CN114851657A - Editable dynamic phosphorescent flexible film and application method thereof - Google Patents

Editable dynamic phosphorescent flexible film and application method thereof Download PDF

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CN114851657A
CN114851657A CN202210517019.8A CN202210517019A CN114851657A CN 114851657 A CN114851657 A CN 114851657A CN 202210517019 A CN202210517019 A CN 202210517019A CN 114851657 A CN114851657 A CN 114851657A
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flexible film
phosphorescent
dynamic
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film
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刘彦峰
严伟
屈军乐
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Shenzhen University
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Shenzhen University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
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    • B32B2307/00Properties of the layers or laminate
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1074Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms

Abstract

The invention discloses an editable dynamic phosphorescent flexible film and an application method thereof, wherein the flexible film comprises a first protective layer, a functional layer and a second protective layer which are sequentially stacked; the functional layer is a thin film layer made of a polyvinylpyrrolidone material doped with a phosphorescent material; the first protective layer and the second protective layer are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer and the second protective layer are respectively bonded with the upper surface and the lower surface of the functional layer through hot pressing. According to the editable dynamic phosphorescent flexible film, the functional layer is made of the polyvinylpyrrolidone material doped with the phosphorescent material, the film protection layers made of the hydrophobic polymer materials are respectively bonded on the upper surface and the lower surface of the functional layer through hot pressing, the activation and editing of the flexible film by the activation light intensity can be directly adjusted in normal atmosphere, the gray scale image is formed to realize reliable gray scale display, and the application scene of the flexible film is greatly expanded.

Description

Editable dynamic phosphorescent flexible film and application method thereof
Technical Field
The invention relates to the technical field of editable film materials, in particular to an editable dynamic phosphorescent flexible film and an application method thereof.
Background
Recently, room temperature phosphorescent materials and devices based on organic materials have attracted much attention in the fields of display, encryption, anti-counterfeiting and the like because of their special characteristics such as long light emitting life, high signal-to-noise ratio, flexible material and the like. In particular, dynamic room temperature phosphorescent materials with editable features are becoming the focus in the related art. Compared with the traditional static phosphorescent material, the phosphorescent intensity and the service life of the dynamic room temperature phosphorescent material are influenced by the activation condition, so that writing, storage and reading of a phosphorescent image can be conveniently realized in a thin film device made of the material by combining a hollow mask and a pre-exposure process, and further, various application functions including micro-recording, image anti-counterfeiting, logistics marking and the like are realized (Sci Adv 2019; ZL 5: eaau 7310.; Chem Sci 2021; 12: 8199-. Nevertheless, the current application of the dynamic room temperature phosphorescent device is limited to the processing and reading of binary images (i.e. only distinguishing between the on/off states of phosphorescence), which limits the further expansion of its application field to some extent. This situation is closely related to the physical properties of the dynamic room temperature phosphorescent material; the current more mature dynamic room temperature phosphor system is mostly designed based on the principle that organic phosphor generates photodynamic oxygen removal through illumination in oxygen-containing thin film, so as to activate phosphorescence emission, and considering that organic phosphor has low system cross-over efficiency, generally needs to emit detectable signal under low concentration oxygen environment, the activation process usually presents obvious delay or threshold effect, the light dose required for activation is large, and the dosage threshold value is usually too high. Therefore, the problem that gray scale image editing cannot be directly performed by adjusting the activation light intensity exists in the editable phosphorescent flexible thin film material in the prior art method.
Disclosure of Invention
The embodiment of the invention provides an editable dynamic phosphorescent flexible film and a manufacturing method thereof, and aims to solve the problem that gray scale image editing cannot be directly performed by adjusting activation light intensity in an editable phosphorescent flexible film material in the prior art.
In a first aspect, embodiments of the present invention provide an editable dynamic phosphorescent flexible film, wherein,
the protective film comprises a first protective layer, a functional layer and a second protective layer which are sequentially stacked;
the functional layer is a thin film layer made of a polyvinylpyrrolidone material doped with a phosphorescent material;
the first protective layer and the second protective layer are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer and the second protective layer are respectively bonded with the upper surface and the lower surface of the functional layer through hot pressing.
