TW201412391A - Method for preparing photochromic structural colors films and its applications - Google Patents

Method for preparing photochromic structural colors films and its applications Download PDF

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TW201412391A
TW201412391A TW101134991A TW101134991A TW201412391A TW 201412391 A TW201412391 A TW 201412391A TW 101134991 A TW101134991 A TW 101134991A TW 101134991 A TW101134991 A TW 101134991A TW 201412391 A TW201412391 A TW 201412391A
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color
changing
oxide
colloidal
polystyrene
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TWI466715B (en
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Hsin-Her Yu
Jen-Yu Shieh
Jen-Yu Kuo
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Univ Nat Formosa
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Abstract

The present invention discloses a method of preparing photochromic structural colors films and applications, which is provided with suspension of a monodisperse colloidal microspheres. The colloidal microspheres of the colloidal suspensions are arranged in a periodic array of colloidal microspheres by a self-assembly method. A liquid of transparent colloidal material is infiltrated into the colloidal microspheres array, so that the air in the gap among the original colloidal microspheres are filled with this liquid of transparent colloidal material, then which is cured and forms a photochromic film which will show structural colors under a light source.

Description

以結構顏色製備光子變色薄膜的方法與應用 Method and application for preparing photon color-changing film by structural color

本發明係有關於一種以結構顏色製備光子變色薄膜的方法與應用,並將之加以應用的技術。 The present invention relates to a method and application for preparing a photonic color-changing film in a structural color and applying the same.

按一般所知,我們在環境週遭所看到的色彩顯示,是人們以工業用的化學顏料與色素所造成的,這將對人體造成危害和環境污染構成嚴重的威脅。人工所製造出來的顏色,其色度和飽和度卻不及自然界來的鮮豔絢麗,在一長時間的環境因素影響下,還會面臨到褪色問題。然而我們發現某些生物體所產生的絢麗色彩並不是自身色素沉積所造成的,而是光線在生物的結構上造成反射、干涉和繞射等光學作用,而形成的結構色彩。其結構顏色經過上億年的時間和環境影響下,仍呈現出一絢麗色彩。生物光子晶體產生的結構顏色和耀眼虹彩是自然的光學現象,因此,近幾年來,奈米技術試圖從生物上模仿出光子晶體結構,並將其應用於許多研究領域,例如光電元件、光纖通訊、顯示器裝置、智能傳感器等。但大多數的光子晶體技術,皆著重在LED光電元件、光纖傳輸技術上,然而光子晶體色彩顯示技術及其它應用,較多處於較基礎的學術研究領域階段。 As is generally known, the colors we see around the environment are caused by industrial chemical pigments and pigments, which pose a serious threat to human harm and environmental pollution. The color produced by man-made, its color and saturation are not as bright and beautiful as the natural world. Under the influence of environmental factors for a long time, it will face the problem of fading. However, we have found that the brilliant colors produced by some organisms are not caused by self-pigmentation, but by the optical effects of light, such as reflection, interference and diffraction, on the structure of the organism. The color of its structure has been shown to be a brilliant color after hundreds of millions of years of time and environmental influence. The structural color and dazzling iridescence produced by biophotonic crystals are natural optical phenomena. Therefore, in recent years, nanotechnology has attempted to mimic the photonic crystal structure biologically and apply it to many research fields, such as optoelectronic components, fiber optic communication. , display devices, smart sensors, etc. However, most of the photonic crystal technology focuses on LED optoelectronic components and optical fiber transmission technology. However, photonic crystal color display technology and other applications are more in the stage of basic academic research.

現今光致變色之色彩顯示技術,是藉由光致變色高分子在一定波長和強度的光作用下,致使分子結構發生化學變化,導致對光的吸收峰產生改變,即顏色相對應之色彩隨之變化。本專利之光子變色薄膜是入射光經由奈米結構相互作用下,產生一物理光學現象,其色彩可由控制入射光的角度和奈米結構的大小予以變化。然而光 子變色薄膜的色彩呈可逆性的變化,且無需任何能源裝置維持,如電力、壓力、溫度等外力影響下,即可將自身結構色彩隱藏並具一透明、高穿透度之特性。 Nowadays, the photochromic color display technology uses a photochromic polymer to cause a chemical change in the molecular structure under the action of light of a certain wavelength and intensity, resulting in a change in the absorption peak of light, that is, the color corresponding to the color Change. The photonic color-changing film of this patent generates a physical optical phenomenon by incident light interacting through a nanostructure, and its color can be changed by controlling the angle of incident light and the size of the nanostructure. However light The color of the sub-color film is reversible, and does not need to be maintained by any energy device. Under the influence of external forces such as electric power, pressure, temperature, etc., the color of the structure can be hidden and have a transparent and high-transparency characteristic.

為避免本發明與他人在先之專利案相同,發明人檢索了相關前案技術得到中華民國公開第201122571號變色薄膜之製備方法及中華民國公開第200907002號光硬化性黏著劑、使用該光硬化性黏著劑之偏光板及其製造方法、光學構件及液晶顯示裝置。經仔細分析,確知本發明與該等前案技術不同。 In order to avoid the present invention being the same as the prior patents of others, the inventors searched for a method for preparing a color-changing film of the Republic of China Public Publication No. 201122571 and a photocurable adhesive of the Republic of China Publication No. 20070072, using the related method. Polarizing plate for an adhesive, a method for producing the same, an optical member, and a liquid crystal display device. After careful analysis, it is ascertained that the present invention is different from the prior art techniques.

本發明之目的,在於提供一種利用結構顏色特殊的光學現象,製備出仿生光子變色薄膜,應用於仿偽顯示技術,此特色在於無須電力或任何能源裝置維持,即可在可見光下從透明薄膜產生出隱藏的結構色彩,其便利性高於用紫外線辨識的仿偽圖案,而高穿透度的特性對於仿偽雷射標籤其應用性更加寬廣。 The object of the present invention is to provide a bionic photonic color-changing film which is prepared by utilizing a special optical phenomenon of a structural color, and is applied to a pseudo-display technology, which is characterized in that it can be produced from a transparent film under visible light without maintenance of electric power or any energy device. The hidden structural color is more convenient than the pseudo-pseudo-pattern recognized by ultraviolet rays, and the high-transparency characteristic is more applicable to the pseudo-pseudo-label.

達成本發明目的之技術手段,係提供一單分散性膠體微球懸浮液。使膠體微球懸浮液內的膠體微球以一自組裝方式而排列成周期性膠體微球陣列。在膠體微球陣列中滲入一液態可透光膠體材料,使原本之膠體微球縫隙間的空氣,在滲入後皆填滿此液態可透光膠體材料並將其固化而形成一光子變色薄膜,使該光子變色薄膜在一光源下照射而可顯現出結構色彩。 A technical means for achieving the object of the present invention is to provide a monodisperse colloidal microsphere suspension. The colloidal microspheres in the colloidal microsphere suspension are arranged in a self-assembling manner into a periodic colloidal microsphere array. A liquid permeable colloidal material is infiltrated into the colloidal microsphere array, so that the air between the gaps of the original colloidal microspheres is filled with the liquid permeable colloidal material after being infiltrated and solidified to form a photonic color-changing film. The photonic color-changing film is irradiated under a light source to reveal a structural color.

