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WO2018110941A1 - Matériau souple de blindage contre les ondes électromagnétiques, module de circuit de type à blindage contre les ondes électromagnétiques le comprenant et dispositif électronique équipé de ce dernier - Google Patents

Matériau souple de blindage contre les ondes électromagnétiques, module de circuit de type à blindage contre les ondes électromagnétiques le comprenant et dispositif électronique équipé de ce dernier Download PDF

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Publication number
WO2018110941A1
WO2018110941A1 PCT/KR2017/014552 KR2017014552W WO2018110941A1 WO 2018110941 A1 WO2018110941 A1 WO 2018110941A1 KR 2017014552 W KR2017014552 W KR 2017014552W WO 2018110941 A1 WO2018110941 A1 WO 2018110941A1
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WIPO (PCT)
Prior art keywords
conductive
fiber
fibrous web
electromagnetic shielding
shielding material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2017/014552
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English (en)
Korean (ko)
Inventor
서인용
정의영
이준우
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Amogreentech Co Ltd
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Amogreentech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Amogreentech Co Ltd filed Critical Amogreentech Co Ltd
Priority to CN201780076855.4A priority Critical patent/CN110073732B/zh
Priority to US16/468,801 priority patent/US10945358B2/en
Priority claimed from KR1020170170428A external-priority patent/KR101948537B1/ko
Publication of WO2018110941A1 publication Critical patent/WO2018110941A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • 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

Definitions

  • the present invention relates to an electromagnetic shielding material, and more particularly, to a flexible electromagnetic shielding material having excellent flexibility, elasticity, and wrinkle / restorability, an electromagnetic shielding circuit module including the same, and an electronic device having the same.
  • Electromagnetic waves are a phenomenon in which energy moves in a sinusoidal shape while an electric field and a magnetic field interoperate with each other, and are useful for electronic devices such as wireless communication and radar.
  • the electric field is generated by a voltage and easily shielded by a distance or an obstacle such as a tree, while the magnetic field is generated by a current and is inversely proportional to the distance but not easily shielded.
  • the electromagnetic shielding material is typically made of a conductive material, and the electromagnetic radiation emitted toward the electromagnetic shielding material is reflected back from the electromagnetic shielding material or flows to the ground to shield the electromagnetic wave.
  • an example of the electromagnetic shielding material may be a metal case or a metal plate, such an electromagnetic shielding material is difficult to express flexibility, elasticity, and once manufactured, it is not easy to deform / restore to a variety of shapes in various applications There is a problem that cannot be easily employed.
  • electric wave shielding materials such as metal plates or metal thin films are difficult to be closely adhered to the components that are the source of electromagnetic waves or parts that need protection from the sources, and cracks may occur due to bending at the stepped or uneven portions, resulting in electromagnetic shielding performance. It may be difficult to express fully.
  • an electromagnetic shielding material in which a conductive coating layer is formed on a lightweight support member such as a polymer film has been recently introduced, but the electromagnetic shielding performance is limited according to the limitation of the area that can be coated on the support member.
  • Films with a certain thickness or more have a lack of flexibility and are difficult to be completely adhered to a stepped or uneven part, and after being manufactured in a specific shape, it may be difficult to freely deform the shape.
  • cracks, peeling, etc. occur frequently in the conductive coating layer coated during the shape deformation.
  • the present invention has been made to solve the above-described problems, and excellent flexibility, elasticity and crease / restoring, so that the shape can be freely transformed as desired, various shapes such as irregularities and steps of the application mounting surface where the electromagnetic shielding material is employed It is an object of the present invention to provide a flexible electromagnetic shielding material that can be provided to be completely in close contact with the structure.
  • another object of the present invention is to provide a flexible electromagnetic shielding material in which the deterioration of the electromagnetic shielding performance is prevented even in various shape changes.
  • the present invention provides an electromagnetic shielding circuit module and an electronic device having the same, which can be easily employed in a light and small and small sized electronic device or a flexible electronic device provided with components with a high density in a small area. There is this.
  • a first embodiment of the present invention is a flexible including a conductive fiber web formed of a fiber portion including a conductive filler and a conductive composite fiber including a metal shell portion coated on the outside of the fiber portion.
  • a conductive fiber web formed of a fiber portion including a conductive filler and a conductive composite fiber including a metal shell portion coated on the outside of the fiber portion.
  • the conductive composite fiber may have a diameter of 0.2 ⁇ 10 ⁇ m.
  • the conductive fiber web may have a thickness of 5 to 200 ⁇ m, and a basis weight of 5 to 100 g / m 2.
  • the conductive fibrous web may have a porosity of 30 to 80%.
  • the conductive filler may include any one or more of one or more metals and conductive polymer compounds selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys and stainless steel.
  • the conductive polymer compound is polythiophene, poly (3,4-ethylenedioxythiophene), polyaniline, polyacetylene, polyacetylene, polydiacetylene (polydiacetylene), poly (thiophenevinylene), polyfluorene (polyfluorene) and poly (3,4-ethylenedioxythiophene) (PEDOT): one selected from the group consisting of polystyrenesulfonate (PSS) It may contain the above.
  • PSS polystyrenesulfonate
  • the conductive filler is a metal, it may be provided to occupy 10 to 50% of the total volume of the fiber portion.
  • the fiber portion includes a first portion with a conductive filler that is a metal and a second portion without a conductive filler, the diameter of the second portion and the diameter of the conductive filler 1: 1 to 5 times.
  • the conductive filler may be a rod type having a predetermined aspect ratio, and preferably, the aspect ratio may be 1.1 to 20.
  • the rod-shaped conductive filler may have a hollow continuous in the longitudinal direction.
  • the fiber part may include 25 to 400 parts by weight of the conductive filler based on 100 parts by weight of the fiber forming component.
  • the fiber portion as a fiber forming component polyurethane (polyurethane), polystyrene (polystylene), polyvinyl alcohol (polyvinylalchol), polymethyl methacrylate (polymethyl methacrylate), polylactic acid (polylactic acid), polyethylene oxide (polyethyleneoxide), Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, PC (polycarbonate), polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate, and fluorine-based compounds have.
  • polyurethane polyurethane
  • polystyrene polystylene
  • polyvinyl alcohol polyvinylalchol
  • polymethyl methacrylate polymethyl methacrylate
  • polylactic acid polylactic acid
  • polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF polyurethane
  • PVDF polyvinylidene fluoride
  • Purethane polyurethane
  • the metal shell may be at least one material selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys and stainless steel.
  • the metal shell portion may have a thickness of 0.1 ⁇ 2 ⁇ m.
  • At least a portion of the conductive filler may be exposed to the outer surface of the fiber portion to be in electrical communication with the metal shell portion.
  • a conductive adhesive may be provided on at least one surface of the conductive fibrous web.