The editable dynamic phosphorescent flexible film is characterized in that the hydrophobic polymer material is one or more of polyethylene terephthalate, polyethylene and polypropylene.
The editable dynamic phosphorescent flexible film is characterized in that the functional layer is prepared by solution casting or blending hot pressing.
The editable dynamic phosphorescent flexible film is characterized in that the mass fraction of the phosphorescent material in the functional layer is 0.1-5%.
The editable dynamic phosphorescence flexible film is characterized in that the phosphorescent material is a small molecule phosphor or a nano luminescent material with a phosphorescence effect.
The editable dynamic phosphorescence flexible film is characterized in that the small molecule phosphor is a water-soluble small molecule with the molecular weight of 100-2000.
The editable dynamic phosphorescence flexible film is characterized in that the nano luminescent material with phosphorescence effect is a carbon dot material.
The editable dynamic phosphorescence flexible film is characterized in that the nano luminescent material with phosphorescence effect is a carbon dot material containing one or more halogen dopes.
In a second aspect, the present invention further provides an application method of an editable dynamic phosphorescent flexible film, where the method is applied to the editable dynamic phosphorescent flexible film of the first aspect, and the method includes:
irradiating a local area or a whole area of the flexible film by adopting a light source with the wavelength of 300-450nm to edit and excite the flexible film; the flexible film comprises a flexible film, a lens system, a mask and a flexible film, wherein the lens system is used for reflecting a two-dimensional gray scale graph or the mask is used for transmitting the two-dimensional gray scale graph so that the two-dimensional gray scale graph is projected on the surface of the flexible film to realize editing and excitation of the flexible film;
and after the flexible film is activated, the phosphorescence intensity imaging and/or service life imaging results at different positions under the same excitation intensity present gray scale images corresponding to the two-dimensional gray scale graph.
The application method of the editable dynamic phosphorescent flexible film is characterized by further comprising the following steps:
and quickly separating different life components in the gray-scale image of the flexible film according to a phasor analysis method to obtain the life statistical information of each life component.
The embodiment of the invention provides an editable dynamic phosphorescent flexible film and an application method thereof, wherein the flexible film comprises a first protective layer, a functional layer and a second protective layer which are sequentially stacked; the functional layer is a thin film layer made of a polyvinylpyrrolidone material doped with a phosphorescent material; the first protective layer and the second protective layer are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer and the second protective layer are respectively bonded with the upper surface and the lower surface of the functional layer through hot pressing. According to the editable dynamic phosphorescent flexible film, the functional layer is made of the polyvinylpyrrolidone material doped with the phosphorescent material, the film protection layers made of the hydrophobic polymer materials are bonded on the upper surface and the lower surface of the functional layer respectively through hot pressing, the activation and editing of the flexible film by the activation light intensity can be directly adjusted in normal atmosphere, the gray scale image is formed to realize reliable gray scale display, the application convenience of the flexible film is improved, and the application scene of the flexible film is greatly expanded.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an editable dynamic phosphorescent flexible film provided by the embodiment of the invention;
FIG. 2 is a schematic diagram illustrating the effect of an editable dynamic phosphorescent flexible film provided in the embodiment of the invention;
FIG. 3 is a schematic diagram of another effect of an editable dynamic phosphorescent flexible film provided by the embodiment of the invention;
FIG. 4 is a schematic diagram illustrating an application effect of an editable dynamic phosphorescent flexible film provided by the embodiment of the invention;
FIG. 5 is a flow chart of a method for applying a dynamic phosphorescent flexible film according to an embodiment of the present invention;
FIG. 6 is a schematic diagram illustrating another application effect of a dynamic phosphorescent flexible film provided in an embodiment of the present invention;
fig. 7 is a schematic diagram illustrating still another application effect of the dynamic phosphorescent flexible film provided in the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
In this embodiment, please refer to fig. 1, wherein fig. 1 is a schematic structural diagram of an editable dynamic phosphorescent flexible film according to an embodiment of the invention. As shown in the figure, the embodiment of the present invention provides an editable dynamic phosphorescent flexible film, which includes a first protective layer 1, a functional layer 2, and a second protective layer 3, which are sequentially stacked; the functional layer 2 is a thin film layer made of a polyvinyl pyrrolidone material doped with a phosphorescent material; the first protective layer 1 and the second protective layer 3 are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer 1 and the second protective layer 3 are respectively bonded with the upper surface and the lower surface of the functional layer 2 through hot pressing.
