WO2020000942A1 - Transparent, flexible and stretchable electromagnetic shielding thin film and method for preparing same - Google Patents

Transparent, flexible and stretchable electromagnetic shielding thin film and method for preparing same Download PDF

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WO2020000942A1
WO2020000942A1 PCT/CN2018/123384 CN2018123384W WO2020000942A1 WO 2020000942 A1 WO2020000942 A1 WO 2020000942A1 CN 2018123384 W CN2018123384 W CN 2018123384W WO 2020000942 A1 WO2020000942 A1 WO 2020000942A1
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layer
transparent
colloidal particles
stretchable
flexible
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PCT/CN2018/123384
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French (fr)
Chinese (zh)
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胡友根
赵涛
张馨予
梁先文
朱朋莉
孙蓉
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中国科学院深圳先进技术研究院
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • 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
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties

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  • the invention relates to an electromagnetic shielding material, particularly a transparent flexible stretchable electromagnetic shielding film and a preparation method thereof.
  • Electromagnetic shielding material is an effective means to protect against electromagnetic radiation pollution, and has received wide attention and application in recent years.
  • Chinese invention patent CN 102063951B proposes a transparent conductive film based on nano-imprint and nano-coating methods. Trenches are formed by nano-imprint, and nano-conductive materials are filled in the trenches, and then sintered to form high-performance conductive films. For making electromagnetic shielding films. During the sintering process of the nano-conductive material, the organic solvent is volatilized, and the metal particles in the conductive material are aggregated to form a conductive grid structure. In this solution, the conductive material is sintered at low temperature, and the contact resistance between metal particles is large, which affects the conductivity of the grid structure, thereby affecting the electromagnetic shielding performance of the thin film produced by this solution.
  • Invention patent CN106061218A discloses a method for manufacturing a transparent electromagnetic shielding film based on photolithography, electrodeposition process and embossing process. It has the advantages of high transparency, good temperature resistance, and can realize flexible bending and complex structure surface bonding. Claim.
  • the photolithography process often requires complex process technology and expensive equipment to support, and the production cost is high, which is not suitable for the low cost requirements of large-scale production.
  • transparent electromagnetic shielding films are based on polyester (PET) or polyimide (PI) materials, and often have only flexible flexibility, but not stretchability. This is suitable for flexible wearable electronics.
  • PET polyester
  • PI polyimide
  • the present invention provides a stretchable flexible transparent electromagnetic shielding film with low cost, simple structure, and convenient manufacture, and a preparation method thereof.
  • the invention first prepares a transparent elastic substrate, and then self-assembles colloidal particles on its surface.
  • a metal layer is prepared by etching and magnetron sputtering techniques. After removing the colloidal particles, a grid-like metal layer is obtained.
  • a transparent elastomer encapsulation layer is prepared, and the structure and performance of the mesh metal layer during mechanical deformation such as bending and stretching are further stabilized by firmly bonding the substrate layer and the encapsulation layer without an interface.
  • the stretchable flexible transparent electromagnetic shielding film provided by the present invention comprises a transparent flexible stretchable substrate layer; a hole grid metal shielding layer and a transparent flexible stretchable encapsulation layer;
  • the grid-like metal shielding layer is between a transparent flexible stretchable substrate layer and a transparent flexible stretchable encapsulation layer.
  • the transparent flexible stretchable substrate layer or transparent flexible stretchable encapsulation layer is made of one or more materials selected from silicone, thermoplastic polyurethane, and polyolefin elastomer transparent elastomer.
  • the silica gel is selected from the group consisting of polydimethylsiloxane, polydimethyldiphenylsiloxane, polyvinyltriisopropoxysilane, and polymethylvinylsiloxane.
  • the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material or different materials.
  • the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material, and the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material. The materials are fused with each other and there is no obvious interface.
  • the grid-shaped metal shielding layer is made of one or more magnetic shielding materials of gold, silver, copper, nickel, aluminum, iron, and carbon, and has a hole-like grid shape.
  • the hole grid metal shielding layer is made of one or more magnetic shielding materials of gold, silver, copper, nickel, aluminum, iron, and carbon by a physical vapor deposition or chemical vapor deposition method. Deposited in a transparent flexible stretchable substrate layer.
  • the minimum value of the grid line width of the grid-shaped metal shielding layer is 10 nm-100 ⁇ m, and preferably 100 nm-10 ⁇ m.
  • the maximum value of the grid line voids of the grid-shaped metal shielding layer is 100 nm-100 ⁇ m, and preferably 500 nm-50 ⁇ m.
  • the light transmittance of the stretchable flexible transparent electromagnetic shielding film is 50% or more, preferably 60% or more or 70% or more.
  • the stretchable flexible transparent electromagnetic shielding effectiveness is 30 dB or more, preferably 35 dB or more, or 50 dB or more.
  • the hole grid metal shielding layer is prepared by the following method:
  • the colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate layer.
  • the diameter of the colloidal particles is higher than the highest value of the grid line voids of the grid-like metal shielding layer.
  • step ii) the distance between the non-closely arranged colloidal particles is higher than or equal to the minimum value of the grid line width of the grid-like metal shielding layer.
  • the etching method includes a plasma etching method and a reactive ion etching method.
  • the colloid particles used are selected from the group consisting of polystyrene microspheres, silica microspheres, polymethyl methacrylate microspheres, polyacrylic microspheres, polyphenolic resin microspheres, and polyurea resin microspheres.
  • Spheres poly (propylene methacrylate) microspheres.
  • the colloidal particles used are selected from 10 nm to 100 ⁇ m, preferably 100 nm to 50 ⁇ m.
  • the thickness of the transparent flexible stretchable substrate layer is 20-500 ⁇ m.
  • the thickness of the transparent flexible stretchable encapsulation layer is 20-500 ⁇ m.
  • the present invention also provides a method for preparing a stretchable flexible transparent electromagnetic shielding film, including the following steps:
  • the magnetic shielding material is sputtered on the non-tightly arranged single-layer colloidal particles and the transparent flexible stretchable substrate layer by physical vapor deposition and chemical vapor deposition methods;
  • the colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate.
  • the preparation method includes the following steps:
  • the silicone prepolymer and its curing agent are mixed and heat-cured through casting, spin coating and other processes to obtain a transparent and flexible stretchable silicone substrate; or transparent thermoplastic polyurethane and polyolefin elastomer are used as raw materials and dissolved in a solvent
  • a transparent flexible stretchable polyurethane or polyolefin substrate is obtained through thermal curing treatment through processes such as injection molding, blow molding, extrusion, and spin coating.
  • Plasma etching, reactive ion etching and other methods are used to etch the close-packed single-layer colloidal particles into a non-close-packed shape
  • magnetic shielding materials such as gold, silver, copper, nickel, aluminum, iron, and carbon are sputtered onto non-tightly arranged single-layer colloidal particles and a transparent flexible stretchable substrate ;
  • the colloidal particles are removed by solvent dissolution and etching to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate.
  • the transparent flexible stretchable substrate, the grid-like metal shielding layer, and the transparent flexible stretchable encapsulation layer together form a flexible transparent stretchable electromagnetic shielding film, in which the grid-like metal shielding layer is on a transparent flexible stretchable liner. Between the bottom and the transparent flexible stretchable encapsulation layer.
