WO2016127938A1 - 一种具有色相和光泽的光学功能材料及其制备与应用 - Google Patents

一种具有色相和光泽的光学功能材料及其制备与应用 Download PDF

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WO2016127938A1
WO2016127938A1 PCT/CN2016/073732 CN2016073732W WO2016127938A1 WO 2016127938 A1 WO2016127938 A1 WO 2016127938A1 CN 2016073732 W CN2016073732 W CN 2016073732W WO 2016127938 A1 WO2016127938 A1 WO 2016127938A1
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functional material
nanospheres
optical functional
material according
nano
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PCT/CN2016/073732
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English (en)
French (fr)
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叶常青
温强
刘德云
宋延林
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苏州中科纳福材料科技有限公司
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Priority claimed from CN201510079857.1A external-priority patent/CN104614808B/zh
Priority claimed from CN201510078604.2A external-priority patent/CN104698536B/zh
Application filed by 苏州中科纳福材料科技有限公司 filed Critical 苏州中科纳福材料科技有限公司
Publication of WO2016127938A1 publication Critical patent/WO2016127938A1/zh
Priority to US15/675,094 priority Critical patent/US20180194928A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
    • G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/101—Nanooptics

Definitions

  • the present invention relates to optically functional materials, and more particularly to an optically functional material in which the hue and gloss are relatively independent.
  • a wide variety of colors can be divided into two major categories of achromatic and colored.
  • Achromatic color means white, black, and various shades of gray formed by blending white and black.
  • Achromatic color can be arranged into a series according to a certain change rule, from white to light gray, medium gray, dark gray to black, and the color is called black and white series.
  • Pure white is the ideal fully reflective object
  • pure black is the ideal fully absorbed object.
  • the color of the achromatic system has only one basic property - brightness. They do not have the properties of hue and purity, that is to say their hue and purity are theoretically equal to zero.
  • the brightness of the color can be expressed in black and white, the closer to white, the higher the brightness; the closer to black, the lower the brightness.
  • White and black as pigments can adjust the reflectivity of the object color, so that the object color improves brightness or reduces brightness.
  • Color refers to colors such as red, orange, yellow, green, cyan, blue, and purple. Red, yellow, green, blue, and purple tones of different brightness and purity belong to the colored system.
  • the chromaticity is determined by the wavelength and amplitude of the light. The wavelength determines the hue and the amplitude determines the hue.
  • the color of the colored system has three basic characteristics: hue, purity (also called chroma, saturation), and brightness. In color science, it is also called the three elements of color or the three attributes of color. Hue is the biggest feature of color.
  • hue refers to a name that can more accurately represent a certain color. Such as rose red, orange, lemon yellow, cobalt blue, ultramarine blue, emerald green...
  • the various hue is determined by the spectral composition of the light incident on the human eye.
  • the appearance of the hue depends entirely on the wavelength of the light; for mixed color light, it depends on the relative amount of light at various wavelengths.
  • the color of an object is determined by the spectral composition of the source and the characteristics of the surface (or transmission) of the object.
  • color is color, including pigment color and structural color. Most of the non-illuminating objects seen in daily life are colored by the pigment color. The visible band of light is irradiated onto the object, and the light waves of different wavelengths are selectively absorbed and reflected (transmitted) by the pigment to obtain a specific reflection. The (transmission) spectrum, which is finally observed in the human brain by the observation of the human eye.
  • the pigment color conforms to the principle of subtractive color mixing. In theory, as long as there are three kinds of subtractive primary colors (usually C, Cyan magenta (M, Magenta) yellow (Y, Yellow), all the colors in the excellent phase ring can be mixed. .
  • Structural colour also known as physical colour, is a lustrous effect produced by interference diffraction between a material's microstructure and a corresponding wavelength of light.
  • Structural color and Irrespective of the coloring pigment of the structural constituent material it is an optical effect caused by the submicroscopic structure of the living body.
  • the ridges, lines, facets and particles of the surface or surface of the organism can reflect or scatter light, resulting in a special color effect.
  • the feather color of birds and the wing color of butterflies are mainly caused by the interference of light; the skin around the head and neck of the turkey is blue and the blue color of the primate face, buttocks and genital area is due to
  • the blue-violet portion of the incident light is reflected by a large number of fine particles in the epidermal tissue (having a diameter equivalent to the wavelength of the blue-violet light), and the red-yellow portion of the incident light is absorbed by the melanin in the dermal tissue through the granular layer.
  • the structural color has the advantages of no fading, environmental protection and iridescent effect, it has broad application prospects in the fields of display, decoration and anti-counterfeiting.
  • Research on the formation mechanism and application of the structure color of living organisms in nature can promote the development of biomimetic structural color processing and micro-nano optical technology.
  • Photonic Crystal was independently proposed by S. John and E. Yablonovitch in 1987. It is an artificial microstructure that is periodically arranged by media of different dielectric constants.
  • Photonic crystals are a class of artificially designed and fabricated crystals with periodic dielectric structures on an optical scale. The special periodic structure of a photonic crystal makes it resistant to photons of a specific wavelength or band, forming a photonic band gap, similar to the electron energy band in a semiconductor, and calling the photonic band gap in a photonic crystal a photonic band gap (Photonic Band-Gap, referred to as PBG).
  • PBG Photonic Band-Gap
  • the periodic arrangement of dielectric constants produces a certain "potential field".
  • optical functional materials including photonic crystal structures
  • most studies on optical functional materials including photonic crystal structures have focused on highlighting the visual effects of structural colors of photonic crystals, for example, Using some dark light absorbing medium to weaken the stray light of the non-structural color of the photonic crystal to improve its color saturation, the optical functional material thus formed can provide a purer, highly saturated structural color luster, due to the single color of the structural color, The color mixing is realized, and the spectral color is not displayed, so that the formed optical functional material presents a single color, which affects its aesthetic sense and limits its practical application.
  • the structural color is independent of the pigment color constituting the structural material itself, and the structural color spectrum is a single specular reflection spectrum of the band, and the relative amount in the overall reflection spectrum is low, and has almost no influence on the hue of the overall material. It is presented as a solid color gloss effect.
  • the object of the present invention is to provide an optical functional material by providing the concept that the gloss and color are independent of each other and the gloss and hue are independent of each other in view of the advantages and disadvantages of the structural color.
  • This optically functional material combines not only the structural color of the photonic crystal but also the characteristics of the material material constituting the photonic crystal.
  • the gloss and color of the optical functional material are independent of each other, which means that the gloss is mainly affected by the microscopic nanoscale structure of the material, and the color thereof is mainly determined by the absorption of light by the substance constituting the optical functional material, although the visual effect in the human eye.
  • Upper, gloss and color interact with each other, but the causes of gloss and color are different, so they are independent of each other.
  • the gloss and hue of the optical functional material are independent of each other, meaning that the gloss is mainly affected by the microscopic nanoscale structure of the material, and the hue of the color is mainly determined by the absorption of light by the substance constituting the optical functional material, although in the human eye.
  • gloss and hue interact with each other, but the causes of gloss and hue are different, so they are independent of each other.
  • the invention combines the structural color of the photonic crystal with the color or hue of the substance constituting the photonic crystal, and obtains a richer color or hue independent of the structural color by adjusting the combination of the two colors or hue, and the structure and structure.
  • the color spectrum is combined to achieve a relatively independent color and color or hue, and a special effect of color that is randomly combined as needed.
  • the gloss and the color are independent of each other; when the color of the optical functional material is a color having a hue, the gloss and the hue are independent of each other.
  • Color in the present application refers to a color having a hue of any one of hue circles.
  • PKI in the present application refers to a polydispersity index of the particle size of the emulsion microspheres.
  • the present invention provides an optical functional material comprising a nano microsphere layer formed by periodically arranging nano microspheres, the nano microsphere layer being a close packed structure,
  • the optical functional material has a luster; and the nano microsphere layer comprises colorless nano microspheres, white nano microspheres, gray nanospheres, black nanospheres or colored nanospheres.
  • the nanosphere layer comprises a plurality of nano-spheres of different colors, and the color of each nano-sphere is selected from white, gray, black or color.
  • optically functional material is transparent, translucent or microtransparent.
  • the nanosphere layer comprises white nanospheres and at least one colored nanosphere.
  • the nanosphere layer comprises colored nanospheres having different hue.
  • the nanosphere layer comprises white nanospheres, black nanospheres, and colored nanospheres.
  • the nanosphere layer comprises black nanospheres and colored nanospheres.
  • the nanosphere layer comprises gray nanospheres and colored nanospheres.
  • the nanosphere layer comprises white nanospheres and black nanospheres.
  • the nanosphere layer comprises gray nanospheres and black nanospheres.
  • the gloss of the optical functional material is infrared light, visible light or ultraviolet light having a wavelength of 200 to 2000 nm.
  • the gloss of the optical functional material is visible light having a wavelength of 480 to 550 nm, 580 to 600 nm, 550 to 600 nm, or 600 to 640 nm.
  • nano microspheres are filled with a filling medium.
  • the filling medium is colorless, white, gray, black or colored.
  • the filling medium may be transparent, translucent or micro-transparent.
  • optically functional material is transparent, translucent or microtransparent.
  • the filling medium is a gas, a liquid or a solid.
  • the filling medium contains a colored substance.
  • the colored substance is a dye, a pigment, or a resin color masterbatch.
  • the colored substance is methyl blue, tartrazine, rhodamine 6G, red acrylic resin masterbatch, orange epoxy masterbatch, blue epoxy masterbatch or green polyurethane resin masterbatch.
  • liquid filling medium is selected from the group consisting of silicone oil, mineral oil, vegetable oil, and animal fat.
