阅读说明：本技术 一种结构稳定的复合结构生色材料及其制备方法 (Composite structure chromogenic material with stable structure and preparation method thereof ) 是由 唐炳涛 孟繁涛 武素丽 张淑芬 于 2019-07-30 设计创作，主要内容包括：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。(The invention relates to a composite structure chromogenic material with a stable structure and a preparation method thereof, belonging to the field of preparation of new materials. A structurally stable composite structural color-generating material is obtained by laminating a transparent thermoplastic polymer and a structural color-generating material layer by layer and then thermally bonding the peripheral edges of the polymer into a whole, wherein the upper surface layer and the lower surface layer of the material are both thermoplastic polymers. The formed composite structure has relatively obvious structural color and good mechanical strength, overcomes the defect of poor structural stability of structural color-generating materials, has simple and convenient operation and low cost, can be applied in a large area, can conveniently realize patterning, and is suitable for the fields of daily necessities, packaging, decoration and the like.)

1. A composite structure chromogenic material with stable structure is characterized in that: the material is obtained by superposing a transparent thermoplastic polymer and a structural color-generating material layer by layer and then thermally bonding the peripheral edges of the polymer into a whole, wherein the upper surface layer and the lower surface layer of the material are both thermoplastic polymers.

2. The material of claim 1, wherein: the total number of layers of the composite structure color-generating material is 3-15.

3. The material of claim 1, wherein: the structural color-producing material is a layer film formed by micro-nano spheres and is formed by orderly or disorderly stacking the micro-nano spheres; the micro-nano ball is an inorganic substance micro-ball or a heat-resistant organic substance micro-ball, the diameter of the micro-nano ball is 10-1000 nm, the micro-nano ball is a solid or hollow micro-nano ball, and the heat-resistant organic substance micro-ball is an organic substance micro-ball with the glass transition temperature higher than that of the thermoplastic polymer.

4. The material of claim 3, wherein: the micro-nano spheres are inorganic microspheres such as silicon dioxide microspheres, titanium dioxide microspheres, zinc oxide microspheres, aluminum oxide microspheres, zirconium dioxide microspheres and vanadium pentoxide microspheres; the heat-resistant organic microspheres are crosslinked polymer microspheres or sulfur-containing resin microspheres.

5. The material of claim 1, wherein: the thermoplastic polymer is one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyformaldehyde, polycarbonate, polyamide, acrylic plastics, other polyolefins and copolymers thereof, polysulfone, polyphenyl ether, polyurethane, polytetrafluoroethylene and polyethylene terephthalate.

6. The method of preparing a structurally stable composite-structured chromogenic material according to any of claims 1 to 5, characterized in that: the method comprises the following process steps:

Orderly or disorderly assembling the emulsion of the micro-nano spheres with the solid content of 5-30% on a transparent thermoplastic polymer layer to form a structural color layer; covering another transparent thermoplastic polymer layer on the obtained thermoplastic polymer layer coated with the structural color layer, laminating the peripheral edges of the two thermoplastic polymer layers by hot pressing, and bonding the two thermoplastic polymer layers into a whole to obtain a composite structural color generating material unit with a stable structure; the peripheral edges of the thermoplastic polymer layers of the obtained composite structure color generating material units and the two polymer layers which are contacted with each other are jointed and bonded into a whole through hot pressing.

7. The method of preparing a structurally stable composite-structured chromogenic material according to any of claims 1 to 5, characterized in that: the method comprises the following process steps: orderly or disorderly assembling the emulsion of the micro-nano spheres with the solid content of 5-30% on a transparent thermoplastic polymer layer to form a structural color layer; covering another transparent thermoplastic polymer layer on the obtained thermoplastic polymer layer coated with the structural color layer, repeating the operation until a target layer number is obtained, and adhering and bonding the peripheral edges of all the thermoplastic polymer layers into a whole through hot pressing; it is also possible to step-wise heat press until the target number of layers is achieved.

8. The method according to claim 6 or 7, characterized in that: in the preparation process of the structure color layer, the micro-nano balls and an adhesive are assembled together, the adhesive is one or more of dopamine and derivatives thereof, gum arabic, natural gum, natural rubber, polyurethanes, polyureas, polyacrylates, phenolic resins, epoxy resins and polyvinyl alcohol, and the mass ratio of the adhesive to the micro-nano ball emulsion is 0-20%.

9. the method according to claim 6 or 7, characterized in that: the method for orderly assembling the micro-nano spheres on the thermoplastic polymer layer comprises a heating assembly method, a deposition method, a blade coating method and a spin coating method; the method for disorderly assembling the micro-nano spheres on the thermoplastic polymer layer is a drop coating method, a spraying method and a printing method.

