of 100nm.
The consumption of the mixture (weight percent 1: 1) of emulsifying agent Sodium dodecylbenzene sulfonate and sodium laurylsulfonate is respectively when changing wherein, 0.034,0.0304,0.019,0.015,0.0113 or during 0.0077g, resultant final latex grain particle size range is respectively 115,120,125,130,150 or 160nm, single dispersion index of emulsion particle is less than or equal to 0.005.
The preparation of embodiment 2:(monodisperse polymer emulsion particle)
With monomer mixture vinyl acetate (0.5 gram), butyl methacrylate (0.5 gram), vinyl toluene (21 gram), acrylamide (0.6 gram) and vinylformic acid (0.4 gram), pH buffer reagent sodium hydrogen phosphate (0.6 gram) is dissolved in the water (100mL) with the mixture and the emulsifier sodium lauryl sulfate (0.0547g) of bicarbonate of ammonia (0.6 gram), resulting mixed system is mixed at 800rpm, and be heated to 85 ℃.The initiator (with ammonium persulphate (0.4 gram) be dissolved in 20 ml waters obtain by Potassium Persulphate (0.6 gram)) that adds 10 milliliters makes reaction begin to carry out, react the initiator solution that adds 5 milliliters after 2 hours again, remaining initiator solution is continuing reaction adding after 2 hours, and reaction continues to finish after 1 hour subsequently.Finally obtain single dispersion index and be less than or equal to 0.005, particle size range is the monodisperse polymer emulsion particle of 100nm.
Be respectively 0.049,0.0437,0.0274,0.0219,0.0163 or during 0.011g when changing wherein the consumption of emulsifier sodium lauryl sulfate, resultant final latex grain particle size range is respectively 115,120,125,130,150 or 160nm, single dispersion index of emulsion particle is less than or equal to 0.005.
The preparation of embodiment 3:(monodisperse polymer emulsion particle)
With monomer mixture Propenoic acid, 2-methyl, isobutyl ester (1.2 gram), vinyl toluene (18 gram) and methacrylic acid (1.2 gram), pH buffer reagent sodium bicarbonate (1.0 gram) and emulsifying agent sodium laurylsulfonate (0.0486mg) are dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium Persulphate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtain single dispersion index and be less than or equal to 0.005, particle size range is about the monodisperse polymer emulsion particle of 100nm.
Be respectively 0.0436,0.0388,0.0243,0.0194,0.0145 or during 0.0976mg when changing wherein the consumption of emulsifying agent sodium laurylsulfonate, resultant final latex grain particle size range is respectively 115,120,125,130,150 or 160nm, single dispersion index of emulsion particle is less than or equal to 0.005.
Embodiment 4:(is applied to pre-antiultraviolet coating) (membrane prepare of latex photonic crystal)
At room temperature be that the monodisperse polymer emulsion particle for preparing among the embodiment 1 of 5wt% evenly covers respectively on glass, silicon chip or the stainless steel plate base material of cleaning with concentration, after treating that wherein dispersion liquid moisture evaporation is done, just form the orderly three-D photon crystal film of periodic arrangement.As shown in Figure 1a.The particle diameter of gained monodisperse polymer emulsion particle is respectively 100,115 among the embodiment 1, and 120,125,130,150 or 160, the photon band gap position of corresponding preparation-obtained colloid photonic crystal film is respectively 253,281,300,319,327,345,380nm is shown in Fig. 1 b.Resulting coating can be directly used in pre-antiultraviolet, and according to base materials employed difference, used coating can be used in automobile adhesive film, on the facilities such as glass.
Embodiment 5:(is as the ultraviolet coating of prevention)
With the latex particle size that wherein adopts embodiment 1 method to prepare is that the bead of 100nm adopts embodiment 4 to prepare the colloid photonic crystal film of photon band gap position at 253nm.It is the ultraviolet source of 254nm that this film is applied to prevent wavelength.