  • a second embodiment of the present invention (1) forming a first conductive portion on the outer surface of the fiber portion; (2) extending the fiber portion formed on the outer surface of the first conductive portion in the longitudinal direction to generate a crack in the first conductive portion; And (3) forming a second conductive portion on an outer surface of the first conductive portion.
  • the step (2) may stretch the fiber portion 1.1 to 20 times the length of the fiber portion before stretching.
  • step (3) is 3-1) to maintain the fiber portion in an extended state to secure a space between the cracks generated in the first conductive portion; And 3-2) forming a second conductive portion on an outer surface of the first conductive portion, including the separation space.
  • a second embodiment of the present invention includes a fiber portion, a first conductive portion coated on the outer surface of the fiber portion, including a crack, and a second conductive portion covering the outer surface of the first conductive portion;
  • a conductive composite fiber for electromagnetic shielding material is provided.
  • the fiber portion may include polyvinylidene fluoride (PVDF) as a fiber forming component with polyurethane and a fluorine-based compound.
  • PVDF polyvinylidene fluoride
  • the polyvinylidene fluoride (PVDF) and polyurethane (polyurethane) may be included in a weight ratio of 1: 0.2 to 2, more preferably 1: 0.4 to 1.5 by weight.
  • first conductive portion may be made of a metal
  • second conductive portion may include a conductive polymer compound
  • first conductive portion may include at least one material selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloy, and stainless steel.
  • the second conductive portion polythiophene polythiophene
  • poly (3,4-ethylenedioxythiophene) poly (3,4-ethylenedioxythiophene)
  • polyaniline polyaniline
  • polyacetylene polyacetylene
  • polydiacetylene polydiacetylene
  • polyfluorene polyfluorene
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • the conductive composite fiber may have a diameter of 0.2 ⁇ 10 ⁇ m.
  • the first conductive portion may have a thickness of 0.1 to 2 ⁇ m, and the second conductive portion may have a thickness of 0.05 to 1 ⁇ m.
  • a second conductive portion may be filled in the space between the cracks of the first conductive portion.
  • the present invention also provides a conductive fibrous web including a fibrous web formed of a fibrous portion, a first conductive portion coated on an outer surface of the fibrous portion and including a crack, and a second conductive portion covering an outer surface of the first conductive portion.
  • a flexible electromagnetic shielding material provided.
  • the thickness of the conductive fiber web is 5 ⁇ 200 ⁇ m
  • the basis weight may be 5 ⁇ 100g / m2.
  • the conductive fibrous web may have a porosity of 30 to 80%.
  • a second conductive portion may be filled in the space between the cracks of the first conductive portion.
  • a conductive adhesive may be provided on at least one surface of the conductive fibrous web.
  • a third embodiment of the present invention is a conductive fibrous web including a conductive composite fiber including a metal shell portion coated on the outside of the fiber portion to form a plurality of pores, and at least a portion of the first conductivity provided in the pores.
  • a flexible electromagnetic shielding material comprising a component.
  • the first conductive component in order to prevent an increase in resistance due to cracks occurring in the metal shell portion, may be electrically disposed in the pores so as to contact at least a portion of the conductive composite fiber. Can be connected.
  • the conductive composite fiber may have a diameter of 0.2 ⁇ 10 ⁇ m.
  • the conductive fiber web may have a thickness of 5 to 200 ⁇ m, and a basis weight of 5 to 100 g / m 2.
  • the conductive fibrous web may have a porosity of 30 to 80%.
  • the first conductive component is a metal particle
  • the metal particles may be a particle having a particle size of 0.80 ⁇ 0.95 times the average pore size of the pores may be 90% or more of the total metal particles.
  • the first conductive component may include any one or more of one or more metals and conductive polymer compounds selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys, and stainless steel.
  • the conductive polymer compound is polythiophene, poly (3,4-ethylenedioxythiophene), polyaniline, polyacetylene, polyacetylene, polydiacetylene (polydiacetylene), poly (thiophenevinylene), polyfluorene (polyfluorene) and poly (3,4-ethylenedioxythiophene) (PEDOT): one selected from the group consisting of polystyrenesulfonate (PSS) It may contain the above.
  • PSS polystyrenesulfonate
  • the metal shell part may include a crack formed at least in part
  • the flexible electromagnetic shielding material may further include a second conductive component interposed in the spaced gap between the cracks to electrically connect the spaced gap.
  • the metal shell may be at least one metal selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys and stainless steel.
  • the metal shell portion may have a thickness of 0.1 ⁇ 2 ⁇ m.
  • the fiber portion may include polyvinylidene fluoride (PVDF) and polyurethane (polyurethane) in a weight ratio of 1: 0.2 to 2 as a fiber forming component.
  • PVDF polyvinylidene fluoride
  • polyurethane polyurethane
  • a conductive adhesive layer may be provided on at least one surface of the conductive fibrous web.
  • a fourth embodiment of the present invention provides a flexible electromagnetic shielding material including a conductive fibrous web formed with a conductive composite fiber including a crimped fiber portion and a conductive portion covering the outside of the fiber portion.
  • the diameter of the conductive composite fiber may be 0.2 ⁇ 10 ⁇ m.
  • the conductive fiber web may have a thickness of 5 to 200 ⁇ m, and a basis weight of 5 to 100 g / m 2.
  • the conductive fibrous web may have a porosity of 30 to 80%.
  • the fiber portion may include polyvinylidene fluoride (PVDF) and polyurethane (polyurethane) in a weight ratio of 1: 0.2 to 2.0 as a fiber forming component.
  • PVDF polyvinylidene fluoride
  • polyurethane polyurethane
  • the conductive portion may include any one or more of one or more metals and conductive polymer compounds selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys and stainless steel.
  • the conductive polymer compound is polythiophene, poly (3,4-ethylenedioxythiophene), polyaniline, polyacetylene, polyacetylene, polydiacetylene (polydiacetylene), poly (thiophenevinylene), polyfluorene (polyfluorene) and poly (3,4-ethylenedioxythiophene) (PEDOT): one selected from the group consisting of polystyrenesulfonate (PSS) It may contain the above.
  • the conductive portion thickness may be 0.1 ⁇ 2 ⁇ m.
  • the surface resistance value measured in the state where the stretching force is removed may vary by 10% or less based on the surface resistance value before stretching.
  • a conductive adhesive layer may be provided on at least one surface of the conductive fibrous web.
  • the present invention also provides an electromagnetic shielding circuit module including a circuit board on which the device is mounted, and an electromagnetic shielding material according to the present invention provided on the circuit board so as to cover at least the upper and side portions of the device.
  • the present invention provides an electronic device including the electromagnetic shielding circuit module according to the present invention.
