CN106003888A - Flexible stretchable electromagnetic shielding film and preparation method thereof - Google Patents

Flexible stretchable electromagnetic shielding film and preparation method thereof Download PDF

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Publication number
CN106003888A
CN106003888A CN201610352538.8A CN201610352538A CN106003888A CN 106003888 A CN106003888 A CN 106003888A CN 201610352538 A CN201610352538 A CN 201610352538A CN 106003888 A CN106003888 A CN 106003888A
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electromagnetic shielding
film
flexible
shielding film
preparation
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CN106003888B (en
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许福军
高扬
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Donghua University
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Donghua University
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    • B32—LAYERED PRODUCTS
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    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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    • B32B38/00—Ancillary operations in connection with laminating processes
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    • 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
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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
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Fluid Mechanics (AREA)
  • Chemical & Material Sciences (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract

The invention provides a flexible stretchable electromagnetic shielding film and a preparation method thereof. The preparation method of the flexible stretchable electromagnetic shielding film comprises the following steps: selecting an elastic membrane as an elastic adhesion matrix, stretching the elastic membrane to a certain elongation, then fixing the elastic membrane, and coating a liquid elastic adhesive layer on the surface of the elastic membrane; crushing a flexible nano electromagnetic shielding complex film on the liquid elastic adhesive layer, coating resin with protective effect at the upper side of the flexible nano electromagnetic shielding complex film to form a resin layer, and curing the liquid elastic adhesive and the resin under certain conditions; and releasing a tensile force applied onto the elastic adhesion matrix, so as to drive the flexible nano electromagnetic shielding complex film to retract, namely the flexible stretchable electromagnetic shielding film is obtained. The prepared flexible stretchable electromagnetic shielding film has good elasticity, high elongation (20-50%) and excellent electromagnetic shielding property (electromagnetic wave absorptivity is more than or equal to 99% at the frequency of 1-5GHz) and can bear certain bending and compression deformation.

Description

A kind of flexible extensible electromagnetic shielding film and preparation method thereof
Technical field
The present invention relates to electromagnetic shielding material field, more particularly, it relates to flexible extensible electromagnetic shielding film neck Territory.
Background technology
Along with developing rapidly of science and technology, electromagnetic wave is in fields such as Aeronautics and Astronautics, communication, household electrical appliance, military affairs Being widely used, electromagnetic pollution problem therewith is the most outstanding day by day.The electromagnetic energy of electromagnetic wave outside radiation is just At the speed increase with annual 7%-14%, electromagnetism is the most serious to the pollution of environment.All over the world, various Information network communicates the valuable information in terms of hundreds of millions of military affairs, politics, economic dispatch and information, due to electricity Electromagnetic wave radiation and the information-leakage event that causes also happen occasionally, and directly threaten national politics, economy, military affairs Safety.Meanwhile, electromagnetic wave also can cause armament systems malfunctioning, brings serious hidden danger to fighting.Therefore, anti- Only electromagenetic wave radiation, to ensure that information, weapons system security and health become urgent task.
A lot of electromagnetic shielding materials are all to be spattered by material surface metal-plated, coat, paste or lead in the market Cross the modes such as blending conductive fiber, during preparation and use, a lot of problem easily occurs, such as metal and material Binding ability is poor, easily comes off, and coating is easily scratched and loses shielding properties, and preparation process is seriously polluted, And material is more thick and stiff, pliability is poor, airtight, handling property is poor, the most wearable, and is difficult to meet existing For the characteristic of " thin, light, wide, strong " needed for electromagnetic shielding material, therefore, have in the urgent need to research and development one High capability of electromagnetic shielding, pliability are good, frivolous, good endurance and wearable electromagnetic shielding material.
Summary of the invention
The technical problem to be solved is to provide one, and to have high capability of electromagnetic shielding, pliability good, light Thin, good endurance and wearable flexible extensible electromagnetic shielding film and preparation method thereof.
In order to solve above-mentioned technical problem, the invention provides a kind of flexible extensible electromagnetic shielding film, its feature Be, including: the elastica that sets gradually from top to bottom, at least one of which flexible nano electromagnetic shielding composite material and Resin bed.
Preferably, note is glued in the downside of described elastica biadhesive colloid.
