CN109575340A - Flexible PET graphene coating electromagnetic shielding membrane material and preparation method thereof - Google Patents
Flexible PET graphene coating electromagnetic shielding membrane material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- C—CHEMISTRY; METALLURGY
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
Abstract
The present invention relates to technical field of electromagnetic shielding, especially a kind of flexibility PET graphene coating electromagnetic shielding membrane material and preparation method thereof.The preparation method includes carrying out sided corona treatment to flexible PET film, preparing viscous paste, blade coating viscous paste, drying and other steps.Water-based acrylic resin is used in preparation method as bonding agent, and graphene and nano-nickel powder has been used to form conductive path simultaneously.Compared with prior art, the present invention prepares the simple process of electromagnetic shielding material, and process environmental protection, uniformly, obtained finished product has many advantages, such as Soft, foldable to blade coating, and electromagnetic shielding performance is excellent, wide market.
Description
Technical field
The present invention relates to electromagnetic shielding material, be particularly based on flexible electromagnetic shielding material of graphene and preparation method thereof and
Using.
Background technique
With information technology, the development of electronics industry, electronics and IT products are applied in all trades and professions, are seen everywhere.Promoting
Into while economical, society is fast-developing, the electromagnetic pollution got worse is also brought.In order to avoid electromagenetic wave radiation is to electronics
The interference of electric product improves the stability that electronic and electrical equipment uses, accuracy.In addition to need to correctly design circuit and reasonable cloth
Outside office's electronic component, implementing anti-radiation protection to it using electromagnetic shielding material is effective method.
Electromagnetic shielding, i.e., enter electromagnetic energy caused by electromagnetic radiation field source not using the reflection of shield, decaying etc.
By shielding area.In general, shield effectiveness shield effectiveness SE (Shielding of the shielding material to space point
Effectiveness it) indicates, i.e. wherein, field strength when E0 is no shielding material, E is that have shield to SE=201g (E0/E)
The field strength afterwards.
When Electromagnetic Wave Propagation reaches shielding material surface, is usually decayed by 3 kinds of different mechanisms (referring to Fig. 1): 1. being existed
The reflection loss of incidence surface；2. the loss that the electromagnetic wave for entering shield not by reflection is absorbed by material；3. in shield
Internal multiple reflections loss.
Electromagnetic wave can be calculated as follows by the total shield effectiveness of shielding material: wherein, SE is electromagnetic shielding effect to SE=A+R+B
Fruit, R are the decaying of surface individual reflection, and A is absorption loss, and B is multiple reflection inside loss.
1) reflection loss reflection loss is due to caused by mismatching between space impedance and the intrinsic resistance of shielded layer.Tool
There is the material of higher conductivity or more low magnetic permeability, reflection loss is bigger, and reflection loss not only has with the impedance of material surface
Close distance dependent of the also with the type of radiation source and shield to radiation source.
2) absorption loss is electric dipole in conductor material or magnetic dipole and electromagnetic field effect as a result, due to absorbing
A is lost to occur in shielding material, it is unrelated with type (electric field wave or the magnetic field wave) of wave, with the thickness of shielded layer, frequency,
Conductivity and magnetic conductivity are related.The thickness of material increases, and A value is also bigger.
3) multipath reflection is lost.After passing through attenuated inside due to transmitted wave, and the other side of shielded layer is encountered, in this side
Face is reflected and is transmitted again, and back wave is so reflected repeatedly again by inside, energy is made to decay rapidly.
Electromagnetic shielding material is mostly metal plate, wire mesh and metallized textiles etc., traditional electromagnetic screen at present
Covering coating is usually to be volatilized largely to body nocuousness in use using organic resin as binder, have dirt to environment
The substance of dye.Not good enough in corrosion resistance, manufacturing process is not environmentally etc..