  • the electromagnetic shielding material according to various embodiments of the present invention is excellent in flexibility, elasticity and wrinkle / recoverability, and can be freely deformed as desired, and also completely in curved shapes such as unevenness or step of the application mounting surface where the electromagnetic shielding material is disposed. It can be attached to make close contact. In addition, deterioration or fluctuation of the electromagnetic shielding performance can be prevented even with various shape changes. Furthermore, even when parts are provided with a high density in a small area, they can be provided in close contact with the mounted parts by overcoming the dense spacing and step between parts, thereby providing excellent electromagnetic shielding performance, thereby minimizing light and small size. Or can be easily employed in flexible electronics.
  • FIG. 1 is a cross-sectional view of a flexible electromagnetic shielding material according to an embodiment of the first embodiment of the present invention
  • FIGS. 2 and 3 are cross-sectional views for explaining the structure and operation of the conductive composite fiber included in one embodiment of the first embodiment of the present invention
  • FIGS. 4A to 4C are perspective views illustrating various examples of the conductive filler included in the first embodiment of the present invention.
  • Figure 5a is a partial cross-sectional view of a conductive composite fiber included in one embodiment of the first embodiment of the present invention
  • Figure 5b is a SEM picture of the conductive fiber web according to an embodiment of the first embodiment of the present invention.
  • FIG. 6a and 6b are views of the conductive composite fiber included in one embodiment of the first embodiment of the present invention
  • Figure 6a is a perspective view and a cross-sectional view of the conductive composite fiber according to an embodiment of the first embodiment
  • Figure 6b is another embodiment Perspective view
  • FIG. 7 is a cross-sectional view of a flexible electromagnetic shielding material according to an embodiment of the second embodiment of the present invention.
  • FIG. 8 is a cross-sectional view of a conductive composite fiber included in one embodiment of the second embodiment of the present invention.
  • Figure 9 is a schematic diagram of the (2) step of the manufacturing method of the conductive composite fiber included in an embodiment of the second embodiment of the present invention.
  • FIG. 10 is a cross-sectional view of a flexible electromagnetic shielding material according to an embodiment of the third embodiment of the present invention.
  • FIG. 11 is a cross-sectional view of the conductive composite fiber included in one embodiment of the third embodiment of the present invention.
  • 12A and 12B are cross-sectional views of a flexible electromagnetic shielding material and a cross-sectional view along X-X ′ boundary line according to another embodiment of the third embodiment of the present invention
  • FIG. 13 is a sectional view of a flexible electromagnetic shielding material and a partially enlarged cross-sectional view of a conductive fiber web according to an embodiment of the fourth embodiment of the present invention
  • FIG. 14 is a cross-sectional view of a conductive composite fiber included in an embodiment of the fourth embodiment of the present invention.
  • 15 is a cross-sectional view of an electromagnetic shielding circuit module according to an embodiment of the present invention.
  • the flexible electromagnetic shielding material 1000 includes a conductive fibrous web 100 including a conductive composite fiber 10, and the conductive fibrous web 100 It may be further provided with a conductive adhesive layer 200 provided on one side or both sides of the).
  • the conductive fibrous web 100 is a three-dimensional network structure including a conductive composite fiber 10, through which the conductive fibrous web 100 may have a plurality of pores, the porosity is 30 to 80% It may be easy to be implemented as a flexible and flexible electromagnetic shielding material through this.
  • the conductive fibrous web 100 may have an air permeability of 0.01 ⁇ 2cfm, if the air permeability is less than 0.01cfm when forming a conductive adhesive layer on any one surface of the conductive fibrous web, the conductive adhesive layer as pores of the fibrous web Impregnation of the formation composition may be difficult, and if it exceeds 2cfm, mechanical properties and electromagnetic shielding performance of the conductive fibrous web may be degraded.
  • the conductive fiber web 100 has a thickness of 5 ⁇ 200 ⁇ m, the basis weight may be 5 ⁇ 100g / m2. If the thickness of the conductive fibrous web exceeds 200 ⁇ m, the metal shell may not be easily formed on the nanofibers included in the entire outer and inner regions of the fibrous web, and there is a concern that the stretch property may be deteriorated. In addition, when the thickness is less than 5 ⁇ m the mechanical strength of the conductive fibrous web is lowered, the handling becomes difficult, it may not be easy to manufacture.
  • the conductive fibrous web may be formed by stacking a single conductive fibrous web or a single conductive fibrous web.
  • a conductive adhesive for bonding each conductive fibrous web may be further interposed therebetween.
  • the conductive adhesive is replaced with the description of the conductive adhesive layer 200 to be described later.
  • the basis weight of the conductive fibrous web 100 is less than 5g / m2 the mechanical strength of the conductive fibrous web is reduced, the handling becomes difficult, may not be easy to manufacture, if the metal shell exceeds 100g / m2 The portion may not be easily formed in the nanofibers included in the entire outer and inner regions of the fibrous web, and there is a fear that the elastic properties are degraded.
  • the conductive composite fiber 10 forming the conductive fiber web 100 includes a fiber part 1 having a conductive filler 1b dispersed in the fiber forming component 1b, and the And a metal shell portion 2 coated on the outside of the fiber portion 1.
  • the conductive composite fiber 10 may have a diameter of 0.2 to 10 ⁇ m, and when the diameter is less than 0.2 ⁇ m, handleability may be degraded, and manufacturing may not be easy, and when the diameter exceeds 10 ⁇ m, elasticity / flexibility may occur. There is a fear of deterioration of electromagnetic wave shielding performance when deterioration, adherence to a stepped or uneven surface, and / or shape deformation during use occurs.
  • the fiber portion 1 includes a fiber forming component 1a and a conductive filler 1b dispersed in the fiber forming component 1a.
  • the fiber part 1 may have a diameter of 0.15 to 5 ⁇ m, but is not limited thereto.
  • the mechanical strength of the conductive composite fiber 10, the thickness of the metal shell part 2, and the inside of the conductive filler 1b may be provided. It may be appropriately changed in consideration of the content.
  • the fiber forming component (1a) is a subject of forming a fiber or a fibrous web in a conductive composite fiber or a conductive fibrous web, expresses the elasticity, compressibility, flexibility and wrinkle / resilience of the fibrous web, and can be generally formed into a fibrous shape
  • Known high molecular compounds can be used without limitation.
  • the fiber forming component (1a) polyurethane (polyurethane), polystyrene (polystylene), polyvinyl alcohol (polyvinylalchol), polymethyl methacrylate (polymethyl methacrylate), polylactic acid (polylactic acid), polyethylene oxide (polyethyleneoxide) , Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, It may include at least one selected from the group consisting of PC (polycarbonate), polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate and fluorine-based compound Can be.
  • PC polycarbonate
  • polyetherimide polyesthersulphone
  • polybenzimidazol polyethylene terephthalate
  • polybutylene terephthalate polyfluorine-
  • the fluorine-based compound is polytetrafluoroethylene (PTFE) -based, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) -based, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) -based, Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE) system, tetrafluoroethylene-ethylene copolymer (ETFE) system, polychlorotrifluoroethylene (PCTFE) system, chlorotrifluoro It may include any one or more compounds selected from the group consisting of a low ethylene-ethylene copolymer (ECTFE) system and a polyvinylidene fluoride (PVDF) system.