  • the solid filling medium is selected from the group consisting of silica, titania, zinc oxide, carbon black, silicone resin, urethane resin, epoxy resin, acrylic resin, alkyd resin, and polyester.
  • the nanosphere layer comprises colored nanospheres, and the color of the filling medium itself is color.
  • the nano microsphere layer comprises colorless nano microspheres, white nano microspheres, gray nanospheres or black nanospheres, and the color of the filling medium itself is color.
  • the raw material of the nano microspheres is selected from the group consisting of polystyrene, polyacrylate, polyacrylic acid, silica, alumina, titania, zirconia, triiron tetroxide, polyimide, silicone, and phenolic aldehyde.
  • nano-microspheres have a monodispersity PDI of less than 0.5.
  • the nano microspheres have a PDI of less than 0.05.
  • the nanospheres have a particle diameter of 80 to 1100 nm.
  • the nanospheres have a particle diameter of 120 to 400 nm.
  • the nanosphere layer forms a photonic crystal.
  • the nanospheres are one of cyan nanospheres, magenta nanospheres, and yellow nanospheres, or any combination thereof.
  • the nanosphere layer has a thickness of 1 to 50 micrometers.
  • the combination of the hue of the nano microsphere and the hue of the filling medium can realize the hue adjustment of the optical functional material.
  • the gloss of the optical functional material is set, and the relationship follows the following formula:
  • ⁇ is the forbidden band wavelength
  • d is the period constant
  • ie the particle diameter of the microspheres
  • nA is the refractive index of the nanospheres
  • nB is the refractive index of the filling medium.
  • 0.74 and 0.26 are the volume fractions of the nanospheres and the interstitial medium in the entire material, respectively.
  • the nanospheres may be selected from one or two or more (including two) materials having similar refractive indices, and the materials of the nanospheres have a refractive index deviation of less than 2%. In a preferred embodiment, the nano microspheres have a refractive index deviation of 0.5% or less.
  • the material of the nano microsphere is selected from the group consisting of polystyrene, polyacrylate, polyacrylic acid, silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, triiron tetroxide, polyimide, and silicone resin. Or a mixture of one or more of phenolic resins.
  • the filling medium is a mixture of one or both of a liquid filling medium, a solid filling medium, a liquid filling medium in which a colored substance is provided, and a solid filling medium in which a colored substance is provided.
  • the liquid filling medium is selected from one or more mixed liquids of silicone oil, mineral oil, vegetable oil or animal fat.
  • the solid filling medium is selected from the group consisting of silica, titania, zinc oxide, carbon black, silicone resin, polyurethane resin, epoxy resin, acrylic resin, alkyd resin, and polyester.
  • the present invention provides an optically functional material comprising a nano-microsphere layer formed by periodic arrangement of nano-microspheres, the nano-microsphere layer being a close-packed structure, such that the optical
  • the functional material has a gloss; characterized in that the nanosphere layer comprises white, gray, black or colored nanospheres; the color of the nanospheres is the color of the nanospheres themselves or formed by coloration.
  • the coloring is performed prior to self-assembly.
  • the coloring is performed during the self-assembly process.
  • the coloring is performed after self-assembly.
  • the present invention provides a method of preparing an optically functional material, comprising the steps of:
  • the nano-microsphere colloidal dispersion self-assembles at the phase interface to form a periodic tightly arranged structure
  • the nanospheres in the step (1) are colored nanospheres.
  • the nano microspheres are colored by adding a coloring agent to the nanosphere colloidal dispersion.
  • a filling medium is filled between the nanospheres of the nanosphere layer.
  • the phase interface described in the step (2) comprises a gas-solid interface, a gas-liquid interface, a solid-solid interface or Liquid and liquid interface.
  • the external force effect described in the step (2) includes capillary force, electrostatic force, magnetic force, gravity, van der Waals force or hydrogen bonding.
  • the filling medium may be added to the nano microsphere emulsion to co-assemble with the nano microspheres during the process of removing the continuous phase, or may be filled into the nano microsphere gap after the nano microspheres are assembled into a periodic tightly arranged structure.
  • the periodic arrangement of the nano microspheres is self-assembled by the nano microsphere emulsion, that is, the nano microspheres are dispersed in another continuous phase, and the non-solvent filling medium is dispersed, supplemented by certain auxiliary agents.
  • Nano microsphere emulsion The continuous phase is removed by corresponding technical means, in which the nanospheres and related additives are co-assembled to form a periodic tightly arranged structure.
  • the nano microsphere emulsion continuous phase may be selected from, but not limited to, one or a combination of one of water, methanol, ethanol, ethylene glycol, and cyclohexane.
  • the nano microspheres have a nanosphere content of 0.5 to 60% by weight, a non-solvent filling medium content of 0 to 35% by weight, and an auxiliary content of 0 to 20% by weight.
  • the nano microsphere emulsion auxiliary agent is used for modulating the rheological properties, the volatility energy, the film forming property and the like of the continuous phase
  • the nano microsphere emulsion auxiliary agent may be selected from, but not limited to, cellulose, acrylic acid. Emulsions, surfactants, epoxy resins, polyurethane resins, etc.
  • the refractive index difference from the filling medium, the gloss of the present invention encompasses the full visible spectrum and can be extended to the ultraviolet and infrared regions.
  • optically functional material of the present invention can be used to prepare ink pastes, pigment toners, and film coatings.
  • optically functional material of the present invention can be applied to paints, printing inks, packaging coatings, daily cosmetics, anti-counterfeiting materials, sensor devices, and optical components in the form of ink pastes, pigment toners or film coatings.
  • the present invention has the following advantages over the prior art:
  • the gloss of the optical functional material having luster and hue of the present invention can be arbitrarily adjusted in the infrared visible or ultraviolet range by adjusting the band gap of the photonic crystal, and the hue can realize the hue circle by setting the combination of the color of the nano particles and the filling medium. All hue. Achieve the effect of relatively independent gloss and hue, and achieve special color effects such as red phase green light, blue phase golden light, etc., and the gloss can be changed with the change of the viewing angle to produce a rainbow color changing effect. It can also reflect specific wavelengths, infrared ultraviolet radiation that is invisible to the naked eye, Therefore, special applications such as anti-counterfeiting and sensing are realized.
  • Example 1 is a SEM photograph of the assembled polystyrene emulsion microspheres in Example 1;
  • Example 2 is a reflection spectrum of the assembly of the polystyrene emulsion microspheres in Example 1, corresponding to the gloss thereof;
  • Figure 3 is an absorption spectrum of the polystyrene emulsion microspheres assembled in Example 1, corresponding to the hue thereof;
  • 4 is a spectrophotometer measuring optical path in the embodiment: 1. a sample to be tested; 2. a light source, an incident angle of 45°; 3. a specularly reflected light path; 4. a measuring optical path 45as-15, and a specular reflection path of -15. °; 5, measuring optical path 45as15, 15° with specular reflection path; 6, measuring optical path 45as25, 25° with specular reflection path; measuring optical path 45as45, 45° with specular reflection path; 8. Measuring optical path 45as75, with mirror The reflected light path is 75°; 9. The measuring optical path 45as110 is 110° from the specular reflected light path.
  • Figure 5 is a SEM photograph of the polystyrene emulsion microspheres assembled in Example 23;
  • Example 1 a preparation of a magenta optically functional material having a blue-green luster, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 215 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • magenta monodisperse polystyrene microsphere emulsion and anhydrous ethanol are compounded at a volume ratio of 7:2.
  • Ultrasonic dispersion for 10 minutes gave a homogeneously mixed magenta nanosphere emulsion solution.
  • Example 2 a preparation of a cyan optically functional material having a cyan gloss, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 215 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Example 3 the preparation of a yellow optically functional material having a blue-green luster, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 215 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Example 4 the preparation of a white optically functional material having a blue-green luster, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 215 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Example 5 the preparation of an optical functional material having a blue-green luster of an orange phase, comprising the steps of:
  • Example 1 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 1 was mixed with the uniformly mixed yellow nano microsphere emulsion solution obtained in Example 3, and the volume ratio was 1:1, and ultrasonic dispersion was carried out for 10 minutes to obtain a mixture. A uniform orange phase nanosphere emulsion solution.
  • Example 6 a preparation of an optical functional material having a blue-green luster of a green phase, comprising the steps of:
  • Example 2 The mixed homogeneous cyan nano microsphere emulsion solution obtained in Example 2 was mixed with the uniformly mixed yellow nano microsphere emulsion solution obtained in Example 3, and the volume ratio was 1:1, and ultrasonic dispersion was carried out for 10 minutes to obtain uniform mixing. Green phase nanosphere microemulsion solution.
  • Example 7 the preparation of an orange-red phase optically functional material having a blue-green luster, comprising the steps of:
  • Example 1 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 1 was mixed with the uniformly mixed yellow nano microsphere emulsion solution obtained in Example 4 at a volume ratio of 3:1, and ultrasonically dispersed for 10 minutes to obtain a mixture. A uniform orange-red phase nano-microsphere emulsion solution.
  • Embodiment 8 a preparation of an optical functional material having a blue-green luster of a purplish red phase, comprising the steps of:
  • Example 1 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 1 was mixed with the uniformly mixed cyan nano microsphere emulsion solution obtained in Example 2, and the volume ratio was 1:1, and ultrasonic dispersion was carried out for 10 minutes to obtain a mixture. A uniform orange-red phase nano-microsphere emulsion solution.
