阅读说明：本技术 基于稀土金属的记忆性电致变色膜及其制备方法和应用 (Memory electrochromic film based on rare earth metal and preparation method and application thereof ) 是由 黄越楷 张�成 高太恒 廖兆雄 廖兆贤 廖德艺 于 2020-07-02 设计创作，主要内容包括：本发明提供一种记忆性电致变色膜及其制备方法和应用,该变色膜包括两层PET基材,两层PET基材之间设有两层ITO导电层,两层ITO导电层之间按照上下顺序依次设置有稀土变色层、离子传导层和离子储存层；稀土变色层是由稀土金属磁控溅射形成的一层薄膜；离子传导层按照重量百分比的组成包括：聚氨酯丙烯酸树酯30～60wt％,单体30～60wt％,功能剂0.1～10wt％,引发剂0.1～5wt％；离子储存层按照重量百分比的组成包括：功能离子型化合物10～50wt％,络合剂10～40wt％,稳定剂1～30wt％,引发剂0.1～10wt％,溶剂20～50％。本发明的变色膜基于1.5～3v的低电压直流电,功耗＜2W/m<Sup>2</Sup>,并且具有记忆功能,颜色均匀,是一种新型电-光响应的环保、功能、装饰材料。(The invention provides a memory electrochromic film and a preparation method and application thereof, wherein the electrochromic film comprises two layers of PET (polyethylene terephthalate) base materials, two ITO (indium tin oxide) conducting layers are arranged between the two layers of PET base materials, and a rare earth electrochromic layer, an ion conducting layer and an ion storage layer are sequentially arranged between the two ITO conducting layers from top to bottom; the rare earth color-changing layer is a film formed by rare earth metal magnetron sputtering; the ion conducting layer comprises the following components in percentage by weight: 30-60 wt% of polyurethane acrylic resin, 30-60 wt% of monomer, 0.1-10 wt% of functional agent and 0.1-5 wt% of initiator; ion storage layer by weightThe components in percentage by weight comprise: 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator and 20-50 wt% of solvent. The color-changing film is based on 1.5-3 v low-voltage direct current, and the power consumption is less than 2W/m 2 The color memory material has the memory function and uniform color, and is a novel environment-friendly, functional and decorative material with electro-optic response.)

1. An ion storage layer material, comprising: the composition comprises the following components in percentage by weight: 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator I and 20-50 wt% of solvent.

2. An ion storage layer material according to claim 1, wherein: the ion storage layer comprises the following components in percentage by weight: 10-20 wt% of functional ionic compound, 30-40 wt% of complexing agent, 1-5 wt% of stabilizer, 1-5 wt% of initiator and 40-50 wt% of solvent.

3. An ion storage layer material according to claim 1 or 2, wherein: the functional ionic compound is Li_(1+x)Mn₂O₄(x ranges from 1 to 7) and LiCoO₂、LiMn₂O₄、LiClO₄、Li₂Co₃、Li₃Sc₂(PO₄)₃、LiFePO₄At least one of (1).

4. An ion storage layer material according to claim 1 or 2, wherein: the chromium mixture is at least one of sodium hexametaphosphate, diethanolamine, sodium aminotriacetate, sodium ethylene diamine tetracetate, tartaric acid, EDTMPS and HPMA.

5. An ion storage layer material according to claim 1 or 2, wherein: the stabilizer is at least one of barium 2-ethylhexanoate, substituted barium benzoate, cadmium laurate, zinc neodecanoate, triphenyl phosphite, diphenyl-decyl phosphite and 2, 6-di-tert-butyl-p-cresol.

6. A rare earth metal-based memory electrochromic film is characterized in that: the ion storage material comprises two PET substrates, two ITO conductive layers are arranged between the two PET substrates, and a rare earth discoloring layer, an ion conductive layer and the ion storage layer as claimed in any one of claims 1 to 5 are sequentially arranged between the two ITO conductive layers from top to bottom; the rare earth discoloring layer is a thin film formed by magnetron sputtering of rare earth metal; the ion conducting layer comprises the following components in percentage by weight: 30-60 wt% of polyurethane acrylic resin, 30-60 wt% of monomer, 0.1-10 wt% of functional agent and 0.1-5 wt% of initiator II.

7. The rare earth metal-based memory electrochromic film according to claim 6, wherein: the rare earth metal is Mo, Nb, Ni, W, Ti, Ir, Rh, Co or at least one of the metal oxides.

8. A rare earth metal-based memory electrochromic film according to claim 1 or 2, characterized in that: the ion conducting layer comprises the following components in percentage by weight: 40-45 wt% of polyurethane acrylic resin, 50-60 wt% of monomer, 0.3-0.5 wt% of functional agent and 2-5 wt% of initiator.