As a kind of carbon material, graphene itself has high conductivity and high-termal conductivity, and theoretically its electron mobility can
Reach 2 × 105cm2/ Vs, 140 times of electron mobility about in silicon, 20 times of GaAs, temperature stability is high, theoretically,
Its conductivity is up to 108S/m, it is lower than nickel, silver, it is conductive best material at room temperature.It, can with graphene as conductive filler
To reduce the cost of electrocondution slurry；Electric conductivity is improved, and then improves the shielding properties of material.Graphene has good chemistry
Stability, excellent electric conductivity and mechanical flexibility.But due to graphene dispersion in resin after, graphene sheet layer and lamella
Between be difficult to form the contact of " bridging " formula, that is, be difficult to form perfect conductive path, and in lamella junction, there are biggish
Contact resistance, so that the sheet resistance of its conductive coating formed is difficult to further decrease.
PET film is a kind of performance than more comprehensive packing film.Its transparency is good, glossy；With good airtight
Property and fragrance protectiveness；Moisture resistance is medium, and rate of perviousness declines at low temperature.The good mechanical performance of PET film, obdurability are all
Best in thermoplastic, tensile strength and impact strength are more much higher than general film；And very power is good, dimensionally stable.PET
Film also has excellent heat-resisting, cold resistance and good chemical resistance and oil resistivity.
Summary of the invention
It is an object of the invention to overcome defect existing in the prior art, a kind of flexibility PET graphene coating electricity is provided
Magnetic shield film material and preparation method thereof.The barrier film material has excellent flexibility, shield effectiveness, Corrosion Protection, resistance to
It is sour, alkaline-resisting, while preparation method also has many advantages, such as that simple process, process are environmentally protective.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by PET film wiped clean, using sided corona treatment appropriate, film surface forms tiny poroid, reaches one
Determine roughness, increases the adhesive strength of subsequent graphene coating film；
It (2) is 1 by mass ratio: (0.55~0.65): (0.004~0.006): the water soluble acrylic acid of (0.045~0.055)
Resin, graphene slurry, defoaming agent, levelling agent sequentially add in vacuum mixer, adjusting negative pressure be -0.04mpa~-
0.06mpa, revolving speed are 1200~1800r/min, stir 3~6h of duration；So that the aqueous solvent and aqueous third in graphene slurry
Olefin(e) acid resin preferably mixes, and graphene and water-based acrylic resin are uniformly dispersed under the action of high shear agitation paddle；
(3) dilute hydrochloric acid that mass fraction is 6~15wt.% is used to carry out pickling to nano-nickel powder to remove its surface oxidation
Object obtains the nano-nickel powder in grey black, for use using distilled water washing, dehydrated alcohol dispersion, drying and processing；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and stone
The nano-nickel powder that black alkene stock quality ratio is 1: 1.3~1: 0.6 is even added in batches in frequency conversion star ball mill, adjusts revolving speed
For 400r/min~800r/min；Periodically 18~for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches the PET film that sided corona treatment is crossed in step (1)
On, it is formed on its surface coat, coat is with a thickness of 0.3-0.8mm；
(6) film obtained by step (5) is put to be dried into baking oven and is electromagnetically shielded to get to the coating of flexibility PET graphene
Membrane material.
Preferably, the PET film prepared in the step (1) with a thickness of 0.02~0.4mm.
Preferably, dilute hydrochloric acid used in the step (3) be use mass fraction for 36wt.% concentrated hydrochloric acid dilution and
At.
Preferably, drying temperature is 40~55 DEG C in the step (6), and drying time is 1.5~3h；More preferably, it does
Dry temperature is 45 DEG C, drying time 2h.
Preferably, the average grain diameter of the nano-nickel powder is 4~8nm.
Preferably, the viscosity for the slurry that the step (4) obtains is 43s~46s.
Preferably, the graphene slurry in the step (2) includes graphene, water and dispersing agent, the graphene, water
And the mass ratio of dispersing agent is (25~35): (64~73): (1~2)；More preferably, the graphene, water and dispersing agent
Mass ratio be 30: 69: 1.Preferably, the dispersing agent is the Silok-7170W type dispersing agent that Si Luoke China provides.
Preferably, the graphene in the graphene slurry is to be prepared using liquid phase ultrasound stripping method, by Hunan state Sheng Shi
Black Co., Ltd provides.It is manufactured using liquid phase ultrasound stripping method, maintains the complete pattern of graphene and electric conductivity, avoid
Defect caused by aoxidizing in the graphene as made from oxidation-reduction method, chemical vapor infiltration can not be restored completely, influence it and lead
Electrical property.