  • Test angle L* a* b* 45as-15 96.71 16.97 -41.59 45as15 99.37 25.08 -70.85 45as25 61.03 18.19 -55.42 45as45 40.49 10.42 -40.69 45as75 42.72 3.24 -31.90 45as110 44.73 1.85 -32.20
  • Example 9 a preparation of a light red phase optically functional material having a blue-green luster, comprising the steps of:
  • Example 1 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 1 was mixed with the uniformly mixed white nano microsphere emulsion solution obtained in Example 4 at a volume ratio of 2:1, and ultrasonically dispersed for 10 minutes to obtain a mixture.
  • Test angle L* a* b* 45as-15 153.81 27.22 -39.80 45as15 73.26 53.54 -14.78
  • Example 10 Preparation of a yellow phase optically functional material having an orange-red luster, comprising the steps of:
  • anhydrous ethanol was mixed at a volume ratio of 1:3:2, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed yellow nanosphere emulsion solution.
  • Embodiment 11 a preparation of a magenta optically functional material having an orange-red luster, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 252 nm was prepared by emulsion polymerization to have a solid content of 10%.
  • the specific preparation method is:
  • Example 12 the preparation of an orange-yellow phase optically functional material having an orange-red luster, comprising the steps of:
  • Example 10 The mixed homogeneous yellow nano microsphere emulsion solution obtained in Example 10 was mixed with the uniformly mixed magenta nano microsphere emulsion solution obtained in Example 11 in a volume ratio of 2:1. Ultrasonic dispersion for 10 minutes gave a homogeneously mixed orange-yellow phase nanosphere emulsion solution.
  • Example 13 a preparation of an optically functional material having a blue-green luster of a light red phase, comprising the steps of:
  • Embodiment 14 the preparation of an optical functional material having a blue-green luster of a blue phase, comprising the steps of:
  • Embodiment 15 a preparation of an optical functional material having a blue-green luster of a purple-red phase, comprising the steps of:
  • Example 13 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 13 was mixed with the uniformly mixed blue nano microsphere emulsion solution obtained in Example 14 at a volume ratio of 1:1, and ultrasonically dispersed for 10 minutes to obtain Mix a uniform purple-red phase nano-microsphere emulsion solution.
  • Example 16 Preparation of an optical functional material having a yellow-green luster in a purple-red phase, package Including the following steps:
  • Embodiment 17 a preparation of an optical functional material having a red luster phase of a purple red phase, comprising the steps of:
  • Embodiment 18 a preparation of an optical functional material having a red-orange luster of a purple-red phase, comprising the steps of:
  • Embodiment 19 a preparation of a magenta-colored optical functional material having a golden red gloss, comprising the steps of:
  • Embodiment 20 the preparation of a blue phase optically functional material having a golden red gloss, comprising the steps of:
  • Embodiment 21 a preparation of a reddish-brown phase optically functional material having a purple-red color, comprising the steps of:
  • Example 22 Preparation of a yellow phase optically functional material having an orange-red luster, comprising the steps of:
  • ethylene glycol was compounded at a volume ratio of 1:3:2, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed yellow nanosphere emulsion solution.
  • Example 23 Preparation of a yellow phase optically functional material having an orange-red luster, comprising the steps of:
  • acetone was compounded at a volume ratio of 1:3:2, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed yellow nanosphere emulsion solution.
  • Embodiment 23 a preparation of an optical functional material having a cyan luster in a red phase, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 210 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Embodiment 24 a preparation of a purple phase optical functional material having a red hue, comprising the steps of:
  • polystyrene monodisperse microspheres having a solid content of 5% (particle size 280 nm, PDI ⁇ 0.005), and the cleaned glass piece 2.5 cm x 2.5 cm was placed on a heat carrier at 75 ° C; After that, 1 ml of the mixed solution is dropped onto the glass piece and spread evenly; after the solvent is volatilized, a bright, brilliant red-toned photonic crystal coating is formed on the surface of the glass.
  • Test angle L* a* b* 45as-15 96.71 16.97 -41.59 45as15 99.37 25.08 -70.85 45as25 61.03 18.19 -55.42 45as45 40.49 10.42 -40.69 45as75 42.72 3.24 -31.90 45as110 44.73 1.85 -32.20
  • Embodiment 25 a preparation of an optical functional material having a yellowish phase with a green luster, comprising the steps of:
  • Embodiment 26 an orange-yellow phase preparation of an optically functional material having a blue-green luster, comprising the steps of:
  • polystyrene monodisperse microspheres having a solid content of 5% (particle diameter: 170 nm, PDI ⁇ 0.005), and a clean glass piece of 2.5 cm ⁇ 2.5 cm was placed on a heat carrier at 75 ° C; After that, 1 ml of the mixed solution is added dropwise onto the glass sheet to spread evenly; after the solvent is volatilized, a bright, bright green luster photonic crystal coating is formed on the surface of the glass.
  • Embodiment 27 a preparation of an optical functional material having a blue-green luster of a red phase, comprising the steps of:
  • red acrylic resin masterbatch Weigh 1g of red acrylic resin masterbatch and disperse it in 8g of acrylic resin, and disperse evenly. After coating the red resin on the photonic crystal coating by coating machine, it will penetrate into the gap of the microsphere, and the solvent will evaporate and become a layer of uniform filling. The coating exhibits a red phase with a functional film of blue-green luster and a layer thickness of 5 microns.
  • the color parameters are measured by the Alice MA-98 spectrophotometer, and the light source is D65/10° measurement light.
  • the road map is shown in Figure 4, and the data is shown in Table 14.
  • Embodiment 28 the preparation of an orange-green optically functional material, comprising the steps of:
  • a commercially available solid dispersion of 5% monodisperse alumina microspheres (particle size 142 nm, PDI ⁇ 0.1), and a clean glass piece 2.5 cm x 2.5 cm were placed on a heat carrier at 75 ° C; after the temperature was stabilized 1ml of the mixed solution is added to the glass sheet and spread evenly; after the solvent is volatilized, a bright, brilliant green-toned photonic crystal coating is formed on the surface of the glass.
  • Embodiment 29 a preparation of an optical functional material having a magenta gloss in a blue-violet phase, comprising the steps of:
  • Embodiment 30 a preparation of an optical functional material having a golden red luster in a green phase, comprising the steps of:
  • a commercially available solid dispersion 5% of monodisperse titanium dioxide microspheres (particle size 135 nm, PDI ⁇ 0.2), and a clean glass piece 2.5 cm x 2.5 cm were placed on a heat carrier at 75 ° C; after the temperature was stabilized, 0.5 ml of the mixed solution was added dropwise to the glass sheet to spread evenly; after the solvent was volatilized, a bright, brilliant photon crystal coating with a golden red luster was formed on the surface of the glass.
  • Embodiment 31 a preparation of an optical functional material having a dark red phase and a red luster, comprising the steps of:
  • monodisperse ferroferric oxide microspheres having a solid content of 5% (particle size: 140 nm, PDI ⁇ 0.2), and a clean glass piece of 2.5 cm x 2.5 cm placed on a heat carrier at 75 ° C; After stabilization, 0.5 ml of the mixed solution was dropped onto the glass piece and spread evenly; after the solvent was volatilized, a bright, brilliant red-toned photonic crystal coating was formed on the surface of the glass.
  • Embodiment 32 the preparation of an orange-green lustrous optical functional material, comprising the steps of: taking a commercially available monodisperse fluorescein polystyrene microsphere having a solid content of 5% (particle size 172 nm, PDI ⁇ 0.005), Place the cleaned glass piece 2.5cmX2.5cm on the heat carrier at 75 °C; after the temperature is stable, add 1ml of the mixed solution to the glass piece and spread it evenly; after the solvent evaporates, the surface of the glass will form a bright and beautiful appearance. Green glossy photonic crystal coating.
  • Embodiment 33 a black optically functional material having a blue-green luster, comprising the following steps
  • Example 1 The mixed homogeneous magenta nano microsphere emulsion solution obtained in Example 1, the uniformly mixed cyan nano microsphere emulsion solution obtained in Example 2, and the uniformly mixed yellow nano microsphere emulsion solution obtained in Example 3 were taken.
  • the volume ratio of the ampoule was 1:1.7:0.8, and the ultrasonic dispersion was carried out for 10 minutes to obtain a uniformly mixed black nanosphere emulsion solution.
  • Embodiment 34 a preparation of an optical functional material having a gray-green luster in gray, comprising the steps of:
  • Example 32 The mixed homogeneous black nano-microsphere emulsion solution obtained in Example 32 was mixed with the white nano-microsphere emulsion solution obtained in Example 4 at a volume ratio of 1:1, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed gray nanometer. Microsphere emulsion solution.
  • Embodiment 35 a preparation of a dark red optically functional material having a blue-green luster, comprising the steps of:
  • Example 34 The mixed homogeneous black nano-microsphere emulsion solution obtained in Example 34 was mixed with the magenta nano-microsphere emulsion solution obtained in Example 1 at a volume ratio of 1:1, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed depth. Red nanosphere emulsion solution.
  • Embodiment 35 a preparation of a dark red optically functional material having a blue-green luster, comprising the steps of:
  • Example 33 The mixed homogeneous black nano-microsphere emulsion solution obtained in Example 33 was mixed with the magenta nano-microsphere emulsion solution obtained in Example 1 at a volume ratio of 1:1, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed dark. Red nanosphere emulsion solution.
  • Embodiment 36 a dark gray optically functional material having a blue-green luster, comprising the steps of:
  • Example 33 The mixed homogeneous black nano-microsphere emulsion solution obtained in Example 33 was mixed with the gray nano-microsphere emulsion solution obtained in Example +2 at a volume ratio of 1:1, and ultrasonically dispersed for 10 minutes to obtain a uniformly mixed gray. Nano microsphere emulsion solution.
