CN116655999A - Electromagnetic shielding material with through hole structure for sealing and preparation method thereof - Google Patents
Electromagnetic shielding material with through hole structure for sealing and preparation method thereof Download PDFInfo
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- CN116655999A CN116655999A CN202310592529.6A CN202310592529A CN116655999A CN 116655999 A CN116655999 A CN 116655999A CN 202310592529 A CN202310592529 A CN 202310592529A CN 116655999 A CN116655999 A CN 116655999A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000007789 sealing Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical group C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 35
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 35
- 229920006254 polymer film Polymers 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 17
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000005553 drilling Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 6
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006132 styrene block copolymer Polymers 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 3
- 238000003486 chemical etching Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 claims description 2
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 claims description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 2
- ZUVOYUDQAUHLLG-OLXYHTOASA-L disilver;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Ag+].[Ag+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O ZUVOYUDQAUHLLG-OLXYHTOASA-L 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229940071575 silver citrate Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 2
- RQZVTOHLJOBKCW-UHFFFAOYSA-M silver;7,7-dimethyloctanoate Chemical compound [Ag+].CC(C)(C)CCCCCC([O-])=O RQZVTOHLJOBKCW-UHFFFAOYSA-M 0.000 claims description 2
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 150000002343 gold Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000011231 conductive filler Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RVCKCEDKBVEEHL-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzyl alcohol Chemical compound OCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl RVCKCEDKBVEEHL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 as shown in FIG. 5 Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- WPHGSKGZRAQSGP-UHFFFAOYSA-N methylenecyclohexane Natural products C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention provides an electromagnetic shielding material with a through hole structure for sealing and a preparation method thereof, and particularly discloses the electromagnetic shielding material for sealing, which comprises a polymer substrate, wherein the polymer substrate is provided with a through hole, and the outer surface of a polymer substrate and the inner surface of the through hole are provided with metal layers; the polymeric substrate has a thickness of 0.02mm to 0.5 mm. The invention provides a composite material with moderate thickness for the first time, which is suitable for electromagnetic shielding between electronic devices. The material can solve the problem that the composite material prepared by adopting the traditional conductive filler in the prior art is difficult to prepare the shielding material with thinner thickness, is more suitable for electromagnetic shielding between small-sized and miniature electronic devices, and has excellent mechanical property and electromagnetic shielding property.
Description
Technical Field
The invention belongs to the field of electronic materials, and particularly relates to an electromagnetic shielding material with a through hole structure for sealing and a preparation method thereof.
Background
As the integration level and the working frequency of electronic devices are higher and higher, the electromagnetic interference phenomenon is more and more serious, and the electromagnetic shielding material is an important means for solving the electromagnetic interference problem. Achieving efficient electromagnetic shielding typically requires wrapping the interference source or sensing element with a good conductor to construct a closed "faraday cage". However, in reality devices often do not have a perfectly closed "faraday cage", electromagnetic leakage often occurs at the contact of two different components, and the use of an omni-directional conductive material in the contact area is an effective way to improve shielding effectiveness and reduce electromagnetic leakage.
The omnibearing conductive foam is usually made by plating metal on the surface of three-dimensional polymer foam or fabric or wrapping the polymer foam or fabric by a metal plating film, and has been widely applied to PCBA electrical interconnection and electromagnetic shielding of electronic elements, but is difficult to use in ultra-narrow or ultra-thin electromagnetic sealing areas due to the unique three-dimensional structure. The electromagnetic sealing strip/sheet/ring/gasket is an ideal choice for narrow and thin electromagnetic sealing, and the electromagnetic sealing strip/sheet/ring/gasket needs to ensure a certain modulus besides proper thickness so as to realize sealing effect between different electronic components. The electromagnetic sealing strip/sheet/ring/gasket commercially used in the current market is generally prepared by adding conductive filler (nickel-coated carbon, silver-coated glass bead, silver-coated copper, silver-coated aluminum, nickel-coated copper and the like) into a polymer matrix. According to the conductive principle of the conductive polymer composite material, stable high conductivity and high shielding effectiveness can be obtained only when the conductive filler reaches a higher filling level, however, too high filling level of the filler often deteriorates the mechanical properties of the polymer matrix, resulting in reduced mechanical compression or mechanical rebound resilience of the electromagnetic sealing material, and further reduced resistance contact stability and reduced electromagnetic shielding effectiveness.