Present invention also offers the preparation method of above-mentioned flexible extensible electromagnetic shielding film, it is characterised in that bag Include:
The first step: be immersed in graphene suspension by carbon nano-tube film, takes out, in room after processing a period of time The lower nature of temperature dries, and obtains flexible nano electromagnetic shielding composite material；
Second step: selection elastica is as elastic attachment matrix, and its two ends are applied certain pulling force, is drawn Fix after reaching certain percentage elongation, coat one layer of hydroelasticity binding agent in elastomeric film surface；
3rd step: the flexible nano electromagnetic shielding composite material pressure stain first step obtained is at hydroelasticity binding agent On, there is in the coating of the upside of flexible nano electromagnetic shielding composite material the resin of protective effect, form resin bed, Make hydroelasticity binding agent and resin solidification under certain condition, or, at flexible nano electromagnetic shielding composite material Upside bond another elastica；
4th step: the pulling force that release is applied on elastic attachment matrix so that it is drive flexible nano electromagnetic shielding multiple Conjunction film bounces back, and can be prepared by flexible extensible electromagnetic shielding film.
Preferably, the described first step is additionally included in the end of flexible nano electromagnetic shielding composite material and sticks electrode.
It is highly preferred that described electrode is copper sheet, copper wire, conductive fiber or other conductive material.
It is highly preferred that described conductive fiber is CNT yarn.
It is highly preferred that described electrode is connected with flexible nano electromagnetic shielding composite material by conductive silver glue.
Preferably, the carbon nano-tube film in the described first step is prepared by single wall or multi-walled carbon nano-tubes, CNT A diameter of 10nm-100nm, film thickness is 10 μm-50 μm, and porosity is 35%-75%, and hot strength is 100MPa-500MPa, electrical conductivity is 104-105S/m。
It is highly preferred that the elastic attachment matrix phase after the size of carbon nano-tube film in the described first step and stretching With.
Preferably, the concentration of described graphene suspension is 1mg/ml～50mg/ml, dip time 1～5h, Impregnate 1～3 time, can design alternative as required.
Preferably, described elastica be polydimethylsiloxanefilm film, acrylate film, polyurethane film or Elastomer thin film.
Preferably, described hydroelasticity binding agent is polydimethylsiloxane, acrylic acid or polyurethane.
Preferably, the described resin with protective effect is polyurethane, polydimethylsiloxane or rubber.Tree The coating thickness of fat can select as required.
Preferably, the 5～50% of the described elongation at break that the percentage elongation in second step is elastica.
The conditions such as described hardening time, temperature, pressure are determined by selected binding agent and resin.
Compared with prior art, the invention have the advantage that
(1) present invention use PDMS film as elastic attachment matrix, and stretching while with flexible nano Electromagnetic shielding film adhesive solidification, thus improve pliability and the elasticity of electromagnetic shielding film.
(2) present invention obtains flexibility with the carbon nano-tube film impregnated graphite alkene suspension of high electromagnetic shielding absorbance Nano electromagnetic shielding composite membrane, electromagnetic performance is better than traditional material, has again bigger draw ratio simultaneously, has Nanometer size effect, relative to other metallic particles and graphite granule, has absorption band width, multi-functional, matter The features such as amount is light, thickness is thin, the most also use the mode of impregnated graphite alkene suspension to further increase its electromagnetism Shielding properties.
(3) mode of coated with resins is used to protect carbon nano-tube film so that it is to be difficult to wear-out failure, electromagnetic shielding Stable performance, improves the durability of material.
(4) this preparation method is simple, is suitable for Industry Promotion, is with a wide range of applications.
(5) present invention prepare flexible extensible electromagnetic shielding film to have good springiness, percentage elongation high (20%-50%), capability of electromagnetic shielding excellent (in 1-5GHz frequency, electromagnetic wave absorptivity more than 99%), Certain bending and compression can be born simultaneously.This elasticity electromagnetic shielding film may be used for intelligence wearable garment and In multifunction electromagnetic armored fabric, have a wide range of applications in dual-use intelligent protection field.
Accompanying drawing explanation
Fig. 1 is flexible extensible electromagnetic shielding film schematic diagram；
Fig. 2 is the elastic electromagnetic shielding film schematic diagram of superhigh shielded usefulness；
Fig. 3 is elastically stretchable electromagnetic shielding adhesive film schematic diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate The present invention rather than restriction the scope of the present invention.In addition, it is to be understood that read the present invention lecture content it After, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within this equally Application appended claims limited range.