  • Embodiment 37 a preparation of a magenta optically functional material having specific ultraviolet reflection, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 165 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Magenta monodisperse polystyrene microsphere emulsion and absolute ethanol were mixed at a volume ratio of 7:2, and ultrasonically dispersed for 10 minutes to obtain a mixed homogeneous magenta nanosphere emulsion solution.
  • Embodiment 38 a magenta preparation of an optically functional material having specific infrared reflection, comprising the steps of:
  • a monodisperse polystyrene microsphere emulsion having a diameter of 365 nm was prepared by emulsion polymerization to have a solid content of 5%.
  • the specific preparation method is:
  • Magenta monodisperse polystyrene microsphere emulsion and absolute ethanol were mixed at a volume ratio of 7:2, and ultrasonically dispersed for 10 minutes to obtain a mixed homogeneous magenta nanosphere emulsion solution.
  • Embodiment 39 a preparation of a magenta optically functional material having a blue-green luster, comprising the steps of:
  • Example 1 The bright, brilliant, magenta phase, blue-green luster photonic crystal coating obtained in Example 1 was used, and the layer thickness was 5 ⁇ m.
  • Embodiment 40 a preparation of a light green optical functional material having a blue-green luster, comprising the steps of:
  • Example 1 The yellow nanosphere-emulsion solution obtained by the dyeing in Example 3 was uniformly mixed with the white emulsion microspheres obtained in Example 4 at a volume ratio of 3:1 to obtain a pale yellow emulsion microsphere solution.
  • Embodiment 41 a preparation of a light red phase optically functional material having a blue-green luster, comprising the steps of:
  • magenta dye solution to a commercially available monodisperse polyimide emulsion (polyimide microspheres with a particle size of 215nm, solid)
  • the content of 10% wt, PDI 0.2
  • absolute ethanol were compounded by volume ratio of 1:3:2, and ultrasonic dispersion was carried out for 10 minutes to obtain a uniformly mixed magenta nanosphere emulsion solution.
  • Embodiment 42 is a light red phase preparation of an optically functional material having a blue-green luster, comprising the steps of:

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Abstract

提供一种光学功能材料，所述光学功能材料包括由纳米微球周期性排布形成的纳米微球层，所述纳米微球层为密堆积结构，使光学功能材料具有光泽，纳米微球层包括无色、白色、灰色、黑色或彩色纳米微球；将光子晶体的结构色与构成光子晶体的物质的色相结合起来，通过调节二者色相的组合来获得独立于结构色之外更加丰富的色相，并将其与结构色光谱结合起来，实现光泽与色相相对独立，获得按需要随意交叉组合的色泽的特殊效果，另外还提供了一种光学功能材料的制备方法。

Description

一种具有色相和光泽的光学功能材料及其制备与应用 技术领域
本发明涉及光学功能材料，特别涉及一种色相和光泽相对独立的光学功能材料。
背景技术
丰富多样的颜色可以分成两个大类无彩色系和有彩色系。
无彩色系是指白色、黑色和由白色黑色调合形成的各种深浅不同的灰色。无彩色按照一定的变化规律，可以排成一个系列，由白色渐变到浅灰、中灰、深灰到黑色，色度学上称此为黑白系列。纯白是理想的完全反射的物体，纯黑是理想的完全吸收的物体。无彩色系的颜色只有一种基本性质——明度。它们不具备色相和纯度的性质，也就是说它们的色相与纯度在理论上都等于零。色彩的明度可用黑白度来表示，愈接近白色，明度愈高；愈接近黑色，明度愈低。白与黑做为颜料，可以调节物体色的反射率，使物体色提高明度或降低明度。
彩色是指红、橙、黄、绿、青、蓝、紫等颜色。不同明度和纯度的红橙黄绿青蓝紫色调都属于有彩色系。有彩色是由光的波长和振幅决定的，波长决定色相，振幅决定色调。有彩色系的颜色具有三个基本特性：色相、纯度(也称彩度、饱和度)、明度。在色彩学上也称为色彩的三大要素或色彩的三属性。色相是有彩色的最大特征。所谓色相是指能够比较确切地表示某种颜色色别的名称。如玫瑰红、桔黄、柠檬黄、钴蓝、群青、翠绿……从光学物理上讲，各种色相是由射入人眼的光线的光谱成分决定的。对于单色光来说，色相的面貌完全取决于该光线的波长；对于混合色光来说，则取决于各种波长光线的相对量。物体的颜色是由光源的光谱成分和物体表面反射(或透射)的特性决定的。
颜色的表现形式即为色彩，包括色素色和结构色。日常生活中所见绝大多数不发光物体色彩都是由色素色呈现的，可见波段的光照射到物体上，通过色素对不同波长的光波进行选择性吸收、反射(透射)，获得特定的反射(透射)光谱，通过人眼的观察最终在人的大脑中形成色彩的感觉。色素色符合减色混合原理，理论上只要有3种减色原色(通常为青(C,Cyan)品红(M,Magenta)黄(Y,Yellow))就可以混合出色相环中所有的色彩。
结构色(structural colour)，又称物理色(physical colour)，是一种由物质微观结构与相应波长光波发生干涉衍射作用产生的一种光泽效果。结构色与该 结构构成物质的着色色素无关，是生物体亚显微结构所导致的一种光学效果。生物体表面或表层的嵴、纹、小面和颗粒能使光发生反射或散射作用，从而产生特殊的颜色效应。例如，鸟类的羽色、蝴蝶的翅色主要是由于光的干涉现象所引起的；火鸡头颈周围皮肤呈蓝色和灵长类脸部、臀部及生殖区皮肤的蓝色，则是由于入射光中的蓝紫部分被表皮组织中的大量细小颗粒(其直径与蓝紫光波长相当)反射出来，而入射光中的红黄部分则透过这个颗粒层被真皮组织中的黑色素吸收。
由于结构色具有不褪色、环保和虹彩效应等优点，在显示、装饰、防伪等领域具有广阔的应用前景。对自然界中生物的结构色形成机理及其应用进行研究，可以促进仿生结构色加工和微纳米光学技术的发展。
光子晶体(Photonic Crystal)是在1987年由S.John和E.Yablonovitch分别独立提出，是由不同介电常数的介质周期性排列而成的人工微结构。从材料结构上看，光子晶体是一类在光学尺度上具有周期性介电结构的人工设计和制造的晶体。光子晶体的特殊周期性结构，使得其对特定波长或波段的光子具有禁阻作用，形成光子带隙，类似半导体中的电子能带，将光子晶体中的光子带隙称为光子禁带(Photonic Band-Gap,简称为PBG)。和半导体材料一样，介电常数的周期性排列产生了一定的“势场”，当两种介质的介电常数相差足够大时，在介质界面上会出现布拉格散射，产生光子带隙，能量落在带隙处的光将不能传播，将以镜面形式反射出去，从而形成结构色,这种反射反射率高，光谱单一，会给人一种明亮纯净具有禁带波长色彩的光泽效果。这也是光子晶体材料的光泽产生的来源。
现有技术中，为了有效利用结构色所具有的不褪色、环保和虹彩效应等优点，对包含光子晶体结构的光学功能材料的研究大部分都关注于凸显光子晶体的结构色的视觉效果，例如利用一些深色吸光介质，削弱光子晶体的非结构色的杂光以提高其色彩饱和度，这样形成的光学功能材料可以提供较纯净，高饱和的结构色彩光泽，由于结构色的波段单一，无法实现混色，也无法呈现谱外色，使得形成的光学功能材料呈现的色彩单一，影响其美感，限制了其实际应用。
前面已经提及，结构色彩与构成该结构材料本身的色素色无关，而结构色光谱为波段单一的镜面反射光谱，在整体反射光谱中的相对量很低，对整体材料的色相几乎没有影响，而呈现为一种纯色光泽的效果。
常规制备光子晶体的方法既有"自上而下"(top-down)的物理加工方法，也可以通过"自下而上"(bottom-up)的化学组装法，组装单分散的纳米微球成密堆积周期结构，周期结构排列的纳米微球与球之间填充介质存在折射率差异，这种存在折射率差异的周期结构就形成了"光子禁带"(Photonic Band Gap,PBG)。自组装法由于具有成本低、方法简单、不需要复杂的设备，可以通过合成过程中对纳米粒子的形态、结构的控制实现不同功能的光子晶体制备等优点。目前关于结构色的文献及专 利大都是从结构色的角度对其结构和材质进行改进，光泽与色相都与禁带波长λ直接对应，在光谱上结构色是一种单一波段的色光，其颜色纯正光泽明亮，但同时也因为其波段单一无法实现混合色相的调配。
因此，需要提供一种光学功能材料，能够通过混配呈现多种颜色，又能独立地呈现饱和纯净的光谱色光泽。
发明内容
本发明的目的在于，针对结构色的优点与不足，本发明提出光泽与颜色相互独立和光泽与色相相互独立的概念，提供一种光学功能材料。这种光学功能材料不仅利用光子晶体的结构色，还与构成光子晶体的物质材料的特性结合起来。该光学功能材料的光泽与颜色相互独立，是指光泽主要受到该材料微观纳米尺度结构的影响，而其颜色主要决定于组成该光学功能材料的物质对光的吸收，尽管在人眼的视觉效果上，光泽和颜色会相互影响，但是光泽和颜色产生的原因不同，因此，二者相互独立。该光学功能材料的光泽与色相相互独立，是指光泽主要受到该材料微观纳米尺度结构的影响，而其颜色的色相主要决定于组成该光学功能材料的物质对光的吸收，尽管在人眼的视觉效果上，光泽和色相会相互影响，但是光泽和色相产生的原因不同，因此，二者相互独立。
本发明将光子晶体的结构色与构成光子晶体的物质的颜色或色相结合起来，通过调节二者颜色或色相的组合来获得独立于结构色之外更加丰富的颜色或色相，并将其与结构色光谱结合起来，实现光泽与颜色或色相相对独立，获得按需要随意交叉组合的色泽的特殊效果。
本申请中，当光学功能材料的颜色为白、灰、黑时，光泽与颜色相互独立；当光学功能材料的颜色为具有色相的彩色时，光泽与色相相互独立。
本申请中的“彩色”指具有色相环中的任意一种色相的颜色。
本申请中的“PDI”是指乳液微球粒径的多分散指数(polydispersity index)。