Disclosure of Invention
The prior art obtains high conductivity and high shielding effectiveness by filling conductive filler into a polymer matrix with high content, and has the defects of high cost, poor mechanical property and the like. According to the invention, through the structural design of the micro through holes, continuous conductive metal layers are grown on the surfaces of the films and the surfaces of the inner walls of the through holes, so that the filling of high-conductivity filler is avoided, the omnibearing high-conductivity and electromagnetic shielding performance are realized, and meanwhile, the mechanical properties of the polymer matrix are maintained as much as possible. The invention can effectively reduce the consumption of conductive metal and realize high omnibearing conductivity. In addition, due to the existence of the through hole structure, the shielding film also has the functions of visualization, ventilation, heat dissipation and the like, and has important application prospects in electromagnetic shielding and heat management of high-integration electronic devices.
One aspect of the present invention provides a conductive electromagnetic shielding material for sealing, which includes a polymer substrate having a through hole thereon, and a metal layer on an outer surface of the polymer substrate and an inner surface of the through hole;
the polymeric substrate has a thickness of 0.02mm to 1mm.
Further, the polymeric substrate has a thickness of 0.03mm to 0.5mm, for example the polymeric substrate has a thickness of 0.03mm, 0.05mm, 0.07mm, 0.09mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5 mm.
Further, the polymeric substrate material is selected from the group consisting of polymers made from any one or more of the following, including styrenic block copolymers, polyurethane thermoplastic elastomers (TPU) polyamides, thermoplastic elastomers (TPAE), polyester thermoplastic elastomers (TPEE), polyamide thermoplastic elastomers (TPAE), and polyolefin thermoplastic elastomers (TPO, TPV);
further, the polymeric substrate material is selected from polymeric materials having a modulus of less than 0.5GPa and a hardness of less than 50 MPa;
the styrenic block copolymer is selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), hydrogenated styrene-ethylene-butadiene-styrene (SEBS), hydrogenated styrene-isoprene-styrene (SEPS).
Further, the polymer substrate is obtained by dissolving a polymer substrate material in a solvent, coating the solvent into a film, and forming the film after volatilizing the solvent; or by hot-pressing the polymeric substrate material into a film.
Further, the aperture of the through hole is 0.02 mm-1.0 mm; for example, 0.05mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm.
Further, the hole distance between the through holes is 0.04 mm-2.0 mm; for example, 0.05mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2mm.
The hole distance between the through holes is the distance between the centers of the two nearest through holes.
Further, the metal layer is made of silver, gold, copper and nickel.
Further, the method for providing the through holes on the polymer substrate is mechanical drilling, laser drilling and chemical etching.
Further, the method for arranging the metal layer on the outer surface of the polymer matrix and in the through hole is to grow the metal conductive layer on the outer surface of the polymer matrix and in the through hole by using a metal salt adsorption reduction method.
Further, the method of disposing a metal layer on the outer surface of the polymer matrix and in the through hole further comprises the step of adding a plasma treatment before the adsorption reduction of the metal salt.
Further, the metal salt adsorption reduction method is to impregnate the polymer matrix into a metal salt solution for adsorption, and then reduce or heat the polymer matrix by adopting a reducing agent for self-reduction, so that the surface of the polymer matrix and the surface of the through hole form a metal conductive layer.
Further, the metal salt is selected from silver salt, gold salt, copper salt, nickel salt.
Further, the metal salt is selected from the group consisting of silver trifluoroacetate, silver nitrate, silver neodecanoate, silver acetate, silver oxalate, silver tartrate, silver citrate, copper acetate, copper formate, copper oleate, copper lactate.
The invention also provides a preparation method of the conductive electromagnetic shielding material for sealing, which comprises the following steps:
s1) preparing a polymer film or sheet;
s2) arranging through holes on the polymer film or sheet;
s3) surface metallizing the polymer film or sheet provided with the through holes.
Further, the method for preparing the polymer film or sheet in step S1) is to dissolve the polymer base material in a solvent, and apply the polymer base material as a film, and evaporate the solvent to form a film; or by hot-pressing the polymeric substrate material into a film.
Further, the method of disposing the through hole on the polymer substrate in the step S2) is mechanical drilling, laser drilling, and chemical etching to form a hole.