  • the structure of the present invention is simple and stable. It is a sandwich sandwich structure of a stretchable transparent film on the upper and lower layers and a grid-like metal layer in the middle layer. The upper and lower materials are firmly bonded through the gap area of the metal grid, thereby making the middle The structure of the metal grid layer can maintain good stability even in the state of bending and stretching.
  • the preparation process of the present invention is simple.
  • the grid-like metal layer adopts colloidal particle self-assembly and etching methods to achieve non-close contact arrangement.
  • the grid-like metal layer can be formed on a transparent elastic substrate through a magnetron sputtering process.
  • the invention has high light transmittance and electromagnetic shielding effectiveness, and it is easy to realize performance regulation.
  • the size of the metal grid line width (tens of nanometers to tens of micrometers) and the grid gap (hundreds of nanometers to tens of micrometers) can be easily realized. , And then control its light transmittance and electromagnetic shielding performance.
  • FIG. 1 is a schematic structural diagram (a plan view) of a stretchable flexible transparent electromagnetic shielding film.
  • FIG. 2 is a schematic structural diagram (section) of a stretchable flexible transparent electromagnetic shielding film.
  • FIG. 3 is a schematic structural view of a stretchable flexible transparent electromagnetic shielding film in a stretched state (plan view).
  • 1 is a transparent flexible stretchable substrate
  • 2 is a transparent flexible stretchable encapsulation layer
  • 3 is a grid-like metal shielding layer.
  • FIG. 4 is a SEM image of a hole-shaped gold film shielding layer vapor-deposited on the surface of the PDMS film without an encapsulation layer.
  • FIG. 5 is a SEM image of a hole-shaped gold film shielding layer vapor-deposited on the surface of the PDMS film without an encapsulation layer.
  • Polydimethylsiloxane (PDMS) precursor and its curing agent were mixed at a mass ratio of 10: 1, and the mixed solution was spin-coated on a glass substrate by a spin coating process, and then heated and cured at 60 ° C for 30 minutes to form a half. Cured PDMS film.
  • the thickness of the final PDMS film (20-500 ⁇ m) can be adjusted by controlling the spin speed (400-2000 rpm) and time (5-30 seconds).
  • the PS microsphere colloid single layer was self-assembled on the surface of the PDMS film by a gas-liquid interface self-assembly method to form a close-packed PS colloid array .
  • the plasma is used to etch the closely arranged PS colloidal particles into a non-closely arranged structure.
  • the degree of etching (the distance between adjacent PS colloidal particles) can be determined by the etching power and the etching time. Regulate and control, in this case, the pitch is controlled to about 1 ⁇ m.
  • Metal silver was deposited on the above-not-closely arranged PS colloidal particles and their PDMS substrate (the front surface of the PS colloidal particles and the PDMS surface between the colloidal particles) by the magnetron sputtering method. Due to the low elastic modulus of semi-cured PDMS, the magnetron sputtered silver will be embedded into the inner surface layer of the PDMS film to some extent, forming a more stable conductive silver layer. Solvents such as N, N-dimethylformamide, toluene, and tetrahydrofuran are used to dissolve and remove the PS colloid particles. In this process, the silver deposited on the surface of the PS colloid particles will be removed by the disappearance of the PS carrier, leaving only the deposition.
  • Solvents such as N, N-dimethylformamide, toluene, and tetrahydrofuran are used to dissolve and remove the PS colloid particles. In this process, the silver deposited on the surface of the PS colloid particles will be removed by
  • the grid-like metallic silver on the PDMS film that is, the electromagnetic shielding metal layer.
  • a PDMS encapsulation layer was prepared on the surface of the grid-like metallic silver PDMS film by spin coating again, and the film formation conditions were 80 ° C and 2 hours. Since the PDMS in the first step is a semi-cured body, during the curing process of the re-encapsulation layer, the two will continue to undergo chemical cross-linking reactions at the interface, thereby forming a strong bond without an obvious interface layer, and further stabilizing the grid-like metallic silver. It is fixed between the PDMS substrate layer and the encapsulation layer.
  • both the PDMS substrate and the encapsulation layer are transparent, and the line width of the grid-like silver conductive network in the middle is only about 1 ⁇ m, which has good light transmittance, the PDMS film can be pulled off from the glass substrate to obtain a pull.
  • Flexible transparent electromagnetic shielding film its light transmittance is 85%, and its electromagnetic shielding effectiveness is 35dB.
  • thermoplastic polyurethane TPU
  • DMF dimethylformamide
  • TPU thermoplastic polyurethane
  • silica (SiO 2 ) microsphere dispersion with an average particle diameter of 500 nm as a colloid a single layer of SiO 2 microsphere colloid was self-assembled on the surface of the TPU film by a self-assembly method to form a closely-aligned SiO 2 colloid array.
  • Re-reactive ion etching etches closely-aligned PS colloidal particles into a non-close-packed structure.
  • the degree of etching (the distance between adjacent SiO 2 colloidal particles) can be measured by gas flow, temperature, and gas pressure. The etching process is controlled, and the shortest distance between SiO 2 colloidal particles is controlled at about 200 nm in this case.
  • Gold was deposited onto the above-not-closely arranged SiO 2 colloidal particles and its TPU substrate (the front surface of the SiO 2 colloidal particles and the surface of the gap TPU between the colloidal particles) by a magnetron sputtering method.
  • the magnetron sputtered gold will be embedded into the inner surface layer of the TPU film to some extent, forming a more stable conductive gold layer.
  • hydrofluoric acid is used to dissolve and remove the SiO 2 colloidal particles.
  • the gold deposited on the surface of the SiO 2 colloidal particles will be removed due to the disappearance of the SiO 2 carrier, leaving only the grid-like metal gold deposited on the TPU film. , That is, the electromagnetic shielding metal layer.
  • a TPU encapsulation layer was prepared on the surface of the TPU film of the grid-like gold layer by spin coating, blade coating, and casting.
  • the solvent contained in the TPU solution of the encapsulation layer can dissolve the TPU of the substrate layer to a certain extent at the interface, the TPU substrate layer and the TPU encapsulation layer can form a strong bond without obvious interface during the film formation process of the encapsulation layer.
  • the grid-like gold layer is stably fixed between the TPU substrate layer and the encapsulation layer. Because the TPU substrate and the encapsulation layer are both transparent, and the line width of the grid-like gold conductive network in the middle is only about 200 nm, which has good light transmittance, a stretchable flexible transparent electromagnetic shielding film is prepared. The optical efficiency is 70% and the electromagnetic shielding effectiveness is 50dB.

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Abstract

Disclosed are a transparent, flexible and stretchable electromagnetic shielding thin film and a method for preparing same. The electromagnetic shielding thin film comprises: a transparent, flexible and stretchable substrate; a grid-shaped metal shielding layer; and a transparent, flexible and stretchable encapsulation layer. The grid-shaped metal shielding layer is between the transparent, flexible and stretchable substrate and the transparent, flexible and stretchable encapsulation layer. The grid-shaped metal shielding layer is prepared by means of a combination of a colloidal etching method and a metal deposition method, and the main steps thereof are: 1) closely arranging a single layer of colloidal particles on the transparent, flexible and stretchable substrate; 2) etching the single layer of closely arranged colloidal particles to be in a non-close arrangement; 3) depositing a nano-metal layer on the transparent, flexible and stretchable substrate for the single layer of non-closely arranged colloidal particles; and 4) removing the colloidal particles to obtain the grid-shaped metal shielding layer deposited on the transparent, flexible and stretchable substrate. The flexible and stretchable electromagnetic shielding thin film prepared according to the present invention is simple in structure and easy to manufacture, and has a good stretchability and electromagnetic shielding performance.