  • ECTFE low ethylene-ethylene copolymer
  • PVDF polyvinylidene fluoride
  • the fiber portion 1 and the conductive fibrous web 100 embodied therein are blended with PVDF, which is a fluorine-based compound, and polyurethane on the spinning solution for the expression of improved elasticity, flexibility, heat resistance, chemical resistance and mechanical strength. It may be radiated.
  • PVDF and polyurethane may be included in a weight ratio of 1: 0.2 to 2, and more preferably 1: 0.4 to 1.5 weight ratio. If the polyurethane weight is less than 0.2 times based on the weight of PVDF, flexibility, elasticity, etc. may be lowered, which may cause tearing when the substrate is provided on the substrate having deformation or step difference in use.
  • the damage of the conductive fibrous web may be greater than the initial designed electromagnetic shielding performance.
  • the polyurethane weight is more than 2 times based on the weight of PVDF, the restoring force due to expansion and contraction is lowered, which may cause permanent deformation of the shape due to failure to restore to the state before stretching. Failure to reduce the spacing between cracks can cause degradation of electromagnetic shielding performance.
  • the chemical resistance is significantly lowered, and the fiber portion may be damaged during the formation of the metal shell. Accordingly, the mechanical properties such as the fiber part is cut off or the fiber web is torn due to the shape deformation of the conductive fiber web may be stretched or wrinkled. Can be degraded.
  • the conductive filler 1b is expressed together with the metal shell portion 2 which describes the electromagnetic shielding performance of the conductive fiber web, and at the same time, the conductive fiber may be cracked in the metal shell portion 2, which may occur when the conductive fiber web is stretched, compressed and wrinkled. It is possible to prevent the increase in resistance of the web to express the electromagnetic shielding performance to the desired level.
  • the conductive composite fiber 20 may generate cracks C in the metal shell part 22 due to shape deformation such as stretching and wrinkles. In this case, the resistance of the metal shell part 22 is greatly increased. There is a risk of increase.
  • the conductive filler 21b provided in the fiber portion 21 may be in contact with each other to reduce the longitudinal resistance and the vertical resistance of the conductive composite fiber 20. In addition, at the same time, the conductive filler 21b may further prevent an increase in the resistance of the conductive fibrous web 20 and maintain the electromagnetic shielding performance as it contacts the metal shell portion 22 in which the crack C is generated. .
  • the conductive fillers 1b and 21b may be used without limitation in the case of known materials having electrical conductivity.
  • the conductive fillers 1b and 21b may be made of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys, and stainless steel. It may be a material of any one or more of one or more metals and conductive polymer compounds selected from the group.
  • the conductive filler (1b, 21b) when the conductive filler (1b, 21b) is a metal may be provided to occupy 10 to 50% of the total volume of the fiber portion. If less than 10% of the total volume of the fiber portion, it may be difficult to prevent the resistance decrease due to the connection between the conductive fillers or increased resistance of the cracked metal shell portion. In addition, if more than 50% of the total volume of the fiber portion If the fiber portion is increased in the number of trimming during spinning, there is a fear that the mechanical strength is significantly reduced even when implemented as a fiber web.
  • the conductive fillers 1b and 21b are not limited in shape, and may be employed without limitation in the case of the shape of a known conductive filler such as a spherical shape having a curved surface, a needle shape, or an amorphous shape. However, it may be a rod type having a predetermined aspect ratio in order to prevent an increase in resistance due to cracks in the metal shells 2 and 22 that may occur due to the shape deformation of the conductive fibrous web.
  • the aspect ratio may be 1.1 to 20, and if the aspect ratio is less than 1.1, it may be difficult to directly contact the metal shell portion in which the mutual contact and cracks between the conductive fillers occur, and in order to induce direct contact, the content of the filler in the fiber portion may be increased. In this case, there is a concern that the mechanical strength of the conductive composite fiber may be significantly reduced.
  • the aspect ratio exceeds 20, when the composite fiber is bent, the conductive filler penetrates the fiber part and damages the metal shell part, which may result in a decrease in electromagnetic shielding performance.
  • the rod-shaped conductive filler may have a diameter of 0.8 ⁇ m to 1.1 ⁇ m and a length of 1 ⁇ m to 5 ⁇ m.
  • the conductive fillers 1b and 21b are metal, as shown in FIGS. 4A and 4B in the cross-sectional shape, the conductive fillers 1b and 1b 'have a curved shape such as a circle or an ellipse in the outer circumference of the cross-section. It may be a regular shape, including polygons such as squares, pentagons, or may be atypical.
  • the conductive filler 1b ′′ may have an aspect ratio, and may have a hollow shape that is continuous in the longitudinal direction while the outer periphery of the cross section perpendicular to the longitudinal direction is in a regular shape or atypical shape.
  • the conductive filler (1b ") having a hollow has the advantage to express the lightweight, more excellent stretch characteristics of the conductive fiber web.
  • the conductive filler is densely arranged inside the fiber portion and is not provided to expose the outer surface it may be difficult to prevent the increase in resistance due to cracks in the metal shell.
  • the conductive filler is preferably disposed toward the outer surface of the fiber as much as possible, it is not easy to adjust the position of the conductive filler when spinning the spinning solution containing the conductive filler. Accordingly, according to an embodiment of the present invention, the diameter of the conductive filler may be larger than that of the fiber that is radiated so that the conductive filler may be located on the outer surface of the fiber portion.
  • the fiber part 31 is provided with a conductive filler 31b in the longitudinal direction of the conductive composite fiber 30. And a second portion (A) having no portion (B) and no conductive filler (31b), wherein the diameter (h) of the second portion (A) and the diameter of the conductive filler (31b) are 1: 1 to 1.
  • the possibility of the conductive filler 31b being exposed to the outer surface of the fiber portion 31 is increased, thereby increasing the possibility of contact with the metal shell portion 32.
  • the diameter of the conductive filler is less than one times the diameter of the second portion, the possibility of the conductive filler being exposed to the outside of the fiber portion decreases, and thus an increase in resistance due to cracks occurring in the metal shell portion may not be minimized.
  • the diameter of the conductive filler is included more than five times the diameter of the second portion, there is a fear of trimming during spinning, lowering the mechanical strength of the implemented composite fiber or fibrous web, conductive when the shape of the conductive fiber web is deformed The shape deformation width according to the contact between the pillars can be reduced.
  • the diameter of the conductive filler 31b if the conductive filler has a shape having an aspect ratio, the diameter of the conductive filler 31b compared with the second portion A may be a length of a short axis. In addition, in the case of an irregular shape, it may be the inscribed circle diameter of the cross section.