9. The method for preparing a memory electrochromic film according to any one of claims 6 to 8, characterized in that: the method comprises the following steps:

forming a rare earth color-changing layer on the ITO surface of the ITO conducting layer positioned above by using rare earth metal through magnetron sputtering;

the ion conducting layer comprises the following components in percentage by weight: 30-60 wt% of polyurethane acrylic resin, 40-60 wt% of monomer, 0.1-10 wt% of functional agent and 0.1-5 wt% of initiator are mixed and uniformly mixed to obtain ion conducting layer liquid medicine, and the ion conducting layer liquid medicine is coated on the surface of the rare earth discoloring layer and is subjected to ultraviolet curing to obtain an ion conducting layer;

the ion storage layer comprises the following components in percentage by weight: 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator I and 20-50% of solvent are uniformly mixed to obtain ion storage layer liquid medicine, and the ion storage layer liquid medicine is coated on the surface of the ion conduction layer and is subjected to ultraviolet curing to obtain an ion storage layer;

assembling an ITO conductive layer below the ion storage layer;

and then assembling a PET substrate on the outer sides of the two ITO conductive layers to obtain the ITO conductive layer.

10. Use of the memory electrochromic film according to any one of claims 6 to 8 or obtained by the production method according to claim 9.

Technical Field

The invention relates to the technical field of electrochromic film preparation, in particular to a rare earth metal-based memory electrochromic film and a preparation method and application thereof.

Background

The electrochromic film belongs to the field of electro-optic response films, and three types of PDLC, SPD and ECG exist in the field, wherein the PDLC has single color (only can be subjected to transparent-milky white conversion), has angle limitation, cannot be memorized and consumes electricity for a long time, and is the most initial electro-optic response film; the SPD has a transparent-color conversion function, the angle limitation is greatly improved compared with that of PDLC, but long-term power consumption (power supply is required all the time in a transparent state) is still required, and the memory function is not provided; the ECG belongs to liquid phase or gel phase, and glass cavity design is with high costs, and thickness is too high, and weatherability is not enough, and the visitor is easily revealed, moreover because double glass structure requires too high to the former carrier of glass, is difficult to produce big space of a whole page and arc product, though two kinds of very big promotion, nevertheless still are difficult to extensive application and popularization because of its self limitation.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a rare earth metal-based memory electrochromic film, and a preparation method and application thereof, wherein the film has the characteristics of flexibility, deformation, good durability, good weather resistance and the like.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

in a first aspect, the present invention provides an ion storage layer material, comprising, by weight: 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator I and 20-50 wt% of solvent.

Preferably, the ion storage layer comprises the following components in percentage by weight: 10-20 wt% of functional ionic compound, 30-40 wt% of complexing agent, 1-5 wt% of stabilizer, 1-5 wt% of initiator and 40-50 wt% of solvent.

Further, the functional ionic compound is Li_(1+x)Mn₂O₄(x ranges from 1 to 7) and LiCoO₂、LiMn₂O₄、LiClO₄、Li₂Co₃、Li₃Sc₂(PO₄)₃、LiFePO₄At least one of (1).

Further, the chromium mixture is at least one of sodium hexametaphosphate, diethanolamine, sodium aminotriacetate, sodium ethylene diamine tetracetate, tartaric acid, EDTMPS and HPMA.

Further, the stabilizer is at least one of barium 2-ethylhexanoate, substituted barium benzoate, cadmium laurate, zinc neodecanoate, triphenyl phosphite, diphenyl-decyl phosphite and 2, 6-di-tert-butyl-p-cresol.

Further, the initiator I is at least one of 1173, 1490, 1700, BP, 184, 907, MBF, IHT-PI184, TPO and alpha-hydroxyalkyl benzophenone.

Further, the solvent is at least one of PC (polycarbonate), THFA (tetrahydrofurfuryl acrylate), HDDA.

Further, the preparation method of the ion storage layer material comprises the following steps: the method comprises the following steps of mixing 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator I and 20-50 wt% of solvent uniformly.

In a second aspect, the invention provides a rare earth metal-based memory electrochromic film, which comprises two PET substrates, wherein two ITO conductive layers are arranged between the two PET substrates, and a rare earth discoloring layer, an ion conductive layer and the ion storage layer are sequentially arranged between the two ITO conductive layers in an up-down order; the rare earth discoloring layer is a thin film formed by magnetron sputtering of rare earth metal; the ion conducting layer comprises the following components in percentage by weight: 30-60 wt% of polyurethane acrylic resin, 30-60 wt% of monomer, 0.1-10 wt% of functional agent and 0.1-5 wt% of initiator II.