Embodiment 1: the stretchable electromagnetic shielding film of ultra-thin elastic
The preparation method of a kind of flexible extensible electromagnetic shielding film, concretely comprises the following steps:
The first step: carbon nano-tube film is immersed in graphene suspension, dip time 3h, impregnate 1 time, Take out, the most naturally dry, obtain flexible nano electromagnetic shielding composite material 2, and at its two ends by leading Electricity elargol sticks copper wire electrode；
Described carbon nano-tube film preferred dimension is 20 × 28cm2Carbon nano-tube film (Chinese Academy of Sciences Su Zhouna Rice technology and nano bionic institute), multi-walled carbon nano-tubes prepare, carbon nanotube diameter is about 20nm, Film thickness is 20um, and porosity is 75%, and hot strength is about 200MPa, electrical conductivity about 1 × 105S/m； The concentration of described graphene suspension is graphene suspension (the limited public affairs of Niu Meitai new material of 2mg/ml Department).
Second step: selection elastica 1 is as elastic attachment matrix, and its two ends is applied certain pulling force, by it It is stretched to certain percentage elongation (the 40% of elongation at break) fix afterwards, at one layer of liquid of elastica 1 surface-coated Elastic adhesive (PDMS binding agent), thickness is about 0.2mm；
Described elastica 1 is square PDMS film, a size of 20 × 20cm2, thickness is 0.3mm.PDMS Film uses PDMS resin (Dow Corning Corporation DC184) to be obtained by coating method.
Described PDMS binding agent uses the SYLGARD184 of Dow Corning Corporation, by solvent (PDMS Liquid, viscosity 5.2Pa-sec) and firming agent (viscosity 3.5Pa-sec) be uniformly mixed so as to obtain by the weight ratio of 10: 1.
3rd step: the flexible nano electromagnetic shielding composite material 2 first step obtained presses stain at hydroelasticity binding agent On, there is resin (the water-soluble poly ammonia of protective effect in the coating of the upside of flexible nano electromagnetic shielding composite material 2 Ester resin, Bayer Science and Technology Ltd., model: U54), forming resin bed 3, thickness is about 0.3mm, Keeping the extended state of elastica 1, make hydroelasticity binding agent and resin solidification at 60 DEG C, the time is the lowest In 12 hours；
4th step: the pulling force that release is applied on elastic attachment matrix so that it is drive flexible nano electromagnetic shielding multiple Close film 2 to bounce back, can be prepared by flexible extensible electromagnetic shielding film.
As it is shown in figure 1, the flexible extensible electromagnetic shielding film of gained includes: the elasticity set gradually from top to bottom 1, one layer of flexible nano electromagnetic shielding composite material 2 of film and resin bed 3.
The stretchable electromagnetic shielding film of this ultra-thin elastic can absorb bandwidth, and electromagnet shield effect is high, at 1-5GHz In frequency, electromagnetic wave absorptivity more than 99%, shield effectiveness, up to 35dB, has " thin, light, wide, strong " Characteristic, can as a new generation flexible electromagnetic shielding material.
Embodiment 2: the elastic electromagnetic shielding film of superhigh shielded usefulness
The preparation method of a kind of flexible extensible electromagnetic shielding film, concretely comprises the following steps:
The first step: 3 carbon nano-tube films are immersed in graphene suspension respectively, dip time 3h, leaching Stain 1 time, takes out, the most naturally dries, obtain 3 layers of flexible nano electromagnetic shielding composite material 2, at it Copper wire electrode is sticked by coating conductive silver glue in one end of middle two panels；
Described carbon nano-tube film preferred dimension is 20 × 30cm2Carbon nano-tube film (Chinese Academy of Sciences Su Zhouna Rice technology and nano bionic institute), multi-walled carbon nano-tubes prepare, carbon nanotube diameter is about 20nm, Film thickness is 20um, and porosity is 75%, and hot strength is about 200MPa, electrical conductivity about 1 × 105S/m； The concentration of described graphene suspension is graphene suspension (the limited public affairs of Niu Meitai new material of 2mg/ml Department).