Further, the surface metallization in step S3) is to grow a metal conductive layer on the outer surface of the polymer matrix and in the through holes by using a metal salt adsorption reduction method.
Further, the method of disposing a metal layer on the outer surface of the polymer matrix and in the through hole further comprises the step of adding a plasma treatment before the adsorption reduction of the metal salt.
Still another method of the present invention provides a sealing conductive electromagnetic shield member made of the sealing conductive electromagnetic shield material described above.
Further, the electromagnetic shielding component for sealing is a sealing ring, a sealing gasket, a sealing sheet and a sealing strip.
In a further aspect, the invention provides the use of the above-mentioned electrically conductive electromagnetic shielding material for sealing in the manufacture of an electrically conductive electromagnetic shielding member for sealing.
Further, the electromagnetic shielding component generates bending, twisting, folding and stretching deformation in the use process.
Advantageous effects
1) The invention provides a composite material with moderate thickness for the first time, which is suitable for electromagnetic shielding between electronic devices.
2) The composite material can solve the problem that the composite material prepared by adopting the conductive filler in the prior art cannot be used for preparing the conductive shielding material with thinner thickness, and is more suitable for electromagnetic shielding between small-sized and miniature electronic devices.
3) The composite material has excellent mechanical properties, can have modulus suitable for sealing, compression resilience and can keep good electromagnetic shielding performance after stretching.
4) In order to ensure that the combination of the polymer substrate and the metal layer is tight and does not fall off, the metal salt and the polymer substrate are specifically matched, the substrate material is subjected to plasma pretreatment and other methods, the in-plane and out-of-plane omnibearing conduction is realized by means of the vertical through hole structure, and the electromagnetic shielding performance is good.
5) The composite material provided by the invention adopts an elastic polymer material as a base material, and can still keep good shielding performance after being stretched or compressed after being covered with a metal layer.
Drawings
Figure 1 load-displacement curve of sbs nanoindentation test.
Fig. 2. Load-displacement curve of pp nanoindentation test.
Fig. 3 load-displacement curve for pi nanoindentation test.
Fig. 4 load-displacement curve of pet nanoindentation test.
FIG. 5. Compression modulus and hardness of different types of polymer sheets.
FIG. 6A schematic of the preparation of a through-hole SBS/Ag flake.
FIG. 7 is a schematic plan view of the through-hole film; (b) schematic cross-sectional structures of three thin film materials.
FIG. 8. (a) SEM image of the SBS film surface 20000X magnification; (b) SEM images of the SBS/Ag thin film surface 20000 x magnification; (c) an Ag element EDS diagram on the surface of the SBS/Ag film; (d 1, d 2) are SEM images of 200X and 20000X magnification of SBS/Ag film cross section, respectively; (e) Ag element EDS diagram of SBS/Ag film section.
(a, b, c) SEM images of the through hole SBS film surface at 50×, 500×, and 20000× magnification, respectively; (d, e) SEM images of through hole SBS/Ag film sections at 200X and 500X magnification, respectively; (f) Ag element EDS diagram of SBS/Ag film section through hole.
FIG. 10 SBS/Ag, SBS/Ag/pore array and SBS/pore array/Ag sheet longitudinal resistances.
FIG. 11 SBS/Ag, SBS/Ag/pore array and SBS/pore array/Ag sheet surface resistances.
FIG. 12.SBS/Ag, SBS/Ag/pore array and SBS/pore array/Ag flakes EMI SE.
Fig. 13.Sbs/pore array/Ag flakes shield performance variations in different variants.
FIG. 14 shows a schematic view of an application scenario of SBS/pore array/Ag flakes.
Detailed Description
The following detailed description of the present invention will be made in detail to make the above objects, features and advantages of the present invention more apparent, but should not be construed to limit the scope of the present invention.
Some specific embodiments of the preparation method of the electromagnetic shielding material for sealing of the present invention are:
1) Preparation of polymer films/sheets
Adding polymer base materials such as SBS, SIS, SEBS, SEPS and other granules into N, N-dimethylformamide, toluene, methylene dichloride, cyclohexane and other organic solvents, stirring and completely dissolving to form a solution with a certain mass ratio, then coating the solution on the surface of a bearing substrate (such as a release film) by adopting methods of spin coating, knife coating, casting and the like, and volatilizing the solvent completely in a hot blast environment at 60-150 ℃ for 0.5-5 h to prepare a polymer film or sheet with the thickness of 0.02-0.5 mm.