Description

一种透明柔性可拉伸的电磁屏蔽薄膜及其制备方法Transparent flexible stretchable electromagnetic shielding film and preparation method thereof 技术领域Technical field
本发明涉及一种电磁屏蔽材料，尤其是透明柔性可拉伸的电磁屏蔽薄膜及其制备方法。The invention relates to an electromagnetic shielding material, particularly a transparent flexible stretchable electromagnetic shielding film and a preparation method thereof.
背景技术Background technique
随着电子产业的迅猛发展和电子设备的广泛应用，电子器件辐射的电磁波不仅可能导致电子器件非正常工作，也影响到人们的健康生活，甚至会破坏军事设备的敏感器件，使无线电通讯指挥系统、武器作战平台等受到损坏。电磁屏蔽材料是一种防护电磁辐射污染的有效手段，近年来受到广泛关注和应用。With the rapid development of the electronics industry and the widespread application of electronic equipment, the electromagnetic waves radiated by electronic devices may not only cause electronic devices to malfunction, but also affect people's healthy lives, and even damage sensitive devices of military equipment, making radio communication command systems. , Weapon combat platforms, etc. were damaged. Electromagnetic shielding material is an effective means to protect against electromagnetic radiation pollution, and has received wide attention and application in recent years.
在不同的应用领域，对电磁屏蔽的效能提出了不同的要求。而在一些特殊用途，对电磁屏蔽材料的透明性及柔性等有相应的特殊要求。比如对光学窗口等透明光学器件，其电磁屏蔽材料除了满足电磁屏蔽效能外，还要求具备良好的光学透明性。为了制备透明电磁屏蔽材料，中国发明专利CN 104661502A采用金属丝网与PET膜复合制作了透光率50％、电磁屏蔽效能25-46dB的透明电磁屏蔽膜，其丝网的平均直径为35μm、间距为300μm。由于金属丝网的线宽较粗，所以难以制备高透光率的电磁屏蔽膜。中国发明专利CN 102063951B提出了一种基于纳米压印和纳米涂布方法实现的透明导电膜，通过纳米压印形成沟槽，在沟槽中填充纳米导电材料，再烧结形成高性能导电膜，可用于制作电磁屏蔽薄膜。在纳米导电材料烧结过程中，有机溶剂挥发，使导电材料中的金属颗粒聚集形成导电网栅结构。该方案中导电材料为低温烧结，金属颗粒间接触电阻较大，使网栅结构导电性受到影响，从而影响该方案制作薄膜的电磁屏蔽性能。发明专利CN106061218A公开了一种基于光刻技术、电沉积工艺与压印工艺的透明电磁屏蔽膜制作方法，具有高透明度、耐温性好的优点，并可实现柔性弯曲及复杂结构表面贴合的要求。但是，光刻工艺往往需要复杂的制程工艺与昂贵设备支撑，生产成本较高，不适合规模生产对低成本的要求。In different application fields, different requirements are imposed on the effectiveness of electromagnetic shielding. In some special applications, there are corresponding special requirements for the transparency and flexibility of electromagnetic shielding materials. For example, for transparent optical devices such as optical windows, in addition to meeting electromagnetic shielding effectiveness, the electromagnetic shielding material also requires good optical transparency. In order to prepare transparent electromagnetic shielding materials, Chinese invention patent CN 104661502A uses a metal mesh and a PET film to make a transparent electromagnetic shielding film with a light transmittance of 50% and an electromagnetic shielding effectiveness of 25-46dB. The average diameter of the screen is 35 μm and the pitch It was 300 μm. Since the wire width of the metal wire mesh is relatively large, it is difficult to prepare an electromagnetic shielding film having a high light transmittance. Chinese invention patent CN 102063951B proposes a transparent conductive film based on nano-imprint and nano-coating methods. Trenches are formed by nano-imprint, and nano-conductive materials are filled in the trenches, and then sintered to form high-performance conductive films. For making electromagnetic shielding films. During the sintering process of the nano-conductive material, the organic solvent is volatilized, and the metal particles in the conductive material are aggregated to form a conductive grid structure. In this solution, the conductive material is sintered at low temperature, and the contact resistance between metal particles is large, which affects the conductivity of the grid structure, thereby affecting the electromagnetic shielding performance of the thin film produced by this solution. Invention patent CN106061218A discloses a method for manufacturing a transparent electromagnetic shielding film based on photolithography, electrodeposition process and embossing process. It has the advantages of high transparency, good temperature resistance, and can realize flexible bending and complex structure surface bonding. Claim. However, the photolithography process often requires complex process technology and expensive equipment to support, and the production cost is high, which is not suitable for the low cost requirements of large-scale production.
此外，上述透明电磁屏蔽膜大部分以聚酯(PET)或聚酰亚胺(PI)材料为衬底，往往仅具备可挠的柔性，而不具备可拉伸性，这对于柔性可穿戴电子的应用具有较大的局限性。In addition, most of the above-mentioned transparent electromagnetic shielding films are based on polyester (PET) or polyimide (PI) materials, and often have only flexible flexibility, but not stretchability. This is suitable for flexible wearable electronics. The application has greater limitations.
发明内容Summary of the invention
有鉴于此，为了克服上述缺陷和问题，本发明提供一种成本低廉、结构简单、制作方便的可拉伸柔性透明电磁屏蔽薄膜与制备方法。本发明首先制备透明的弹性衬底，再在其表面自组装胶体颗粒，通过刻蚀与磁控溅射技术制备金属层，去除胶体颗粒后，便得到网格状的金属层，在此基础上制备透明弹性体封装层，通过衬底层与封装层的无界面牢固粘结，进一步实现网格金属层在弯曲、拉伸等机械变形过程中的结构与性能稳定。In view of this, in order to overcome the above-mentioned defects and problems, the present invention provides a stretchable flexible transparent electromagnetic shielding film with low cost, simple structure, and convenient manufacture, and a preparation method thereof. The invention first prepares a transparent elastic substrate, and then self-assembles colloidal particles on its surface. A metal layer is prepared by etching and magnetron sputtering techniques. After removing the colloidal particles, a grid-like metal layer is obtained. On this basis, A transparent elastomer encapsulation layer is prepared, and the structure and performance of the mesh metal layer during mechanical deformation such as bending and stretching are further stabilized by firmly bonding the substrate layer and the encapsulation layer without an interface.
本发明的具体方案如下：The specific scheme of the present invention is as follows:
本发明提供的可拉伸柔性透明电磁屏蔽膜，其包括透明柔性可拉伸衬底层；孔洞网格状金属屏蔽层以及透明柔性可拉伸封装层；The stretchable flexible transparent electromagnetic shielding film provided by the present invention comprises a transparent flexible stretchable substrate layer; a hole grid metal shielding layer and a transparent flexible stretchable encapsulation layer;
所述网格状金属屏蔽层在透明柔性可拉伸衬底层与透明柔性可拉伸封装层之间。The grid-like metal shielding layer is between a transparent flexible stretchable substrate layer and a transparent flexible stretchable encapsulation layer.