壹.本發明的基本技術特徵 壹. Basic technical features of the present invention

本發明所研發之以結構顏色製備光子變色薄膜的方法,其基本技術特徵,係包含有以下步驟:(a)提供一單分散性膠體微球懸浮液(該微球材料係選自金 屬、有機高分子及無機化合物至少其中一種,該金屬材料係選自金Au、銀Ag、銅Cu、鐵Fe、Co、鎳Ni、鈀Pd、鉑Pt、鋁Al、矽Si、鈦Ti、鋯Zr、釩V、鈮Nb、鉬Mo、鎢W及錳Mn至少其中一種;該有機高分子材料係選自聚苯乙烯系列、聚甲基丙烯酸甲酯系列、聚馬來酸系列、聚乳酸系列、聚胺基酸系列的高分子至少其中一種;該無機化合物材料係選自氧化銀Ag2O、氧化銅CuO、氧化鋅ZnO、氧化鎘CdO、氧化鎳NiO、氧化鈀PdO、氧化鈷CoO、氧化鎂MgO、二氧化矽SiO2、二氧化錫SnO2、二氧化鈦TiO2、二氧化鋯ZrO2、二氧化鉿HfO2、二氧化釷ThO2、二氧化鈰CeO2、二氧化鈷CoO2、二氧化錳MnO2、二氧化銥IrO2、二氧化釩VO2、三氧化鎢WO3、三氧化鉬MoO3、三氧化二鋁Al2O3、三氧化二釔Y2O3、三氧化二鐿Yb2O3、三氧化二鏑Dy2O3、三氧化二硼B2O3、三氧化二鉻Cr2O3、三氧化二鐵Fe2O3、四氧化三鐵Fe3O4、五氧化二釩V2O5、五氧化二鈮Nb2O5、硫化鋅ZnS、硒化鋅ZnSe、碘化鋅ZnTe、硫化鎘CdS、硒化鎘CdSe、碘化鎘CdTe、硫化鐵FeS、硒化鐵FeSe、FeTe、硫化鈷CoS、硒化鈷CoSe、碘化鈷CoTe、硫化鎳NiS、硒化鎳NiSe、NiTe、硫化鉛PbS、硒化鉛PbSe、碘化鉛PbTe、硫化錳MnS、硒化錳MnSe、MnTe、硫化錫SnS、硒化錫SnSe、碘錫SnTe、二硫化鉬MoS2、二硒化鉬MoSe2、二碘化鉬MoTe2、二硫化鎢WS2、二硒化鎢WSe2、二碘化鎢WTe2、硫化二銅Cu2S、硒化二銅Cu2Se、碘化二銅Cu2Te、三硫化二鉍Bi2S3、三硒化二鉍Bi2Se3、三碘化二鉍Bi2Te3、碳化釸SiC、碳化鈦TiC、碳化鋯ZrC、碳化鎢WC、碳化鈮NbC、碳化鉭TaC、碳化二鉬Mo2C、氮化硼BN、氮化鋁AlN、氮化鈦TiN、氮化鋯ZrN、氮化釩VN、氮化鈮NbN、氮化鉭TaN、四氮化三矽Si3N4及四氮化三鋯Zr3N4至少其中一種。)(本發明實 驗例為聚苯乙烯微球懸浮乳液);(b)使該膠體微球懸浮液內的膠體微球以一自組裝方式而排列成周期性膠體微球陣列(該自組裝方式係選自浸拉法、重力沉降法、垂直沉積法、溶劑蒸發法、離心沉積法、磁場加速沉降法及電泳輔助沉積法至少其中一種,本發明實驗例係為浸拉法);及(c)在膠體微球陣列中滲入一液態可透光膠體材料(該液態可透光膠體材料係選自環氧樹脂系列、苯偶酰系列、烷基苯酮系列、二苯甲酮系列、安息香醚系列、硫雜蔥酮系列及聚二甲基矽氧烷系列至少其中一種,本發明實驗例中,該液態可透光膠體材料為聚二甲基矽氧烷基板(PDMS)),使原本之膠體微球縫隙間的空氣,在滲入後皆填滿此液態可透光膠體材料並將其固化而形成一光子變色薄膜,使該光子變色薄膜在一光源下照射而可顯現出結構色彩。 The method for preparing a photonic color-changing film by structural color according to the present invention has the following basic technical features: (a) providing a monodisperse colloidal microsphere suspension (the microsphere material is selected from the group consisting of metal and organic) At least one of a polymer and an inorganic compound selected from the group consisting of gold Au, silver Ag, copper Cu, iron Fe, Co, nickel Ni, palladium Pd, platinum Pt, aluminum Al, lanthanum Si, titanium Ti, zirconium Zr, At least one of vanadium V, niobium Nb, molybdenum Mo, tungsten W and manganese Mn; the organic polymer material is selected from the group consisting of polystyrene series, polymethyl methacrylate series, polymaleic acid series, polylactic acid series, poly At least one of the amino acid series polymers; the inorganic compound material is selected from the group consisting of silver oxide Ag 2 O, copper oxide CuO, zinc oxide ZnO, cadmium oxide CdO, nickel oxide NiO, palladium oxide PdO, cobalt oxide CoO, magnesium oxide. MgO, cerium oxide SiO 2 , tin dioxide SnO 2 , titanium dioxide TiO 2 , zirconium dioxide ZrO 2 , cerium oxide HfO 2 , cerium oxide ThO 2 , cerium oxide CeO 2 , cobalt dioxide CoO 2 , dioxide manganese MnO 2, iridium oxide IrO 2, vanadium dioxide VO 2, ozone Tungsten, WO 3, molybdenum trioxide MoO 3, aluminum oxide Al 2 O 3, yttria Y 2 O 3, ytterbium oxide Yb 2 O 3, dysprosium oxide Dy 2 O 3, boron trioxide B 2 O 3 , chromium oxide Cr 2 O 3 , ferric oxide Fe 2 O 3 , ferroferric oxide Fe 3 O 4 , vanadium pentoxide V 2 O 5 , niobium pentoxide Nb 2 O 5 , Zinc sulfide ZnS, zinc selenide ZnSe, zinc iodide ZnTe, cadmium sulfide CdS, cadmium selenide CdSe, cadmium iodide CdTe, iron sulfide FeS, iron selenide FeSe, FeTe, cobalt sulfide CoS, cobalt selenide CoSe, iodization Cobalt CoTe, nickel sulfide NiS, nickel selenide NiSe, NiTe, lead sulfide PbS, lead selenide PbSe, lead iodide PbTe, manganese sulfide MnS, manganese selenide MnSe, MnTe, tin sulfide SnS, tin selenide SnSe, tin iodide SnTe, molybdenum disulfide MoS 2, molybdenum diselenide MoSe 2, molybdenum diiodide MoTe 2, tungsten disulfide WS 2, tungsten diselenide WSe 2, tungsten diiodide WTe 2, copper sulfide Cu 2 S, Se Cu 2 Se, Cu 2 Te iodide, Bi 2 S 3 trisulphide, Bi 2 Se 3 selenide, Bi 2 Te 3 triiodide, Bismuth carbide SiC, Titanium carbide TiC, zirconium carbide ZrC, tungsten carbide WC, niobium carbide NbC, carbon Tantalum TaC, two molybdenum carbide Mo 2 C, boron nitride BN, aluminum nitride AlN, titanium nitride TiN, zirconium nitride ZrN, vanadium nitride VN, niobium nitride NbN, tantalum nitride TaN, silicon nitride At least one of Si 3 N 4 and trizirconium nitride Zr 3 N 4 . (The experimental example of the present invention is a polystyrene microsphere suspension emulsion); (b) aligning the colloidal microspheres in the colloidal microsphere suspension into a periodic colloidal microsphere array in a self-assembling manner (the self-assembly method) The method is selected from the group consisting of a dip method, a gravity sedimentation method, a vertical deposition method, a solvent evaporation method, a centrifugal deposition method, a magnetic field accelerated sedimentation method, and an electrophoresis-assisted deposition method, and the experimental example of the present invention is a dip method; and (c) Infiltrating a liquid permeable colloidal material into the colloidal microsphere array (the liquid permeable colloidal material is selected from the group consisting of epoxy resin series, benzil series, alkyl benzophenone series, benzophenone series, benzoin ether) At least one of a series, a thiouranone series and a polydimethyl methoxy oxane series, in the experimental example of the present invention, the liquid permeable colloidal material is a polydimethyl oxyalkylene plate (PDMS), so that the original The air between the gaps of the colloidal microspheres fills the liquid permeable colloidal material after infiltration and solidifies to form a photonic color-changing film, so that the photonic color-changing film can be illuminated under a light source to exhibit structural color.