Preferably, the levelling agent in the step (2) is GSK-550 polyether modified siloxane levelling agent, by Dongguan City height
This is produced into Fine Chemical Co., Ltd；Defoaming agent in the step (2) is DQ-2209 defoaming agent, macro by Dongguan City a century
Scheme Chemical Industry Science Co., Ltd's production.
Preferably, PET film surface is completely handled in the step (1), is to use to have soaked ethanol solution
Non-dust cloth wiping method.
Preferably, a kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by the PET film wiped clean of 0.2mm thickness, using sided corona treatment appropriate, film surface forms Small Holes
Shape reaches certain roughness, increases the adhesive strength of subsequent graphene coating film；
(2) water-based acrylic resin by mass ratio for 1: 0.6: 0.005: 0.05, graphene slurry, defoaming agent, levelling
Agent sequentially adds in vacuum mixer, and adjusting negative pressure is -0.05mpa, revolving speed 1600r/min, stirs duration 4h；So that graphite
Aqueous solvent in alkene slurry preferably mixes with water-based acrylic resin, and graphene and water-based acrylic resin are stirred in high speed shear
It mixes and is uniformly dispersed under the action of paddle；
(3) dilute hydrochloric acid that mass fraction is 6-15wt.% is used to carry out pickling to nano-nickel powder to remove its surface oxidation
Object obtains the nano-nickel powder in grey black, for use using distilled water washing, dehydrated alcohol dispersion, drying and processing；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and stone
The nano-nickel powder that black alkene stock quality ratio is 1: 0.833 is even added in batches in frequency conversion star ball mill, and nano-nickel powder is put down
Equal partial size is 8nm, and adjusting revolving speed is 800r/min；Timing is for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches the PET film that sided corona treatment is crossed in step (1)
On, it is formed on its surface coat, coat is with a thickness of 0.4mm；
(6) film obtained by step (5) is put and is dried into baking oven, adjusting drying temperature is 45 DEG C, drying time 2h,
Obtain flexible PET graphene coating electromagnetic shielding membrane material.
Obtained flexible PET graphene is coated into electromagnetic shielding membrane material and carries out aging process, is placed on air drying ring
Aging is for 24 hours in border.Then its electromagnet shield effect is tested.In 300KHZ~1.5GHZ band limits, electromagnetic shielding effectiveness
Greater than 41dB, there is excellent shield effectiveness.Meanwhile the flexible PET graphene coating electromagnetic shielding membrane material that the present invention is made
Resistivity measurement method is visited using four, tests to obtain resistivity≤0.06 Ω cm.
In addition, the application the invention further relates to the resulting finished product of above-mentioned preparation method in electromagnetic shielding field.
Compared with prior art, the advantages and beneficial effects of the present invention are:
(1) coating of flexibility PET graphene is electromagnetically shielded membrane material as electromagnetic shielding film in the present invention, when preparation only with
The conventional samples such as graphene slurry and water-based acrylic resin, defoaming agent, levelling agent, nano-nickel powder, reagent, and use vacuum
The conventional equipments such as blender, frequency conversion star ball mill, doctor knife coater, dryer have manufacture craft simple and environmentally-friendly, low in cost
The features such as.
It (2) the use of medicament and raw material is all innocuous substance in the present invention, preparation process is environmentally protective.
(3) flexibility PET graphene coating electromagnetic shielding membrane material prepared by the present invention, has superior barrier efficiency, anti-corrosion
It is corrosion energy, acidproof, alkaline-resisting.And due to being flexible material, usage scenario is more extensive.Graphene flexible electrical made of the present invention
Magnetic shield film, thickness be only 0.3~1.2mm, it is bent, distort, tear open and be cut into various shape, use scope is wide.
(4) traditional resin in the construction process and in solidification process, will be discharged using organic solvent
A large amount of organic volatiles, cause the pollution of atmosphere, environment, or even cause harm to the human body；The present invention uses water soluble acrylic acid tree
Rouge enhances adhesive strength as bonding agent, and be good for the environment.