Or: adding SBS, SIS, SEBS, SEPS and other granules into a die with a specific size, and adopting a hot pressing method to prepare polymer films or sheets with different thicknesses, wherein the hot pressing temperature is as follows: 150-200 ℃ and hot pressing time: 5-30 min, hot pressing pressure: 2-50 MPa.
2) Preparation of through-hole structured polymer films/sheets
The polymer film/sheet is processed by adopting a mechanical drilling or laser drilling method to prepare a through hole structure, the aperture and the hole spacing (the distance between the centers of two adjacent holes) of the through hole structure can be regulated and controlled according to requirements, and certain processing limits exist under the constraint of the processing method. The technological parameters of the laser drilling method are as follows: picosecond laser, 70% of power, 2000kHz of frequency, 1200s of marking time and 11 times of vibrating mirror processing times, and the aperture is 0.02-1.0 mm and the hole spacing is 0.04-2.0 mm.
3) Preparation of metallized through-hole structured polymer films/sheets
Ultrasonically cleaning the polymer film/sheet with ethanol/water to remove surface and hole wall stains, then treating the polymer film/sheet with oxygen/argon plasma for 30min, soaking the polymer film/sheet in silver trifluoroacetate/ethanol solution (the concentration is 5 wt%) for 10s, repeatedly adsorbing for 5 times, taking out, putting the polymer film/sheet into hydrazine hydrate/ethanol solution (25 wt%) for reduction growth of a nano silver conductive layer, taking out, washing with ethanol and drying to obtain the polymer film/sheet with a metallized through hole structure, wherein the reduction temperature is room temperature and the time is 1-10 min.
Example 1
The experiment is the preparation of an experimental group, namely, a polymer film/sheet with a metallized through hole structure. The metallized through hole structured polymer sheet is denoted SBS/pore array/Ag.
Adding SBS granules into organic solvent such as toluene which can dissolve SBS, stirring to completely dissolve to form solution with a certain mass ratio, then adopting spin coating, blade coating and casting method to coat the solution on the surface of bearing substrate (such as release film), and volatilizing the solvent completely in hot blast environment at 60-150 ℃ for 0.5-5 h so as to obtain the polymer sheet with thickness of 0.07 mm. And processing the polymer sheet by adopting a laser drilling method to prepare the through hole structure. The laser drilling method comprises the following technological parameters: picosecond laser, 70% of power, 2000kHz of frequency, 1200s of marking time and 11 times of vibrating mirror processing times, and the aperture is 0.02-1.0 mm and the hole spacing is 0.04-2.0 mm. The pore diameter obtained was 0.1mm and the pore spacing was 0.3mm. Ultrasonically cleaning the polymer sheet with ethanol/water to remove surface and hole wall stains, then treating the polymer sheet with plasma for 30min, immersing the polymer sheet with plasma treatment gas of oxygen or argon in silver trifluoroacetate/ethanol solution (the concentration is 5 wt%) for 10s, repeatedly adsorbing for 5 times, taking out, putting the polymer sheet into hydrazine hydrate/ethanol solution (25 wt%) for reduction growth of a nano silver conductive layer, taking out, washing with ethanol and drying to obtain SBS/pore array/Ag, wherein the reduction temperature is room temperature and the time is 1-10 min.
Experimental example 2
The experiment was a control group 1, preparation of metallized polymeric flakes, the metallized flakes being indicated by SBS/Ag.
Adding SBS granules into toluene and other solvents, stirring to completely dissolve to form a solution with a certain mass ratio, then adopting methods of spin coating, knife coating, pouring and the like to coat the solution on the surface of a bearing substrate (such as a release film), and volatilizing the solvent completely in a hot blast environment at 60-150 ℃ for 0.5-5 h to prepare a polymer sheet with the thickness of 0.07 mm. Ultrasonically cleaning the upper polymer film/sheet with ethanol/water to remove surface stains, then treating the upper polymer film/sheet with plasma for 30min, immersing the upper polymer film/sheet in silver trifluoroacetate/ethanol solution (with the concentration of 5 wt%) for 10s after the plasma treatment, repeatedly adsorbing for 5 times, taking out, putting into hydrazine hydrate/ethanol solution (with the concentration of 25 wt%) for reduction growth of a nano silver conductive layer, taking out, washing with ethanol and drying to obtain SBS/Ag, wherein the reduction temperature is room temperature and the time is 1-10 min.