为实现上述目的，本发明提供了一种光学功能材料,所述光学功能材料包括由纳米微球周期性排布形成的纳米微球层，所述纳米微球层为密堆积结构，使所述光学功能材料具有光泽；其特征在于，所述纳米微球层包括无色纳米微球、白色纳米微球、灰色纳米微球、黑色纳米微球或彩色纳米微球。
进一步地，所述纳米微球层包括多种不同颜色的纳米微球，每种纳米微球的颜色选自白色、灰色、黑色或彩色。
进一步地，所述光学功能材料是透明的、半透明的或微透明的。
进一步地，所述纳米微球层包括白色纳米微球与至少一种彩色纳米微球。
进一步地，所述纳米微球层包括具有不同色相的彩色纳米微球。
进一步地，所述纳米微球层包括白色纳米微球、黑色纳米微球和彩色纳米微球。
进一步地，所述纳米微球层包括黑色纳米微球和彩色纳米微球。
进一步地，所述纳米微球层包括灰色纳米微球和彩色纳米微球。
进一步地，所述纳米微球层包括白色纳米微球和黑色纳米微球。
进一步地，所述纳米微球层包括灰色纳米微球和黑色纳米微球。
进一步地，所述光学功能材料的光泽是波长为200～2000nm的红外光、可见光或紫外光。优选地，所述光学功能材料的光泽为波长为480～550nm、580～600nm、550～600nm或600～640nm的可见光。
进一步地，所述纳米微球间填充有填充介质。
进一步地，所述填充介质为无色、白色、灰色、黑色或彩色。
进一步地，所述填充介质可以是透明的、半透明的或微透明的。
进一步地，所述光学功能材料是透明的、半透明的或微透明的。
进一步地，所述填充介质为气体、液体或固体。
进一步地，所述填充介质含有有色物质。
进一步地，所述有色物质为染料、颜料、或树脂色母料。
进一步地，所述有色物质为甲基蓝、柠檬黄、罗丹明6G、红色丙烯酸树脂色母料、橙色环氧树脂色母料、蓝色环氧树脂色母料或绿色聚氨酯树脂色母料。
进一步地，所述液体填充介质选自硅油、矿物油、植物油和动物油脂组成的组。
进一步地，，所述固体填充介质选自二氧化硅、二氧化钛、氧化锌、炭黑、硅树脂、聚氨酯树酯、环氧树脂、丙烯酸树脂、醇酸树脂、和聚酯组成的组。
进一步地，所述纳米微球层包括彩色纳米微球，所述填充介质自身的颜色为彩色。
进一步地，所述纳米微球层包括无色纳米微球、白色纳米微球、灰色纳米微球或黑色纳米微球，所述填充介质自身的颜色为彩色。
进一步地，，所述纳米微球的原料选自聚苯乙烯、聚丙烯酸酯、聚丙烯酸、二氧化硅、氧化铝、二氧化钛、氧化锆、四氧化三铁、聚酰亚胺、硅树脂和酚醛树脂组成的组。
进一步地，所述纳米微球粒的单分散性PDI小于0.5。
进一步地，所述纳米微球粒的PDI小于0.05。
进一步地，所述纳米微球粒径为80～1100nm。
进一步地，所述纳米微球粒径为120～400nm。
进一步地，所述纳米微球层形成光子晶体。
进一步地，所述纳米微球是青色纳米微球、品红色纳米微球和黄色纳米微球中的一种或其任意组合。
进一步地，所述纳米微球层的厚度为1～50微米。
上述技术方案中，纳米微球自身色相与填充介质色相的组合，可实现光学功能材料的色相调节。通过设置纳米微球层与填充介质的周期排布的特征以及折射率来 设置所述光学功能材料的光泽，其关系遵循如下公式：
Figure PCTCN2016073732-appb-000001
其中λ为禁带波长，d为周期常数即微球粒径，nA为纳米微球折射率，nB为填充介质折射率。0.74和0.26分别是纳米微球与间隙介质在整个材料中的体积分数。
所述纳米微球可选自一种或两种以上(含两种)折射率相近的材料，所述纳米微球的材料的折射率偏差在2％以下。优选的技术方案中，所述纳米微球的折射率偏差在0.5％以下。
上述技术方案中，所述纳米微球的材料选自：聚苯乙烯、聚丙烯酸酯、聚丙烯酸、二氧化硅、氧化铝、二氧化钛、氧化锆、四氧化三铁、聚酰亚胺、硅树脂或酚醛树酯中的一种或一种以上的混合物。
上述技术方案中，所述填充介质为液体填充介质、固体填充介质、内部设有有色物质的液体填充介质、内部设有有色物质的固体填充介质中的一种或二者的混合。所述液体填充介质选自：硅油、矿物油、植物油或动物油脂的一种或一种以上混合液体。所述固体填充介质选自：二氧化硅、二氧化钛、氧化锌、炭黑、硅树脂、聚氨酯树脂、环氧树脂、丙烯酸树脂、醇酸树脂、聚酯。
另一方面，本发明提供了一种光学功能材料,所述光学功能材料包括由纳米微球周期性排布形成的纳米微球层，所述纳米微球层为密堆积结构，使所述光学功能材料具有光泽；其特征在于，所述纳米微球层包括白色、灰色、黑色或彩色纳米微球；所述纳米微球的颜色是纳米微球自身的颜色或通过着色形成的。
进一步地，所述着色是在自组装之前进行的。
进一步地，所述着色是在自组装过程中进行的。
进一步地，所述着色是在自组装之后进行的。
另一方面，本发明提供了一种光学功能材料的制备方法，包括以下步骤：
(1)将纳米微球分散于连续相中，形成纳米微球胶体分散系；
(2)外力作用下，纳米微球胶体分散系在相界面处自组装形成周期性紧密排布结构；
(3)根据需要去除部分或全部连续相；
进一步地，步骤(1)中的纳米微球是经过着色的纳米微球。优选地，形成纳米微球胶体分散系后，在纳米微球胶体分散系中加入着色剂对纳米微球进行着色。
进一步地，去除连续相后在纳米微球层的纳米微球间填充填充介质。
优选地，步骤(2)中所述的相界面处包括气固界面、气液界面、固固界面或 液液界面。
优选地，步骤(2)中所述的外力作用包括毛细管力、静电力、磁力、重力、范德华力或氢键。
上述技术方案中，填充介质可以加入纳米微球乳液在去除连续相过程中与纳米微球共组装，也可在纳米微球组装成周期性紧密排布结构后填充进入纳米微球间隙。
上述技术方案中，纳米微球周期性紧密排布结构通过纳米微球乳液自组装构筑，即将纳米微球分散于另一连续相中，选择分散非溶剂性填充介质，辅以一定助剂，形成纳米微球乳液。连续相通过相应技术手段去除，在该过程中纳米微球及相关助剂发生共组装形成周期性紧密排布结构。
上述技术方案中，纳米微球乳液连续相质可以选自但不限于：水，甲醇，乙醇，乙二醇，环己烷中的一种或一种以上的组合。纳米微球乳液中纳米微球含量0.5～60％wt，非溶剂填充介质含量0～35％wt，助剂含量0～20％wt。
上述技术方案中，纳米微球乳液助剂用于调变连续相的流变性能，挥发性能，成膜性能等参数，所述纳米微球乳液助剂可以选自但不限于：纤维素，丙烯酸乳液，表面活性剂，环氧树脂，聚氨酯树脂等。
一种具有光泽和色相的光学功能材料，其光泽主要通过存在折射率差的呈周期性紧密排布纳米微球及填充介质形成的光子晶体禁带呈现，通过调节纳米微球尺寸及纳米微球与填充介质的折射率差，其光泽的呈现范围囊括全可见光谱，并可向紫外、红外区延展。
本发明的光学功能材料可以用于制备油墨色浆、颜料色粉、薄膜涂层。
本发明的光学功能材料可以以油墨色浆、颜料色粉或薄膜涂层的形式应用在制备于涂料、印刷油墨、包装涂层、日化美妆、防伪材料、传感器件、光学元件中。
由于上述技术方案的应用，本发明和现有技术相比具有以下优点：
本发明所述具有光泽和色相的光学功能材料光泽可以通过对光子晶体的带隙的调控在红外可见乃至紫外范围内随意调节，而色相可以通过设置纳米粒子与填充介质色相的组合实现色相环的所有的色相。达到光泽与色相相对独立的效果，实现如红色相泛绿光，蓝色相泛金光等特殊色泽效果，且光泽可随视角改变而变换，产生彩虹色变幻效果。亦可在特定角度反射特定波长，肉眼不可见的红外紫外辐射， 从而实现的防伪、传感等特殊应用。
以下将结合附图对本发明的构思、具体结构及产生的技术效果作进一步说明，以充分地了解本发明的目的、特征和效果。
附图说明
附图1为实施例1中聚苯乙烯乳液微球组装后SEM照片；
附图2为实施例1中聚苯乙烯乳液微球组装的反射光谱，对应其光泽；
附图3为实施例1中聚苯乙烯乳液微球组装后的吸收光谱，对应其色相；
附图4为实施例中的分光光度仪测量光路：1、被测样品；2、光源，入射角45°；3、镜面反射光路；4、测量光路45as-15，与镜面反射光路呈-15°；5、测量光路45as15，与镜面反射光路呈15°；6、测量光路45as25，与镜面反射光路呈25°；测量光路45as45，与镜面反射光路呈45°；8、测量光路45as75，与镜面反射光路呈75°；9、测量光路45as110，与镜面反射光路呈110°。
附图5，实施例23中聚苯乙烯乳液微球组装后SEM照片；
附图6，实施例24中聚苯乙烯乳液微球组装的反射光谱，对应其光泽；
附图7，实施例24中聚苯乙烯乳液微球组装后的吸收光谱，对应其色相；
具体实施方式
实施例1，一种品红色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为215nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.58g十二烷基硫酸钠，0.2g罗丹明6G溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径215nm，PDI＝0.02。
②品红色单分散聚苯乙烯微球乳液及无水乙醇按体积比7:2复配， 超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml步骤②所得均匀的品红色纳米微球乳液溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表1所示。
表1
测试角度 L* a* b*
45as-15 138.84 27.02 -39.71
45as15 53.26 53.02 -14.78
45as25 51.56 52.04 -9.38
45as45 50.35 51.62 -1.87
45as75 53.94 48.92 0.23
45as110 51.03 43.41 -1.08
实施例2，一种青色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为215nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.58g十二烷基硫酸钠溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径215nm，PDI＝0.02。
②称取0.18g酸性蓝5，溶于20ml去离子水中，超声溶解20分钟；将蓝色染料溶液与单分散聚苯乙烯微球乳液及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的青色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品青色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表2所示。
表2
测试角度 L* a* b*
45as-15 51.38 3.44 -45.60
45as15 127.46 4.57 -53.06
45as25 83.07 1.93 -53.79
45as45 51.35 1.64 -59.23
45as75 52.89 5.91 -51.94
45as110 56.51 -8.56 -53.53
实施例3，一种黄色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为215nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.58g十二烷基硫酸钠溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径215nm，PDI＝0.02。
②称取0.30g酸性黄9，溶于20ml去离子水中，超声溶解20分钟；将黄色染料溶液与单分散聚苯乙烯微球乳液及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的黄色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品黄色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表3所示。
表3
测试角度 L* a* b*
45as-15 114.92 -14.80 58.19
45as15 87.48 1.25 37.64
45as25 86.85 1.25 36.90
45as45 89.09 1.89 37.163
45as75 92.88 3.11 36.43
45as110 93.19 5.78 34.35
实施例4，一种白色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为215nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.58g十二烷基硫酸钠溶于90ml去离子水，于250ml三口烧 瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径215nm，PDI＝0.02。