10. The method according to claim 6 or 7, wherein the device for bonding and integrating the two thermoplastic polymer layers by hot pressing is a hot pressing device, the temperature of the hot pressing is 80-250 ℃, and the pressure is 4-16 kN.

Technical Field

The invention relates to a composite structure chromogenic material with a stable structure and a preparation method thereof, belonging to the field of preparation of new materials.

Background

Chemical staining contamination is a major source of industrial contamination. The dyeing and finishing process may produce a large amount of polluted wastewater and toxic substances, and the ecological environment is seriously influenced. Meanwhile, such a chemical color may gradually fade or disappear due to the influence of environmental factors.

Notably, structural color is considered to be another alternative coloring pathway, which results from the interaction of visible light with microscopic physical structures. The structural colors are classified into rainbow colors and non-rainbow colors, in which a photonic crystal is a periodic ordered dielectric structure having a photonic band gap characteristic, and the photonic crystal may exhibit rainbow colors when its photonic band gap is located in a visible wavelength range. And non-iridescent colors can be displayed by an amorphous photon structure with characteristic size of visible wavelength magnitude, and microstructure units of the amorphous photon structure are in short-range ordered and long-range disordered arrangement. However, the existing artificially constructed structural chromogenic material has no additional protection on the colloidal microsphere array, and has poor structural stability, so that the wide application of the colloidal microsphere array is limited. Therefore, the research of the structural color-generating material with stable structure has important significance.

Disclosure of Invention

The invention aims to provide a composite structure chromogenic material with stable structure and a preparation method thereof.

A structurally stable composite structural color-generating material is obtained by laminating a transparent thermoplastic polymer and a structural color-generating material layer by layer and then thermally bonding the peripheral edges of the polymer into a whole, wherein the upper surface layer and the lower surface layer of the material are both thermoplastic polymers.

The composite structure chromogenic material with stable structure is formed by superposing a polymer and a structure chromogenic material layer by layer from bottom to top. The structure fixes the structural color-generating material between the continuous polymer layers on both sides, and the structure is stable.

Further, the number of layers of the composite structure chromogenic material can be selected and combined according to the requirements of the required color, pattern and other effects, and is not particularly limited in principle. The composite structure chromogenic material is obtained by superposing a polymer layer and a structure color layer, and at least 3 layers, namely, two polymer layers sandwich the middle structure color layer. When in superposition, the structural color layers are superposed with the polymer layers in sequence upwards, and the structural color layers are ensured to be clamped by the two polymer layers.

Further, the total number of layers of the composite structure color generation material is preferably 3-15.

in the composite structure chromogenic material with stable structure, the structure chromogenic material is a layer film formed by micro-nano spheres, and the layer film is formed by orderly or disorderly stacking the micro-nano spheres. The micro-nano spheres are arranged and stacked between polymer layers on two sides to form a single-layer arrangement or multi-layer stacking structure. The arrangement and stacking may be ordered or disordered.

In the composite structure chromogenic material with stable structure, the structure chromogenic material comprises micro-nano spheres and can also comprise a binder and/or a black pigment. The micro-nano spheres can be assembled with a binder to further enhance the structural stability; the addition of black pigments further enhances the saturation of the structural colors.

Preferably, when the structural color generation material contains the binder, the mass ratio of the binder to the micro-nano sphere emulsion is 0-20%.

Preferably, the binder is one or more of dopamine and derivatives thereof, gum arabic, natural gum, natural rubber, polyurethanes, polyureas, polyacrylates, phenolic resins, epoxy resins, and polyvinyl alcohol.

In the composite structure chromogenic material with stable structure, the micro-nano spheres are inorganic microspheres or heat-resistant organic microspheres.

The heat-resistant organic microspheres are organic microspheres with the glass transition temperature higher than that of the thermoplastic polymer.

In the composite structure chromogenic material with stable structure, the micro-nano spheres are solid or hollow micro-nano spheres.

In the composite structure chromogenic material with the stable structure, the diameter of the micro-nano ball is 10-1000 nm.

Preferably, the structural chromogenic material is a layer film formed by micro-nano spheres and is formed by orderly or disorderly stacking the micro-nano spheres; the micro-nano spheres are inorganic microspheres or heat-resistant organic microspheres, the diameter of each micro-nano sphere is 10-1000 nm, and each micro-nano sphere is a solid or hollow micro-nano sphere.