Second step: selection elastica 1 is as elastic attachment matrix, and its two ends is applied certain pulling force, by it It is stretched to certain percentage elongation (the 50% of elongation at break) fix afterwards, at one layer of liquid of elastica 1 surface-coated Elastic adhesive (PDMS binding agent), thickness is about 0.2mm；
Described elastica 1 is square PDMS film, a size of 20 × 20cm2, thickness is 0.4mm.PDMS Film uses PDMS resin (Dow Corning Corporation DC184) to be obtained by coating method.
Described PDMS binding agent uses the SYLGARD184 of Dow Corning Corporation, by solvent (PDMS Liquid, viscosity 5.2Pa-sec) and firming agent (viscosity 3.5Pa-sec) be uniformly mixed so as to obtain by the weight ratio of 10: 1.
3rd step: the 3 layers of flexible nano electromagnetic shielding composite material 2 first step obtained press stain at liquid shell successively On property binding agent, the flexible nano electromagnetic shielding composite material 2 of receiving with electrode is positioned at upper and lower two-layer, adjacent two layers Adhesive phase 4 is formed between flexible nano electromagnetic shielding composite material 2；
Upside coating at the flexible nano electromagnetic shielding composite material 2 of the superiors has the resin of protective effect (PDMS binding agent, same to second step), forms resin bed 3, and thickness is about 0.3mm, keeps elastica 1 Extended state, at 80 DEG C, make hydroelasticity binding agent and resin solidification, the time is not less than 12 hours；
4th step: the pulling force that release is applied on elastic attachment matrix so that it is drive flexible nano electromagnetic shielding multiple Close film 2 to bounce back, can be prepared by flexible extensible electromagnetic shielding film.
As in figure 2 it is shown, the flexible extensible electromagnetic shielding film of gained includes: the elasticity set gradually from top to bottom 1, three layers of flexible nano electromagnetic shielding composite material 2 of film and resin bed 3.
This elasticity electromagnetic shielding film have employed 3 layers of nano electromagnetic shielding composite membrane, and shielding test result can reach 50dB, i.e. shield effectiveness, can be the most anti-as flexible electromagnetic shielding material industrial, military up to 99.999% Only electromagenetic wave radiation and leakage, guarantees personal safety, safeguards national information, politics, military security.
Embodiment 3: elastically stretchable electromagnetic shielding adhesive film
The preparation method of a kind of flexible extensible electromagnetic shielding film, concretely comprises the following steps:
The first step: carbon nano-tube film is immersed in graphene suspension, dip time 3h, impregnate 1 time, Take out, the most naturally dry, obtain flexible nano electromagnetic shielding composite material 2, and at its two ends by leading Electricity elargol sticks copper wire electrode；
Described carbon nano-tube film preferred dimension is 20 × 30cm2Carbon nano-tube film (Chinese Academy of Sciences Su Zhouna Rice technology and nano bionic institute), multi-walled carbon nano-tubes prepare, carbon nanotube diameter is about 20nm, Film thickness is 20um, and porosity is 75%, and hot strength is about 200MPa, electrical conductivity about 1 × 105S/m； The concentration of described graphene suspension is graphene suspension (the limited public affairs of Niu Meitai new material of 2mg/ml Department).
Second step: selection elastica 1 is as elastic attachment matrix, and its two ends is applied certain pulling force, by it It is stretched to certain percentage elongation (the 40% of elongation at break) fix afterwards, at one layer of liquid of elastica 1 surface-coated Elastic adhesive (PDMS binding agent), thickness is about 0.2mm；
Described elastica 1 is square PDMS film, a size of 20 × 20cm2, thickness is 0.4mm.PDMS Film uses PDMS resin (Dow Corning Corporation DC184) to be obtained by coating method.
Described PDMS binding agent uses the SYLGARD184 of Dow Corning Corporation, by solvent (PDMS Liquid, viscosity 5.2Pa-sec) and firming agent (viscosity 3.5Pa-sec) be uniformly mixed so as to obtain by the weight ratio of 10: 1.
3rd step: the flexible nano electromagnetic shielding composite material 2 first step obtained presses stain at hydroelasticity binding agent On, there is resin (the water-soluble poly ammonia of protective effect in the coating of the upside of flexible nano electromagnetic shielding composite material 2 Ester resin, Bayer Science and Technology Ltd., model: U54, thickness is about 0.3mm, keeps drawing of elastica 1 Stretching state, make hydroelasticity binding agent and resin solidification at 60 DEG C, the time is not less than 12 hours；
4th step: the pulling force that release is applied on elastic attachment matrix so that it is drive flexible nano electromagnetic shielding multiple Closing film 2 to bounce back, the lower surface in elastica 1 adheres to one layer of biadhesive colloid 5, and can be prepared by flexibility can draw Stretch electromagnetic shielding film.