3 of the blank silica glasss of employing same size, with the particle diameter that adopts embodiment 1 method to prepare is that the acetone soln of 100nm latex is filmed on a silica glass, with same particle diameter is that the latex of 100nm adopts embodiment 4 methods to prepare the colloid photonic crystal film of photon band gap position at 253nm on another piece silica glass, and the 3rd block of silica glass do not apply any material; 3 blocks of silica glasss being covered on the DTM solution of same concentrations (molecular structural formula of DTM shown in Fig. 2 a, a base pair in this molecule similar DNA) respectively, is the ultraviolet light irradiation solution (shown in Fig. 2 b) of 254nm with the wavelength of same intensity.After 6 hours, detect the decay of DTM solution under the uv irradiation situation at irradiation by UV-VIS.Found that: adopt film cover solution can effectively pre-antiultraviolet to the destruction of DTM molecule, have better protective effect and cover light epitaxial with certain photon band gap position.This explanation covers the protective effect that light epitaxial not only has general film and had, and its periodic arrangement makes it have better protectiving ultraviolet radiation effect.The result is shown in Fig. 2 c.The UV-VIS detected result of continuous irradiation after 18 hours is shown in Fig. 2 d.Twice experimental result shows: irradiation makes the light epitaxial show stronger anti-ultraviolet radiation advantage for a long time.
Embodiment 6:(is as the ultraviolet coating of prevention)
The monodisperse polymer emulsion particle that will prepare with embodiment 1, particle diameter is respectively 100,115,120,125,130,150 or 160, the colloid photonic crystal film that adopts embodiment 4 methods to prepare is peeled off (consumption is 10wt%) from glass baseplate respectively, is crushed to the micron order size, mix use mutually with acrylic varnish (60wt%) and a certain amount of ethanol (30wt%) respectively, all obtain pre-antiultraviolet coating.
Embodiment 7:(is applied to prevent ultraviolet lipstick)
TiO
2(10wt%), colloidal photon crystal (8.0wt% replaces the UV light absorber part), gama wax (5.0wt%), solid paraffin (4.0wt%), carnauba wax (2.0wt%), Viscotrol C (30.0wt%), Unimac 5680 two glyceryl ester (28.50wt%), polyoxyethylene (25) polyoxypropylene (202) tetradecane ether (1.5wt%), deionized water (8.0wt%), glycerine (2.0wt%), propylene glycol (1.0wt%).
Method for making: with TiO
2And the particle diameter for preparing with previous embodiment 1 is that the monodisperse polymer emulsion particle of 100nm adopts in colloidal photon crystal (being crushed to the micron size) the adding Viscotrol C that embodiment 4 methods prepare, and uses roller process; With deionized water, glycerine, propylene glycol forms water 80 ℃ of homogeneous dissolvings; After other composition Hybrid Heating fusion, aforementioned roller process part and aqueous portion are added, use homogeneous stirrer homogeneous to disperse, subsequently, making it flow into the mould postcooling becomes thin round strip.
Claims (10)
1. a photon band gap is characterized in that at the photon crystal membrane of polymer colloid of ultraviolet region: the photon crystal membrane of polymer colloid of described photon band gap in the ultraviolet region is that monodisperse polymer emulsion particle with hard core-soft core structure is piled up and formed; Thick 20～the 50nm of the shell of monodisperse polymer emulsion particle, the latex particle size scope is 100～160nm, polydispersity index is less than or equal to 0.005.
2. colloid photonic crystal film according to claim 1 is characterized in that: the photon band gap of described colloid photonic crystal film is distributed in the ultraviolet region of 200～400nm; Along with the descending variation of latex particle size, the peak generation blue shift of the reflection spectrum of resulting colloid photonic crystal film.