The upper surface and the lower surface of the functional layer 2 are respectively adhered with a thin film protective layer which is made of hydrophobic polymer materials, namely, the functional layer has waterproof performance. The functional layer 2 is made of polyvinylpyrrolidone material doped with phosphorescent material, and the obtained flexible film is irradiated by a specific light source, so that the phosphorescent material in the flexible film can be activated, and the flexible film can be edited and excited. The chemical formula of polyvinylpyrrolidone (PVP) is shown as follows:
Figure BDA0003640083370000041
in a specific embodiment, the hydrophobic polymer material is one or more of polyethylene terephthalate, polyethylene, and polypropylene. In the specific application process, one or more of polyethylene terephthalate, polyethylene and polypropylene can be used as hydrophobic polymer materials to prepare the first protective layer 1 and the second protective layer 3, and the first protective layer 1 and the second protective layer prepared from the hydrophobic polymer materials can ensure that the flexible film has good light transmission and improve the waterproofness of the flexible film.
In a specific embodiment, the functional layer is prepared by solution casting or blending hot pressing. Specifically, the mass fraction of the phosphorescent material in the functional layer is 0.1% to 5%. In the specific preparation, the functional layer 2 may be prepared by solution casting or blending hot pressing, for example, the functional layer may be prepared by dissolving the polyvinylpyrrolidone material in water to make it in a solution state, adding the phosphorescent material therein, casting, heating to evaporate the solvent, and cooling. Or after the polyvinylpyrrolidone material and the phosphorescent material are mixed, the mixture is subjected to hot press molding through a hot press, so that the functional layer is prepared. In a specific implementation, the thickness of the functional layer may be set to 10-150 μm.
In a specific embodiment, the phosphorescent material is a small molecule phosphor or a nano-luminescent material with a phosphorescent effect. Specifically, the small molecule phosphor is a water-soluble small molecule with a molecular weight of 100-2000. Wherein, the nano luminescent material with phosphorescence effect is a carbon dot material; the nano luminescent material with the phosphorescence effect is a carbon dot material containing one or more halogen dopes.
In the specific application process, the phosphorescent material can be small molecule phosphor or nano luminescent material with phosphorescence effect, the small molecule phosphor can be water-soluble small molecule, and the molecular weight of the small molecule phosphor can be 100-2000. Carbon dot (dots) materials can also be used as the nano-luminescent material having the phosphorescence effect, and in a more preferred embodiment, carbon dot materials containing one or more halogen dopants can be used as the nano-luminescent material, that is, the nano-luminescent material is doped with one or more of F, Cl, Br and I elements.
The following is a comparison of several examples to illustrate the specific implementation and beneficial effects of the scheme.
Example 1
Weighing 1g of 5.8 ten thousand molecular weight PVP, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 1mg of molecular A into the PVP at one time, heating and stirring uniformly at 65 ℃, and volatilizing the ethanol. Wherein the molecular formula of the molecule A is shown as follows:
Figure BDA0003640083370000051
the whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). The obtained product is transferred to a vacuum oven at 120 ℃ for heating and drying for 2h, and then is taken out and is subjected to plastic packaging by using a 50 mu m PET (polyethylene glycol terephthalate) film to obtain an editable dynamic phosphorescent flexible film 1.
Example 2
Weighing 1g of 36 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 20mg of molecular B into the mixture at one time, heating and stirring uniformly at 65 ℃, and volatilizing the ethanol. Wherein the molecular formula of the molecule B is shown as follows:
Figure BDA0003640083370000061
the whole solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm and heated on a hot plate at 30 ℃ overnight to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 50-micrometer PET film to obtain an editable dynamic phosphorescent flexible film 2.
Example 3
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 20mg of molecular C into the mixture at one time, heating and stirring uniformly at 65 ℃, and volatilizing the ethanol. Wherein the molecular formula of molecule C is shown as follows:
Figure BDA0003640083370000062
the whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 50-micrometer PET film to obtain an editable dynamic phosphorescent flexible film 3.