Acrylic transparent double face glue (the emerging composite wood of Shanghai gem that described double faced adhesive tape 4 selects thickness to be 0.5mm Material company limited).
As it is shown on figure 3, the flexible extensible electromagnetic shielding film of gained includes: the elasticity set gradually from top to bottom 1, one layer of flexible nano electromagnetic shielding composite material 2 of film and resin bed 3.Note is glued in the downside of described elastica 1 There is biadhesive colloid 5 (a size of 20 × 30cm2)。
This electromagnetic shielding adhesive film can stick to rapidly need the structure of shielding (such as tent, electromagnetic generator Deng) surface, form quick effectiveness.
The invention is not limited in that above-mentioned embodiment, above-mentioned embodiment are only illustrative, and non-limiting, Those skilled in the art is under the enlightenment of the present invention, without departing from present inventive concept and claimed model Under enclosing, it is also possible to make a variety of form, these belong among protection scope of the present invention.

Claims (10)

1. a flexible extensible electromagnetic shielding film, it is characterised in that including: set gradually from top to bottom Elastica (1), at least one of which flexible nano electromagnetic shielding composite material (2) and resin bed (3).
2. flexible extensible electromagnetic shielding film as claimed in claim 1, it is characterised in that described elasticity Note is glued in the downside of film (1) biadhesive colloid (5).
3. the preparation method of the flexible extensible electromagnetic shielding film described in claim 1 or 2, it is characterised in that Including:
The first step: be immersed in graphene suspension by carbon nano-tube film, takes out, in room after processing a period of time The lower nature of temperature dries, and obtains flexible nano electromagnetic shielding composite material (2)；
Second step: selection elastica (1) is as elastic attachment matrix, and its two ends are applied certain pulling force, Fix, at one layer of hydroelasticity binding agent of elastica (1) surface-coated after being stretched to certain percentage elongation；
3rd step: flexible nano electromagnetic shielding composite material (2) the pressure stain first step obtained is glued in hydroelasticity On mixture, there is in the coating of the upside of flexible nano electromagnetic shielding composite material (2) resin of protective effect, shape Resin layer (3), makes hydroelasticity binding agent and resin solidification under certain condition, or, receive in flexibility The upside of rice electromagnetic shielding composite material (2) bonds another elastica (1)；
4th step: the pulling force that release is applied on elastic attachment matrix so that it is drive flexible nano electromagnetic shielding multiple Close film (2) retraction, can be prepared by flexible extensible electromagnetic shielding film.
4. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, it is characterised in that The described first step is additionally included in the end of flexible nano electromagnetic shielding composite material (2) and sticks electrode.
5. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 4, it is characterised in that Described electrode is connected with flexible nano electromagnetic shielding composite material (2) by conductive silver glue.
6. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, it is characterised in that Carbon nano-tube film in the described first step is prepared by single wall or multi-walled carbon nano-tubes, and carbon nanotube diameter is 10nm-100nm, film thickness is 10 μm-50 μm, and porosity is 35%-75%, and hot strength is 100MPa-500MPa, electrical conductivity is 104-105S/m。
7. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, it is characterised in that The concentration of described graphene suspension is 1mg/ml～50mg/ml, dip time 1～5h, impregnates 1～3 time.
8. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, it is characterised in that Described elastica (1) is polydimethylsiloxanefilm film, acrylate film, polyurethane film or high-elastic rubber Glue thin film.
9. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, it is characterised in that Described hydroelasticity binding agent is polydimethylsiloxane, acrylic acid or polyurethane.
10. the preparation method of flexible extensible electromagnetic shielding film as claimed in claim 3, its feature exists In, the described resin with protective effect is polyurethane, polydimethylsiloxane or rubber.
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CN109628006A (en) * 2018-12-18 2019-04-16 中国科学院苏州纳米技术与纳米仿生研究所 A kind of carbon nanotube base electromagnetic screen material, adhesive tape and preparation method thereof
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CN110379544A (en) * 2019-07-31 2019-10-25 广东南海启明光大科技有限公司 A kind of retractable and flexible conductive film and preparation method thereof
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