WO2021017631A1 - 一种结构稳定的复合结构生色材料及其制备方法 - Google Patents

一种结构稳定的复合结构生色材料及其制备方法 Download PDF

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WO2021017631A1
WO2021017631A1 PCT/CN2020/094112 CN2020094112W WO2021017631A1 WO 2021017631 A1 WO2021017631 A1 WO 2021017631A1 CN 2020094112 W CN2020094112 W CN 2020094112W WO 2021017631 A1 WO2021017631 A1 WO 2021017631A1
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micro
thermoplastic polymer
microspheres
layer
composite structure
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PCT/CN2020/094112
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English (en)
French (fr)
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唐炳涛
孟繁涛
武素丽
张淑芬
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大连理工大学
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Priority to US17/631,267 priority Critical patent/US11964461B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0076—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised in that the layers are not bonded on the totality of their surfaces
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2255/20—Inorganic coating
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
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    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/06—PVC, i.e. polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes

Definitions

  • the invention relates to a chromogenic material with a stable structure and a composite structure and a preparation method thereof, belonging to the field of new material preparation.
  • Chemical dyeing pollution is the main source of industrial pollution.
  • the dyeing and finishing process may produce a large amount of polluted wastewater and toxic substances, which will seriously affect the ecological environment. At the same time, due to environmental factors, this chemical color may gradually fade or disappear.
  • structural color is considered to be another alternative coloring method, which comes from the interaction of visible light and microscopic physical structure.
  • the structural colors are divided into iridescent and non-iridescent colors.
  • the photonic crystal is a periodic ordered dielectric structure with photonic band gap characteristics. When the photonic band gap is in the visible wavelength range, the photonic crystal can exhibit iridescent colors. Non-iridescent colors can be exhibited by an amorphous photonic structure with a characteristic size on the order of the wavelength of visible light, and its microstructure units are arranged in short-range order and long-range disorder.
  • the current artificially constructed structural chromogenic materials, the colloidal microsphere array has no external protection, and the structural stability is poor, which limits its wide application. Therefore, the study of structurally stable chromogenic materials is of great significance.
  • the purpose of the present invention is to provide a composite structure chromogenic material with stable structure and a preparation method thereof.
  • a structurally stable composite structure chromogenic material the material is obtained by layering a transparent thermoplastic polymer and a structural chromogenic material and thermally bonding the peripheral edges of the polymer into a whole.
  • the upper surface layer and the lower surface of the material are all thermoplastic polymers.
  • the structurally stable composite structure chromogenic material of the present invention is formed by stacking a polymer and a structural chromogenic material layer by layer from bottom to top.
  • the structure fixes the structural chromogenic material between the continuous polymer layers on both sides, and the structure is stable.
  • the number of layers of the composite structure chromogenic material of the present invention can be selected and combined according to the effect requirements such as required colors, patterns, etc. There is no special restriction in principle.
  • the composite structure chromogenic material of the present invention is obtained by superposing a polymer layer and a structural color layer, at least 3 layers, that is, two polymer layers sandwiching an intermediate structural color layer. When superimposing, the structural color layer and the polymer layer are superimposed in order upwards to ensure that each structural color layer is sandwiched by two polymer layers.
  • the total number of layers of the composite structure chromogenic material is 3-15 layers.
  • the structural chromogenic material is a layer film composed of micro-nano spheres, and the layer film is composed of an orderly or disorderly stack of micro-nano spheres.
  • the micro-nano spheres are arranged and stacked between the polymer layers on both sides to form a single-layer arrangement or a multilayer stack structure. The arrangement and stacking can be ordered or disordered.
  • the structural chromogenic material includes micro-nanospheres, and may also include a binder and/or black pigment.
  • the co-assembly of micro-nanospheres and binders can further enhance the structural stability; adding black pigments can further enhance the saturation of the structural colors.
  • the mass fraction of the binder in the emulsion of micro-nanospheres is 0-20%.
  • the binder is dopamine and its derivatives, gum arabic, natural gum, natural rubber, polyurethane, polyurea, polyacrylate, phenolic resin, epoxy resin, polyvinyl alcohol One or more of them.
  • the micro-nanospheres are inorganic microspheres or heat-resistant organic microspheres.