  • the conductive filler may have a diameter of 1 ⁇ 5 ⁇ m, through which the possibility of being exposed to the outside of the fiber portion has an advantage of preventing the reduction of the electromagnetic shielding efficiency. If the diameter is less than 1 ⁇ m may not minimize the reduction of electromagnetic shielding efficiency, if the diameter exceeds 5 ⁇ m may cause the fiber part to be cut during spinning, there may be a decrease in the mechanical strength of the fiber web.
  • the conductive filler included in the fiber portion may be conductive polymer compounds 41b and 41b ', as shown in FIGS. 6A and 6B, and the conductive polymer compound 41b surrounds the fiber forming component 41a. It may be provided in the fiber portion 41 (see Fig. 6a), or irregularly mixed with the conductive polymer compound (41b ') and the fiber forming component (41a') may be provided in the fiber portion 41 '( 6b). In this case, the conductive polymer compounds 41b and 41b 'are exposed to the outer surface of the fiber portion 41 as shown in FIG. 6A, or at least a portion of the conductive polymer compounds 41b and 41b' is exposed to the outer surface of the fiber portion 41 'as shown in FIG.
  • the spaced gap between the cracks of the metal shell part 42 is a fiber part ( 41,41 ') As it can be electrically connected through the conductive polymer compound (41b, 41b') exposed to the outer surface it is possible to further prevent the degradation of the electromagnetic shielding performance.
  • the conductive polymer compounds 41b and 41b ' may be used without limitation in the case of a known polymer compound having electrical conductivity, and as an example thereof, a polymer resin including an electron withdrawing group may be used.
  • the electron withdrawing group is also referred to as an electron attracting group, and means an atomic group that attracts electrons from surrounding atomic groups by resonance or triggering effects.
  • the electron withdrawing group is an oxadiazole group, an azole group, a benzothiadiazole group, a cyano group, a quinoline group, a bornyl group, a silol group, a perfluorine group, a halogen group, a nitro group, a carbonyl group, a carboxyl group, a nitrile group, a halogenated alkyl group, an amino group And sulfonyl groups.
  • the conductive polymer compound may include polythiophene, poly (3,4-ethylenedioxythiophene), polyaniline, and polyacetylene.
  • polyacetylene, polydiacetylene, poly (thiophenevinylene), polyfluorene and poly (3,4-ethylenedioxythiophene) PEDOT: polystyrenesulfonate (PSS) It may include one or more selected from the group consisting of.
  • the conductive filler (41b, 41b ') is a conductive polymer compound
  • the conductive filler (41b, 41b') is 25 to 400 parts by weight, more preferably 90 to 400 with respect to 100 parts by weight of the fiber forming component of the fiber portion It may be provided in parts by weight. If the conductive filler is provided in less than 25 parts by weight of the fiber-forming component, it may be difficult to express a desired level of electromagnetic shielding performance or it may be difficult to electrically connect all of the cracked parts when a crack occurs in the metal shell part. It can be difficult to maintain performance. In addition, if the conductive filler is provided in excess of 400 parts by weight, the mechanical strength of the composite fiber is lowered, there is a fear that the spinning properties during the manufacture of the fiber portion may be significantly reduced.
  • the metal shell portions 2, 22, 32, and 42 covering the outside of the fiber portion together with the above-described conductive fillers 1b, 1b ', 1b ", 21b, 31b, 41b, and 41b' provide resistance to the conductive fiber web.
  • the metal shell parts 2, 22, 32, and 42 may be used without limitation in the case of a conventional electrically conductive metal material, for example, the metal shell parts may include aluminum, nickel, copper, It may be one or more materials selected from the group consisting of silver, gold, chromium, platinum, titanium alloys, and stainless steel, and, for example, the metal shell may be formed of three layers of nickel, copper, and nickel.
  • the copper layer may exhibit excellent electromagnetic shielding performance as the conductive fibrous web may have a low electrical resistance, and minimize cracking of the metal shell part even when the conductive fibrous web is wrinkled or stretched. Can improve the characteristics
  • the nickel layer formed on the copper layer can prevent a decrease in electromagnetic wave shielding performance by preventing oxidation of the copper layer.
  • the metal shell portion may have a thickness of 0.1 to 2.0 ⁇ m, and if the thickness of the metal shell portion exceeds 2 ⁇ m, the shape of the conductive composite fibers 10, 20, 30, 40, and 40 ′ may change. When it is less than 0.1 ⁇ m, it may be difficult to express the electromagnetic shielding performance at a desired level, and the peeling of the metal shell may be caused by elongation due to external force during use, resulting in resistance despite the presence of the conductive filler. Can increase.
  • the conductive fiber web 100 may be manufactured through the manufacturing method described below, but is not limited thereto.
  • the conductive fibrous web 100 may be made of a fibrous web having a three-dimensional network structure through the manufactured conductive composite fibers 10, 20, 30, 40, and 40 '. Or (1) spinning a spinning solution comprising a conductive filler and a fiber forming component to produce a fibrous web formed of a fiber portion in which the conductive filler is dispersed, and (2) forming a metal shell to cover the outside of the fiber portion to form a conductive fiber. It can be produced through the step of manufacturing a web.
  • the conductive composite fiber is a metal paste capable of spinning a spinning solution containing a conductive filler and a fiber forming component through the inner nozzle of the double spinning nozzle and forming a metal shell through the outer nozzle. After extruding, the metal paste may be fired.
  • the conductive composite fiber may be prepared by forming a metal shell on the outer surface of the fiber prepared through the spinning solution containing the conductive filler and the fiber forming component.
  • the spinning solution may further include a solvent appropriately selected according to the spinning method, the type of the fiber-forming component provided, or the like, or may be a molten solution in which the fiber-forming component is melted.
  • the method of spinning the spinning solution may be appropriately selected in consideration of the diameter of the desired conductive composite fiber and the type of the fiber forming component.
  • the spinning solution may be electrospinning or a method in which the spinning solution is extruded through the spinneret using pressure. have.
  • dry spinning or wet spinning can be appropriately selected in consideration of the type of the fiber forming component, the type of the solvent provided in the spinning solution, and the present invention is not particularly limited thereto.
  • the method of forming the metal shell on the outer surface of the manufactured fiber may be performed by a known metal coating method or plating method.
  • the fiber may be subjected to drying and / or sintering after immersing the fiber in a metal paste.
  • the plating may be performed through electroless plating using a known plating method.
  • the conductive composite fiber produced may be a method of manufacturing a known fibrous web, for example, a dry nonwoven fabric such as a chemical bonding nonwoven fabric, a thermal bonding nonwoven fabric, an airlay nonwoven fabric, a wet nonwoven fabric, a spanless nonwoven fabric, a needle punching nonwoven fabric, or a meltblown fabric. Can be made into a conductive fibrous web.