貳.本發明的實驗例 贰. Experimental example of the present invention

為達成本發明之目的,本發明人進行了具體的實驗,實驗例中係以無皂乳液聚合法合成聚苯乙烯奈米微球,藉由自組裝方式,將聚苯乙烯微球排列呈一有序的周期奈米結構,澆注及滲入PDMS膠體於自組裝聚苯乙烯奈米微球週邊成光子變色薄膜。 In order to achieve the object of the present invention, the inventors conducted specific experiments in which the polystyrene nanospheres were synthesized by soap-free emulsion polymerization, and the polystyrene microspheres were arranged in a self-assembly manner. An ordered periodic nanostructure, cast and infiltrated into a PDMS colloid into a photonic color-changing film around the self-assembled polystyrene nanospheres.

本發明之實驗例包括的具體詳細作業流程有:合成聚苯乙烯奈米微球懸浮液、PDMS基板製備、製備光子變色薄膜、分析聚苯乙烯奈米微球對結構顏色之影響、分析自組裝浸拉法對聚苯乙烯微球有序度和堆疊厚度之影響及分析光子變色薄膜光學特性,茲將各作業流程分述如下。 The specific detailed operation procedures included in the experimental examples of the present invention include: synthesis of polystyrene nanosphere suspension, preparation of PDMS substrate, preparation of photonic color-changing film, analysis of influence of polystyrene nanospheres on structural color, and analysis of self-assembly The effect of the immersion method on the ordering degree and stacking thickness of the polystyrene microspheres and the analysis of the optical properties of the photonic color-changing film are described below.

1.聚苯乙烯奈米微球合成出聚苯乙烯微球懸浮乳液:本發明實驗例中,係以無皂乳液聚合法製備均一粒徑之聚苯乙烯微球(polystyrene spheres,PS),四頸反應瓶內添加苯乙烯(St)單體15mL、10mg~100mg對-苯乙烯硫酸鈉鹽(NaSS)共親單體和去離子水(DI water)135mL均勻攪拌,升溫至70℃,加入起始劑(KPS)0.1g開始聚合反應,整個反應過程在一迴流冷凝管和氮氣環境下,反應24小時後,即可合成出聚苯乙烯微球懸浮乳液。控制對-苯乙烯硫酸鈉鹽(NaSS)共親單體之含量可聚合出不同粒徑大小的聚苯乙烯微球。 1. Polystyrene nanospheres synthesize polystyrene microsphere suspension emulsion: In the experimental example of the present invention, polystyrene spheres (PS) of uniform particle size are prepared by soap-free emulsion polymerization method, Add 15 mL of styrene (St) monomer, 10 mg to 100 mg of sodium styrene sulfate (NaSS) co-parent and 135 mL of deionized water (DI water) to the neck reaction flask, and heat up to 70 ° C. The polymerization agent was started at 0.1 g of the starting agent (KPS), and the whole reaction process was carried out for 24 hours under a reflux condenser and a nitrogen atmosphere to synthesize a polystyrene microsphere suspension emulsion. Controlling the content of the p-styrene sulfate (NaSS) co-parent monomer can polymerize polystyrene microspheres of different particle sizes.

2.聚二甲基矽氧烷基板(PDMS基板)製備:本發明實驗例中製備PDMS基板,係由主劑和硬化劑以質量比10:1均勻混合形成PDMS預聚物膠體,在真空下去除PDMS預聚物膠體內的氣泡,將此PDMS預聚物膠體澆注於一玻璃基板表面做為PDMS模板,PDMS模板在溫度50℃下固化8小時後硬化,將硬化後的PDMS模板自玻璃基板表面掀除,進而獲得PDMS基板。由於前述步驟所獲得之PDMS基板呈疏水性,以氧電漿清洗機(Plasma Cleaner)對此PDMS基板的疏水性表面以電漿加以轟擊以進行表面改質,使得PDMS基板表面呈一親水特性。本發明實施例所採用一微機電精密浸拉裝置顯示於第一圖,電腦經由USB單軸運動控制器1控制步進閉迴路伺服馬達2,馬達承軸著馬達螺桿聯軸器4轉動精密級滾珠螺桿5,其光學旋轉式絕對型編碼器3為防止機械產生誤差,將記憶位址、精準定位精密級的線性移動滑軌6移動。將試片夾具組7固定親水性PDMS基板8,其親水性PDMS基板8浸於燒杯內 之聚苯乙烯懸浮液9,微機電精密浸拉裝置和聚苯乙烯懸浮液9皆放置於防震光學桌上10。 2. Polydimethylsiloxane alkylene plate (PDMS substrate) preparation: In the experimental example of the present invention, a PDMS substrate was prepared by uniformly mixing a main agent and a hardener at a mass ratio of 10:1 to form a PDMS prepolymer colloid under vacuum. The bubbles in the PDMS prepolymer gel were removed, and the PDMS prepolymer colloid was cast on the surface of a glass substrate as a PDMS template. The PDMS template was cured after curing at a temperature of 50 ° C for 8 hours, and the hardened PDMS template was applied from the glass substrate. The surface is removed to obtain a PDMS substrate. Since the PDMS substrate obtained in the foregoing step is hydrophobic, the hydrophobic surface of the PDMS substrate is bombarded with a plasma by a plasma cleaner to perform surface modification, so that the surface of the PDMS substrate has a hydrophilic property. A microelectromechanical precision immersion device according to an embodiment of the present invention is shown in the first figure, and the computer controls the step closed loop servo motor 2 via the USB single axis motion controller 1, and the motor bearing shaft rotates the precision of the motor screw coupling 4 The ball screw 5, the optical rotary absolute type encoder 3, moves the linear moving slide 6 of the memory level and the precise positioning precision level to prevent mechanical errors. The test piece clamp group 7 is fixed to the hydrophilic PDMS substrate 8, and the hydrophilic PDMS substrate 8 is immersed in the beaker. The polystyrene suspension 9, the microelectromechanical precision immersion device and the polystyrene suspension 9 are placed on the anti-shock optical table 10.