  • the heat-resistant organic microspheres of the present invention are organic microspheres whose glass transition temperature is higher than the glass transition temperature of the thermoplastic polymer.
  • the micro-nano spheres are solid or hollow micro-nano spheres.
  • the diameter of the micro-nanospheres is 10-1000 nm.
  • the structural chromogenic material is a layer film composed of micro-nano spheres, which is composed of orderly or disorderly stacking of micro-nano spheres; the micro-nano spheres are inorganic microspheres or heat-resistant organic microspheres, and The diameter of the micro-nano spheres is 10-1000 nm, and the micro-nano spheres are solid or hollow micro-nano spheres.
  • micro-nanospheres are inorganic microspheres such as silicon dioxide microspheres, titanium dioxide microspheres, zinc oxide microspheres, alumina microspheres, zirconium dioxide microspheres, and vanadium pentoxide microspheres.
  • the heat-resistant organic microspheres are cross-linked polymer microspheres or sulfur-containing resin microspheres.
  • micro/nanospheres of the present invention are bisphenol formaldehyde resin microspheres.
  • inorganic microspheres and heat-resistant organic microspheres can be prepared according to the methods disclosed in the prior art.
  • thermoplastic polymer is polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic plastic, linear polyolefin and its copolymer, polysulfone, polyphenylene Ether, one of polyurethane, polytetrafluoroethylene, polyethylene terephthalate.
  • linear polyolefins refer to other linear polyolefins other than polyethylene, polypropylene, polyvinyl chloride, polystyrene, and acrylic plastics.
  • thermoplastic polymer of the present invention is a polyvinyl chloride (PVC) film or a thermoplastic polyurethane (TPU) film.
  • Another object of the present invention is to provide a method for preparing the above-mentioned structurally stable composite structure chromogenic material.
  • the present invention provides two alternative technical solutions for preparing the above-mentioned structural chromogenic material with stable structure.
  • a technical solution is: a method for preparing a structurally stable chromogenic material, including the following process steps:
  • thermoplastic polymer layer An emulsion of micro-nanospheres with a solid content of 5%-30% is assembled on a transparent thermoplastic polymer layer in order or disorder to form a structural color layer; the resulting thermoplastic polymer layer coated with the structural color layer Covered with another transparent thermoplastic polymer layer, the two layers of thermoplastic polymer layer are bonded together by hot pressing and bonded into a whole to obtain a structurally stable color-bearing material unit; The peripheral edges of the thermoplastic polymer layer of the structural chromogenic material unit and the two contacting polymer layers are attached and bonded into a whole.
  • Another technical solution is: a method for preparing a structured chromogenic material with stable structure, including the following process steps: an emulsion of micro-nanospheres with a solid content of 5% to 30% is carried out on a transparent thermoplastic polymer layer Orderly or disorderly assembly to form a structural color layer; the resulting thermoplastic polymer layer coated with the structural color layer is covered with another transparent thermoplastic polymer layer, and the above operations are repeated until the target number of layers is obtained. Press to make all the edges of the thermoplastic polymer layer adhere and bond into a whole; it can also be hot pressed step by step until the target number of layers is obtained.
  • the micro-nanospheres and the binder are co-assembled, and the binder is dopamine and its derivatives, gum arabic, natural gum, natural rubber, One or more of polyurethane, polyurea, polyacrylate, phenolic resin, epoxy resin, and polyvinyl alcohol.
  • the mass fraction of the binder in the micro/nanosphere emulsion is 0%-20 %.
  • the method of orderly assembling micro-nanospheres on the thermoplastic polymer layer is heating assembly method, deposition method, blade coating method, spin coating method; disorderly assembly of micro-nanospheres on the thermoplastic polymer layer
  • the methods of nanoballing are drip coating, spraying and printing.
  • the device for bonding and bonding the two thermoplastic polymer layers into a whole by hot pressing is a hot pressing device, the temperature of the hot pressing is 80-250°C, and the pressure is 4-16kN .
  • thermoplastic material is one of the most widely used polymers in daily life, and has the advantages of convenient processing and good comprehensive performance.
  • the combination of commercial thermoplastic materials and structural colors is a new, economical and environmentally friendly strategy.
  • the molded composite structure has relatively obvious structural colors, good mechanical strength, and overcomes the shortcomings of poor structural stability of structural color materials. This method operates It is simple, low-cost, can be used in a large area, and can be easily patterned, and is suitable for daily necessities, packaging, decoration and other fields.