Experimental example 3
In the experiment, as a control group 2, the metallized film prepared in example 2 was further perforated, and the metallized polymer sheet SBS/Ag was processed by using the same technological parameters of the laser perforation method as in example 1 to prepare a via structure, so as to obtain a hole diameter of 0.1mm and a hole spacing of 0.3mm. The metallized polymer sheet via structure in this example is shown as SBS/Ag/pore array.
Effect evaluation of examples
Matrix material selection
The reason for choosing such thermoplastic elastomer bodies as SBS is that SBS has a low compression modulus and can be used as a seal, as shown in FIGS. 1-4, and the load displacement curves of different polymer matrixes are tested by nanoindentation and fit to the compression modulus and hardness of different polymers, as shown in FIG. 5, SBS has a low modulus and hardness (modulus < 0.5GPa and hardness < 50 MPa), and is more suitable for use as an electromagnetic seal elastomer matrix selection.
Processing sequence
And metallization is performed after micropore processing, so that the surface and the upper and lower omnibearing conduction are realized. As shown in fig. 9, microscopic morphology and EDS elements were observed using SEM, and it can be seen that silver was deposited on the inner walls of the micropores. As shown in FIG. 10, it can be seen that the longitudinal resistance of the sheet SBS/pore array/Ag of the metallized through-hole structure is in milliohm level, while the longitudinal resistances of the sheet SBS/Ag and the sheet SBS/Ag/pore array of the metallized through-hole structure are almost in an insulating state (longitudinal resistance value > 10) 6 European, beyond the range of the test equipment), indicating that the metallized through-hole structural wafer achieves excellent electrical conductivity of the upper and lower surfaces.
Sheet resistance
Further comparing the experimental group with the control group, as shown in fig. 11, the square resistances of the experimental group and the control group were tested using four probes, and it can be seen that the square resistance of the experimental group is about half that of the control group.
Shielding effectiveness
As shown in fig. 12, the shielding effectiveness of the experimental group and the control group was tested by using the vector network analyzer, and it can be seen that the shielding effectiveness of the experimental group is highest, which is significantly higher than that of the control group.
As shown in fig. 13, the test groups were tested for the change of shielding effectiveness at different frequencies under different deformation conditions, and it can be seen that the test materials were bent, twisted, folded, and stretched under the condition of 8.2-12.4GHz, and the shielding effectiveness was hardly changed. Meanwhile, the experimental materials can still keep the shielding effectiveness above 60dB under different changes. Wherein the change in stretching is maximum, stretching is 10%, and the shielding performance is reduced by only 0.14. The material disclosed by the invention can still keep good electromagnetic shielding performance under different deformation conditions, has excellent mechanical properties, and is suitable for a composite material for electromagnetic shielding between flexible or folding precise electronic devices.
Example 4
Metallized through-hole structured polymer films/sheets of different pore sizes and pore spacing were prepared using the method of example 1, and metallized through-hole free polymer films/sheets were prepared using the method of example 2 and tested for surface sheet resistance, thickness longitudinal resistance (Ω) and bulk shielding effectiveness (dB), with experimental results shown in table 1. Experimental results show that the aperture and the through hole spacing within the scope of the invention can achieve the effects of the invention.
TABLE 1 through-hole Structure parameters and conductive and electromagnetic shielding Properties of representative groups of samples
Claims (10)
1. A conductive electromagnetic shielding material for sealing, the conductive electromagnetic shielding material for sealing comprises a polymer substrate, and is characterized in that the polymer substrate is provided with a through hole, and the outer surface of the polymer substrate and the inner surface of the through hole are provided with metal layers;
the polymeric substrate has a thickness of 0.02mm to 1mm.