3.製備光子變色薄膜:聚苯乙烯微球的自組裝排列過程請參照第二圖,藉由電腦控制浸拉速率,將表面具親水性之PDMS基板8拉出聚苯乙烯懸浮液11的表面,表面具親水性之PDMS基板8和聚苯乙烯懸浮液11間將形成一彎液面13,其毛細作用力致使聚苯乙烯微球12自組裝排列成有序的聚苯乙烯微球膠體陣列14。本發明實驗例的光子變色薄膜如第三圖所示,將有序的聚苯乙烯微球膠體陣列14,澆注滲入PDMS預聚物15,其聚苯乙烯微球膠體陣列14之孔隙將滲滿PDMS預聚物15,隨之放置烘箱內並加熱溫度於50℃固化,在8小時後取出即得一光子變色薄膜。 3. Preparation of photon color-changing film: self-assembly arrangement process of polystyrene microspheres. Referring to the second figure, the surface of the hydrophilic PDMS substrate 8 is pulled out of the surface of the polystyrene suspension 11 by computer controlled immersion rate. A hydrophilic liquid PDMS substrate 8 and a polystyrene suspension 11 will form a meniscus 13 whose capillary force causes the polystyrene microspheres 12 to self-assemble into an ordered polystyrene microsphere colloidal array. 14. The photonic color-changing film of the experimental example of the present invention, as shown in the third figure, casts the ordered polystyrene microsphere colloid array 14 into the PDMS prepolymer 15, and the pores of the polystyrene microsphere colloid array 14 are filled. The PDMS prepolymer 15 was placed in an oven and cured at a heating temperature of 50 ° C. After 8 hours, a photonic color-changing film was taken out.

4.分析聚苯乙烯奈米微球對結構顏色之影響:本發明合成出不同粒徑的微球,藉由其粒徑大小差異變化結構色彩。隨著對-苯乙烯硫酸鈉鹽(NaSS)共親單體含量的增加,聚合初期所形成的微球胞數量多,但粒徑小。在未添加對-苯乙烯硫酸鈉鹽(NaSS)共親單體所聚合出來的聚苯乙烯微球(PS)之粒徑大小約在1155nm,而隨著對-苯乙烯硫酸鈉鹽(NaSS)共親單體含量由10mg增加至100mg,聚苯乙烯微球(PS)之粒徑則從377.4nm遞減至116.6nm,如第八圖2(a)所示。不同對-苯乙烯硫酸鈉鹽(NaSS)共親單體含量所聚合而成的聚苯乙烯微球(PS)之微球大小及其反射所對應之色彩如第八圖2(b)所示。當對-苯乙烯硫酸鈉鹽(NaSS)共親單體含量在20~80mg之間,聚苯乙烯微球(PS)之平均粒徑在310nm到145nm左右,才能顯出紅光至藍光的色彩,如表1所示。 4. Analysis of the effect of polystyrene nanospheres on the color of the structure: The present invention synthesizes microspheres of different particle sizes, and the structural color is varied by the difference in particle size. As the content of the co-monomer of sodium styrene sulfate (NaSS) increases, the number of microspheres formed at the initial stage of polymerization is large, but the particle size is small. The particle size of the polystyrene microspheres (PS) polymerized without the addition of the sodium styrene sulfate (NaSS) co-parent is about 1155 nm, and the sodium styrene sulfate (NaSS) The content of the co-parent monomer was increased from 10 mg to 100 mg, and the particle size of the polystyrene microsphere (PS) was decreased from 377.4 nm to 116.6 nm, as shown in Fig. 2(a). The size of the microspheres of the polystyrene microspheres (PS) polymerized by different co-monomer content of sodium styrene sulfate (NaSS) and the color corresponding to the reflection are as shown in Fig. 2(b). . When the content of co-monomer of sodium styrene sulfate (NaSS) is between 20 and 80 mg, the average particle size of polystyrene microspheres (PS) is between 310 nm and 145 nm to show the red to blue color. ,As shown in Table 1.

5.分析自組裝浸拉法對聚苯乙烯微球有序度和堆疊厚度之影響:為了觀察在不同浸拉速率下,自組裝排列所形成聚苯乙烯微球(PS)的表面形貌,我們選擇聚苯乙烯微球(PS)之粒徑為258nm。並以純水將聚苯乙烯微球懸浮液稀釋成10wt%濃度,以1000~0.1μm/s間的浸拉速率進行自組裝排列。以SEM觀察發現在較快的浸拉速率下,如1000~100μm/s見附件1圖(a-b)所示,聚苯乙烯微球(PS)之排列呈一雜亂無序的結構。PDMS基板在快速拉出聚苯乙烯微球懸浮液的表面同時,由於聚苯乙烯微球(PS)之間的凡得瓦爾引力和靜電斥力在聚苯乙烯微球懸浮液和空氣的界面處於一不平衡的狀態,導致聚苯乙烯微球(PS)呈一無序排列。而在一中等浸拉速率10~1μm/s時,由於聚苯乙烯微球(PS)有足夠時間使其表面的靜電斥力和凡得瓦爾引力達到較佳的平衡狀態,所以由附件1圖(c-d)可觀察到聚苯乙烯微球(PS)之的排列較緊密,但仍有局部線缺陷和空位存在。附件1圖(e)為在極緩慢的浸拉速率0.1μm/s下,聚苯乙烯微球(PS)之呈一緻密有序的週期結構排列。 5. Analysis of the effect of self-assembly immersion method on the ordering degree and stacking thickness of polystyrene microspheres: in order to observe the surface morphology of polystyrene microspheres (PS) formed by self-assembly at different immersion rates, We chose polystyrene microspheres (PS) to have a particle size of 258 nm. The polystyrene microsphere suspension was diluted to a concentration of 10% by weight with pure water, and self-assembled at a leaching rate of 1000 to 0.1 μm/s. It was found by SEM observation that at a faster immersion rate, such as 1000-100 μm/s, as shown in Figure 1 (a-b) of Annex 1, the arrangement of polystyrene microspheres (PS) showed a disordered structure. The PDMS substrate is rapidly pulled out of the surface of the polystyrene microsphere suspension while the van der Waals attraction and electrostatic repulsion between the polystyrene microspheres (PS) are at the interface of the polystyrene microsphere suspension and air. The unbalanced state causes the polystyrene microspheres (PS) to be arranged in a disorderly manner. At a medium immersion rate of 10~1μm/s, since the polystyrene microspheres (PS) have enough time to achieve a better equilibrium between the electrostatic repulsion of the surface and the van der Waals attraction, Cd) It can be observed that the arrangement of polystyrene microspheres (PS) is tight, but there are still local line defects and vacancies. Figure (e) of Annex 1 shows a consistently ordered periodic structure of polystyrene microspheres (PS) at a very slow immersion rate of 0.1 μm/s.

由於在10wt%懸浮液濃度下,因不易從縱剖面觀察到聚苯乙烯微球(PS)在不同浸拉速率下之堆疊厚度與堆疊層次,為了讓聚苯乙烯微球(PS)之堆疊厚度有明顯差異,因此我們調整聚苯乙烯微球懸浮液的濃度至50wt%。在遞減的浸拉速率下1000→100→10→1→0.1μm/s,聚苯乙烯微球(PS)之堆疊厚度(見附件1圖(f-j))則是從0.487→0.825→2.953→25.36→330.9μm逐漸增加。由比較縱剖面(如附件1圖(f-j))和頂視圖(如附件1圖(a-e))照片發現,浸拉速率愈快(100μm/s以上),聚苯乙烯微球來不及自組裝而呈無序排列,堆疊的厚度較薄。而當浸拉速率較慢(10μm/s以下),聚苯乙烯微球(PS)有足夠的時間自組裝排列呈一有序的週期結構,且堆疊的厚度愈厚。 Due to the fact that at 10% by weight of the suspension concentration, it is difficult to observe the stack thickness and stacking level of polystyrene microspheres (PS) at different immersion rates from the longitudinal section, in order to make the stack thickness of the polystyrene microspheres (PS) There is a significant difference, so we adjusted the concentration of the polystyrene microsphere suspension to 50% by weight. At a decreasing leaching rate of 1000 → 100 → 10 → 1 → 0.1 μm / s, the stack thickness of polystyrene microspheres (PS) (see Figure 1 (fj) of Annex 1) is from 0.487 → 0.825 → 2.953 → 25.36 →330.9 μm gradually increased. From the comparison of the longitudinal profile (such as Figure 1 (fj)) and the top view (such as Figure 1 (ae)), it is found that the faster the immersion rate (above 100 μm/s), the polystyrene microspheres are not self-assembled. Arranged in disorder, the thickness of the stack is thin. When the immersion rate is slow (10 μm/s or less), the polystyrene microspheres (PS) have sufficient time to self-assemble in an ordered periodic structure, and the thickness of the stack is thicker.