Example 4
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of molecular D into the PVP at one time, heating and stirring uniformly at 65 ℃, and volatilizing the ethanol. Wherein the molecular formula of molecule D is shown below:
Figure BDA0003640083370000063
the whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a PET film with the thickness of 50 mu m to obtain an editable dynamic phosphorescent flexible film 4.
Example 5
2mmol (216mg) of o-phenylenediamine was dissolved in 100mL of ethanol, and 50. mu.L of concentrated hydrochloric acid was added dropwise to the solution. The mixed solution was transferred to a 200mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 20% methanol/dichloromethane mixed solvent) to obtain carbon dot material 1.
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of carbon dot material 1 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
The whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 50 mu m PET film to obtain an editable dynamic phosphorescent flexible film 5.
Example 6
0.5mmol of p-benzoquinone (54mg) was weighed out and dissolved in 100mL of ethanol, and 1mmol of ethylenediamine monohydrate (81. mu.L) was added to the above solution under stirring until uniformly dispersed. The mixed solution was transferred to a 200mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 20% methanol/dichloromethane mixed solvent) to obtain carbon dot material 2.
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of carbon dot material 2 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
The whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 50 mu m PET film to obtain an editable dynamic phosphorescent flexible film 6.
Example 7
0.5mmol of tetrachlorop-benzoquinone (123mg) was weighed out and dissolved in 100mL of ethanol, and 1mmol of ethylenediamine monohydrate (81. mu.L) was added to the above solution under stirring until uniformly dispersed. The mixed solution was transferred to a 200mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 5% methanol/dichloromethane mixed solvent) to obtain carbon dot material 3.
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of carbon dot material 3 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
The whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 50 mu m PET film to obtain an editable dynamic phosphorescent flexible film 7.
Example 8
0.5mmol of tetrabromo-p-benzoquinone (212mg) was weighed out and dissolved in 100mL of ethanol, and 1mmol of ethylenediamine monohydrate (81. mu.L) was added to the above solution under stirring to disperse uniformly. The mixed solution was transferred to a 200mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 5% methanol/dichloromethane mixed solvent) to obtain carbon dot material 4.
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of carbon dot material 4 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
12.5mL of the solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm by 20cm and heated on a hot plate at 30 ℃ overnight to remove most of the solvent, thereby obtaining a functional layer film (10 μm in thickness). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out, and then carrying out plastic package by using a 100 mu m PET film to obtain an editable dynamic phosphorescent flexible film 8.
Example 9
0.5mmol of tetrafluorop-benzoquinone (90mg) was weighed out and dissolved in 100mL of ethanol, and 1mmol of ethylenediamine monohydrate (81. mu.L) was added to the above solution under stirring until uniform dispersion. The mixed solution was transferred to a 200mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 10% methanol/dichloromethane mixed solvent) to obtain carbon dot material 5.
Weighing 4g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 100mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 5mg of carbon dot material 5 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
The whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness: 200 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 10-micron polyethylene film to obtain an editable dynamic phosphorescent flexible film 9.
Example 10
0.5mmol of tetraiodop-benzoquinone (305mg) was weighed out and dissolved in 200mL of ethanol, and 1mmol of ethylenediamine monohydrate (81. mu.L) was added to the above solution under stirring until uniformly dispersed. The mixed solution was transferred to a 400mL hydrothermal reaction vessel, sealed, heated at 160 ℃ for 12 hours, and naturally cooled to room temperature. Filtering, rotary distilling to remove solvent, collecting product, dialyzing, and purifying with silica gel column chromatography (eluent: 5% methanol/dichloromethane mixed solvent) to obtain carbon dot material 6.
Weighing 1g of 130 ten thousand PVP with molecular weight, dissolving the PVP in 40mL of double distilled water under stirring, heating to 50 ℃, adding ethanol dissolved with 50mg of carbon dot material 6 into the solution at one time, heating and stirring the solution uniformly at 65 ℃, and volatilizing the ethanol.
The whole of the above solution was transferred to a square flat-bottomed polystyrene petri dish of 20cm × 20cm, and heated overnight on a heating plate at 30 ℃ to remove most of the solvent, thereby obtaining a functional layer film (thickness 50 μm). And transferring the film to a vacuum oven at 120 ℃, heating and drying for 2h, taking out the film, and plastically packaging the film by using a 200 mu m PET film to obtain the editable dynamic phosphorescent flexible film 10.