(5) present invention is dried the semi-finished product after blade coating using suitable temperature, controls rate of drying, keeps away
The phenomenon that cavity occurs in graphene film layer is exempted from.
(6) water-based acrylic resin that the present invention uses is the main object for scratching the film-forming after PET film substrate surface
Matter, graphene and nano-nickel powder are filled wherein as conductive materials, play the role of fixed, bracket, lead conductive materials formation
Electric network.Water-based acrylic resin can be shunk in solidification, so that it is close to each other to fill graphene therein, nano nickel, mutually
Contact, is more likely formed conductive channel, and this synergistic effect enhances electric conductivity, improves conductive stability.Use nanometer
Before nickel particle, first its surface is cleaned using dilute hydrochloric acid, it is that may be present in NiO, NiO to remove surface2And Ni2O3
Equal oxides, influence electric conductivity.
(7) present invention is first stirred in vacuum mixer, using the form of two kinds of stirrings in the work of high shear
It is mixed rapidly with lower solvent with resin, is conducive to the dispersion of graphene and nano nickel；Again in ball grinding stirring in tank abrading-ball high speed
It is mutually collided in movement, grinds and mix sample, nickel powder is evengranular to be embedded between graphene；Disperse conductive particles are more
Uniformly.
(8) present invention is conductive bodies using the graphene and nano-nickel powder of high conductivity, wherein graphene can be with
Nano-nickel powder mixing, preferably forms conductive path (that is: nano nickel is filled to the junction of graphene sheet layer), and can be significantly
Ground reduces the dosage of nano nickel, and compared to conventional pure nano silver, Nanometer Copper conductive filler, cost is more cheap.Nickel has excellent
Different magnetic conductivity has natural advantage as shielding material.
(9) present invention has widened the purposes of graphene, improves the practical application value of graphene to a certain extent.
Detailed description of the invention
Fig. 1 is principle of electromagnetic shield-ing schematic diagram.
Fig. 2 is the structural schematic diagram of flexibility PET graphene coating electromagnetic shielding membrane material.
Fig. 3 a is the graphene coating film of blade coating in the dry preceding status diagram of coat.
Fig. 3 b be blade coating graphene coating film after coat is dry status diagram.
Fig. 4 a is the SEM spectrum for the graphene that the present invention uses.
Fig. 4 b is the Raman map for the graphene that the present invention uses.
Fig. 5 is the finished product schematic of flexibility PET graphene produced by the present invention coating electromagnetic shielding membrane material.
Fig. 6 is the shielding efficiency of the coating electromagnetic shielding membrane material of flexibility PET graphene made from embodiment three.
Appended drawing reference:
1, the PET film that sided corona treatment is crossed；2, coat.
Specific embodiment
With reference to the accompanying drawings and examples, further description of the specific embodiments of the present invention.Following embodiment is only
For clearly illustrating technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment one:
A kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by the PET film wiped clean after 0.02mm, using sided corona treatment appropriate, film surface forms tiny
It is poroid, reach certain roughness, increases the adhesive strength of subsequent graphene coating film；
(2) water-based acrylic resin by mass ratio for 1: 0.55: 0.004: 0.045, graphene slurry, defoaming agent, stream
Flat agent sequentially adds in vacuum mixer, and adjusting negative pressure is -0.04mpa, revolving speed 1200r/min, stirs duration 3h；So that stone
Aqueous solvent in black alkene slurry preferably mixes with water-based acrylic resin, and graphene and water-based acrylic resin are in high speed shear
It is uniformly dispersed under the action of agitating paddle；
Graphene slurry includes graphene, water and dispersing agent, and the mass ratio of the graphene, water and dispersing agent is 25
:73:2.The dispersing agent is the Silok-7170W type dispersing agent that Si Luoke China provides.Graphite in the graphene slurry
Alkene is to be prepared using liquid phase ultrasound stripping method, is provided by Hunan Guo Sheng graphite Co., Ltd.Graphene SEM figure and Raman map point
Not as shown in figures 4 a and 4b.Levelling agent is GSK-550 polyether modified siloxane levelling agent, by Dongguan City Gauss into fine chemistry industry
Co., Ltd's production；Defoaming agent is DQ-2209 defoaming agent, is produced by Dongguan City a century grand plan Chemical Industry Science Co., Ltd.