6.分析光子變色薄膜光學特性: 6. Analysis of photonic color film optical properties:

(1)反射光譜 (1) Reflection spectrum

以258nm聚苯乙烯微球(PS)在不同聚苯乙烯微球懸浮液濃度下,在PDMS基板上以浸拉速率1μm/s製備聚苯乙烯微球(PS)自組裝排列微球之反射率(R%)變化(見第四圖)。隨聚苯乙烯微球懸浮液濃度從20wt%增加至100wt%(見第四圖(a-e))所示,其反射率(R%)從33.8%降至10.1%,其反射峰值從522nm漂移至497nm呈藍移現象。PDMS基板上之聚苯乙烯微球(PS)堆疊厚度是影響反射率R%之主因。由於聚苯乙烯微球懸浮液為白色乳液狀,使聚苯乙烯微球(PS)排列於PDMS基板上也略呈白色。然而隨聚苯乙烯微球懸浮液濃度增加至100wt%時,PDMS基板上的聚苯乙 烯微球堆疊厚度也隨之增加,致使光線散射於聚苯乙烯微球之間,反射率R%亦也隨之降低。而造成藍移現象是由於聚苯乙烯微球(PS)(n=1.6)和空氣(n=1)的折射率差異過大造成光強烈散射,導致反射峰值漂移。 The reflectance of self-assembled microspheres prepared by polystyrene microspheres (PS) at a immersion rate of 1 μm/s on a PDMS substrate at 258 nm polystyrene microspheres (PS) at different polystyrene microsphere suspension concentrations (R%) change (see figure 4). As the polystyrene microsphere suspension concentration increases from 20 wt% to 100 wt% (see Figure 4 (ae)), the reflectance (R%) decreases from 33.8% to 10.1%, and its reflection peak shifts from 522 nm to 497nm is blue-shifted. The thickness of the polystyrene microsphere (PS) stack on the PDMS substrate is the main cause of the reflectance R%. Since the polystyrene microsphere suspension is in the form of a white emulsion, the polystyrene microspheres (PS) are also arranged in a white color on the PDMS substrate. However, when the polystyrene microsphere suspension concentration is increased to 100% by weight, the polystyrene on the PDMS substrate The thickness of the olefin microsphere stack is also increased, causing light to scatter between the polystyrene microspheres, and the reflectance R% is also reduced. The blue shift phenomenon is caused by the large difference in refractive index between polystyrene microspheres (PS) (n=1.6) and air (n=1), resulting in strong scattering of light, resulting in reflection peak drift.

光子變色薄膜其反射光譜,如第五圖所示,隨聚苯乙烯微球懸浮液濃度從20wt%增加至100wt%,反射率(R%)從8.8%(如第六圖(a))降至2.7%(如第五圖(e)),其反射峰位置皆落在531nm左右。澆注滲入PDMS預聚物於聚苯乙烯微球之前的反射率為33.8%,而在滲入PDMS預聚物於聚苯乙烯微球(PS)的週遭之後其反射率降低至8.8%,這是因為光經光子變色薄膜後造成全反射。根據Snell’s Law光線從光密介質PDMS(n=1.43)進入光疏介質空氣(n=1),當入射角大於臨界角(θc=44.4°),即會造成全反射。然而光子變色薄膜之反射峰並不隨聚苯乙烯微球懸浮液濃度變化而造成影響,因光子變色薄膜在聚苯乙烯微球(PS)和PDMS之間有一較匹配的折射率,造成反射峰皆落在531nm附近。 The reflection spectrum of the photonic color-changing film, as shown in the fifth figure, increases with the polystyrene microsphere suspension concentration from 20 wt% to 100 wt%, and the reflectance (R%) decreases from 8.8% (as shown in Fig. 6(a)). To 2.7% (as in Figure 5 (e)), the reflection peak positions are all around 531 nm. The reflectivity of the infiltrated PDMS prepolymer before the polystyrene microspheres was 33.8%, and the reflectance decreased to 8.8% after infiltration of the PDMS prepolymer into the polystyrene microspheres (PS). The light passes through the photonic color changing film to cause total reflection. According to Snell's Law light entering the light-draining medium air (n=1) from the optically dense medium PDMS (n=1.43), when the incident angle is larger than the critical angle (θc=44.4°), total reflection is caused. However, the reflection peak of the photonic color-changing film does not affect the concentration of the suspension of the polystyrene microspheres, because the photonic color-changing film has a matching refractive index between the polystyrene microspheres (PS) and the PDMS, resulting in a reflection peak. Both fall near 531nm.

(2)穿透光譜 (2) Penetration spectrum

光線照射PDMS模板上排列的聚苯乙烯微球(PS)後會產生反射和折射,從第六圖的穿透光譜呈現一光子禁帶(photonic band gap),即光線因無法傳播而被反射出來,當聚苯乙烯微球懸浮液濃度從20wt%增加至100wt%,由第六圖(a-e)發現其平均穿透率從77.5%降至8.3%。隨聚苯乙烯微球懸浮液濃度的增加,聚苯乙烯微球自組裝排列堆疊厚度越厚,由於光線在PDMS基板上的聚 苯乙烯微球間散射,導致光學穿透率降低。 The light illuminates the polystyrene microspheres (PS) arranged on the PDMS template to produce reflection and refraction. From the breakthrough spectrum of the sixth graph, a photonic band gap is formed, that is, the light is reflected because it cannot propagate. When the polystyrene microsphere suspension concentration was increased from 20 wt% to 100 wt%, it was found from the sixth graph (ae) that the average transmittance decreased from 77.5% to 8.3%. As the concentration of polystyrene microsphere suspension increases, the polystyrene microspheres self-assemble the thicker the stack thickness, due to the accumulation of light on the PDMS substrate. Scattering between styrene microspheres results in reduced optical transmittance.