②将蒸馏水，单分散聚苯乙烯微球乳液及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的白色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品白色，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表4所示。
表4
测试角度 L* a* b*
45as-15 130.70 11.04 -29.56
45as15 96.46 6.27 -14.64
45as25 91.54 2.34 0.12
45as45 92.49 0.86 8.41
45as75 96.88 -3.69 12.16
45as110 96.55 -4.21 8.08
实施例5，一种橙色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例1中得到的混合均匀的品红色纳米微球乳液溶液与实施例3中得到的混合均匀的黄色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的橙色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现橙色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表5所示。
表5
测试角度 L* a* b*
45as-15 128.10 -39.78 51.48
45as15 112.94 -9.48 60.71
45as25 85.03 13.56 37.23
45as45 63.94 34.60 13.23
45as75 66.55 40.47 11.14
45as110 68.71 42.23 10.14
实施例6，一种绿色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例2中得到的混合均匀的青色纳米微球乳液溶液与实施例3中得到的混合均匀的黄色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的绿色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表6所示。
表6
测试角度 L* a* b*
45as-15 69.18 6.35 -36.63
45as15 97.66 8.77 -58.82
45as25 59.45 -4.87 -42.90
45as45 50.71 0.86 8.41
45as75 54.38 -27.49 -15.93
45as110 57.07 -29.95 -15.88
实施例7，一种橙红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例1中得到的混合均匀的品红色纳米微球乳液溶液与实施例4中得到的混合均匀的黄色纳米微球乳液溶液安体积比3:1复配，超声分散10分钟，得到混合均匀的橙红色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现橙红色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表7所示。
表7
测试角度 L* a* b*
45as-15 128.10 -39.78 51.48
45as15 112.94 -9.48 60.71
45as25 85.03 13.56 37.23
45as45 63.94 34.60 13.23
45as75 66.55 40.47 11.14
45as110 68.71 42.23 10.14
实施例8，一种紫红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例1中得到的混合均匀的品红色纳米微球乳液溶液与实施例2中得到的混合均匀的青色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的橙红色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表8所示。
表8
测试角度 L* a* b*
45as-15 96.71 16.97 -41.59
45as15 99.37 25.08 -70.85
45as25 61.03 18.19 -55.42
45as45 40.49 10.42 -40.69
45as75 42.72 3.24 -31.90
45as110 44.73 1.85 -32.20
实施例9，一种浅红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例1中得到的混合均匀的品红色纳米微球乳液溶液与实施例4中得到的混合均匀的白色纳米微球乳液溶液安体积比2:1复配，超声分散10分钟，得到混合均匀的浅红色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现浅红色相，蓝绿光泽的光子晶体涂层，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如附图4所示，数据如表9所示。
表9
测试角度 L* a* b*
45as-15 153.81 27.22 -39.80
45as15 73.26 53.54 -14.78
45as25 71.56 52.64 -9.68
45as45 70.35 51.62 -2.04
45as75 74.67 49.17 0.43
45as110 71.03 42.41 -1.78
实施例10，一种黄色相的具有橙红色光泽的光学功能材料的制备，包括以下步骤：
①称取0.30g酸性黄9，溶于20ml去离子水中，超声溶解20分钟；将黄色染料溶液与市售单分散聚苯乙烯微球乳液(251nm，固含量10％wt,PDI＝0.1
)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的黄色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现黄色相，橙红光泽的光子晶体涂层，层厚8微米。
实施例11，一种品红色的具有橙红色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为252nm的单分散聚苯乙烯微球乳液，固含量为10％。具体制备方法为:
a.称取0.5g十二烷基硫酸钠溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入10.5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应8小时，所得聚苯乙烯纳米微球粒径252nm，PDI＝0.01。
②称取0.4g酸性红36，溶于20ml去离子水中，超声溶解20分钟；将红色染料溶液与单分散聚苯乙烯微球乳液及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相，橙红光泽的光子晶体涂层，层厚8微米。
实施例12，一种橙黄色相的具有橙红色光泽的光学功能材料的制备，包括以下步骤：
①取实施例10中得到的混合均匀的黄色纳米微球乳液溶液与实施例11中得到的混合均匀的品红色纳米微球乳液溶液安体积比2:1复配， 超声分散10分钟，得到混合均匀的橙黄色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现橙黄相，橙红光泽的光子晶体涂层，层厚8微米。
实施例13，一种浅红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①称取0.20g碱性品红14，溶于20ml去离子水中，超声溶解20分钟；将品红色染料溶液与市售单分散二氧化硅球乳液(195nm，固含量10％wt,PDI＝0.2)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相，蓝绿光泽的光子晶体涂层，层厚5微米。
实施例14，一种蓝色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①称取0.10g亚甲基蓝，溶于20ml去离子水中，超声溶解20分钟；将亚甲基蓝染料溶液与市售单分散二氧化硅球乳液(195nm，固含量10％wt,PDI＝0.2)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的蓝色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品蓝色相，蓝绿光泽的光子晶体涂层，层厚5微米。
实施例15，一种紫红相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例13中得到的混合均匀的品红纳米微球乳液溶液与实施例14中得到的混合均匀的蓝色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的紫红色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，蓝绿光泽的光子晶体涂层，层厚5微米。
实施例16，一种紫红相的具有黄绿光泽的光学功能材料的制备，包 括以下步骤：
①称取0.1g酸性红60及0.1g酸性蓝5溶于20ml去离子水中，超声溶解20分钟，将混合燃料溶液与市售单分散聚苯乙烯/聚丙烯酸/聚甲基丙烯酸甲酯共聚乳液微球(235nm，固含量10％wt,PDI＝0.2)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的紫红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，黄绿光泽的光子晶体涂层，层厚6微米。
实施例17，一种紫红相的具有红色光泽的光学功能材料的制备，包括以下步骤：
①称取0.1g碱性红14及0.05g亚甲基蓝溶于20ml去离子水中，超声溶解20分钟，将混合燃料溶液与市售单分散四氧化三铁乳液微球(185nm，固含量6％wt,PDI＝0.3)及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的紫红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，红色光泽的光子晶体涂层，层厚6微米。
实施例18，一种紫红相的具有橙红光泽的光学功能材料的制备，包括以下步骤：
①称取0.1g碱性红14及0.05g亚甲基蓝溶于20ml去离子水中，超声溶解20分钟，将混合燃料溶液与市售单分散氧化铝铁乳液微球(195nm，固含量6％wt,PDI＝0.33)及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的紫红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，橙红光泽的光子晶体涂层，层厚6微米。
实施例19，一种紫红相的具有金红光泽的光学功能材料的制备，包括以下步骤：
①称取0.1g碱性红14及0.05g亚甲基蓝溶于20ml去离子水中，超声溶解20分钟，将混合燃料溶液与市售单分散氧化锆乳液微球(178nm，固含量6％wt,PDI＝0.28)及无水乙醇按体积比1:6:2复配，超 声分散10分钟，得到混合均匀的紫红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红色相，金红光泽的光子晶体涂层，层厚6微米。
实施例20，一种蓝色相的具有金红光泽的光学功能材料的制备，包括以下步骤：
①称取0.5g亚甲基蓝溶于20ml去离子水中，超声溶解20分钟，将混合燃料溶液与市售单分散二氧化钛乳液微球(183nm，固含量6％wt,PDI＝0.28)及无水乙醇按体积比1:6:2复配，超声分散10分钟，得到混合均匀的蓝色相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现蓝色相，金红光泽的光子晶体涂层，层厚6微米。
实施例21，一种红褐色相的具有紫红光泽的光学功能材料的制备，包括以下步骤：
①将市售单分散酚醛树酯乳液微球(270nm，固含量2％wt,PDI＝0.4)及无水乙醇按体积比6:1复配，超声分散10分钟，得到混合均匀的红褐相纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现红褐色相，紫红光泽的光子晶体涂层，层厚4微米。
实施例22，一种黄色相的具有橙红色光泽的光学功能材料的制备，包括以下步骤：