3. colloid photonic crystal film according to claim 1 is characterized in that, described monodisperse polymer emulsion particle prepares by following method:
With the monomer 1 that wetting ability increases successively, monomer 2, monomer 3 blending dispersion are in the aqueous solution that contains pH buffer reagent and emulsifying agent; Be to mix under the rotating speed of 300～800rpm resulting emulsion polymerization systems at rotating speed, and be heated to 65～85 ℃, the initiator that adds initiator total amount 1/2 makes reaction begin to carry out, react the initiator that adds initiator total amount 1/4 after 2～4.5 hours again, remaining initiator is continuing reaction adding after 2～4.5 hours, 0.2～1wt% of the suitable total monomer weight of the total consumption of described initiator; Obtain single dispersion index after reaction finishes and be less than or equal to 0.005, particle size range is the monodisperse polymer emulsion particle with hard core-soft core structure of 100～160nm;
11～17wt% that described monomeric total consumption is the emulsion polymerization systems gross weight; The consumption of monomer 1 is 88～94wt% of total monomer weight in the emulsion polymerization systems, and monomer 2 is 3～6wt%, and monomer 3 is 3～6wt%; The concentration of pH buffer reagent in emulsion polymerization systems is 0.02～0.99wt%, and the concentration of emulsifying agent in emulsion polymerization systems is 0.0068～0.067wt%;
Described monomer 1 is selected from vinylbenzene, vinyl toluene or their mixture;
Described monomer 2 is selected from esters of acrylic acid, vinyl acetate or their mixture;
Described monomer 3 is selected from vinylformic acid, methacrylic acid, acrylamide, propylene cyanogen or their any mixture.
4. colloid photonic crystal film according to claim 3 is characterized in that: described esters of acrylic acid is selected from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, isobutyl acrylate or their any mixture.
5. colloid photonic crystal film according to claim 3 is characterized in that: described initiator is that the form with the aqueous solution is incorporated in the polymerization system, and its strength of solution is 2～5wt%; Initiator is selected from alkali metal sulfates, ammonium persulphate or their mixture.
6. colloid photonic crystal film according to claim 3 is characterized in that: described emulsifying agent is selected from one or more the mixture in sodium laurylsulfonate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate.
7. colloid photonic crystal film according to claim 3 is characterized in that: described pH buffer reagent is selected from one or more the mixture in bicarbonate of ammonia, sodium bicarbonate, the sodium hydrogen phosphate.
8. the preparation method according to each described colloid photonic crystal film of claim 1～7 is characterized in that, described method may further comprise the steps:
(1) under the room temperature monodisperse polymer emulsion particle is dispersed in the water, then resulting monodisperse polymer emulsion particle emulsion is evenly covered on the flat substrates, wherein the concentration of monodisperse polymer emulsion particle emulsion is 5～30wt%;
(2) make step (1) disperse the aqueous solvent volatilization of monodisperse polymer emulsion particle under the normal temperature and pressure, the monodisperse polymer emulsion particle is piled up with face-centered cubic on base material, behind dried coating film, peel off from base material, obtain the photon crystal membrane of polymer colloid of photon band gap in the ultraviolet region;
The photon crystal membrane of polymer colloid of described photon band gap in the ultraviolet region is that monodisperse polymer emulsion particle with hard core-soft core structure is piled up and formed, thick 20～the 50nm of the shell of monodisperse polymer emulsion particle, the latex particle size scope is 100～160nm, and polydispersity index is less than or equal to 0.005.
9. the preparation method of colloid photonic crystal film according to claim 8 is characterized in that, described monodisperse polymer emulsion particle prepares by following method:
With the monomer 1 that wetting ability increases successively, monomer 2, monomer 3 blending dispersion are in the aqueous solution that contains pH buffer reagent and emulsifying agent; Be to mix under the rotating speed of 300～800rpm resulting emulsion polymerization systems at rotating speed, and be heated to 65～85 ℃, the initiator that adds initiator total amount 1/2 makes reaction begin to carry out, react the initiator that adds initiator total amount 1/4 after 2～4.5 hours again, remaining initiator is continuing reaction adding after 2～4.5 hours, 0.2～1wt% of the suitable total monomer weight of the total consumption of described initiator; Obtain single dispersion index after reaction finishes and be less than or equal to 0.005, particle size range is the monodisperse polymer emulsion particle with hard core-soft core structure of 100～160nm;
11～17wt% that described monomeric total consumption is the emulsion polymerization systems gross weight; The consumption of monomer 1 is 88～94wt% of total monomer weight in the emulsion polymerization systems, and monomer 2 is 3～6wt%, and monomer 3 is 3～6wt%; The concentration of pH buffer reagent in emulsion polymerization systems is 0.02～0.99wt%, and the concentration of emulsifying agent in emulsion polymerization systems is 0.0068～0.067wt%;
Described monomer 1 is selected from vinylbenzene, vinyl toluene or their mixture;
Described monomer 2 is selected from esters of acrylic acid, vinyl acetate or their mixture;
Described monomer 3 is selected from vinylformic acid, methacrylic acid, acrylamide, propylene cyanogen or their any mixture;
Described initiator is that the form with the aqueous solution is incorporated in the polymerization system, and its strength of solution is 2～5wt%; Initiator is selected from alkali metal sulfates, ammonium persulphate or their mixture;
Described emulsifying agent is selected from one or more the mixture in sodium laurylsulfonate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate;
Described pH buffer reagent is selected from one or more the mixture in bicarbonate of ammonia, sodium bicarbonate, the sodium hydrogen phosphate.