光子變色薄膜中之聚苯乙烯微球縫隙間由於注滿PDMS預聚物,由第七圖(a-e)發現當聚苯乙烯微球懸浮液濃度從20wt%增加至100wt%時,平均穿透率從95.2%降至31.2%。在此以PDMS預聚物澆注PDMS模板前後之最高平均穿透率之聚苯乙烯微球懸浮液濃度20wt%作為探討基礎。澆注PDMS預聚物前之PDMS基板上的聚苯乙烯微球平均穿透率為77.5%(如第六圖(a)),而在澆注後其穿透率明顯提升至95.2%(如第七圖(a)),造成此高穿透率的原因在於PDMS材料本身的光學特性。入射光經聚苯乙烯微球由不同方向的折射和多次反射後,由於大部分的光線無法自聚苯乙烯微球(PS)膠體晶體穿透,讓人產生偏白的視覺。在澆注滲入PDMS預聚物後,光進入光子變色薄膜時與聚苯乙烯微球(PS)相遇後造成散射,散射光沿著微球向前行進傳播,並藉由PDMS自身高穿透特性,光穿透了光子變色薄膜,進而提升光子變色薄膜之穿透率。 The average transmittance of the polystyrene microspheres in the photonic color-changing film due to the filling of the PDMS prepolymer is shown by the seventh diagram (ae) when the polystyrene microsphere suspension concentration is increased from 20 wt% to 100 wt%. From 95.2% to 31.2%. Here, the highest average transmittance of the polystyrene microsphere suspension concentration before and after pouring the PDMS template into the PDMS prepolymer is 20 wt%. The average penetration of polystyrene microspheres on the PDMS substrate before pouring the PDMS prepolymer was 77.5% (as in Figure 6 (a)), and the penetration rate increased significantly to 95.2% after casting (as in the seventh Figure (a)), the reason for this high transmittance is the optical properties of the PDMS material itself. After the incident light is refracted and multi-reflected by the polystyrene microspheres in different directions, most of the light cannot penetrate from the polystyrene microsphere (PS) colloidal crystal, which gives a white vision. After the infiltration of the PDMS prepolymer, the light enters the photonic color-changing film and collides with the polystyrene microspheres (PS) to cause scattering. The scattered light travels along the microspheres forward, and the PDMS itself has high penetration characteristics. Light penetrates the photonic color-changing film, thereby increasing the transmittance of the photonic color-changing film.

我們以一紙幣作為背景,其紙幣右側有一直排的雷射仿偽圖樣,隨後將本發明實驗所製備出的光子變色薄膜放置於紙幣上,如附件2照片(a)所示。可觀察到其高穿透特性,傾斜紙幣後在某一反射可見光的視角下,光子變色薄膜會反射出內部的隱藏結構色彩,可明顯看到一個綠色字母「U」和藍色字母「N」顯示在光子變色薄膜上,如附件2照片(b)所示。其紙幣右側的雷射仿偽條張貼在字樣上,導致紙鈔中重疊區域的文字被仿偽條蓋住。但光 子變色薄膜具有95%高穿透特性,當其覆蓋在紙鈔表面時,紙鈔上的圖文清晰可見。光子透明薄膜在任一可見光光源下隨著角度變化,即會反射出隱藏的結構色彩,光子透明薄膜可變化其顏色和圖案,其仿偽便利性高於以紫外光源照射的隱藏設計,未來此技術可應用於仿偽、隱藏加密文件及發展為特殊裝潢塗料之潛力。 We use a banknote as the background, and there is a laser-like pseudo-pattern on the right side of the banknote. Then, the photonic color-changing film prepared by the experiment of the present invention is placed on the banknote, as shown in the photo (a) of Attachment 2. It can be observed that its high penetrating property, after tilting the banknote, the photonic color-changing film will reflect the hidden structure color inside, which can clearly see a green letter "U" and a blue letter "N". Displayed on the photonic color film as shown in photo (b) of Attachment 2. The laser-like pseudo-bar on the right side of the banknote is posted on the typeface, causing the text in the overlapping area of the banknote to be covered by the dummy strip. But light The sub-color film has a 95% high penetration property, and the image on the banknote is clearly visible when it is covered on the surface of the banknote. The photonic transparent film will reflect the hidden structure color under any visible light source, and the photonic transparent film can change its color and pattern. The pseudo-pseudo-facilitability is higher than the hidden design illuminated by the ultraviolet light source. It can be applied to the potential of pseudo-pseudo, hidden encrypted files and developed into special decorative coatings.

參.結論 Reference

依據前述之說明及分析,本發明確實具有以下技術特點和功效: According to the foregoing description and analysis, the present invention does have the following technical features and effects:

1.本發明之色彩顯示技術,並非由材料吸收光後而產生化學變化,而是藉由奈米結構和入射光相互交互作用下所產生之物理光學現象,此一光致變色過程,亦無需任何能源裝置或驅動,即可產生色彩轉變,此為結構顏色之特殊光學特性。 1. The color display technology of the present invention does not cause a chemical change after the material absorbs light, but a physical optical phenomenon generated by the interaction between the nanostructure and the incident light, and the photochromic process does not need any The energy device or drive produces a color transition, which is a special optical property of the structural color.

2.本發明之光子變色薄膜具有一高光學穿透特性約95%,然而在一視角變化同時具有隱藏式之結構色彩顯現,即從透明薄膜變化至色彩薄膜。 2. The photonic color-changing film of the present invention has a high optical transmission characteristic of about 95%, but has a hidden structural color appearance at the same time, that is, changes from a transparent film to a color film.

3.本發明係採用浸拉法致使聚苯乙烯微球自組裝排列成有序結構,然而在不同浸拉速率和聚苯乙烯懸浮液濃度變化下,可使聚苯乙烯微球堆疊不同型貌和厚度,影響其穿透度和色彩強度。 3. The present invention uses the dip-draw method to cause the polystyrene microspheres to self-assemble into an ordered structure, but the polystyrene microspheres can be stacked in different shapes under different dip-drawing rates and polystyrene suspension concentrations. And thickness, affecting its penetration and color intensity.

4.結構色彩可由聚苯乙烯微球的粒徑大小控制,並藉由聚苯乙烯微球縫隙間滲入聚二甲基矽氧烷(PDMS)並加以固化,除了可增強薄膜機械強度之外,亦也提升光學穿透度。 4. The structural color can be controlled by the particle size of the polystyrene microspheres, and the polydimethylsiloxane (PDMS) is infiltrated between the gaps of the polystyrene microspheres and cured, in addition to enhancing the mechanical strength of the film. It also increases optical penetration.

以上所述,僅為本創作之一可行實施例,並非用以限定本創作之專利範圍,凡舉依據下列請求項所述之內容、特徵以及其精 神而為之其他變化的等效實施,皆應包含於本創作之專利範圍內。本創作除上述優點外,並深具產業之利用性,可有效改善習用所產生之缺失,而且所具體界定於請求項之特徵,未見於同類物品,故而具實用性與進步性,已符合新型專利要件,爰依法具文提出申請,謹請 鈞局依法核予專利,以維護本申請人合法之權益。 The above description is only one of the possible embodiments of the present invention, and is not intended to limit the scope of the patent of the present invention, and the content, characteristics and fineness thereof according to the following claims are mentioned. The equivalent implementation of God's other changes shall be included in the scope of this creation's patent. In addition to the above advantages, this creation has deep industrial applicability, can effectively improve the lack of use, and is specifically defined in the characteristics of the request item, not found in similar items, so it is practical and progressive, and has been in line with the new type. For patents, the application shall be filed in accordance with the law. The Bureau shall be required to approve the patent in accordance with the law to protect the lawful rights and interests of the applicant.