①称取0.30g酸性黄9，溶于20ml去离子水中，超声溶解20分钟；将黄色染料溶液与市售单分散聚苯乙烯微球乳液(251nm，固含量10％wt,PDI＝0.1
)及乙二醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的黄色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将6ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现黄色相，橙红光泽的光子晶体涂层，层厚40微米。
实施例23，一种黄色相的具有橙红色光泽的光学功能材料的制备，包括以下步骤：
①称取0.30g酸性黄9，溶于20ml去离子水中，超声溶解20分钟；将黄色染料溶液与市售单分散聚苯乙烯微球乳液(251nm，固含量10％wt,PDI＝0.1
)及丙酮按体积比1:3:2复配，超声分散10分钟，得到混合均匀的黄色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将0.3ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现黄色相，橙红光泽的光子晶体涂层，层厚2微米。
实施例23，一种红色相具有青绿色光泽的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为210nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.58g十二烷基硫酸钠溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径210nm，PDI＝0.002。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml步骤①所得苯乙烯微球乳液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现蓝绿光泽的光子晶体涂层
③称取0.18g罗丹明6G，溶于20ml聚氨酯树酯中，搅拌分散；将红色树酯滴在光子晶体涂层上后渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出红色相带有蓝绿色光泽的功能薄膜，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如图4所示，数据如表10所示。
表10
测试角度 L* a* b*
45as-15 51.58 3.24 -45.63
45as15 127.46 4.57 -53.16
45as25 83.17 1.96 -53.79
45as45 51.25 1.64 -59.23
45as75 52.89 5.93 -51.94
45as110 56.53 -8.57 -53.52
实施例24，一种紫色相的具有红色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的聚苯乙烯单分散微球(粒径280nm，PDI<0.005)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现红色光泽的光子晶体涂层，
称取0.18g甲基蓝，溶于20ml聚氨酯树脂中，搅拌分散；利用涂布机将蓝色树酯涂布在光子晶体涂层上后渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出紫色色相，带有红色光泽的功能薄膜，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如图4所示，数据如表11所示。
测试角度 L* a* b*
45as-15 96.71 16.97 -41.59
45as15 99.37 25.08 -70.85
45as25 61.03 18.19 -55.42
45as45 40.49 10.42 -40.69
45as75 42.72 3.24 -31.90
45as110 44.73 1.85 -32.20
表11
实施例25，一种黄色相具有绿色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的二氧化硅单分散微球(粒径192nm，PDI<0.005)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色光泽的光子晶体涂层，
称取0.18g柠檬黄，溶于20ml硅树脂中，搅拌分散；利用喷涂设备将黄色树脂涂布在光子晶体涂层上后渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出黄色色相，带有绿色光泽的功能薄膜，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如图4所示，数据如表12所示。
测试角度 L* a* b*
45as-15 114.92 -14.80 58.19
45as15 87.48 1.25 37.64
45as25 86.85 1.25 36.90
45as45 89.09 1.89 37.163
45as75 92.88 3.11 36.43
45as110 93.19 5.78 34.35
表12
实施例26，一种橙黄色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的聚苯乙烯单分散微球(粒径170nm，PDI<0.005)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色光泽的光子晶体涂层，
称取0.18g柠檬黄，0.2g罗丹明6G，溶于20ml正硅酸乙酯的乙醇溶液中，搅拌分散；利用喷涂设备将橙黄色树脂涂布在光子晶体涂层上后渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出橙黄色相，带有绿色光泽的功能薄膜，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光路图如图4所示，数据如表13所示。
测试角度 L* a* b*
45as-15 128.10 -39.78 51.48
45as15 112.94 -9.48 60.71
45as25 85.03 13.56 37.23
45as45 63.94 34.60 13.23
45as75 66.55 40.47 11.14
45as110 68.71 42.23 10.14
表13
实施例27，一种红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的聚氧化锆单分散微球(粒径70nm，PDI<0.005)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色光泽的光子晶体涂层。
称取1g红色丙烯酸树脂色母料分散于8g丙烯酸树脂，分散均匀；利用涂布机将红色树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出红色相，带有蓝绿色光泽的功能薄膜，层厚5微米。其色泽参数通过艾丽色MA-98分光光度仪测定，光源为D65/10°测量光 路图如图4所示，数据如表14所示。
测试角度 L* a* b*
45as-15 153.81 27.22 -39.80
45as15 73.26 53.54 -14.78
45as25 71.56 52.64 -9.68
45as45 70.35 51.62 -2.04
45as75 74.67 49.17 0.43
45as110 71.03 42.41 -1.78
表14
实施例28，一种橙色具有绿色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的单分散氧化铝微球(粒径142nm，PDI<0.1)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色光泽的光子晶体涂层。
称取1g橙色环氧树脂色母料分散于10g环氧树脂，分散均匀；利用涂布机将橙色树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出橙色相，带有绿色光泽的功能薄膜，层厚5微米。
实施例29，一种蓝紫色相具有紫红光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的单分散酚醛树脂微球(粒径275nm，PDI<0.1)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将5ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现紫红光泽的光子晶体涂层。
称取1g蓝色环氧树脂色母料分散于10g环氧树脂，分散均匀；利用涂布机将蓝色树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出蓝紫色相，带有紫红光泽的功能薄膜，层厚20微米。
实施例30，一种绿色相具有金红光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的单分散二氧化钛微球(粒径135nm，PDI<0.2)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将0.5ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现金红光泽的光子晶体涂层。
称取0.2g绿色环氧树脂色母料分散于3g环氧树脂，分散均匀；利用涂布机将绿色树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为 一层均匀填充的涂层，呈现出绿色相，带有金红光泽的功能薄膜，层厚2微米。
实施例31，一种暗绿色相具有红色光泽的光学功能材料的制备，包括以下步骤：
取市售的固含量为5％的单分散四氧化三铁微球(粒径140nm，PDI<0.2)，将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将0.5ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现红色光泽的光子晶体涂层。
称取0.2g绿色聚氨酯树脂色母料分散于3g环氧树脂，分散均匀；利用涂布机将绿色树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出暗绿色相，带有金红光泽的功能薄膜，层厚2微米。
实施例32，一种橙色具有绿色光泽的光学功能材料的制备，包括以下步骤：取市售的固含量为5％的单分散荧光素聚苯乙烯微球(粒径172nm，PDI<0.005)，将清洗干净的玻璃片2.5cmX2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现绿色光泽的光子晶体涂层。
称取1g红色环氧树脂色母料分散于10g环氧树脂，分散均匀；利用涂布机将品红树脂涂布在光子晶体涂层上后，渗入微球间隙内，溶剂挥发干后成为一层均匀填充的涂层，呈现出橙色相，带有绿色光泽的功能薄膜，层厚5微米。其色泽参数可通过艾丽色MA-98分光光度仪测定。
实施例33，一种黑色具有蓝绿色光泽的光学功能材料的制备，包括以下步骤
①取实施例1中得到的混合均匀的品红色纳米微球乳液溶液、实施例2中得到的混合均匀的青色纳米微球乳液溶液与实施例3中得到的混合均匀的黄色纳米微球乳液溶液安体积比1:1.7：0.8复配，超声分散10分钟，得到混合均匀的黑色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层黑色呈现蓝绿光泽的光子晶体涂层，层厚5微米。
实施例34，一种灰色具有蓝绿色光泽的光学功能材料的制备，包括以下步骤:
①取实施例32中得到的混合均匀的黑色纳米微球乳液溶液与实施例4中得到的白色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的灰色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待 温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层灰色呈现蓝绿光泽的光子晶体涂层，层厚5微米。
实施例35，一种深红色具有蓝绿色光泽的光学功能材料的制备，包括以下步骤:
①取实施例34中得到的混合均匀的黑色纳米微球乳液溶液与实施例1中得到的品红色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的深红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层深红色呈现蓝绿光泽的光子晶体涂层，层厚5微米。