(3) use mass fraction be 6wt.% dilute hydrochloric acid to nano-nickel powder carry out pickling to remove its oxide on surface,
Using distilled water washing, dehydrated alcohol dispersion, drying and processing, the nano-nickel powder in grey black is obtained, for use；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and stone
The nano-nickel powder that black alkene stock quality ratio is 1: 1.3 is even added in batches in frequency conversion star ball mill, and nano-nickel powder is averaged
Partial size is 4nm (by Aladdin reagent, Co., Ltd is provided), and adjusting revolving speed is 400r/min/min；Timing 18h；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches the PET film 1 that sided corona treatment is crossed in step (1)
On, it is formed on its surface coat 2, coat is with a thickness of 0.3mm；
(6) film obtained by step (5) is put and is dried into baking oven, drying temperature is 40 DEG C, drying time 1.5h, i.e.,
Obtain flexible PET graphene coating electromagnetic shielding membrane material.
Embodiment two:
A kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by the PET film wiped clean of 0.4mm thickness, using sided corona treatment appropriate, film surface forms Small Holes
Shape reaches certain roughness, increases the adhesive strength of subsequent graphene coating film；
(2) water-based acrylic resin by mass ratio for 1: 0.65: 0.006: 0.055, graphene slurry, defoaming agent, stream
Flat agent sequentially adds in vacuum mixer, and adjusting negative pressure is -0.06mpa, revolving speed 1800r/min, stirs duration 6h；So that stone
Aqueous solvent in black alkene slurry preferably mixes with water-based acrylic resin, and graphene and water-based acrylic resin are in high speed shear
It is uniformly dispersed under the action of agitating paddle；
Graphene slurry includes graphene, water and dispersing agent, and the mass ratio of the graphene, water and dispersing agent is 35
:64:1.The dispersing agent is the Silok-7170W type dispersing agent that Si Luoke China provides.Graphite in the graphene slurry
Alkene is to be prepared using liquid phase ultrasound stripping method, is provided by Hunan Guo Sheng graphite Co., Ltd.Graphene SEM figure and Raman map point
Not as shown in figures 4 a and 4b.Levelling agent is GSK-550 polyether modified siloxane levelling agent, by Dongguan City Gauss into fine chemistry industry
Co., Ltd's production；Defoaming agent is DQ-2209 defoaming agent, is produced by Dongguan City a century grand plan Chemical Industry Science Co., Ltd.
(3) use mass fraction be 15wt.% dilute hydrochloric acid to nano-nickel powder carry out pickling to remove its oxide on surface,
Using distilled water washing, dehydrated alcohol dispersion, drying and processing, the nano-nickel powder in grey black is obtained, for use；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and stone
The nano-nickel powder that black alkene stock quality ratio is 1: 0.6 is even added in batches in frequency conversion star ball mill, and nano-nickel powder is averaged
Partial size is 8nm (by Aladdin reagent, Co., Ltd is provided), and adjusting revolving speed is 800r/min；Timing is for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches the PET film 1 that sided corona treatment is crossed in step (1)
On, it is formed on its surface coat 2, coat is with a thickness of 0.8mm；
(6) film obtained by step (5) is put and is dried into baking oven, drying temperature is 55 DEG C, drying time be 3h to get
Electromagnetic shielding membrane material is coated to flexible PET graphene.