2. The electrically conductive electromagnetic shielding material for sealing as set forth in claim 1, wherein the polymer base material is selected from the group consisting of a polymer made of any one or more of the following, including styrenic block copolymers, polyurethane thermoplastic elastomer (TPU) polyamides, thermoplastic elastomers (TPAE), polyester-based thermoplastic elastomers (TPEE), polyamide-based thermoplastic elastomers (TPAE), and polyolefin-based thermoplastic elastomers (TPO, TPV);
preferably, the polymeric substrate material is selected from polymeric materials having a modulus of less than 0.5GPa and a hardness of less than 50 MPa;
preferably, the styrenic block copolymer is selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), hydrogenated styrene-ethylene-butadiene-styrene (SEBS), hydrogenated styrene-isoprene-styrene (SEPS).
3. The electroconductive electromagnetic shielding material for sealing according to claim 1, wherein the polymer substrate is obtained by dissolving a polymer substrate material in a solvent and coating as a film, and forming a film after volatilizing the solvent; or by hot-pressing the polymeric substrate material into a film.
4. The conductive electromagnetic shielding material for sealing as set forth in claim 1, wherein the aperture of the through hole is 0.02mm to 1.0mm.
5. The conductive electromagnetic shielding material for sealing as set forth in claim 1, wherein the pitch between the through holes is 0.04mm to 2.0mm; the hole distance between the through holes is the distance between the centers of the two nearest through holes.
6. The electrically conductive electromagnetic shielding material for sealing as set forth in claim 1, wherein the method of providing the through-holes in the polymer substrate is a mechanical drilling, a laser drilling method, a chemical etching method.
7. The conductive electromagnetic shielding material for sealing as set forth in claim 1, wherein the material of the metal layer is silver, gold, copper, nickel;
preferably, the method for arranging the metal layer on the outer surface of the polymer matrix and in the through hole is to grow a metal conductive layer on the outer surface of the polymer matrix and in the through hole by using a metal salt adsorption reduction method;
preferably, the method for disposing the metal layer on the outer surface of the polymer matrix and in the through hole further comprises the step of adding plasma treatment before the adsorption reduction of the metal salt;
preferably, the metal salt adsorption reduction method is that a polymer matrix is immersed in a metal salt solution for adsorption, and then a reducing agent is adopted for reduction, so that a metal conductive layer is formed on the surface of the polymer matrix and the surface of the through hole;
preferably, the metal salt is selected from silver salts, gold salts, copper salts, nickel salts;
preferably, the metal salt is selected from the group consisting of silver trifluoroacetate, silver nitrate, silver neodecanoate, silver acetate, silver oxalate, silver tartrate, silver citrate, copper acetate, copper formate, copper oleate, copper lactate.
8. A method for producing the conductive electromagnetic shielding material for sealing as claimed in any one of claims 1 to 7, comprising the steps of:
s1) preparing a polymer film or sheet;
s2) arranging through holes on the polymer film or sheet;
s3) carrying out surface metallization on the polymer film or sheet provided with the through holes;
preferably, the method for preparing the polymer film or sheet in step S1) is to dissolve the polymer base material in a solvent and apply the polymer base material as a film, and form the film after volatilizing the solvent; or by hot-pressing the polymer base material into a film;
preferably, the method for providing the through holes on the polymer substrate in the step S2) is mechanical drilling, laser drilling and chemical corrosion pore forming;
preferably, the surface metallization in step S3) is performed by growing a metal conductive layer on the outer surface of the polymer matrix and in the through holes by using a metal salt adsorption reduction method;
more preferably, the method of disposing a metal layer on the outer surface of the polymer matrix and in the through holes in step S3) further includes a step of adding a plasma treatment before adsorption reduction of the metal salt.
9. A conductive electromagnetic shield member for sealing, characterized in that the conductive electromagnetic shield member for sealing is made of the conductive electromagnetic shield material for sealing according to any one of claims 1 to 7;
preferably, the conductive electromagnetic shielding component can generate bending, twisting, folding and stretching deformation in the use process;
preferably, the sealing conductive electromagnetic shielding component is a sealing ring, a sealing gasket, a sealing sheet and a sealing strip.
10. Use of the electroconductive electromagnetic shielding material for sealing according to any one of claims 1 to 7 for producing an electroconductive electromagnetic shielding member for sealing;
preferably, the conductive electromagnetic shielding component can generate bending, twisting, folding and stretching deformation in the use process;
preferably, the sealing conductive electromagnetic shielding component is a sealing ring, a sealing gasket, a sealing sheet and a sealing strip.
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