在本发明的技术方案中，所述透明柔性可拉伸衬底层或透明柔性可拉伸封装层为硅胶、热塑性聚氨酯、聚烯烃弹性体透明弹性体中的一种或多种材料制成。In the technical solution of the present invention, the transparent flexible stretchable substrate layer or transparent flexible stretchable encapsulation layer is made of one or more materials selected from silicone, thermoplastic polyurethane, and polyolefin elastomer transparent elastomer.
在本发明的技术方案中，所述的硅胶选自聚二甲基硅氧烷、聚二甲基二苯基硅氧烷、聚乙烯基三异丙氧基硅烷、聚甲基乙烯基硅氧烷、聚甲基氢硅氧烷等中的一种或多种。In the technical solution of the present invention, the silica gel is selected from the group consisting of polydimethylsiloxane, polydimethyldiphenylsiloxane, polyvinyltriisopropoxysilane, and polymethylvinylsiloxane. One or more of alkane, polymethylhydrosiloxane, and the like.
在本发明的技术方案中，所述透明柔性可拉伸衬底层与透明柔性可拉伸封装层采用的材料为相同材料或不同材料。In the technical solution of the present invention, the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material or different materials.
在本发明的技术方案中，所述透明柔性可拉伸衬底层与透明柔性可拉伸封装层采用的材料为相同材料，且述透明柔性可拉伸衬底层与透明柔性可拉伸封装层采用的材料为相互融合，无明显界面。In the technical solution of the present invention, the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material, and the transparent flexible stretchable substrate layer and the transparent flexible stretchable packaging layer are made of the same material. The materials are fused with each other and there is no obvious interface.
在本发明的技术方案中，所述网格状金属屏蔽层为金、银、铜、镍、铝、铁、碳中的一种或多种磁屏蔽材料制成，呈孔洞网格状。In the technical solution of the present invention, the grid-shaped metal shielding layer is made of one or more magnetic shielding materials of gold, silver, copper, nickel, aluminum, iron, and carbon, and has a hole-like grid shape.
在本发明的技术方案中，所述孔洞网格状金属屏蔽层通过物理气相沉积、化学气相沉积方法将金、银、铜、镍、铝、铁、碳中的一种或多种磁屏蔽材料沉积在透明柔性可拉伸衬底层中。In the technical solution of the present invention, the hole grid metal shielding layer is made of one or more magnetic shielding materials of gold, silver, copper, nickel, aluminum, iron, and carbon by a physical vapor deposition or chemical vapor deposition method. Deposited in a transparent flexible stretchable substrate layer.
在本发明的技术方案中，网格状金属屏蔽层的网格线宽度最低值为10nm-100μm，优选为100nm-10μm。In the technical solution of the present invention, the minimum value of the grid line width of the grid-shaped metal shielding layer is 10 nm-100 μm, and preferably 100 nm-10 μm.
在本发明的技术方案中，网格状金属屏蔽层的网格线空隙最高值为100nm-100μm，优选为500nm-50μm。In the technical solution of the present invention, the maximum value of the grid line voids of the grid-shaped metal shielding layer is 100 nm-100 μm, and preferably 500 nm-50 μm.
在本发明的技术方案中，可拉伸柔性透明电磁屏蔽膜的透光率在50％以上，优选为60％以上或70％以上。In the technical solution of the present invention, the light transmittance of the stretchable flexible transparent electromagnetic shielding film is 50% or more, preferably 60% or more or 70% or more.
在本发明的技术方案中，可拉伸柔性透明电磁屏蔽效能为30dB以上，优选为35dB以上，或50dB以上。In the technical solution of the present invention, the stretchable flexible transparent electromagnetic shielding effectiveness is 30 dB or more, preferably 35 dB or more, or 50 dB or more.
在本发明的技术方案中，所述孔洞网格状金属屏蔽层通过以下方法制备：In the technical solution of the present invention, the hole grid metal shielding layer is prepared by the following method:
ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒Ⅰ) Tightly arrange a single layer of colloidal particles on a transparent flexible stretchable substrate
通过自组装方法在透明柔性可拉伸衬底层上沉积紧密排列的单层胶体颗粒；Depositing closely arranged single-layer colloidal particles on a transparent flexible stretchable substrate layer by a self-assembly method;
ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状Ii) Etching tightly arranged single-layer colloidal particles into non-closely arranged
通过刻蚀方法将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Etching the closely arranged single-layered colloidal particles into a non-closely arranged pattern by an etching method;
ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层Ⅲ) Deposition of a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles
通过物理气相沉积、化学气相沉积方法将金、银、铜、镍、铝、铁、碳等磁屏蔽材料溅射在将非紧密排列的单层胶体颗粒及透明柔性可拉伸衬底上；Use physical vapor deposition and chemical vapor deposition methods to sputter magnetic shielding materials such as gold, silver, copper, nickel, aluminum, iron, and carbon on non-tightly arranged single-layer colloidal particles and transparent flexible stretchable substrates;
ⅳ)去除胶体颗粒Ⅳ) Remove colloid particles
采用溶剂溶解、刻蚀方法去除胶体颗粒，便得到沉积在透明柔性可拉伸衬底层上的网格状金属屏蔽层。The colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate layer.
所述胶体颗粒的直径高于网格状金属屏蔽层网格线空隙最高值。The diameter of the colloidal particles is higher than the highest value of the grid line voids of the grid-like metal shielding layer.
步骤ii)中非紧密排列状胶体颗粒的间距高于或等于网格状金属屏蔽层的网格线宽度最低值。In step ii), the distance between the non-closely arranged colloidal particles is higher than or equal to the minimum value of the grid line width of the grid-like metal shielding layer.
在本发明的技术方案中，刻蚀方法包括等离子体刻蚀、反应离子刻蚀方法。In the technical solution of the present invention, the etching method includes a plasma etching method and a reactive ion etching method.
在本发明的技术方案中，采用的胶体颗粒选自聚苯乙烯微球、二氧化硅微球、聚甲基丙烯酸甲酯微球、聚丙烯酸微球、聚酚醛树脂微球、聚脲醛树脂微球、聚甲基丙烯酸环氧丙酯微球。In the technical solution of the present invention, the colloid particles used are selected from the group consisting of polystyrene microspheres, silica microspheres, polymethyl methacrylate microspheres, polyacrylic microspheres, polyphenolic resin microspheres, and polyurea resin microspheres. Spheres, poly (propylene methacrylate) microspheres.
在本发明的技术方案中，采用的胶体颗粒选自10nm-100μm，优选为100nm-50μm。In the technical solution of the present invention, the colloidal particles used are selected from 10 nm to 100 μm, preferably 100 nm to 50 μm.
在本发明的技术方案中，透明柔性可拉伸衬底层的厚度为20-500μm。In the technical solution of the present invention, the thickness of the transparent flexible stretchable substrate layer is 20-500 μm.
在本发明的技术方案中，透明柔性可拉伸封装层的厚度为20-500μm。In the technical solution of the present invention, the thickness of the transparent flexible stretchable encapsulation layer is 20-500 μm.