实施例35，一种暗红色具有蓝绿色光泽的光学功能材料的制备，包括以下步骤:
①取实施例33中得到的混合均匀的黑色纳米微球乳液溶液与实施例1中得到的品红色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的暗红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层暗红色呈现蓝绿光泽的光子晶体涂层，层厚5微米。
实施例36，一种深灰色具有蓝绿色光泽的光学功能材料的制备，包括以下步骤:
①取实施例33中得到的混合均匀的黑色纳米微球乳液溶液与实施例+2中得到的灰色纳米微球乳液溶液安体积比1:1复配，超声分散10分钟，得到混合均匀的灰色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层深灰色呈现蓝绿光泽的光子晶体涂层，层厚5微米。
实施例37，一种品红色的具有特异紫外反射的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为165nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.98g十二烷基硫酸钠，0.2g罗丹明6G溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径165nm，PDI＝0.03。
②品红色单分散聚苯乙烯微球乳液及无水乙醇按体积比7:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml步骤②所得均匀的品红色纳米微球乳液溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相光子晶体涂层，层厚5微米。通过光纤光谱测定其禁带处在近紫外区，峰值280nm。
实施例38，一种品红色的具有特异红外反射的光学功能材料的制备，包括以下步骤：
①通过乳液聚合的方法，制备直径为365nm的单分散聚苯乙烯微球乳液，固含量为5％。具体制备方法为:
a.称取0.28g十二烷基硫酸钠，0.2g罗丹明6G溶于90ml去离子水，于250ml三口烧瓶中300r/min搅拌，通入氮气鼓泡30min；
b.水浴加热至85℃稳定后,加入5g苯乙烯单体；
c.15min后，加入0.10g过硫酸钾，在搅拌、氮气保护下85℃反应5小时，所得聚苯乙烯纳米微球粒径365nm，PDI＝0.015。
②品红色单分散聚苯乙烯微球乳液及无水乙醇按体积比7:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
④将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml步骤②所得均匀的品红色纳米微球乳液溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相光子晶体涂层，层厚5微米。通过光纤光谱测定其禁带处在红外区，峰值1100nm。
实施例39，一种紫红色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例1中所得的鲜亮、艳丽呈现品红色相，蓝绿光泽的光子晶体涂层，层厚5微米。
②再称取0.1亚甲基蓝，溶于20ml聚氨酯树脂中，搅拌分散；将蓝色色树脂滴在光子晶体涂层上后渗入微球间隙内，溶剂挥发树脂固化后干后成为一层均匀填充的涂层，呈现出紫红色相带有蓝绿色光泽的功能薄膜，层厚5微米。
实施例40，一种浅绿色的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①取实施例3中染色所得到混合均匀的黄色纳米微球乳液溶液与实施例4中所得到的白色乳液微球荣亚按体积比3:1复配，获得浅黄色的乳液微球溶液。
②再称取0.1亚甲基蓝，溶于20ml水性聚氨酯树脂中，搅拌分散；将此蓝色树脂与上述步骤所得的浅黄色乳液微球荣亚按体积比2:8复配，搅拌分散，超声30分钟，得到粘稠的浅绿色将乳液。
③将清洗干净的玻璃片2.5cm×2.5cm放置于95℃的热载体上；待温度稳定后，将1ml混合乳液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现浅绿色相，蓝绿光泽的光子晶体涂层，层厚5微米。
实施例41，一种浅红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①称取0.20g碱性品红14，溶于20ml去离子水中，超声溶解20分钟；将品红色染料溶液与市售单分散聚酰亚胺乳液(聚酰亚胺微球粒径215nm，固含量10％wt,PDI＝0.2)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于75℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相，蓝绿光泽的光子晶体涂层，层厚5微米。
实施例42，一种浅红色相的具有蓝绿色光泽的光学功能材料的制备，包括以下步骤：
①称取0.20g酸性红14，溶于20ml去离子水中，超声溶解20分钟；将品红色染料溶液与市售单分散硅树脂乳液(硅树脂微球粒径225nm，固含量10％wt,PDI＝0.18)及无水乙醇按体积比1:3:2复配，超声分散10分钟，得到混合均匀的品红色纳米微球乳液溶液。
②将清洗干净的玻璃片2.5cm×2.5cm放置于85℃的热载体上；待温度稳定后，将1ml混合溶液滴加到玻璃片上铺展均匀；溶剂挥发后玻璃的表面会形成一层鲜亮、艳丽呈现品红色相，蓝绿光泽的光子晶体涂层，层厚5微米。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。

Claims (42)

  1. 一种光学功能材料,所述光学功能材料包括由纳米微球周期性排布形成的纳米微球层，所述纳米微球层为密堆积结构，使所述光学功能材料具有光泽；其特征在于，所述纳米微球层包括无色纳米微球、白色纳米微球、灰色纳米微球、黑色纳米微球或彩色纳米微球。
  2. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括多种不同颜色的纳米微球，每种纳米微球的颜色选自白色、灰色、黑色或彩色。
  3. 如权利要求1所述的光学功能材料，其特征在于，所述光学功能材料是透明的、半透明的或微透明的。
  4. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括白色纳米微球与至少一种彩色纳米微球。
  5. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括具有不同色相的彩色纳米微球。
  6. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括白色纳米微球、黑色纳米微球和彩色纳米微球。
  7. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括黑色纳米微球和彩色纳米微球。
  8. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括灰色纳米微球和彩色纳米微球。
  9. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括白色纳米微球和黑色纳米微球。
  10. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层包括灰色纳米微球和黑色纳米微球。
  11. 如权利要求1所述的光学功能材料，其特征在于，所述光学功能材料的光泽是波长为200～2000nm的红外光、可见光或紫外光。
  12. 如权利要求11所述的光学功能材料，其特征在于，所述光学功能材料的光泽为波长为480～550nm、580～600nm、550～600nm或600～640nm的可见光。
  13. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球间填充有填充介质。
  14. 如权利要求13所述的光学功能材料，其特征在于，所述填充介质为无色、白色、灰色、黑色或彩色。
  15. 如权利要求13所述的光学功能材料，其特征在于，所述光学功能材料是透明的、半透明的或微透明的。
  16. 如权利要求13所述的光学功能材料，其特征在于，所述填充介质为气体、 液体或固体。
  17. 如权利要求13所述的光学功能材料，其特征在于，所述填充介质含有有色物质。
  18. 如权利要求17所述的光学功能材料，其特征在于，所述有色物质为染料、颜料、或树脂色母料。
  19. 如权利要求18所述的光学功能材料，其特征在于，所述有色物质为甲基蓝、柠檬黄、罗丹明6G、红色丙烯酸树脂色母料、橙色环氧树脂色母料、蓝色环氧树脂色母料或绿色聚氨酯树脂色母料。
  20. 如权利要求16所述的光学功能材料，其特征在于，所述液体填充介质选自硅油、矿物油、植物油和动物油脂组成的组。
  21. 如权利要求16所述的光学功能材料，其特征在于，所述固体填充介质选自二氧化硅、二氧化钛、氧化锌、炭黑、硅树脂、聚氨酯树脂、环氧树脂、丙烯酸树脂、醇酸树脂和聚酯组成的组。
  22. 如权利要求13所述的光学功能材料，其特征在于，所述纳米微球层包括彩色纳米微球，所述填充介质自身的颜色为彩色。
  23. 如权利要求13所述的光学功能材料，其特征在于，所述纳米微球层包括无色纳米微球、白色纳米微球、灰色纳米微球或黑色纳米微球，所述填充介质自身的颜色为彩色。
  24. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球的原料选自聚苯乙烯、聚丙烯酸酯、聚丙烯酸、二氧化硅、氧化铝、二氧化钛、氧化锆、聚酰亚胺、硅树脂、四氧化三铁和酚醛树脂组成的组。
  25. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球粒的单分散性PDI小于0.5。
  26. 如权利要求25所述的光学功能材料，其特征在于，所述纳米微球粒的PDI小于0.05。
  27. 如权利要求26所述的光学功能材料，其特征在于，所述纳米微球粒径为80～1100nm。
  28. 如权利要求27所述的光学功能材料，其特征在于，所述纳米微球粒径为120～400nm。
  29. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球层形成光子晶体。
  30. 如权利要求1所述的光学功能材料，其特征在于，所述纳米微球是青色纳米微球、品红色纳米微球和黄色纳米微球中的一种或其任意组合。
  31. 一种光学功能材料,所述光学功能材料包括由纳米微球周期性排布形成的纳米微球层，所述纳米微球层为密堆积结构，使所述光学功能材料具有光泽； 其特征在于，所述纳米微球层包括白色、灰色、黑色或彩色纳米微球；所述纳米微球的颜色是纳米微球自身的颜色或通过着色形成的。
  32. 如权利要求31所述的光学功能材料,所述着色是在自组装之前进行的。
  33. 如权利要求31所述的光学功能材料,所述着色是在自组装过程中进行的。
  34. 如权利要求31所述的光学功能材料,所述着色是在自组装之后进行的。
  35. 一种光学功能材料的制备方法，包括以下步骤：
    (1)将纳米微球分散于连续相中，形成纳米微球胶体分散系；
    (2)外力作用下，纳米微球胶体分散系在相界面处自组装形成周期性紧密排布结构；
    (3)根据需要去除部分或全部连续相；
  36. 如权利要求35所述的制备方法，其特征在于，步骤(1)中的纳米微球是经过着色的纳米微球。
  37. 如权利要求35所述的制备方法，其特征在于，形成纳米微球胶体分散系后，在纳米微球胶体分散系中加入着色剂对纳米微球进行着色。
  38. 如权利要求35所述的制备方法，其特征在于，去除连续相后在纳米微球层的纳米微球间填充填充介质。
  39. 如权利要求35所述的制备方法，步骤(2)中所述的相界面处包括气固界面、气液界面、固固界面或液液界面。
  40. 如权利要求35所述的制备方法，步骤(2)中所述的外力作用包括毛细管力、静电力、磁力、重力、范德华力或氢键。
  41. 如权利要求1所述的光学功能材料在制备油墨色浆、颜料色粉、薄膜涂层中的应用。
  42. 如权利要求1所述的光学功能材料以油墨色浆、颜料色粉或薄膜涂层的形式在制备于涂料、印刷油墨、包装涂层、日化美妆、防伪材料、传感器件、光学元件中的应用。
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