  • a dry nonwoven fabric such as a chemical bonding nonwoven fabric, a thermal bonding nonwoven fabric, an airlay nonwoven fabric, a wet nonwoven fabric, a spanless nonwoven fabric, a needle punching nonwoven fabric, or a meltblown fabric.
  • the conductive fibrous web is another manufacturing method, comprising the steps of: (1) spinning a spinning solution containing a conductive filler and a fiber forming component to produce a fibrous web formed of a fiber portion in which the conductive filler is dispersed; It can be prepared including the step of forming a conductive fiber web by forming a metal shell portion to cover.
  • Step (1) may be performed by manufacturing the fibrous web in a state in which the metal shell is not formed after preparing the fiber having the conductive filler in the above-described method.
  • the fibrous web may be implemented in a manner of undergoing a calendering process for the fibrous mat collected and accumulated in the collector by spinning the conductive filler and the fiber forming component.
  • the fibrous web prepared in step (1) is a step (2), in which a metal shell portion is formed to cover the fibrous portion of the fibrous web.
  • Step (2) may employ a known method for coating the metal shell portion, for example, may be a metal shell portion deposition, plating, coating method through a conductive paste, and the like.
  • the metal shell portion may be deposited only on the outside of the fiber portion positioned on the surface portion of the fiber web, and the metal shell portion may be difficult to be provided in the fiber portion located in the center portion of the fiber web, and thus, electromagnetic waves may be at a desired level. It may be difficult to develop masking effects.
  • the surface portion of the fibrous web on which the metal shell is deposited may decrease the elastic properties of the fibrous web as the pores may be closed, and there is a concern that the deposited portion may be easily crushed or peeled off during the stretching.
  • the fibrous portion in the case of coating the fibrous web with a conductive paste, the fibrous portion may be evenly coated on the surface / center portion of the fibrous web, but the elastic properties may be remarkably reduced due to the pore closure, thereby causing the metal shell to break during stretching. Peeling can be serious.
  • the metal shell may be formed through plating on the fibrous web, and more preferably, the plating may be electroless plating.
  • a conductive adhesive layer 200 may be further provided on at least one surface of the conductive fibrous web 100 including the conductive composite fibers 10, 20, 30, 40, and 40 ′ as shown in FIG. 1. .
  • the conductive adhesive layer 200 may be a known conductive adhesive layer.
  • the conductive filler 220 may be dispersed in the adhesive matrix 210.
  • the adhesive matrix may be formed of at least one resin selected from acrylic resin and urethane resin, and the conductive filler may be selected from the group consisting of nickel, nickel-graphite, carbon black, graphite, alumina, copper, and silver. It may be more than one species.
  • the conductive adhesive layer 200 may be provided with the conductive filler 220 at 5 to 95% by weight based on the total weight of the conductive adhesive layer 200.
  • the conductive adhesive layer 200 may have a thickness of 10 to 30 ⁇ m. When the thickness of the conductive adhesive layer 200 is excessive, as the vertical resistance of the electromagnetic shielding material 1000 is increased, the electromagnetic shielding performance may not be expressed at a desired level.
  • the conductive adhesive layer 200 may be formed by treating and impregnating a conductive adhesive layer forming composition on one surface of the conductive fiber web 100 to be formed, and thus, a portion of the conductive adhesive layer 200 is conductive. It is formed on the fibrous web 100, the remaining portion may be provided to be filled in the pores of the conductive fibrous web 100 to be located inside the conductive fibrous web (100). Alternatively, unlike FIG. 1, all parts may be disposed in the conductive fibrous web 100.
  • the flexible electromagnetic shielding material 1100 includes a conductive fiber web 110 including a conductive composite fiber 50, and the conductive fiber web 110. It may be further provided with a conductive adhesive layer 200 provided on one side or both sides of the).
  • the conductive composite fiber 50 is coated on the fiber portion 51, the outer surface of the fiber portion 51, as shown in Figure 8, the first conductive portion 52 containing a crack and the first conductive And a second conductive portion 53 covering the outer surface of the portion 52.
  • the crack formed on the first conductive portion 52 complements the elasticity and flexibility of the fiber portion 51 which can be reduced by the coating of the first conductive portion 52, and the crack has the first conductive portion 52 formed thereon.
  • the second conductive portion 53 formed on the top serves to compensate for the decrease in the electrical conductivity due to the increase in resistance caused by the occurrence of cracks.
  • the second conductive portion 53 may penetrate and fill the spaces of the first conductive portions 52a and 52b in which the cracks occur, thereby increasing resistance due to the crack of the first conductive portion 52. To maintain the desired level of conductivity.
  • first conductive portion on the outer surface of the fiber portion to produce a conductive composite fiber 50 having such a structure; (2) extending the fiber portion formed on the outer surface of the first conductive portion in the longitudinal direction to generate a crack in the first conductive portion; And (3) forming a second conductive portion on an outer surface of the first conductive portion in a state where the fiber portion is extended.
  • the step of forming the first conductive portion on the outer surface of the fiber portion is performed.
  • the fiber part 51 is disposed on the composite fiber core part and is a theme to express the elasticity and flexibility of the conductive composite fiber, and supports the first conductive part 52 and the second conductive part 53 which will be described later.
  • Serves as The fiber portion 51 may be used without limitation as a fiber forming component in the case of a known polymer compound that can be formed in a fibrous form.
  • the fiber-forming component is one in which the conductive composite fiber 50 is spun and blended on the spinning solution with PVDF and polyurethane, which are fluorine-based compounds, for the purpose of more improved elasticity, flexibility, compressibility, heat resistance, chemical resistance and mechanical strength.
  • PVDF and polyurethane may be included in a weight ratio of 1: 0.2 to 2, and more preferably 1: 0.4 to 1.5 weight ratio. If the polyurethane weight is less than 0.2 times based on the weight of PVDF, flexibility, elasticity, etc. may be lowered, and thus, lower than the initially designed electromagnetic shielding performance when provided on a substrate having deformation or step in use. Can be large. In addition, if the polyurethane weight is more than 2 times based on the PVDF weight, the restoring force due to expansion and contraction decreases, and thus the state of being stretched during the process and / or the use of cracking in the first conductive portion in step (2) described later. Deformation of the shape can be caused by not being restored to.
  • the chemical resistance is significantly lowered, and mechanical properties such as the fiber part is cut off or the fiber web is torn due to the shape deformation such as stretching and wrinkles due to the damage of the fiber part during the formation of the first conductive part or the second conductive part may be deteriorated. have.
  • the fiber portion 51 may be prepared by a known method that can be produced in a fibrous form of the fiber-forming component, for example, is produced by the spinning solution is extruded through the spinneret using an electrospinning or pressure It may have been.
  • the specific spinning method is to select the type of fiber-forming component or the fineness of the desired fiber.