另外，本发明还提供了一种可拉伸柔性透明电磁屏蔽膜的制备方法，包括下述步骤：In addition, the present invention also provides a method for preparing a stretchable flexible transparent electromagnetic shielding film, including the following steps:
(1)制备透明柔性可拉伸衬底(1) Preparation of transparent flexible stretchable substrate
(2)制备网格状金属屏蔽层(2) Preparation of grid-like metal shielding layer
ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒Ⅰ) Tightly arrange a single layer of colloidal particles on a transparent flexible stretchable substrate
通过自组装方法在透明柔性可拉伸衬底上沉积紧密排列的单层胶体颗粒；Depositing closely arranged single-layer colloidal particles on a transparent flexible stretchable substrate by a self-assembly method;
ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状Ii) Etching tightly arranged single-layer colloidal particles into non-closely arranged
通过刻蚀方法将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Etching the closely arranged single-layered colloidal particles into a non-closely arranged pattern by an etching method;
ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层Ⅲ) Deposition of a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles
通过物理气相沉积、化学气相沉积方法将磁屏蔽材料溅射在将非紧密排列的单层胶体颗粒及透明柔性可拉伸衬底层上；The magnetic shielding material is sputtered on the non-tightly arranged single-layer colloidal particles and the transparent flexible stretchable substrate layer by physical vapor deposition and chemical vapor deposition methods;
ⅳ)去除胶体颗粒Ⅳ) Remove colloid particles
采用溶剂溶解、刻蚀方法去除胶体颗粒，得到沉积在透明柔性可拉伸衬底上的网格状金属屏蔽层。The colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate.
(3)制备透明柔性可拉伸封装层(3) Preparation of transparent flexible stretchable packaging layer
在网格状金属屏蔽层上旋涂或浇注硅胶溶液、热塑性聚氨酯溶液、聚烯烃弹性体溶液等，固化成型后形成透明柔性可拉伸封装层。Spin-coated or cast a silicone solution, a thermoplastic polyurethane solution, a polyolefin elastomer solution, etc. on the grid-like metal shielding layer to form a transparent flexible stretchable encapsulation layer after curing.
具体地，制备方法包括以下步骤：Specifically, the preparation method includes the following steps:
(1)制备透明柔性可拉伸衬底(1) Preparation of transparent flexible stretchable substrate
以硅胶预聚物及其固化剂混合，通过浇注、旋涂等工艺经热固化处理得到透明柔性可拉伸的硅胶衬底；或以透明的热塑性聚氨酯、聚烯烃弹性体为原料，采用溶剂溶解配成溶液后，通过注塑、吹塑、挤出、旋涂等工艺经热固化处理得到透明柔性可拉伸的聚氨酯或聚烯烃衬底。The silicone prepolymer and its curing agent are mixed and heat-cured through casting, spin coating and other processes to obtain a transparent and flexible stretchable silicone substrate; or transparent thermoplastic polyurethane and polyolefin elastomer are used as raw materials and dissolved in a solvent After being prepared into a solution, a transparent flexible stretchable polyurethane or polyolefin substrate is obtained through thermal curing treatment through processes such as injection molding, blow molding, extrusion, and spin coating.
(2)制备网格状金属屏蔽层(2) Preparation of grid-like metal shielding layer
ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒Ⅰ) Tightly arrange a single layer of colloidal particles on a transparent flexible stretchable substrate
通过自组装方法在透明柔性可拉伸衬底上沉积紧密排列的单层胶体颗粒；Depositing closely arranged single-layer colloidal particles on a transparent flexible stretchable substrate by a self-assembly method;
ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状Ii) Etching tightly arranged single-layer colloidal particles into non-closely arranged
通过等离子体刻蚀、反应离子刻蚀等方法将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Plasma etching, reactive ion etching and other methods are used to etch the close-packed single-layer colloidal particles into a non-close-packed shape;
ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层Ⅲ) Deposition of a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles
通过物理气相沉积、化学气相沉积等方法将等金、银、铜、镍、铝、铁、碳等磁屏蔽材料溅射在将非紧密排列的单层胶体颗粒及透明柔性可拉伸衬底上；By physical vapor deposition, chemical vapor deposition, and other methods, magnetic shielding materials such as gold, silver, copper, nickel, aluminum, iron, and carbon are sputtered onto non-tightly arranged single-layer colloidal particles and a transparent flexible stretchable substrate ;
ⅳ)去除胶体颗粒Ⅳ) Remove colloid particles
采用溶剂溶解、刻蚀等方法去除胶体颗粒，便得到沉积在透明柔性可拉伸衬底上的网格状金属屏蔽层。The colloidal particles are removed by solvent dissolution and etching to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate.
(3)制备透明柔性可拉伸封装层(3) Preparation of transparent flexible stretchable packaging layer
在网格状金属屏蔽层上旋涂或浇注硅胶溶液、热塑性聚氨酯溶液、聚烯烃弹性体溶液等，固化成型后形成透明柔性可拉伸封装层。Spin-coated or cast a silicone solution, a thermoplastic polyurethane solution, a polyolefin elastomer solution, etc. on the grid-like metal shielding layer to form a transparent flexible stretchable encapsulation layer after curing.
透明柔性可拉伸衬底、网格状金属屏蔽层及透明柔性可拉伸封装层三者共同组成柔性透明可拉伸的电磁屏蔽薄膜，其中网格状金属屏蔽层在透明柔性可拉伸衬底与透明柔性可拉伸封装层之间。The transparent flexible stretchable substrate, the grid-like metal shielding layer, and the transparent flexible stretchable encapsulation layer together form a flexible transparent stretchable electromagnetic shielding film, in which the grid-like metal shielding layer is on a transparent flexible stretchable liner. Between the bottom and the transparent flexible stretchable encapsulation layer.
本发明提供的可拉伸柔性透明电磁屏蔽膜与制备方法，其优点如下：The stretchable flexible transparent electromagnetic shielding film and the preparation method provided by the present invention have the following advantages:
1、本发明结构简单并稳定，为上下层可拉伸的透明薄膜与中间层网格状金属层的三明治夹芯结构，上下层材料透过金属网格空隙区域实现牢固粘结，进而使得中间金属网格层的结构即使在弯曲、拉伸等状态下也能保持良好的稳定性。1. The structure of the present invention is simple and stable. It is a sandwich sandwich structure of a stretchable transparent film on the upper and lower layers and a grid-like metal layer in the middle layer. The upper and lower materials are firmly bonded through the gap area of the metal grid, thereby making the middle The structure of the metal grid layer can maintain good stability even in the state of bending and stretching.
2、本发明制备工艺简单，网格状金属层采用胶体颗粒自组装与刻蚀的方法实现非紧密接触排列，通过磁控溅射工艺即可在透明弹性衬底上形成网格状金属层。2. The preparation process of the present invention is simple. The grid-like metal layer adopts colloidal particle self-assembly and etching methods to achieve non-close contact arrangement. The grid-like metal layer can be formed on a transparent elastic substrate through a magnetron sputtering process.
3、本发明高透光率与电磁屏蔽效能，且容易实现性能调控。通过胶体颗粒粒径的优化、自组装胶体颗粒刻蚀工艺的控制，可简便实现金属网格线宽(几十纳米至几十微米)与网格空隙(数百纳米至数十微米)的尺寸，进而调控其透光率与电磁屏蔽性能。3. The invention has high light transmittance and electromagnetic shielding effectiveness, and it is easy to realize performance regulation. By optimizing the particle size of colloidal particles and controlling the etching process of self-assembled colloidal particles, the size of the metal grid line width (tens of nanometers to tens of micrometers) and the grid gap (hundreds of nanometers to tens of micrometers) can be easily realized. , And then control its light transmittance and electromagnetic shielding performance.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为可拉伸柔性透明的电磁屏蔽薄膜的结构示意图(平面俯视)。FIG. 1 is a schematic structural diagram (a plan view) of a stretchable flexible transparent electromagnetic shielding film.