10. purposes according to each described colloid photonic crystal film of claim 1～7, it is characterized in that: described latex crystal film with photon is as the ultraviolet material of prevention or as the material of prevention in the ultraviolet makeup, or with the latex crystal film with photon as the UV light absorber or the membrane-forming agent of antiultraviolet coating in advance.
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| CN101327479B (en) * | 2008-06-25 | 2011-01-12 | 中国科学院化学研究所 | Method for preparing compound band-gap colloid photon crystal membrane using ink-jet printing method |
| CN103091867A (en) * | 2013-01-14 | 2013-05-08 | 河南科技大学 | Photonic crystal ultraviolet protection glasses |
| CN104044342A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院化学研究所 | Ink-jet-printed photonic crystal pattern and application of photonic crystal pattern |
| CN108298824A (en) * | 2017-08-18 | 2018-07-20 | 深圳先进技术研究院 | A kind of novel heat insulation material and preparation method thereof |
| CN109851707A (en) * | 2018-12-26 | 2019-06-07 | 平湖石化有限责任公司 | A kind of ternary hybrid photon crystal film and preparation method thereof |
| CN110804127A (en) * | 2019-11-14 | 2020-02-18 | 浙江理工大学 | Flexible photonic crystal element nano-microsphere and preparation method thereof |
| CN113189025A (en) * | 2021-03-05 | 2021-07-30 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Photonic crystal sensing material for quickly detecting ricin in ultrasensitive unmarked manner and preparation method and application thereof |
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| CN104418972B (en) * | 2013-08-26 | 2017-04-05 | 中国科学院化学研究所 | Photonic crystal capsule pigment and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB9921048D0 (en) * | 1999-09-07 | 1999-11-10 | Secr Defence | Colloidal photonic crystals |
| US6582807B2 (en) * | 2000-04-07 | 2003-06-24 | Case Western Reserve University | Polymer 1D photonic crystals |
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| CN101327479B (en) * | 2008-06-25 | 2011-01-12 | 中国科学院化学研究所 | Method for preparing compound band-gap colloid photon crystal membrane using ink-jet printing method |
| CN103091867A (en) * | 2013-01-14 | 2013-05-08 | 河南科技大学 | Photonic crystal ultraviolet protection glasses |
| CN104044342A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院化学研究所 | Ink-jet-printed photonic crystal pattern and application of photonic crystal pattern |
| CN108298824A (en) * | 2017-08-18 | 2018-07-20 | 深圳先进技术研究院 | A kind of novel heat insulation material and preparation method thereof |
| CN109851707A (en) * | 2018-12-26 | 2019-06-07 | 平湖石化有限责任公司 | A kind of ternary hybrid photon crystal film and preparation method thereof |
| CN110804127A (en) * | 2019-11-14 | 2020-02-18 | 浙江理工大学 | Flexible photonic crystal element nano-microsphere and preparation method thereof |
| CN113189025A (en) * | 2021-03-05 | 2021-07-30 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Photonic crystal sensing material for quickly detecting ricin in ultrasensitive unmarked manner and preparation method and application thereof |
| CN113189025B (en) * | 2021-03-05 | 2023-01-06 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Photonic crystal sensing material for quickly detecting ricin in ultrasensitive unmarked manner and preparation method and application thereof |
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