  • Figure 1 (a) ⁇ (c) are photos of the stable composite structure chromogenic material obtained in Example 1;
  • Example 2 is a cross-sectional scanning electron micrograph of the composite structure chromogenic material c with stable structure obtained in Example 1;
  • Figure 3 shows the peeling curve of the PVC test strip prepared under the hot pressing conditions in Example 1 (the width of the strip is 2.5cm, the length of the hot pressing overlap is 5mm), and the peeling force is 273N;
  • Example 4 is a comparison diagram before and after the friction test of the structure-stable composite structure chromogenic material c obtained in Example 1.
  • the test condition is that a load of 1 kg is dragged horizontally on 100-mesh sandpaper at a speed of 5 cm/s for 10 cm reciprocating 15 times;
  • Figure 5 (a) and (b) are photos and bending photos of the structure-stable composite structure chromogenic material mobile phone case obtained in Example 2;
  • Fig. 6 is a photo of the structurally stable composite structure chromogenic material obtained in Example 3.
  • FIG. 7 is a schematic diagram of the structure of the composite structure chromogenic material with stable structure according to the present invention.
  • test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.
  • the bisphenol formaldehyde resin microsphere emulsion with a diameter of 283nm, 239nm and 197nm with a solid content of 10% was sprayed on the PVC film by spraying method under the cover of the hollow mold to prepare three colors of amorphous photons. Structure pattern.
  • the hot pressing equipment is preheated to 120°C, and another layer of PVC film is covered on the PVC film coated with amorphous photonic structure pattern, and the two layers of PVC film are laminated and bonded into a whole by hot pressing, the pressure is 8kN ,
  • the structural stability was verified by a peel test, and the peel force of the PVC test specimen prepared under this hot pressing condition was 273N. Further through the friction test, the composite structure chromogenic material loaded with 1kg weight was dragged horizontally on 100-mesh sandpaper for 10cm at a speed of 5cm/s, reciprocating 15 times, and the shape and color of the pattern could be maintained.
  • the bisphenol formaldehyde resin microsphere emulsion with a diameter of 283nm, 239nm and 197nm with a solid content of 10% is compounded with a carbon black aqueous solution with a solid content of 0.01g/ml at a mass ratio of 20:1 to obtain a mixed emulsion.
  • a carbon black aqueous solution with a solid content of 0.01g/ml at a mass ratio of 20:1 to obtain a mixed emulsion.
  • three kinds of bisphenol-formaldehyde resin microsphere mixed emulsion were sprayed on the TPU film in disorderly assembly to prepare the pattern of amorphous photonic structure.
  • the hot pressing equipment is preheated to 120°C, the TPU mobile phone case is covered with the TPU film coated with amorphous photonic structure pattern, and the two TPU films are laminated and bonded into a whole through hot pressing, and the pressure is 8kN to obtain Cell phone case with stable structure and composite structure chromogenic material
  • a PVC film is placed on the heating plate at a temperature of 60°C, and the bisphenol formaldehyde resin microsphere emulsion with a solid content of 10% and a diameter of 283nm is assembled on the PVC film to prepare photonic crystals.
  • the hot pressing equipment is preheated to 120°C, the PVC film coated with the photonic crystal layer is covered with another layer of PVC film, and the two layers of PVC film are laminated and bonded into a whole by hot pressing.
  • the pressure is 8kN to obtain Structurally stable composite structure chromogenic material.
  • the pattern of amorphous photonic structure is prepared by spraying the silica microsphere emulsion with a solid content of 10% on the PVC film under the cover of the hollow mold by spraying method.
  • the hot pressing equipment is preheated to 120°C, and another layer of PVC film is covered on the PVC film coated with amorphous photonic structure pattern, and the two layers of PVC film are laminated and bonded into a whole by hot pressing, the pressure is 8kN , To obtain a composite structure chromogenic material with stable structure.
  • the polysulfide resin microsphere emulsion with a solid content of 10% is drip-coated on the TPU film under the cover of the hollow mold by the drip coating method to prepare an amorphous photonic structure pattern.
  • the hot pressing equipment is preheated to 110°C, and the TPU film coated with the amorphous photonic structure pattern is covered with another TPU film, and the two TPU films are laminated and bonded into a whole by hot pressing.