1‧‧‧USB單軸運動控制器 1‧‧‧USB single axis motion controller

2‧‧‧步進閉迴路伺服馬達 2‧‧‧Step closed loop servo motor

3‧‧‧光學旋轉式絕對型編碼器 3‧‧‧Optical rotary absolute encoder

4‧‧‧馬達螺桿聯軸器 4‧‧‧Motor screw coupling

5‧‧‧精密級滾珠螺桿 5‧‧‧Precision ball screw

6‧‧‧精密級線性移動滑軌 6‧‧‧Precision linear moving slide

7‧‧‧試片夾具組 7‧‧‧Film holder

8‧‧‧PDMS基板 8‧‧‧PDMS substrate

9‧‧‧燒杯 9‧‧‧ beaker

10‧‧‧防震光學桌 10‧‧‧Anti-vibration optical table

11‧‧‧聚苯乙烯懸浮液 11‧‧‧ polystyrene suspension

12‧‧‧聚苯乙烯微球 12‧‧ ‧ polystyrene microspheres

13‧‧‧彎液面 13‧‧‧ Meniscus

14‧‧‧膠體陣列 14‧‧‧colloid array

15‧‧‧PDMS預聚物 15‧‧‧PDMS prepolymer

第一圖係本發明所採用之微機電精密浸拉裝置示意圖。 The first figure is a schematic diagram of a microelectromechanical precision immersion device used in the present invention.

第二圖係本發明聚苯乙烯微球自組裝排列過程示意圖。 The second figure is a schematic diagram of the self-assembly alignment process of the polystyrene microspheres of the present invention.

第三圖係本發明光子變色薄膜示意圖。 The third figure is a schematic diagram of the photonic color-changing film of the present invention.

第四圖係PDMS基板上聚苯乙烯微球懸浮液濃度20wt%~100wt%變化之反射光譜。 The fourth graph is the reflection spectrum of the polystyrene microsphere suspension concentration on the PDMS substrate varying from 20 wt% to 100 wt%.

第五圖係光子變色薄膜聚苯乙烯微球懸浮液濃度20wt%~100wt%變化之反射光譜。 The fifth figure is the reflection spectrum of the photochromic color film polystyrene microsphere suspension concentration change of 20 wt% to 100 wt%.

第六圖係PDMS基板上聚苯乙烯微球懸浮液濃度20wt%~100wt%變化之穿透光譜。 The sixth graph is the breakthrough spectrum of the polystyrene microsphere suspension concentration on the PDMS substrate varying from 20 wt% to 100 wt%.

第七圖係光子變色薄膜聚苯乙烯微球懸浮液濃度20wt%~100wt%變化之穿透光譜。 The seventh figure shows the breakthrough spectrum of the photochromic color film polystyrene microsphere suspension concentration of 20 wt% to 100 wt%.

第八圖為不同NaSS含量聚合成的聚苯乙烯微球(PS)之微球大小及其反射所對應之波長(色彩)。 The eighth figure shows the size of the microspheres of the polystyrene microspheres (PS) polymerized by different NaSS content and the wavelength (color) corresponding to the reflection.

附件1:圖(a-b)為本發明以SEM觀察在不同浸拉速率下,聚苯乙烯微球(PS)之排列結構;圖(f-j)為本發明在遞減的浸拉速率下, 聚苯乙烯微球(PS)之堆疊厚度。 Annex 1: Figure (a-b) is an SEM observation of the arrangement structure of polystyrene microspheres (PS) at different immersion rates by SEM; Figure (f-j) is the dip leaching rate of the present invention. Stacking thickness of polystyrene microspheres (PS).

附件2:照片(a)為本發明實驗所製備出的光子變色薄膜放置於紙幣上的態樣;照片(b)為本發明紙幣傾斜反射出內部的隱藏結構色彩而顯現出字母「U」和「N」的態樣。 Attachment 2: Photo (a) is the aspect in which the photon color-changing film prepared by the experiment of the present invention is placed on the banknote; the photograph (b) is the hidden structure color of the banknote obliquely reflected inside the banknote of the present invention, and the letter "U" and The appearance of "N".

8‧‧‧PDMS基板 8‧‧‧PDMS substrate

9‧‧‧燒杯 9‧‧‧ beaker

11‧‧‧聚苯乙烯懸浮液 11‧‧‧ polystyrene suspension

12‧‧‧聚苯乙烯微球 12‧‧ ‧ polystyrene microspheres

13‧‧‧彎液面 13‧‧‧ Meniscus

14‧‧‧膠體陣列 14‧‧‧colloid array

Claims (10)