Furthermore, the two ITO conductive layers are conductive layers formed by uniformly sputtering ITO on one side of the transparent PET film, the thickness of the transparent PET film is 23-195 μm, and the thickness error is not more than 2 μm.

Further, the thickness of the rare earth discoloring layer is 25-30 nm.

Further, the rare earth metal is Mo, Nb, Ni, W, Ti, Ir, Rh, Co, or at least one of the foregoing metal oxides.

Preferably, the ion conducting layer comprises, in weight percent: 40-45 wt% of polyurethane acrylic resin, 50-60 wt% of monomer, 0.3-0.5 wt% of functional agent and 2-5 wt% of initiator.

Further, the polyurethane acrylic resin is at least one of LM302, UH312, UH322 and water-based PUA.

Further, the monomer is at least one of DCPA, THF, IBOA, TBCH, PMMA and HEMA.

Further, the functional agent is at least one of polyethylene glycol, polypropylene glycol, polyvinyl alcohol and dihydric alcohol.

Further, the second initiator is at least one of 1173, 1490, 1700, BP, 184, 907, MBF, IHT-PI184, TPO and alpha-hydroxyalkyl benzophenone.

In a second aspect, the present invention provides a method for preparing the above memory electrochromic film, comprising the steps of:

forming a rare earth color-changing layer on the ITO surface of the ITO conducting layer positioned above by using rare earth metal through magnetron sputtering;

the ion conducting layer comprises the following components in percentage by weight: 30-60 wt% of polyurethane acrylic resin, 40-60 wt% of monomer, 0.1-10 wt% of functional agent and 0.1-5 wt% of initiator are mixed and uniformly mixed to obtain ion conducting layer liquid medicine, and the ion conducting layer liquid medicine is coated on the surface of the rare earth discoloring layer and is subjected to ultraviolet curing to obtain an ion conducting layer;

the ion storage layer comprises the following components in percentage by weight: 10-50 wt% of functional ionic compound, 10-40 wt% of complexing agent, 1-30 wt% of stabilizer, 0.1-10 wt% of initiator I and 20-50% of solvent are uniformly mixed to obtain ion storage layer liquid medicine, and the ion storage layer liquid medicine is coated on the surface of the ion conduction layer and is subjected to ultraviolet curing to obtain an ion storage layer;

assembling an ITO conductive layer below the ion storage layer;

and then assembling a PET substrate on the outer sides of the two ITO conductive layers to obtain the ITO conductive layer.

Further, the rare earth metal is formed into the rare earth discoloring layer through magnetron sputtering, and the content of oxygen atmosphere in magnetron sputtering is 1-50%.

Further, the control parameters of the preparation process of the ion conducting layer liquid medicine are as follows: the temperature is 20-50 ℃, the stirring speed is more than 300rpm, and the stirring time is 4-10 min.

Further, the control parameters of the preparation process of the ion storage layer liquid medicine are as follows: the temperature is 25-65 ℃, the stirring speed is more than 300rpm, and the stirring time is 4-10 min.

Further, the control parameters of the preparation process of the ion conducting layer liquid medicine and the preparation process of the ion storage layer liquid medicine for ultraviolet curing are as follows: the ultraviolet light intensity is not less than 24 mu m/cm²The curing time is 4-10 min.

In a third aspect, the present invention provides the use of the above-described memory electrochromic film or the memory electrochromic film obtained by the above-described production method.

Compared with the prior art, the invention has the beneficial effects that:

firstly, the invention can produce the solid flexible coiled color-changing film by creatively designing the solid ion conducting layer and the ion storage layer, the film has the characteristic of flexibility and deformability, and the composition is a cured colloid, so the invention has the advantages of no leakage, weather resistance, convenient processing and no fear of water vapor invasion, and the invention has simple raw materials, simplified process and easy industrial production.

Secondly, the color-changing film is based on 1.5-3 v low-voltage direct current, and the power consumption is less than 2W/m²The color memory material has the memory function and uniform color, and is a novel environment-friendly, functional and decorative material with electro-optic response.

Drawings

Fig. 1 is a schematic structural view of a memory electrochromic film according to embodiment 1 of the present invention, in which 1-an upper PET substrate, 2-an upper ITO conductive layer, 3-a rare earth electrochromic layer, 4-an ion conductive layer, 5-an ion storage layer, 6-a lower ITO conductive layer, and 7-a lower PET substrate.

Detailed Description

In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.