图2为可拉伸柔性透明的电磁屏蔽薄膜的结构示意图(剖面)。FIG. 2 is a schematic structural diagram (section) of a stretchable flexible transparent electromagnetic shielding film.
图3为可拉伸柔性透明的电磁屏蔽薄膜在拉伸状态下的结构示意图(平面俯视)。FIG. 3 is a schematic structural view of a stretchable flexible transparent electromagnetic shielding film in a stretched state (plan view).
其中1为透明柔性可拉伸衬底，2为透明柔性可拉伸封装层，3为网格状金属屏蔽层。Among them, 1 is a transparent flexible stretchable substrate, 2 is a transparent flexible stretchable encapsulation layer, and 3 is a grid-like metal shielding layer.
图4为PDMS薄膜表面蒸镀有孔洞状金膜屏蔽层且未布置封装层的SEM图。FIG. 4 is a SEM image of a hole-shaped gold film shielding layer vapor-deposited on the surface of the PDMS film without an encapsulation layer.
图5为PDMS薄膜表面蒸镀有孔洞状金膜屏蔽层且未布置封装层的SEM图。FIG. 5 is a SEM image of a hole-shaped gold film shielding layer vapor-deposited on the surface of the PDMS film without an encapsulation layer.
具体实施方式detailed description
实施例1Example 1
以聚二甲基硅氧烷(PDMS)的前驱体与其固化剂以质量比10:1混合，通过旋涂工艺将该混合溶液旋涂在玻璃基板上，然后在60℃下加热固化30min形成半固化的PDMS薄膜。通过旋涂转速(400～2000rpm)与时间(5～30s)的控制可调节最终PDMS膜的厚度(20～500μm)。以平均粒径10μm的聚苯乙烯(PS)微球乙醇/水分散液为胶体，通过气液界面自组装方法将PS微球胶体单层自组装在PDMS薄膜表面，形成紧密排列的PS胶体阵列。再通过等离子体(Plasma)在氧气气氛中将紧密排列的PS胶体颗粒刻蚀为非紧密排列结构，刻蚀的程度(相邻PS胶体颗粒之间的距离)可通过刻蚀功率、刻蚀时间进行调控，本案例中将间距控制在1μm左右。通过磁控溅射法将金属银沉积到上述非紧密排列的PS胶体颗粒及其PDMS衬底上(PS胶体颗粒的正表面及胶体颗粒之间的空隙PDMS表面)。由于半固化PDMS的弹性模量较低，磁控溅射的银会某种程度嵌入PDMS薄膜的内表层，形成较为稳定的导电银层。再用溶剂N,N-二甲基甲酰胺、甲苯、四氢呋喃等溶剂将PS胶体颗粒溶解去除，在此过程中沉积在PS胶体颗粒表面的银会因为PS载体的消失而去除，只留下沉积在PDMS薄膜上的网格状金属银，即电磁屏蔽金属层。再次通过旋涂的方法在网格状金属银的PDMS薄膜表面制备一层PDMS封装层，成膜条件为80℃、2h。由于第一步的PDMS为半固化体，再封装层PDMS固化过程中二者会在界面处继续发生化学交联反应，进而形成无明显界面层的牢固粘结，将网格状金属银进一步稳定固定在PDMS衬底层与封装层之间。由于PDMS衬底与封装层均为透明，且中间的网格状银导电网络的线宽仅约为1μm左右，具备良好的透光性，将PDMS膜从玻璃基板上撕下便制得可拉伸柔性透明电磁屏蔽薄膜，其透光率为85％，电磁屏蔽效能为35dB。Polydimethylsiloxane (PDMS) precursor and its curing agent were mixed at a mass ratio of 10: 1, and the mixed solution was spin-coated on a glass substrate by a spin coating process, and then heated and cured at 60 ° C for 30 minutes to form a half. Cured PDMS film. The thickness of the final PDMS film (20-500 μm) can be adjusted by controlling the spin speed (400-2000 rpm) and time (5-30 seconds). Using a polystyrene (PS) microsphere ethanol / water dispersion with an average particle size of 10 μm as a colloid, the PS microsphere colloid single layer was self-assembled on the surface of the PDMS film by a gas-liquid interface self-assembly method to form a close-packed PS colloid array . Then the plasma (Plasma) is used to etch the closely arranged PS colloidal particles into a non-closely arranged structure. The degree of etching (the distance between adjacent PS colloidal particles) can be determined by the etching power and the etching time. Regulate and control, in this case, the pitch is controlled to about 1 μm. Metal silver was deposited on the above-not-closely arranged PS colloidal particles and their PDMS substrate (the front surface of the PS colloidal particles and the PDMS surface between the colloidal particles) by the magnetron sputtering method. Due to the low elastic modulus of semi-cured PDMS, the magnetron sputtered silver will be embedded into the inner surface layer of the PDMS film to some extent, forming a more stable conductive silver layer. Solvents such as N, N-dimethylformamide, toluene, and tetrahydrofuran are used to dissolve and remove the PS colloid particles. In this process, the silver deposited on the surface of the PS colloid particles will be removed by the disappearance of the PS carrier, leaving only the deposition. The grid-like metallic silver on the PDMS film, that is, the electromagnetic shielding metal layer. A PDMS encapsulation layer was prepared on the surface of the grid-like metallic silver PDMS film by spin coating again, and the film formation conditions were 80 ° C and 2 hours. Since the PDMS in the first step is a semi-cured body, during the curing process of the re-encapsulation layer, the two will continue to undergo chemical cross-linking reactions at the interface, thereby forming a strong bond without an obvious interface layer, and further stabilizing the grid-like metallic silver. It is fixed between the PDMS substrate layer and the encapsulation layer. Since both the PDMS substrate and the encapsulation layer are transparent, and the line width of the grid-like silver conductive network in the middle is only about 1 μm, which has good light transmittance, the PDMS film can be pulled off from the glass substrate to obtain a pull. Flexible transparent electromagnetic shielding film, its light transmittance is 85%, and its electromagnetic shielding effectiveness is 35dB.