  • the pressure is 8kN , To obtain a composite structure chromogenic material with stable structure.
  • the photonic crystal is prepared by orderly assembling the titanium dioxide microsphere emulsion with the solid content of 10% on the PVC film by the knife coating method.
  • the hot pressing equipment is preheated to 120°C, the PVC film coated with the photonic crystal layer is covered with another layer of PVC film, and the two layers of PVC film are laminated and bonded into a whole by hot pressing.
  • the pressure is 8kN to obtain Structurally stable composite structure chromogenic material.
  • the photonic crystal is prepared by orderly assembling the zinc oxide microsphere emulsion with the solid content of 10% on the TPU film by the spin coating method.
  • the hot pressing equipment is preheated to 120°C, the TPU film coated with the photonic crystal layer is covered with another TPU film, and the two TPU films are laminated and bonded into a whole by hot pressing, and the pressure is 8kN to obtain Structurally stable composite structure chromogenic material.
  • the amorphous photonic structure is prepared by spraying the bisphenol formaldehyde resin microsphere emulsion with a diameter of 239nm with a solid content of 10% on a PVC film by spraying method, and the amorphous photonic structure is coated on the PVC film Cover with another layer of PVC film.
  • the hot pressing equipment is preheated to 120°C, and all the edges of the PVC layers are adhered and bonded into a whole through hot pressing, and the pressure is 8kN to obtain a composite structure color material with stable structure.
  • the hot pressing equipment is preheated to 120°C, and another layer of PVC film is covered on the PVC film printed with the structural color pattern, and the two layers of PVC film are laminated and bonded into a whole by hot pressing.
  • the pressure is 8kN to obtain the structure Stable composite structure chromogenic material.
  • the hot pressing equipment is preheated to 120°C, and another layer of PVC film is covered on the PVC film coated with amorphous photonic structure pattern, and the two layers of PVC film are laminated and bonded into a whole by hot pressing, the pressure is 8kN , To obtain a composite structure chromogenic material with stable structure.