Further, the micro-nano spheres are inorganic microspheres such as silicon dioxide microspheres, titanium dioxide microspheres, zinc oxide microspheres, aluminum oxide microspheres, zirconium dioxide microspheres and vanadium pentoxide microspheres.

Further, the heat-resistant organic microspheres are crosslinked polymer microspheres or sulfur-containing resin microspheres.

Furthermore, the micro-nano spheres are bisphenol formaldehyde resin microspheres.

The inorganic microspheres and the heat-resistant organic microspheres can be prepared by the method disclosed by the prior art.

Further, the thermoplastic polymer is one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic plastic, linear polyolefin and copolymer thereof, polysulfone, polyphenylene oxide, polyurethane, polytetrafluoroethylene, polyethylene terephthalate.

The linear polyolefin refers to other linear polyolefins besides polyethylene, polypropylene, polyvinyl chloride, polystyrene and acrylic plastics.

Still further, the thermoplastic polymer of the present invention is a polyvinyl chloride (PVC) film, a Thermoplastic Polyurethane (TPU) film.

Another object of the present invention is to provide a method for preparing the above structurally stable composite structure color-developing material.

The invention provides two alternative technical schemes for preparing the structural color-generating material with stable structure.

One technical scheme is as follows: a method for preparing a structural color-generating material with stable structure comprises the following process steps:

Orderly or disorderly assembling the emulsion of the micro-nano spheres with the solid content of 5-30% on a transparent thermoplastic polymer layer to form a structural color layer; covering another transparent thermoplastic polymer layer on the obtained thermoplastic polymer layer coated with the structural color layer, laminating the peripheral edges of the two thermoplastic polymer layers by hot pressing, and bonding the two thermoplastic polymer layers into a whole to obtain a structural color generating material unit with a stable structure; the peripheral edges of the thermoplastic polymer layers of the obtained structural color generating material units and the two polymer layers which are contacted with each other are jointed and bonded into a whole by hot pressing.

The other technical scheme is as follows: a method for preparing a structural color-generating material with stable structure comprises the following process steps: orderly or disorderly assembling the emulsion of the micro-nano spheres with the solid content of 5-30% on a transparent thermoplastic polymer layer to form a structural color layer; covering another transparent thermoplastic polymer layer on the obtained thermoplastic polymer layer coated with the structural color layer, repeating the operation until a target layer number is obtained, and adhering and bonding the peripheral edges of all the thermoplastic polymer layers into a whole through hot pressing; it is also possible to step-wise heat press until the target number of layers is achieved.

According to the technical scheme of the two preparation methods, in the preparation process of the structure color layer, the micro-nano balls and the adhesive are assembled together, the adhesive is one or more of dopamine and derivatives thereof, gum arabic, natural gum, natural rubber, polyurethanes, polyureas, polyacrylates, phenolic resins, epoxy resins and polyvinyl alcohol, and the mass ratio of the adhesive to the micro-nano ball emulsion is 0-20%.

In the two preparation methods, the method for orderly assembling the micro-nano spheres on the thermoplastic polymer layer is a heating assembly method, a deposition method, a blade coating method and a spin coating method; the method for disorderly assembling the micro-nano spheres on the thermoplastic polymer layer is a drop coating method, a spraying method and a printing method.

In the two preparation methods, the equipment for bonding and bonding the two thermoplastic polymer layers into a whole through hot pressing is hot pressing equipment, the hot pressing temperature is 80-250 ℃, and the pressure is 4-16 kN.

The invention has the beneficial effects that: thermoplastic materials are one of the most widely used polymers in daily life, and have the advantages of convenient processing and good comprehensive performance. The commercial thermoplastic material and the structural hue are combined to form a novel, economic and environment-friendly strategy, the formed composite structure has relatively obvious structural color and good mechanical strength, the defect of poor structural stability of a structural chromogenic material is overcome, the method is simple and convenient to operate, low in cost, capable of being applied in a large area, capable of conveniently realizing patterning, and suitable for the fields of daily necessities, packaging, decoration and the like.

Drawings

FIGS. 1(a) to (c) are photographs of the structurally stable composite-structure color-producing material obtained in example 1;

FIG. 2 is a sectional scanning electron microscope image of a structurally stable composite-structure color-producing material c obtained in example 1;

FIGS. 3(a) and (b) are photographs and curved photographs of the structurally stabilized composite structural color-producing material cell phone case obtained in example 2;

FIG. 4 is a photograph of the structurally stabilized composite structural color-producing material obtained in example 3.

FIG. 5 is a schematic structural diagram of a structurally stabilized composite structure chromonic material of the invention.

Detailed Description

The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.