实施例2Example 2
以热塑性聚氨酯(TPU)为原料，用N,N-二甲基甲酰胺(DMF)溶解溶解配制成一定浓度的TPU/DMF溶液，浇注到平整的聚四氟容器中，加热干燥后成型为TPU透明薄膜。以平均粒径500nm的二氧化硅(SiO 2)微球分散液为胶体，通过自组装方法将SiO 2微球胶体单层自组装在TPU薄膜表面，形成紧密排列的SiO 2胶体阵列。再通反应离子刻蚀(RIE)中将紧密排列的PS胶体颗粒刻蚀为非紧密 排列结构，刻蚀的程度(相邻SiO 2胶体颗粒之间的距离)可通过气体流量、温度、气体压强等刻蚀工艺进行调控，本案例中将SiO 2胶体颗粒最短间距控制在200nm左右。通过磁控溅射法将金沉积到上述非紧密排列的SiO 2胶体颗粒及其TPU衬底上(SiO 2胶体颗粒的正表面及胶体颗粒之间的空隙TPU表面)。由于TPU薄膜的弹性模量较低，磁控溅射的金会某种程度嵌入TPU薄膜的内表层，形成较为稳定的导电金层。再用氢氟酸将SiO 2胶体颗粒溶解去除，在此过程中沉积在SiO 2胶体颗粒表面的金会因为SiO 2载体的消失而去除，只留下沉积在TPU薄膜上的网格状金属金，即电磁屏蔽金属层。再次通过旋涂、刮涂、浇注等方法在网格状金层的TPU薄膜表面制备一层TPU封装层。由于封装层TPU溶液中含有的溶剂可以在界面处一定程度溶解衬底层的TPU，进而在封装层的成膜过程中使TPU衬底层与TPU封装层形成无明显界面的牢固粘结，同时进一步将网格状金层稳定固定在TPU衬底层与封装层之间。由于TPU衬底与封装层均为透明，且中间的网格状金导电网络的线宽仅约为200nm左右，具备良好的透光性，因而制得可拉伸柔性透明电磁屏蔽薄膜，其透光率为70％，电磁屏蔽效能为50dB。 Using thermoplastic polyurethane (TPU) as raw material, N, N-dimethylformamide (DMF) is dissolved and dissolved to prepare a certain concentration of TPU / DMF solution, poured into a flat Teflon container, heated and dried to form TPU. Transparent film. Using silica (SiO 2 ) microsphere dispersion with an average particle diameter of 500 nm as a colloid, a single layer of SiO 2 microsphere colloid was self-assembled on the surface of the TPU film by a self-assembly method to form a closely-aligned SiO 2 colloid array. Re-reactive ion etching (RIE) etches closely-aligned PS colloidal particles into a non-close-packed structure. The degree of etching (the distance between adjacent SiO 2 colloidal particles) can be measured by gas flow, temperature, and gas pressure. The etching process is controlled, and the shortest distance between SiO 2 colloidal particles is controlled at about 200 nm in this case. Gold was deposited onto the above-not-closely arranged SiO 2 colloidal particles and its TPU substrate (the front surface of the SiO 2 colloidal particles and the surface of the gap TPU between the colloidal particles) by a magnetron sputtering method. Due to the low elastic modulus of the TPU film, the magnetron sputtered gold will be embedded into the inner surface layer of the TPU film to some extent, forming a more stable conductive gold layer. Then hydrofluoric acid is used to dissolve and remove the SiO 2 colloidal particles. During this process, the gold deposited on the surface of the SiO 2 colloidal particles will be removed due to the disappearance of the SiO 2 carrier, leaving only the grid-like metal gold deposited on the TPU film. , That is, the electromagnetic shielding metal layer. A TPU encapsulation layer was prepared on the surface of the TPU film of the grid-like gold layer by spin coating, blade coating, and casting. Because the solvent contained in the TPU solution of the encapsulation layer can dissolve the TPU of the substrate layer to a certain extent at the interface, the TPU substrate layer and the TPU encapsulation layer can form a strong bond without obvious interface during the film formation process of the encapsulation layer. The grid-like gold layer is stably fixed between the TPU substrate layer and the encapsulation layer. Because the TPU substrate and the encapsulation layer are both transparent, and the line width of the grid-like gold conductive network in the middle is only about 200 nm, which has good light transmittance, a stretchable flexible transparent electromagnetic shielding film is prepared. The optical efficiency is 70% and the electromagnetic shielding effectiveness is 50dB.
虽然本发明以较佳实施例揭露如上，然其并非用以限定本发明，任何所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作些许的更动与润饰，因此本发明的保护范围当视权利要求书的申请专利范围所界定者为准。Although the present invention is disclosed as above with the preferred embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope defined by the claims for patent application.

Claims (13)

  1. 可拉伸柔性透明电磁屏蔽膜，其包括透明柔性可拉伸衬底层；孔洞网格状金属屏蔽层以及透明柔性可拉伸封装层；Stretchable flexible transparent electromagnetic shielding film, which includes a transparent flexible stretchable substrate layer; a hole grid metal shielding layer; and a transparent flexible stretchable encapsulation layer;
    所述网格状金属屏蔽层在透明柔性可拉伸衬底层与透明柔性可拉伸封装层之间。The grid-like metal shielding layer is between a transparent flexible stretchable substrate layer and a transparent flexible stretchable encapsulation layer.
  2. 根据权利要求1所述的可拉伸柔性透明电磁屏蔽膜，所述孔洞网格状金属屏蔽层通过沉积方法将金、银、铜、镍、铝、铁、碳中的一种或多种磁屏蔽材料沉积在透明柔性可拉伸衬底层中而制成。The stretchable flexible transparent electromagnetic shielding film according to claim 1, wherein the hole-grid metal shielding layer magnetically deposits one or more of gold, silver, copper, nickel, aluminum, iron, and carbon by a deposition method. The shielding material is made by depositing in a transparent flexible stretchable substrate layer.
  3. 根据权利要求1或2所述的可拉伸柔性透明电磁屏蔽膜，所述孔洞网格状金属屏蔽层通过以下方法制备：The stretchable flexible transparent electromagnetic shielding film according to claim 1 or 2, wherein the hole-grid metal shielding layer is prepared by the following method:
    ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒；Ⅰ) tightly arranging a single layer of colloidal particles on a transparent flexible stretchable substrate;
    ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Ii) etching the closely arranged single layer of colloidal particles into a non-closely arranged state;
    ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层；Ii) depositing a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles;
    ⅳ)去除胶体颗粒。Ii) Remove colloidal particles.
  4. 根据权利要求1或2所述的可拉伸柔性透明电磁屏蔽膜，所述孔洞网格状金属屏蔽层通过以下方法制备：The stretchable flexible transparent electromagnetic shielding film according to claim 1 or 2, wherein the hole-grid metal shielding layer is prepared by the following method:
    ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒Ⅰ) Tightly arrange a single layer of colloidal particles on a transparent flexible stretchable substrate
    通过自组装方法在透明柔性可拉伸衬底层上沉积紧密排列的单层胶体颗粒；Depositing closely arranged single-layer colloidal particles on a transparent flexible stretchable substrate layer by a self-assembly method;
    ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状Ii) Etching tightly arranged single-layer colloidal particles into non-closely arranged
    通过刻蚀方法将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Etching the closely arranged single-layered colloidal particles into a non-closely arranged pattern by an etching method;
    ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层Ⅲ) Deposition of a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles
    通过物理气相沉积、化学气相沉积方法将金、银、铜、镍、铝、铁、碳等磁屏蔽材料溅射在将非紧密排列的单层胶体颗粒及透明柔性可拉伸衬底上；Use physical vapor deposition and chemical vapor deposition methods to sputter magnetic shielding materials such as gold, silver, copper, nickel, aluminum, iron, and carbon on non-tightly arranged single-layer colloidal particles and transparent flexible stretchable substrates;
    ⅳ)去除胶体颗粒Ⅳ) Remove colloid particles
    采用溶剂溶解、刻蚀方法去除胶体颗粒，便得到沉积在透明柔性可拉伸衬底层上的网格状金属屏蔽层。The colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate layer.
  5. 根据权利要求1-3任一项所述的可拉伸柔性透明电磁屏蔽膜，所述透明柔性可拉伸衬底层或透明柔性可拉伸封装层为硅胶、热塑性聚氨酯、聚烯烃弹性体透明弹性体中的一种或多种材料制成。The stretchable flexible transparent electromagnetic shielding film according to any one of claims 1-3, wherein the transparent flexible stretchable substrate layer or transparent flexible stretchable encapsulation layer is silicone rubber, thermoplastic polyurethane, polyolefin elastomer, transparent elasticity The body is made of one or more materials.