Abstract

本发明涉及一种结构稳定的复合结构生色材料及其制备方法，属于新材料制备领域。一种结构稳定的复合结构生色材料，所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得，所述材料的上表面层和下表面层均为热塑性聚合物。本发明所述成型复合结构具有相对明显的结构色，良好的机械强度，克服了结构生色材料结构稳定性差的缺点，本方法操作简便，成本低廉，可以大面积应用，还可以方便实现图案化，适用于日用品、包装、装饰等领域。

Description

一种结构稳定的复合结构生色材料及其制备方法 技术领域
本发明涉及一种结构稳定的复合结构生色材料及其制备方法，属于新材料制备领域。
背景技术
化学染色污染是工业污染的主要来源。染整过程可能产生大量污染废水和有毒物质，严重影响生态环境。同时，由于环境因素的影响，这种化学色可能逐渐退色或消失。
值得注意的是，结构色被认为是另一种可选的着色途径，它来自可见光与微观物理结构的相互作用。结构色分为彩虹色和非彩虹色，其中光子晶体是一种具有光子带隙特性的周期性有序电介质结构，当其光子带隙位于可见波长范围内时，光子晶体可以呈现出彩虹色。而非彩虹色可以通过具有特征尺寸为可见光波长量级的非晶光子结构展现，其微观结构单元呈短程有序、长程无序排列。但是目前人工构建的结构生色材料，胶体微球阵列无外加保护，结构稳定性差，限制了其广泛的应用。因此，结构稳定的结构生色材料的研究具有重要的意义。
发明内容
本发明的目的是提供一种结构稳定的复合结构生色材料及其制备方法。
一种结构稳定的复合结构生色材料，所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得，所述材料的上表面层和下表面层均为热塑性聚合物。
本发明所述结构稳定的复合结构生色材料由聚合物与结构生色材料由下至上逐层叠加而成。该结构将结构生色材料固定在两侧的连续的聚合物层间，结构稳定。
进一步地，本发明所述复合结构生色材料的层数可根据所需颜色、图案等效果需求进行选择和组合，原则上无特殊限制。本发明所述复合结构生色材料由聚合物层与结构色层叠加获得，至少3层，即两层聚合物层夹着中间结构色层。叠加时向上按次序结构色层与聚合物层叠加，保证各结构色层被两层聚合物层夹着。
进一步地，优选所述复合结构生色材料的总层数为3～15层。
本发明所述结构稳定的复合结构生色材料中，所述结构生色材料为微纳球构成的层膜，所述层膜由微纳球有序或无序堆叠构成。微纳球在两侧的聚合物层间进行排列、堆叠，形成单层排列或多层堆叠的结构。所述排列和堆叠可为有序或无序。
本发明所述结构稳定的复合结构生色材料中，所述结构生色材料包括微纳球，还可包括粘结剂和/或黑色色素。其中，微纳球与粘结剂共组装可以进一步增强结构稳定性；添加黑色色素可以进一步增强结构色的饱和度。
优选地，当结构生色材料中包含粘结剂时，所述粘结剂在微纳球的乳液中的质量分数为0～20％。
优选地，所述粘结剂为多巴胺及其衍生物、阿拉伯树胶、天然树胶、天然橡胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中的一种或几种。
本发明所述结构稳定的复合结构生色材料中，所述微纳球为无机物微球或耐热的有机物微球。
本发明所述耐热的有机物微球为玻璃化温度高于热塑性聚合物玻璃化温度的有机物微球。
本发明所述结构稳定的复合结构生色材料中，所述微纳球为实心或空心微纳球。
本发明所述结构稳定的复合结构生色材料中，所述微纳球的直径为10～1000nm。
优选地，所述结构生色材料为微纳球构成的层膜，由微纳球有序或无序堆叠构成；所述微纳球为无机物微球或耐热的有机物微球，所述微纳球的直径为10～1000nm，所述微纳球为实心或空心微纳球。
进一步地，所述微纳球为无机物微球为二氧化硅微球，二氧化钛微球，氧化锌微球，氧化铝微球，二氧化锆微球，五氧化二钒微球。
进一步地，所述耐热的有机物微球为交联的聚合物微球或含硫树脂微球。
更进一步地，本发明所述微纳球为双酚甲醛树脂微球。
上述无机物微球和耐热的有机物微球均可按现有技术公开的方法制得。
进一步地，所述热塑性聚合物为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛，聚碳酸酯，聚酰胺、丙烯酸类塑料、线性聚烯烃及其共聚物、聚砜、聚苯醚，聚氨酯、聚四氟乙烯、聚对苯二甲酸乙二醇酯中的一种。
上述线性聚烯烃指聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、丙烯酸类塑料外的其他线性聚烯烃。
更进一步地，本发明所述热塑性聚合物为聚氯乙烯(PVC)膜，热塑性聚氨酯(TPU)膜。
本发明的另一目的是提供上述结构稳定的复合结构生色材料的制备方法。
本发明提供两种可选的技术方案用于制备上述结构稳定的结构生色材料。
一个技术方案为：一种结构稳定的结构生色材料的制备方法，包括下述工艺步骤：
将固含量为5％～30％的微纳球的乳液在一透明热塑性聚合物层上进行有序或无序组装，形成结构色层；将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层，通过热压使其两层热塑性聚合物层四周边缘贴合，并粘结成一个整体，得到结构稳定的结构生色材料单元；通过热压使所得结构生色材料单元的热塑性聚合物层的四周边缘及相接触的两层聚合物层贴合并粘结成整体。