一種以結構顏色製備光子變色薄膜的方法,包含以下步驟:(a)提供一單分散性膠體微球懸浮液;(b)使該膠體微球懸浮液內的膠體微球以一自組裝方式而排列成周期性膠體微球陣列;及(c)在膠體微球陣列中滲入一液態可透光膠體材料,使原本之膠體微球縫隙間的空氣,在滲入後皆填滿此液態可透光膠體材料並將其固化而形成一光子變色薄膜,使該光子變色薄膜在一光源下照射而可顯現出結構色彩。 A method for preparing a photonic color-changing film in a structural color, comprising the steps of: (a) providing a monodisperse colloidal microsphere suspension; and (b) allowing the colloidal microspheres in the colloidal microsphere suspension to be self-assembled. Arranging into a periodic colloidal microsphere array; and (c) infiltrating a liquid permeable colloidal material into the colloidal microsphere array, so that the air between the gaps of the original colloidal microspheres is filled with the liquid after permeation The colloidal material is solidified to form a photonic color-changing film, and the photonic color-changing film is irradiated under a light source to exhibit a structural color. 如請求項1所述光子變色薄膜的方法,其中步驟(a)之該微球平均粒徑尺寸為100奈米到500奈米之間。 The method of claim 1, wherein the microspheres of step (a) have an average particle size of between 100 nm and 500 nm. 如請求項1所述光子變色薄膜的方法,其中步驟(a)之該微球材料係選自金屬、有機高分子及無機化合物至少其中一種。 The method of claim 1, wherein the microsphere material is at least one selected from the group consisting of a metal, an organic polymer, and an inorganic compound. 如請求項3所述光子變色薄膜的方法,其中該金屬材料係選自金Au、銀Ag、銅Cu、鐵Fe、鈷Co、鎳Ni、鈀Pd、鉑Pt、鋁Al、矽Si、鈦Ti、鋯Zr、釩V、鈮Nb、鉬Mo、鎢W及錳Mn至少其中一種。 The method of claim 3, wherein the metal material is selected from the group consisting of gold Au, silver Ag, copper Cu, iron Fe, cobalt Co, nickel Ni, palladium Pd, platinum Pt, aluminum Al, 矽Si, titanium. At least one of Ti, zirconium Zr, vanadium V, niobium Nb, molybdenum Mo, tungsten W, and manganese Mn. 如請求項3所述光子變色薄膜的方法,其中該有機高分子材料係選自聚苯乙烯系列、聚甲基丙烯酸甲酯系列、聚馬來酸系列、聚乳酸系列、聚胺基酸系列的高分子至少其中一種。 The method of claim 3, wherein the organic polymer material is selected from the group consisting of polystyrene series, polymethyl methacrylate series, polymaleic acid series, polylactic acid series, and polyamino acid series. At least one of the polymers. 如請求項3所述光子變色薄膜的方法,其中該無機化合物材料係選自氧化銀Ag2O、氧化銅CuO、氧化鋅ZnO、氧化鎘CdO、氧化鎳NiO、氧化鈀PdO、氧化鈷CoO、氧化鎂MgO、二氧化矽SiO2、二氧化錫SnO2、二氧化鈦TiO2、二氧化鋯ZrO2、二氧化鉿HfO2、二氧化釷ThO2、二氧化鈰CeO2、二氧化鈷CoO2、二氧化錳MnO2、 二氧化銥IrO2、二氧化釩VO2、三氧化鎢WO3、三氧化鉬MoO3、三氧化二鋁Al2O3、三氧化二釔Y2O3、三氧化二鐿Yb2O3、三氧化二鏑Dy2O3、三氧化二硼B2O3、三氧化二鉻Cr2O3、三氧化二鐵Fe2O3、四氧化三鐵Fe3O4、五氧化二釩V2O5、五氧化二鈮Nb2O5、硫化鋅ZnS、硒化鋅ZnSe、碘化鋅ZnTe、硫化鎘CdS、硒化鎘CdSe、碘化鎘CdTe、硫化鐵FeS、硒化鐵FeSe、FeTe、硫化鈷CoS、硒化鈷CoSe、碘化鈷CoTe、硫化鎳NiS、硒化鎳NiSe、NiTe、硫化鉛PbS、硒化鉛PbSe、碘化鉛PbTe、硫化錳MnS、硒化錳MnSe、MnTe、硫化錫SnS、硒化錫SnSe、碘錫SnTe、二硫化鉬MoS2、二硒化鉬MoSe2、二碘化鉬MoTe2、二硫化鎢WS2、二硒化鎢WSe2、二碘化鎢WTe2、硫化二銅Cu2S、硒化二銅Cu2Se、碘化二銅Cu2Te、三硫化二鉍Bi2S3、三硒化二鉍Bi2Se3、三碘化二鉍Bi2Te3、碳化釸SiC、碳化鈦TiC、碳化鋯ZrC、碳化鎢WC、碳化鈮NbC、碳化鉭TaC、碳化二鉬Mo2C、氮化硼BN、氮化鋁AlN、氮化鈦TiN、氮化鋯ZrN、氮化釩VN、氮化鈮NbN、氮化鉭TaN、四氮化三矽Si3N4及四氮化三鋯Zr3N4至少其中一種。 The method of claim 3, wherein the inorganic compound material is selected from the group consisting of silver oxide Ag 2 O, copper oxide CuO, zinc oxide ZnO, cadmium oxide CdO, nickel oxide NiO, palladium oxide PdO, cobalt oxide CoO, Magnesium oxide MgO, cerium oxide SiO 2 , tin dioxide SnO 2 , titanium dioxide TiO 2 , zirconium dioxide ZrO 2 , cerium oxide HfO 2 , cerium oxide ThO 2 , cerium oxide CeO 2 , cobalt dioxide CoO 2 , Manganese dioxide MnO 2 , cerium oxide IrO 2 , vanadium dioxide VO 2 , tungsten trioxide WO 3 , molybdenum trioxide MoO 3 , aluminum oxide Al 2 O 3 , antimony trioxide Y 2 O 3 , trioxide Diterpenoid Yb 2 O 3 , antimony trioxide Dy 2 O 3 , boron trioxide B 2 O 3 , chromium oxide Cr 2 O 3 , ferric oxide Fe 2 O 3 , ferroferric oxide Fe 3 O 4 , vanadium pentoxide V 2 O 5 , antimony pentoxide Nb 2 O 5 , zinc sulfide ZnS, zinc selenide ZnSe, zinc iodide ZnTe, cadmium sulfide CdS, cadmium selenide CdSe, cadmium iodide CdTe, iron sulfide FeS, iron selenide FeSe, FeTe, cobalt sulfide CoS, cobalt selenide CoSe, cobalt iodide CoTe, nickel sulfide NiS, nickel selenide NiSe, NiTe, lead sulfide PbS, lead selenide PbSe, Lead PbTe, manganese sulfide MnS, manganese selenide, MnSe, MnTe, tin sulfide SnS, tin selenide SnSe, tin iodide SnTe, molybdenum disulfide MoS 2, molybdenum diselenide MoSe 2, molybdenum diiodide MoTe 2, disulfide tungsten WS 2, tungsten diselenide WSe 2, tungsten diiodide WTe 2, copper sulfide Cu 2 S, copper (II) selenide, Cu 2 Se, copper (II) iodide, Cu 2 Te, trisulfide, bismuth Bi 2 S 3, Bis selenium Bi 2 Se 3 , diiodide Bi 2 Te 3 , tantalum carbide SiC, titanium carbide TiC, zirconium carbide ZrC, tungsten carbide WC, niobium carbide NbC, tantalum carbide TaC, molybdenum carbide Mo 2 C Boron nitride BN, aluminum nitride AlN, titanium nitride TiN, zirconium nitride ZrN, vanadium nitride VN, tantalum nitride NbN, tantalum nitride TaN, tetrazolium nitride Si 3 N 4 and tetrazinc nitride At least one of zirconium Zr 3 N 4 . 如請求項1所述光子變色薄膜的方法,其中該自組裝方式係選自浸拉法、重力沉降法、垂直沉積法、溶劑蒸發法、離心沉積法、磁場加速沉降法及電泳輔助沉積法至少其中一種。 The method of claim 1, wherein the self-assembly method is selected from the group consisting of a dip method, a gravity sedimentation method, a vertical deposition method, a solvent evaporation method, a centrifugal deposition method, a magnetic field accelerated sedimentation method, and an electrophoresis-assisted deposition method. one of them. 如請求項1所述光子變色薄膜的方法,其中該膠體微球懸浮液為聚苯乙烯微球懸浮液,其濃度為20wt%至100wt%,該浸拉法係以一浸拉速率將一表面具親水性之PDMS基板浸入及拉出該聚苯乙烯懸浮液的表面,藉毛細作用力致使該聚苯乙烯微球自組裝排列成有序的聚苯乙烯微球膠體陣列,該浸拉速率為100至0.1μm/s,該液態可透光膠體材料為PDMS預聚物。 The method of claim 1, wherein the colloidal microsphere suspension is a polystyrene microsphere suspension having a concentration of 20% by weight to 100% by weight, and the immersion method is a surface at a leaching rate The hydrophilic PDMS substrate is immersed in and pulled out of the surface of the polystyrene suspension, and the polystyrene microspheres are self-assembled into an ordered polystyrene microsphere colloid array by capillary force, and the immersion rate is The liquid permeable colloidal material is a PDMS prepolymer of 100 to 0.1 μm/s. 如請求項1所述光子變色薄膜的方法,其中該液態可透光膠體材料係選自環氧樹脂系列、苯偶酰系列、烷基苯酮系列、二苯甲酮系列、安息香醚系列、硫雜蔥酮系列及聚二甲基矽氧烷系列至少其中一種。 The method of claim 1, wherein the liquid permeable colloidal material is selected from the group consisting of epoxy resin series, benzil series, alkyl benzophenone series, benzophenone series, benzoin ether series, sulfur At least one of the onion ketone series and the polydimethyl siloxane series. 一種應用有如請求項1所述之光子變色薄膜的物件,該物件係選自變色指甲、變色花瓣、變色鏡框、變色筆殼、筆桿、筆蓋、變色皮帶頭、變色髮夾、變色領帶夾、變色手表表帶、手機或電話之變色外殼、變色徽章、變色磁鐵條上之圖飾、變色杯具、變色滑鼠圖飾、筆記型電腦、平板電腦之變色外殼、變色鑰匙圈、變色耳環吊飾、變色塗料、變色飲料杯蓋、杯身。 An object using the photonic color-changing film according to claim 1, wherein the object is selected from the group consisting of a color changing nail, a color changing petal, a color changing frame, a color changing pen case, a pen holder, a pen cover, a color changing belt head, a color changing hair clip, a color changing tie clip, Color-changing watch strap, mobile phone or telephone color-changing shell, color-changing badge, graphic decoration on color-changing magnet strip, color-changing cup, color-changing mouse graphic, notebook computer, tablet computer color changing shell, color changing key ring, color changing earring Decorative, color-changing paint, color-changing beverage cup lid, cup body.
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