  6. 根据权利要求5所述的可拉伸柔性透明电磁屏蔽膜，所述的硅胶选自聚二甲基硅氧烷、聚二甲基二苯基硅氧烷、聚乙烯基三异丙氧基硅烷、聚甲基乙烯基硅氧烷、聚甲基氢硅氧烷等中的一种或多种。The stretchable flexible transparent electromagnetic shielding film according to claim 5, wherein the silica gel is selected from the group consisting of polydimethylsiloxane, polydimethyldiphenylsiloxane, and polyvinyltriisopropoxysilane. Or polymethylvinylsiloxane, polymethylhydrogensiloxane, or the like.
  7. 根据权利要求1-6任一项所述的可拉伸柔性透明电磁屏蔽膜，所述透明柔性可拉伸衬底层与透明柔性可拉伸封装层采用的材料为相同材料；The stretchable flexible transparent electromagnetic shielding film according to any one of claims 1-6, wherein the transparent flexible stretchable substrate layer and the transparent flexible stretchable encapsulation layer are made of the same material;
    优选地，所述透明柔性可拉伸衬底层与透明柔性可拉伸封装层采用的材料为相互融合，无明显界面。Preferably, the materials used for the transparent flexible stretchable substrate layer and the transparent flexible stretchable encapsulation layer are fused with each other and have no obvious interface.
  8. 根据权利要求3所述的可拉伸柔性透明电磁屏蔽膜，所述胶体颗粒选自10nm-100μm，优选为100nm-50μm；The stretchable flexible transparent electromagnetic shielding film according to claim 3, wherein the colloidal particles are selected from 10 nm to 100 μm, preferably 100 nm to 50 μm;
    优选地，胶体颗粒选自聚苯乙烯微球、二氧化硅微球、聚甲基丙烯酸甲酯微球、聚丙烯酸微球、聚酚醛树脂微球、聚脲醛树脂微球、聚甲基丙烯酸环氧丙酯微球。Preferably, the colloidal particles are selected from polystyrene microspheres, silica microspheres, polymethyl methacrylate microspheres, polyacrylic acid microspheres, polyphenolic resin microspheres, polyurea resin microspheres, and polymethacrylic rings Oxypropyl ester microspheres.
  9. 根据权利要求1-8任一项所述的可拉伸柔性透明电磁屏蔽膜，所述网格状金属屏蔽层为金、银、铜、镍、铝、铁、碳中的一种或多种磁屏蔽材料制成，呈孔洞网格状。The stretchable flexible transparent electromagnetic shielding film according to any one of claims 1 to 8, wherein the mesh-shaped metal shielding layer is one or more of gold, silver, copper, nickel, aluminum, iron, and carbon It is made of magnetic shielding material and has a grid pattern of holes.
  10. 根据权利要求1-9任一项所述的可拉伸柔性透明电磁屏蔽膜，网格状金属屏蔽层的网格线宽度最低值为10nm-100μm，优选为100nm-10μm；网格状金属屏蔽层的网格线空隙最高值为100nm-100μm，优选为500nm-50μm。The stretchable flexible transparent electromagnetic shielding film according to any one of claims 1 to 9, the minimum value of the grid line width of the grid-shaped metal shielding layer is 10 nm to 100 μm, preferably 100 nm to 10 μm; the grid-shaped metal shield The maximum grid line void of the layer is 100 nm to 100 μm, and preferably 500 nm to 50 μm.
  11. 一种可拉伸柔性透明电磁屏蔽膜的制备方法，包括下述步骤：A method for preparing a stretchable flexible transparent electromagnetic shielding film includes the following steps:
    (1)制备透明柔性可拉伸衬底(1) Preparation of transparent flexible stretchable substrate
    (2)制备网格状金属屏蔽层(2) Preparation of grid-like metal shielding layer
    ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒；Ⅰ) tightly arranging a single layer of colloidal particles on a transparent flexible stretchable substrate;
    ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Ii) etching the closely arranged single layer of colloidal particles into a non-closely arranged state;
    ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层；Ii) depositing a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles;
    ⅳ)去除胶体颗粒；Ii) removing colloidal particles;
    (3)制备透明柔性可拉伸封装层。(3) A transparent flexible stretchable encapsulation layer is prepared.
  12. 一种布置孔洞网格状金属屏蔽层的方法，通过以下方法制备：A method for arranging a hole-shaped metal shielding layer is prepared by the following methods:
    ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒；Ⅰ) tightly arranging a single layer of colloidal particles on a transparent flexible stretchable substrate;
    ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Ii) etching the closely arranged single layer of colloidal particles into a non-closely arranged state;
    ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层；Ii) depositing a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles;
    ⅳ)去除胶体颗粒。Ii) Remove colloidal particles.
  13. 根据权利要求11所述的可拉伸柔性透明电磁屏蔽膜的制备方法或者权利要求12所述的布置孔洞网格状金属屏蔽层的方法，其中孔洞网格状金属屏蔽层的方法通过以下方法制备：The method for preparing a stretchable flexible transparent electromagnetic shielding film according to claim 11 or the method for arranging a hole-shaped metal shielding layer according to claim 12, wherein the method of hole-shaped metal shielding layer is prepared by :
    ⅰ)在透明柔性可拉伸衬底上紧密排列单层胶体颗粒Ⅰ) Tightly arrange a single layer of colloidal particles on a transparent flexible stretchable substrate
    通过自组装方法在透明柔性可拉伸衬底层上沉积紧密排列的单层胶体颗粒；Depositing closely arranged single-layer colloidal particles on a transparent flexible stretchable substrate layer by a self-assembly method;
    ⅱ)将紧密排列单层胶体颗粒刻蚀为非紧密排列状Ii) Etching tightly arranged single-layer colloidal particles into non-closely arranged
    通过刻蚀方法将紧密排列单层胶体颗粒刻蚀为非紧密排列状；Etching the closely arranged single-layered colloidal particles into a non-closely arranged pattern by an etching method;
    ⅲ)在非紧密排列单层胶体颗粒的透明柔性可拉伸衬底上沉积纳米金属层Ⅲ) Deposition of a nano-metal layer on a transparent flexible stretchable substrate with non-tightly arranged single-layer colloidal particles
    通过物理气相沉积、化学气相沉积方法将金、银、铜、镍、铝、铁、碳等磁屏蔽材料溅射在将非紧密排列的单层胶体颗粒及透明柔性可拉伸衬底上；Use physical vapor deposition and chemical vapor deposition methods to sputter magnetic shielding materials such as gold, silver, copper, nickel, aluminum, iron, and carbon on non-tightly arranged single-layer colloidal particles and transparent flexible stretchable substrates;
    ⅳ)去除胶体颗粒Ⅳ) Remove colloid particles
    采用溶剂溶解、刻蚀方法去除胶体颗粒，便得到沉积在透明柔性可拉伸衬底层上的网格状金属屏蔽层。The colloidal particles are removed by solvent dissolution and etching methods to obtain a grid-like metal shielding layer deposited on a transparent flexible stretchable substrate layer.
PCT/CN2018/123384 2018-06-25 2018-12-25 Transparent, flexible and stretchable electromagnetic shielding thin film and method for preparing same WO2020000942A1 (en)

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