Embodiment three:
A kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by the PET film wiped clean of 0.2mm thickness, using sided corona treatment appropriate, film surface forms Small Holes
Shape reaches certain roughness, increases the adhesive strength of subsequent graphene coating film；
(2) water-based acrylic resin by mass ratio for 1: 0.6: 0.005: 0.05, graphene slurry, defoaming agent, levelling
Agent sequentially adds in vacuum mixer (using weighing the water-based acrylic resin of 10g, graphene slurry, the 0.05g of 6g when operation
Defoaming agent, 0.5g GSK-550 polyether modified siloxane levelling agent sequentially add in vacuum mixer), adjust negative pressure be-
0.05mpa, revolving speed 1600r/min stir duration 4h；So that aqueous solvent and water-based acrylic resin in graphene slurry are more
Good mixes, and graphene and water-based acrylic resin are uniformly dispersed under the action of high shear agitation paddle；The dispersing agent is
The Silok-7170W type dispersing agent that Si Luoke China provides.Graphene in the graphene slurry is to be shelled using liquid phase ultrasound
It prepares from method, is provided by Hunan Guo Sheng graphite Co., Ltd.Graphene SEM figure is with Raman map respectively such as Fig. 4 a and Fig. 4 b institute
Show.Levelling agent is GSK-550 polyether modified siloxane levelling agent, is produced by Dongguan City Gauss into Fine Chemical Co., Ltd；Disappear
Infusion is DQ-2209 defoaming agent, is produced by Dongguan City a century grand plan Chemical Industry Science Co., Ltd.
(3) use mass fraction be 15wt.% dilute hydrochloric acid to nano-nickel powder carry out pickling to remove its oxide on surface,
Using distilled water washing, dehydrated alcohol dispersion, drying and processing, the nano-nickel powder in grey black is obtained, for use；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and stone
Black alkene stock quality ratio is even added to frequency conversion for 1: 0.833 nano-nickel powder (Co., Ltd provides by Aladdin reagent) in batches
In star ball mill, the average grain diameter of nano-nickel powder is 8nm, and adjusting revolving speed is 800r/min；Timing is for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches the PET film 1 that sided corona treatment is crossed in step (1)
On, it is formed on its surface coat 2, coat is with a thickness of 0.4mm；According to quasi- GB/T1723-1993 " viscosity of the coating measuring method "
Its viscosity is tested, its viscosity is obtained in 40s, is suitble to blade coating；
(6) film obtained by step (5) is put and is dried into baking oven, adjusting drying temperature is 45 DEG C, drying time 2h,
Obtain flexible PET graphene coating electromagnetic shielding membrane material.Finished figure is as shown in Figure 5.
Obtained flexible PET graphene is coated into electromagnetic shielding membrane material and carries out aging process, is placed on air drying ring
Aging is for 24 hours in border.
) test the shielding properties of this film；According to GB/T 30142-2013, (plane electromagnetic shielding material shield effectiveness is surveyed
Amount method), with coaxial flange method test material electromagnetic shielding effectiveness, in 300KHZ~1.5GHZ band limits, electromagnetic wave
Shield effectiveness is 41.452~50.256dB.Specific test data is as shown in table 1:
The test of 1 electromagnet shield effect of table
The grapheme material that the present invention uses is a kind of highly conductive nano material, and joined nano-nickel powder, to have
Effect improves electromagnet shield effect, while in the case where film layer, there is good shield effectiveness in the same old way, and the present invention is made
Coating film visits resistivity measurement method using four, tests to obtain resistivity≤0.06 Ω cm.
In addition, attached to the coating of graphene coating film according to SJ/T10674--1995 (coating coating general technical specifications)
Performance, impact resistance, water resistance, resistance to temperature change, salt fog, corrosion resistance etc. be tested, reached conjunction
Case marker is quasi-.The results are shown in Table 2:
The detection of 2 flexibility PET graphene electromagnetic shielding material traditional performance of table
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by PET film wiped clean, using sided corona treatment appropriate, film surface forms tiny poroid, reaches certain thick
Rugosity increases the adhesive strength of subsequent graphene coating film；
It (2) is 1 by mass ratio: (0.55~0.65): (0.004~0.006): the water soluble acrylic acid tree of (0.045~0.055)
Rouge, graphene slurry, defoaming agent, levelling agent sequentially add in vacuum mixer, and adjusting negative pressure is -0.04mpa~-0.06mpa,
Revolving speed is 1200~1800r/min, stirs 3~6h of duration；So that aqueous solvent and water-based acrylic resin in graphene slurry
It preferably mixes, graphene and water-based acrylic resin are uniformly dispersed under the action of high shear agitation paddle；
(3) use mass fraction be 6~15wt.% dilute hydrochloric acid to nano-nickel powder carry out pickling to remove its oxide on surface,
Using distilled water washing, dehydrated alcohol dispersion, drying and processing, the nano-nickel powder in grey black is obtained, for use；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and graphene
The nano-nickel powder that stock quality ratio is 1: 1.3~1: 0.6 is even added in batches in frequency conversion star ball mill, is adjusted revolving speed and is
400r/min~800r/min；Periodically 18~for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches on the PET film that sided corona treatment is crossed in step (1),
Its surface forms coat, and coat is with a thickness of 0.3-0.8mm；
(6) film obtained by step (5) is put to be dried into baking oven and is electromagnetically shielded membrane material to get to the coating of flexibility PET graphene
Material.
2. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as described in claim 1, it is characterised in that:
The PET film prepared in the step (1) with a thickness of 0.02~0.4mm；Drying temperature is 40~55 DEG C in the step (5),
Drying time is 1.5~3h.
3. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as claimed in claim 2, it is characterised in that:
Drying temperature is 45 DEG C, drying time 2h.
4. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as described in claim 1, it is characterised in that:
Graphene slurry in the step (2) includes graphene, water and dispersing agent, the matter of the graphene, water and dispersing agent
Amount is than being (25~35): (64~73): (1~2)；The average grain diameter of the nano-nickel powder is 4~8nm.
5. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as claimed in claim 4, it is characterised in that:
The mass ratio of the graphene, water and dispersing agent is 30: 69: 1.
6. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as described in claim 1, it is characterised in that:
PET film surface is completely handled in the step (1), is the side using the non-dust cloth wiping for having soaked ethanol solution
Method.
7. a kind of preparation method of flexibility PET graphene coating electromagnetic shielding membrane material, comprising the following steps:
(1) first by the PET film wiped clean of 0.2mm thickness, using sided corona treatment appropriate, film surface formed it is tiny poroid,
Reach certain roughness, increases the adhesive strength of subsequent graphene coating film；
(2) by mass ratio be 1: 0.6: 0.005: 0.05 water-based acrylic resin, graphene slurry, defoaming agent, levelling agent according to
In secondary addition vacuum mixer, adjusting negative pressure is -0.05mpa, revolving speed 1600r/min, stirs duration 4h；So that graphene is starched
Aqueous solvent in material preferably mixes with water-based acrylic resin, and graphene and water-based acrylic resin are in high shear agitation paddle
Under the action of be uniformly dispersed；
(3) dilute hydrochloric acid that mass fraction is 6-15wt.% is used to carry out pickling to nano-nickel powder to remove its oxide on surface, then
By distilled water washing, dehydrated alcohol dispersion, drying and processing, the nano-nickel powder in grey black is obtained, for use；
(4) slurry that step (2) obtains is transferred in frequency conversion star ball mill, then will be obtained in step (3) and graphene
The nano-nickel powder that stock quality ratio is 1: 0.833 is even added in batches in frequency conversion star ball mill, the average grain of nano-nickel powder
Diameter is 8nm, and adjusting revolving speed is 800r/min；Timing is for 24 hours；
(5) slurry for obtaining step (4) takes out, smooth, uniformly scratches on the PET film that sided corona treatment is crossed in step (1),
Its surface forms coat, and coat is with a thickness of 0.4mm；
(6) film obtained by step (5) is put and is dried into baking oven, adjusting drying temperature is 45 DEG C, drying time be 2h to get
Electromagnetic shielding membrane material is coated to flexible PET graphene.
8. the preparation method of flexibility PET graphene coating electromagnetic shielding membrane material as claimed in claim 7, it is characterised in that:
Graphene slurry in the step (2) includes graphene, water and dispersing agent, the matter of the graphene, water and dispersing agent
Amount is than being 30: 69: 1；PET film surface is completely handled in the step (1), is to use to have soaked ethanol solution
The method of non-dust cloth wiping.
9. a kind of flexibility PET graphene coating electromagnetic shielding membrane material, using such as described in any item preparation sides claim 1-8
Method is made.
10. application of the flexible PET graphene coating electromagnetic shielding membrane material in electromagnetic shielding field described in claim 9.
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