Referring to fig. 5, fig. 5 is a flowchart of a method for applying an editable dynamic phosphorescent flexible film according to an embodiment of the invention, wherein the application method is applied to the editable dynamic phosphorescent flexible film, as shown in fig. 5, and the method includes steps S110 to S120.
S110, irradiating a local area or a whole area of the flexible film by using a light source with the wavelength of 300-450nm to edit and excite the flexible film.
Irradiating a local area or a whole area of the flexible film by adopting a light source with the wavelength of 300-450nm to edit and excite the flexible film; the flexible film comprises a flexible film, a lens system, a mask and a flexible film, wherein the lens system is used for collecting a two-dimensional gray scale reflected light pattern or the mask is used for transmitting the two-dimensional gray scale pattern, so that the two-dimensional gray scale pattern is projected on the surface of the flexible film, and the flexible film is edited and excited. After the flexible thin film is prepared, a light source can be adopted to irradiate a local area or a whole area of the flexible thin film, for example, a lens system is adopted to collect a two-dimensional gray-scale reflected light pattern or a mask is adopted to transmit the two-dimensional gray-scale pattern, so that the two-dimensional gray-scale pattern is projected on the surface of the flexible thin film, and the purpose of editing and exciting the flexible thin film is achieved.
S120, displaying gray scale images corresponding to the two-dimensional gray scale graph according to the phosphorescence intensity imaging and/or service life imaging results at different positions under the same excitation intensity after the flexible film is activated.
In an embodiment, the step S120 further includes the following steps: and quickly separating different life components in the gray-scale image of the flexible film according to a phasor analysis method to obtain the life statistical information of each life component.
In the specific application process, the mask or the objective lens is used for adjusting the distribution of ultraviolet light intensity, and the editing and reading of any gray scale two-dimensional graph can be realized on the surface of the flexible film.
For example, the activation curves of the dynamic phosphorescence of the flexible thin film 6 and the flexible thin film 7 prepared as described above (the flexible thin film 6 and the flexible thin film 7 correspond to the thin films prepared in examples 6 and 7, respectively) were measured using a spectrometer (edinburgh FLS980/FLS1000) equipped with a xenon flash lamp under the following measurement conditions: 50 Hz; excitation wavelength: 400 nm; phosphorescence collection wavelength: 580 nm; light intensity at sample: 0.1mW/cm 2 . The measurement result is shown in fig. 2, and fig. 2 is a dynamic phosphorescence activation curve obtained by measuring the dynamic phosphorescence flexible film, wherein the y-axis value is normalized phosphorescence intensity; the x-axis value is the light dose and is obtained by multiplying the light intensity at the sample by the irradiation time. Further, the data is processed as follows: 1. intersecting with the x-axis along the curve at the initial point of phosphorescence enhancement, and the intercept is the illumination dose threshold (marked as D) for dynamic phosphorescence activation of the flexible film th ). 2. The illumination dose corresponding to the x-axis is taken at a normalized phosphorescence intensity of 50%, and is recorded as D 1/2 . 3. Calculating D th And D 1/2 Is marked as R th . The calculation results are shown in table 1, and the information shown in table 1 is the dynamic phosphor activation kinetic parameters of the flexible film 6 and the flexible film 7.
TABLE 1
Flexible film 6 Flexible film 7
D th (mJ/cm 2 ) 12.3 0.7
D 1/2 (mJ/cm 2 ) 32.5 7.1
R th 0.38 0.09
In the above results, D th The numerical value of (2) shows the lowest absolute light dose of the flexible film when the flexible film is subjected to gray scale image processing, namely the lower limit of the light dose in the ideal working range; r th The numerical value of (a) shows the lowest relative light dose of the flexible film when gray scale image processing is performed, i.e. the lower limit of the light transmittance of the ideal working range when the mask method is adopted.
In the subsequent test process, the light intensity is 10mW/cm 2 The 400nm ultraviolet light penetrates through an ITE standard gray scale card mask to expose a flexible thin film 7 for 2s, intensity and service life numerical values at gray scales of 1-11 are shown in figure 3, the figure 3 is a schematic diagram of display effects of phosphorescence intensity and service life gray scale of a dynamic phosphorescence flexible thin film, wherein a graph (a) in figure 3 is the phosphorescence intensity of the thin film, and a graph (b) in figure 3 is the display effects of the service life gray scale.