另一技术方案为：一种结构稳定的结构生色材料的制备方法，包括下述工艺步骤：将固含量为5％～30％的微纳球的乳液在一透明的热塑性聚合物层上进行有序或无序组装，形成结构色层；将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层，重复上述操作，直至获得目标层数，通过热压使所有热塑性聚合物层四周边缘贴合并粘结成整体；也可以分步热压直至获得目标层数。
上述两种制备方法的技术方案中，所述结构色层的制备过程中，微纳球与粘合结剂共组装，粘结剂为多巴胺及其衍生物、阿拉伯树胶、天然树胶、天然橡胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中的一种或几种，粘结剂在微纳球乳液中的质量分数为0％～20％。
上述两种制备方法的技术方案中，在热塑性聚合物层上有序组装微纳球的方法为加热组装法，沉积法，刮涂法，旋涂法；在热塑性聚合物层上无序组装微纳球的方法为滴涂法，喷涂法，打印法。
上述两种制备方法的技术方案中，所述通过热压使两层热塑性聚合物层贴合并粘结成整体的设备为热压设备，热压的温度为80～250℃，压力为4～16kN。
本发明的有益效果为：热塑性材料是日常生活中应用最广泛的聚合物之一，并且具有加工方便、综合性能好的优点。商品化热塑性材料与结构色相结合是一种新型、经济、环保的策略，该成型复合结构具有相对明显的结构色，良好的机械强度，克服了结构生色材料结构稳定性差的缺点，本方法操作简便，成本低廉，可以大面积应用，还可以方便实现图案化，适用于日用品、包装、装饰等领域。
附图说明
图1(a)～(c)为实施例1所得的结构稳定的复合结构生色材料的照片；
图2为实施例1所得的结构稳定的复合结构生色材料c的截面扫描电镜图；
图3为实施例1对应热压条件下制备的PVC测试样条的剥离曲线(样条宽2.5cm，热压重合长度5mm)，显示剥离力为273N；
图4为实施例1所得的结构稳定的复合结构生色材料c的摩擦测试前后对比图， 测试条件为负载1kg重量以5cm/s的速度在100目砂纸上水平拖动10cm往复15次；
图5(a)和(b)为实施例2所得的结构稳定的复合结构生色材料手机壳的照片及弯曲照片；
图6为实施例3所得的结构稳定的复合结构生色材料照片；
图7为本发明所述结构稳定的复合结构生色材料的结构示意图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
1、通过喷涂法在镂空模具的遮盖下，分别喷涂固含量为10％的直径为283nm，239nm和197nm的双酚甲醛树脂微球乳液在PVC膜上无序组装制备三种颜色的非晶光子结构的图案。
2、热压设备预热至120℃，将涂覆有非晶光子结构图案的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。通过剥离测试验证了其结构稳定性，这一热压条件下制备的PVC测试样条的剥离力为273N。进一步通过摩擦测试，复合结构生色材料负载1kg重量以5cm/s的速度在100目砂纸上水平拖动10cm，往复15次，可以保持图案的形状与颜色。
实施例2
1、分别将固含量为10％的直径为283nm，239nm和197nm的双酚甲醛树脂微球乳液按20:1的质量比与固含量为0.01g/ml的炭黑水溶液复配得混合乳液，通过喷涂法在镂空模具的遮盖下，分别喷涂3种双酚甲醛树脂微球混合乳液在TPU膜上无序组装制备非晶光子结构的图案。
3、热压设备预热至120℃，将涂覆有非晶光子结构图案的TPU膜上覆盖TPU手机壳，通过热压使其两层TPU膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料手机壳。
实施例3
1、通过加热组装法，在加热板上放置一PVC膜，温度为60℃，将固含量为10％ 的直径为283nm的双酚甲醛树脂微球乳液在PVC膜上有序组装制备光子晶体。
2、热压设备预热至120℃，将涂覆有光子晶体层的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例4
1、通过喷涂法在镂空模具的遮盖下，喷涂固含量为10％的二氧化硅微球乳液在PVC膜上无序组装制备非晶光子结构的图案。
2、热压设备预热至120℃，将涂覆有非晶光子结构图案的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例5
1、通过滴涂法在镂空模具的遮盖下，滴涂固含量为10％的聚硫树脂微球乳液在TPU膜上无序组装制备非晶光子结构的图案。
2、热压设备预热至110℃，将涂覆有非晶光子结构图案的TPU膜上覆盖另一层TPU膜，通过热压使其两层TPU膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例6
1、通过刮涂法，将固含量为10％的二氧化钛微球乳液在PVC膜上有序组装制备光子晶体。
2、热压设备预热至120℃，将涂覆有光子晶体层的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例7