  • the present invention is not particularly limited in this regard, since the known procedures and conditions may be adopted or appropriately modified in each method.
  • the first conductive portion 52 formed on the outer surface of the fiber portion 51 described above can be used without limitation when the material is electrically conductive and has no problem in material compatibility with the fiber portion 51.
  • the first conductive portion 52 may be, for example, at least one metal selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys, and stainless steel.
  • the first conductive portion 52 may be formed by a known metal coating method or a plating method.
  • the first conductive part 52 may be manufactured by immersing the fiber part in a metal paste and then drying and / or sintering the same. have.
  • the plating may be performed through electroless plating using a known plating method.
  • the first conductive portion 52 may be a laminate of two or more kinds of materials, for example, the first conductive portion may be a three-layer structure of a nickel layer / copper layer / nickel layer.
  • the first conductive portion 52 may be formed of three layers of a nickel layer / copper layer / nickel layer, and the copper layer may provide excellent electromagnetic shielding performance as the conductive fiber web may have a low electrical resistance.
  • the crack of the first conductive part may be minimized even when the conductive fiber web is deformed, such as wrinkles or stretches, and the stretch property may be improved.
  • the nickel layer formed on the copper layer can prevent the degradation of the electromagnetic shielding performance by preventing oxidation of the copper layer.
  • the first conductive portion 52 may have a thickness of 0.1 to 2 ⁇ m, and more preferably, the first conductive portion may have a thickness of 0.1 to 1.0 ⁇ m. If the thickness of the first conductive portion exceeds 2 ⁇ m, when the shape of the conductive composite fiber 50 changes, such as bending, additional cracks and peelings generated during use other than the cracks formed in step (2) are likely to occur. If less than 0.1 ⁇ m, peeling occurs in step (2) to be described later, even after the second conductive portion is formed, it may not express the desired level of initial electromagnetic shielding performance, and due to elongation generated during use, There is a risk of increased volatility.
  • the first conductive portion 52 is formed on the outer surface of the fiber portion 51 already manufactured.
  • the fiber portion 51 and the first conductive portion 52 may be formed integrally without making it.
  • the first conductive part 52 is a metal
  • the spinning solution containing the fiber-forming component is spun through the inner nozzle of the double spinning nozzle, and the metal paste capable of forming the first conductive part is extruded through the outer nozzle. After that, by firing the metal paste, the first conductive portion 52 can be integrally formed on the outside of the fiber portion 51.
  • the first conductive portion 52 extends the fiber portion 51 formed on the outer surface in the longitudinal direction to generate a crack in the first conductive portion 52. do.
  • the crack compensates for the decrease in the flexibility of the fiber part according to the coating of the first conductive part, so that the conductive composite fiber expresses the flexibility in the state in which the first conductive part is formed.
  • the first conductive portion 52 may elongate the fibrous portion 51 formed on the outside in the longitudinal direction to generate a crack c.
  • the step (2) may be performed by stretching 1.1 to 20 times, more preferably 1.1 to 8 times, even more preferably 1.1 to 2 times the length of the fiber portion before stretching. If it is stretched to less than 1.1 times, the crack of the first conductive portion is insignificant and cannot be expressed to the desired level for the flexible complementary effect. If it is stretched more than 20 times, peeling of the first conductive portion occurs, trimming or stretching. There is a fear that the shape may be deformed after being restored.
  • the second conductive portion 53 is formed on the outer surface of the first conductive portion 52 in the state in which the fiber portion 51 is extended.
  • the second conductive portion 53 serves to minimize or prevent an increase in resistance due to a crack formed in the first conductive portion 52 as the second conductive portion 53 covers the outer surface of the first conductive portion 52 in which the crack is generated.
  • step (3) preferably, 3-1) securing the separation space between the cracks generated in the first conductive part 52 by maintaining the fiber part 51 in an extended state and 3-2.
  • the second conductive portion 53 may be formed on the outer surface of the first conductive portion 52 including the separation space. That is, when the fiber portion is elongated to generate a crack in the first conductive portion and then contracted again to form the second conductive portion in such a state, fine gaps of the first conductive portion crack may exist, and in this case, the first conductive portion may be present.
  • the fibrous part 51 is maintained in an extended state to secure the separation space which is a gap of the crack generated in the first conductive part 52, and then the step 3-2) is performed on the upper part thereof.
  • the second conductive portion 53 is coated therethrough, the second conductive portion 53 penetrates not only between an outer surface of the first conductive portion 52 but also a space between cracks of the first conductive portion 52 as shown in FIG. 8. It may be easy to fill some or all of the separation space.
  • the second conductive portion 53 may be used without limitation in the case of a known conductive material, but preferably, a conductive polymer compound may be used so as not to inhibit the stretching and flexibility of the fiber portion.
  • the specific kind of the conductive polymer compound replaces the description of the conductive polymer compound in the first embodiment.
  • the second conductive portion may be formed through a second conductive portion formation composition including a conductive polymer compound and a dispersion solvent.
  • the dispersion solvent may be a known solvent capable of smoothly dispersing the conductive polymer compound, and may be differently selected according to the conductive polymer compound selected, and thus the present invention is not particularly limited thereto.
  • the dispersion solvent may be isopropyl alcohol.
  • the conductive polymer compound and the dispersion solvent may be mixed in a ratio of 1: 0.5 to 10, but may be changed according to the type of the conductive polymer compound and the dispersion solvent to be selected.
  • the second conductive portion forming composition may be formed on the first conductive portion through a conventional coating method, for example, by a known method such as dip coating, bar coating, comma coater.
  • the thickness of the second conductive portion 53 may be 0.05 ⁇ 1 ⁇ m. If the thickness of the second conductive portion is less than 0.05 ⁇ m, it may be difficult to prevent an increase in resistance due to the first conductive portion in which the crack occurs, and it may be difficult to sufficiently fill the second conductive portion in the crack. In addition, if the thickness of the second conductive portion is greater than 1 ⁇ m, although the first conductive portion is provided due to the rather high electrical resistance of the conductive polymer compound, the electrical resistance of the conductive fibrous web may increase rapidly, thereby achieving the desired level. It may be difficult to express electromagnetic shielding performance. In addition, the flexible extension property may decrease due to the increase in the thickness of the second conductive portion, which may cause tearing of the conductive fiber web due to external force generated during use.
  • the conductive composite fiber 50 manufactured through the above-described manufacturing method may have a diameter of 0.2 to 10 ⁇ m, and when the diameter is less than 0.2 ⁇ m, handleability is lowered, manufacturing may not be easy, and the diameter may be 10 ⁇ m. When it exceeds, there exists a possibility of elasticity fall and electromagnetic wave shielding performance fall.
  • the above-described conductive composite fiber 50 is implemented in any one of a woven fabric, knitted fabric and non-woven fabric can be utilized as an electromagnetic shielding material, the specific implementation method of the woven fabric, knitted fabric and nonwoven fabric known in the woven, knitted and web According to the present invention, a special description thereof will be omitted.