FIG. 4 is a schematic diagram of the process and effect of editing and reading multiple gray scale phosphorescent patterns by the dynamic phosphorescent flexible film. In the subsequent application, as shown in FIG. 4, a light intensity of 10mW/cm was used 2 The flexible film 7 was exposed to 400nm UV light through the mask 1 for 2 seconds, and after removing the mask, the whole was set at 10mW/cm 2 Exposing for 20ms under 400nm ultraviolet light, and observing gray scale phosphorescent patterns corresponding to the shapes of the masks after excitation is closed; after exposure is continued for more than 10 seconds (overexposure), the image disappears, and the flexible film 7 can be restored to the original state by further heating. When editing again, the light intensity is 10mW/cm 2 The flexible film 7 was exposed to 400nm UV light through the mask 2 for 2 seconds, and the mask was removed and the whole was set at 10mW/cm 2 And exposing the mask to 400nm ultraviolet light for 20ms, and observing a gray-scale phosphorescent pattern corresponding to the shape of the mask after the excitation is closed.
Fig. 6 is a schematic diagram of an application of the dynamic phosphorescent flexible thin film device to perform gray scale image acquisition through an objective lens, wherein (a) in fig. 6 is a schematic diagram of a gray scale image acquisition system, and (b) in fig. 6 is a final restored gray scale image.
In the subsequent application process, as shown in fig. 6 (a), the flexible film 7 is attached to the imaging screen and a convex lens (objective lens) is used to collect the ultraviolet light reflected by the object, so as to obtain a corresponding reflected image. After a period of exposure, the flexible film 7 was recovered and integrated at 10mW/cm 2 And is exposed for 20ms to 400nm ultraviolet light, and an ultraviolet reflection image of the object can be observed after the excitation is turned off as shown in (b) of fig. 6.
FIG. 7 is a schematic diagram of the effect of the dynamic phosphorescent flexible thin film after mask processing, in which (a) in FIG. 7 is a graph of the effect of a multi-level gray-scale phosphorescent pattern, (b) in FIG. 7 is a lifetime imaging result, and (c) in FIG. 7 is a phasor analysis result. During the subsequent application, the flexible film 7 was processed following the editing method as in fig. 4 using a mask having a multilevel gray-scale transmittance, and the whole was 10mW/cm 2 After exposure to 400nm UV light for 20ms, a gray scale phosphorescent pattern of corresponding shape was observed after off-excitation as shown in FIG. 7 (a). The luminescence lifetime at various positions of the flexible film 7 was analyzed under the phosphorescent lifetime imaging conditions, and the results are shown in (b) of fig. 7. Further, processing the imaging result based on the phasor analysis method can rapidly separate the corresponding portions of different gray levels, and the result is shown in (c) of fig. 7.
The specific process of the phasor analysis method comprises the following steps: based on the collected life imaging data, the attenuation of the luminous intensity of each pixel point in the image along with the time is converted, and the specific process is shown as a formula (1) and a formula (2):
Figure BDA0003640083370000121
Figure BDA0003640083370000122
where ω is the angular frequency of the pulsed laser employed to acquire the lifetime imaging results, C k Is the intensity of a certain pixel at a specific time (corresponding to the k-th frame), I is C k The sum of the values is accumulated, N is the total number of acquisition frames, t k Is the length of time between two frames. The (G, S coordinates) corresponding to each pixel point are obtained through the above conversion, and the result shown in (c) of fig. 7 is plotted in a polar coordinate system.