1、通过旋涂法，将固含量为10％的氧化锌微球乳液在TPU膜上有序组装制备光子晶体。
2、热压设备预热至120℃，将涂覆有光子晶体层的TPU膜上覆盖另一层TPU膜，通过热压使其两层TPU膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例8
1、通过喷涂法，在一PVC膜上喷涂固含量为10％的直径为239nm的双酚甲醛树脂微球乳液无序组装制备非晶光子结构，将涂覆有非晶光子结构的PVC膜上覆盖另一 层PVC膜。
2、重复上述操作，形成5层的复合结构，其中结构生色材料分别在两侧的连续的聚合物层间。
3、热压设备预热至120℃，通过热压使所有PVC层四周边缘贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例9
1、通过打印法在PVC膜上打印固含量为10％的直径为230nm二氧化钛微球乳液，无序组装制备结构色图案。
2、热压设备预热至120℃，将打印有结构色图案的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
实施例10
1、通过喷涂法在镂空模具的遮盖下，喷涂固含量为10％的双酚甲醛树脂微球乳液(聚丙烯酸酯粘结剂在微纳球乳液中的质量分数为1％)在PVC膜上无序组装制备非晶光子结构的图案。
2、热压设备预热至120℃，将涂覆有非晶光子结构图案的PVC膜上覆盖另一层PVC膜，通过热压使其两层PVC膜贴合并粘结成整体，压力为8kN，得到结构稳定的复合结构生色材料。
以上实例只是用于帮助更好的理解本发明的核心思想及技术方法，但不能以此限制本发明的保护范围。应当指出，对于该领域的普通技术人员，在依据本发明原理的基础上，还可以对本发明进行一定的改进与拓展，这些改进与拓展也在本发明权利要求的保护范围内；凡依据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的权利要求保护范围内。

Claims (10)

  1. 一种结构稳定的复合结构生色材料，其特征在于：所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得，所述材料的上表面层和下表面层均为热塑性聚合物。
  2. 根据权利要求1所述的材料，其特征在于：所述复合结构生色材料的总层数为3～15层。
  3. 根据权利要求1所述的材料，其特征在于：所述结构生色材料为微纳球构成的层膜，由微纳球有序或无序堆叠构成；所述微纳球为无机物微球或耐热的有机物微球，所述微纳球的直径为10～1000nm，所述微纳球为实心或空心微纳球，所述耐热的有机物微球为玻璃化温度高于热塑性聚合物玻璃化温度的有机物微球。
  4. 根据权利要求3所述的材料，其特征在于：所述无机物微球为二氧化硅微球，二氧化钛微球，氧化锌微球，氧化铝微球，二氧化锆微球，五氧化二钒微球；所述耐热的有机物微球为交联的聚合物微球或含硫树脂微球。
  5. 根据权利要求1所述的材料，其特征在于：所述热塑性聚合物为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛，聚碳酸酯，聚酰胺、丙烯酸类塑料、其它聚烯烃及其共聚物、聚砜、聚苯醚，聚氨酯、聚四氟乙烯、聚对苯二甲酸乙二醇酯中的一种。
  6. 权利要求1～5任一项所述的结构稳定的复合结构生色材料的制备方法，其特征在于：包括下述工艺步骤：
    将固含量为5％～30％的微纳球的乳液在一透明热塑性聚合物层上进行有序或无序组装，形成结构色层；将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层，通过热压使其两层热塑性聚合物层四周边缘贴合，并粘结成一个整体，得到结构稳定的复合结构生色材料单元；通过热压使所得复合结构生色材料单元的热塑性聚合物层的四周边缘及相接触的两层聚合物层贴合并粘结成整体。
  7. 权利要求1～5任一项所述的结构稳定的复合结构生色材料的制备方法，其特征在于：包括下述工艺步骤：将固含量为5％～30％的微纳球的乳液在一透明的热塑性聚合物层上进行有序或无序组装，形成结构色层；将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层，重复上述操作，直至获得目标层数，通过热压使所有热塑性聚合物层四周边缘贴合并粘结成整体；也可以分步热压直至获得目标层数。
  8. 根据权利要求6或7所述的方法，其特征在于：所述结构色层的制备过程中，微纳球与粘结剂共组装，粘结剂为多巴胺及其衍生物、阿拉伯树胶、天然树胶、天然橡胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中 的一种或几种，所述粘结剂在微纳球乳液中的质量分数为0％～20％。
  9. 根据权利要求6或7所述的方法，其特征在于：在热塑性聚合物层上有序组装微纳球的方法为加热组装法，沉积法，刮涂法，旋涂法；在热塑性聚合物层上无序组装微纳球的方法为滴涂法，喷涂法，打印法。
  10. 根据权利要求6或7所述的方法，其特征在于，所述通过热压使两层热塑性聚合物层贴合并粘结成整体的设备为热压设备，热压的温度为80～250℃，压力为4～16kN。
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