In the phasor diagram of the diagram (c) of fig. 7, the scatter coordinates correspond to the lifetime attenuation characteristics of each pixel in the original image, and the color represents the density of the scatter distribution. In the graph (c) of fig. 7, the clusters of points located near the semi-circular curves have a characteristic close to single exponential decay, corresponding to the dominant luminescence signal in the image; clusters of points that deviate significantly from the semi-circular curve have multi-exponential decay characteristics corresponding to refracted/scattered noise signals inside the flexible film. In the signal part, the signal part can be divided into two parts of a selection area 1 and a selection area 2 according to the position on the semicircular curve, wherein the selection area 1 corresponds to the component with longer service life (77 milliseconds), and the selection area 2 corresponds to the component with shorter service life (66 milliseconds). The phasor analysis only needs to carry out coordinate conversion on the intensity and the time, and does not relate to fitting based on a least square method, and the calculated amount related to the processing of the service life information in the flexible thin film display gray scale graph by adopting the phasor analysis is far less than that of the service life fitting-based analysis, so that the flexible thin film has the advantages of being more convenient and efficient in practical application, and the application scene of the flexible thin film can be greatly expanded while the convenience of the flexible thin film application is improved. Can be widely applied to specific products such as greenhouses, artware editing and the like.
The embodiment of the invention provides an editable dynamic phosphorescent flexible film and an application method thereof, wherein the flexible film comprises a first protective layer, a functional layer and a second protective layer which are sequentially stacked; the functional layer is a thin film layer made of a polyvinylpyrrolidone material doped with a phosphorescent material; the first protective layer and the second protective layer are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer and the second protective layer are respectively bonded with the upper surface and the lower surface of the functional layer through hot pressing. According to the editable dynamic phosphorescent flexible film, the functional layer is made of the polyvinylpyrrolidone material doped with the phosphorescent material, the film protection layers made of the hydrophobic polymer materials are bonded on the upper surface and the lower surface of the functional layer respectively through hot pressing, the activation and editing of the flexible film by the activation light intensity can be directly adjusted in normal atmosphere, the gray scale image is formed to realize reliable gray scale display, the application convenience of the flexible film is improved, and the application scene of the flexible film is greatly expanded.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The editable dynamic phosphorescent flexible film is characterized by comprising a first protective layer, a functional layer and a second protective layer which are sequentially stacked;
the functional layer is a thin film layer made of a polyvinylpyrrolidone material doped with a phosphorescent material;
the first protective layer and the second protective layer are both thin film protective layers made of hydrophobic polymer materials, and the first protective layer and the second protective layer are respectively bonded with the upper surface and the lower surface of the functional layer through hot pressing.
2. The editable dynamic phosphorescent flexible film according to claim 1, wherein the hydrophobic polymer material is one or more of polyethylene terephthalate, polyethylene and polypropylene.
3. The editable dynamic phosphorescent flexible film according to claim 1, wherein the functional layer is prepared by solution casting or hot-pressing blending.
4. An editable dynamic phosphorescent flexible film according to claim 1 or 3, wherein the mass fraction of the phosphorescent material in the functional layer is 0.1-5%.
5. The editable dynamic phosphorescent flexible film according to claim 4, wherein the phosphorescent material is a small molecule phosphor or a nano luminescent material with a phosphorescent effect.
6. The editable dynamic phosphorescent flexible film according to claim 5, wherein the small molecule phosphor is a water-soluble small molecule with a molecular weight of 100-2000.
7. The editable dynamic phosphorescent flexible film according to claim 5, wherein the nano luminescent material with phosphorescent effect is a carbon dot material.
8. The editable dynamic phosphorescent flexible film according to claim 7, wherein the nano luminescent material with phosphorescent effect is a carbon dot material containing one or more halogen dopants.
9. A method of applying an editable dynamic phosphorescent flexible film, wherein the method is applied to the editable dynamic phosphorescent flexible film according to any one of claims 1 to 8, and the method comprises the following steps:
irradiating a local area or a whole area of the flexible film by adopting a light source with the wavelength of 300-450nm to edit and excite the flexible film; the flexible film comprises a flexible film, a lens system, a mask and a flexible film, wherein the lens system is used for reflecting a two-dimensional gray scale graph or the mask is used for transmitting the two-dimensional gray scale graph so that the two-dimensional gray scale graph is projected on the surface of the flexible film to realize editing and excitation of the flexible film;
and after the flexible film is activated, the phosphorescence intensity imaging and/or service life imaging results at different positions under the same excitation intensity present gray scale images corresponding to the two-dimensional gray scale graph.
10. The method of applying an editable dynamic phosphorescent flexible film according to claim 9, wherein the method further comprises:
and quickly separating different life components in the gray-scale image of the flexible film according to a phasor analysis method to obtain the life statistical information of each life component.
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