  • the electromagnetic shielding material 1100 implemented by forming the conductive fiber web 110 through the above-described conductive composite fiber 50 will be described.
  • the conductive fibrous web 110 has a three-dimensional network structure and includes a plurality of pores.
  • the plurality of pores may be formed by being surrounded by conductive composite fibers 50, which is an example of forming the conductive fibrous web 110.
  • the porosity of the conductive fibrous web 110 may be 30 to 80%, through which it can be easily implemented as a flexible and flexible electromagnetic shielding material.
  • the conductive fibrous web 110 may have an air permeability of 0.01 to 2 cfm. If the air permeability is less than 0.01 cfm, when the conductive adhesive layer is formed on any one surface of the conductive fibrous web, the conductive adhesive layer is formed by pores of the fibrous web. Impregnation of the formation composition may be difficult, and if it exceeds 2cfm, mechanical properties and electromagnetic shielding performance of the conductive fibrous web may be degraded.
  • the conductive fiber web 110 has a thickness of 5 ⁇ 200 ⁇ m, the basis weight may be 5 ⁇ 100g / m2. If the thickness of the conductive fibrous web exceeds 200 ⁇ m, it may not be easy to form the conductive portion on the outer surface of the fibrous portion located at the center of the fibrous web, and there is a concern that the stretching property is degraded. In addition, when the thickness is less than 5 ⁇ m the mechanical strength of the conductive fibrous web is lowered, the handling becomes difficult, it may not be easy to manufacture.
  • the conductive fibrous web 110 may be formed by stacking a single conductive fibrous web or a single conductive fibrous web.
  • a conductive adhesive for bonding each conductive fibrous web may be further interposed therebetween.
  • the conductive adhesive is replaced with the description of the conductive adhesive layer 200 to be described later.
  • the basis weight of the conductive fibrous web 110 is less than 5g / m2 the mechanical strength of the conductive fibrous web is lowered, handling becomes difficult, may not be easy to manufacture, if the fiber web exceeds 100g / m2 It may not be easy to form the conductive portion on the outer surface of the fiber portion located in the center of the, and there is a fear that the elastic properties are lowered.
  • the conductive fibrous web 110 is a method for producing a known conductive fibrous web 50, such as chemical bonding non-woven fabric, thermal bonding non-woven fabric, air-ray non-woven fabric such as dry nonwoven fabric or wet nonwoven fabric, span nonwoven fabric, It may be manufactured using a method such as needle punching nonwoven fabric or melt blown, but is not limited thereto.
  • the conductive fibrous web 110 is not made of a conductive fibrous web through the conductive composite fibers 50 separately prepared as described above, it may be first made of a fibrous web and then made of a conductive fibrous web.
  • the conductive fibrous web 110 includes (I) forming a first conductive portion on the outer surface of the fiber portion forming the fibrous web; (II) stretching the fibrous web in any one or more directions to generate cracks in the first conductive portion; And (III) forming a second conductive portion on an outer surface of the first conductive portion in the stretched state of the fiber portion.
  • the step (I) the step of forming the first conductive portion on the outer surface of the fiber portion forming the fibrous web.
  • the fibrous web may be manufactured by manufacturing a fiber part through chemical spinning or electrospinning, and then manufacturing a known fibrous web.
  • the method for producing a fibrous web through the electrospun fiber portion can be produced into a fibrous web through a calendering process for the fibrous mat collected and accumulated in the collector by electrospinning.
  • heat and / or pressure may be applied to the fiber mat, and the temperature and pressure may be appropriately changed in consideration of the diameter of the fiber portion, the basis weight of the desired fiber web, the thickness, and the like, and the present invention is particularly limited thereto. I never do that.
  • the first conductive part is formed on the outer surface of the fiber part of the manufactured fibrous web.
  • the material of the first conductive part may be a metal as described above, and the method of forming the first conductive part of the metal on the fibrous web may include deposition, plating, and the like. The coating method through a conductive paste, etc. can be used.
  • the first conductive portion may be deposited only outside the fiber portion positioned on the surface portion of the fibrous web, and the first conductive portion may be difficult to be provided in the fiber portion located at the center portion of the fibrous web. It may be difficult to express the electromagnetic shielding effect at the level.
  • the surface portion of the fibrous web on which the first conductive portion is deposited may hinder the stretching and flexible properties of the fibrous web, and the first conductive portion is deposited. There is a concern that the first conductive portion deposited may be easily crushed or peeled off when stretching or bending the fibrous web.
  • the first conductive portion when the first conductive portion is formed by coating the fibrous web with the conductive paste, the first conductive portion may be evenly provided on the fiber portion positioned on the surface / center of the fibrous web. In this case, however, the first conductive portion penetrates the pores. By fixing the fiber portion surrounding the pores, there is a fear that the stretching and flexible properties of the fiber web is inhibited, and the first conductive portion can be easily broken or peeled off.
  • the first conductive portion may be formed through plating on the fibrous web, and more preferably, the plating may be electroless plating.
  • the fibrous web is elongated in one or more directions to generate cracks in the first conductive portion.
  • the fiber web In order to generate a crack in the first conductive portion, it is preferable to stretch the fiber web by 1.1 to 20 times the length of the fiber web before stretching in the direction to be stretched. If the fibrous web is stretched less than 1.1 times, it may be difficult to achieve the desired level of stretch and flexibility. In addition, when the fibrous web is stretched more than 20 times, the peeling of the first conductive portion is remarkably increased, which may cause a decrease in the electromagnetic wave shielding performance or the fibrous web may be torn.
  • step (III) the step of forming a second conductive portion on the outer surface of the first conductive portion where the crack is generated.
  • the method of forming the second conductive portion is the same as the description of step (3) in the method of manufacturing the conductive composite fiber described above, and the detailed description thereof will be omitted.
  • step (III) may be preferably performed in a state in which the fibrous web is elongated, through which the second conductive portion easily penetrates into the space between the cracks of the first conductive portion, and the electromagnetic shielding material is flexible and flexible.
  • the electromagnetic shielding material is flexible and flexible.
  • the method of forming the conductive web is realized by first forming the fibrous web and then forming the conductive part.
  • the electromagnetic shielding material is implemented in the form of a woven or knitted fabric other than the fibrous web
  • the woven or knitted fabric is manufactured first.
  • the conductive material is formed by forming a first conductive portion in the fabric or knitted fabric, and forming the second conductive portion in a state in which a crack is generated in the first conductive portion by stretching it.
  • the shielding material is also within the scope of the present invention.
  • the conductive fibrous web 110 manufactured by the above-described method is implemented by the electromagnetic shielding material 1100 including the same, and the conductive fibrous web 110 is a fibrous web formed of the fibrous portion 51, the fibrous portion 51. And a first conductive portion 52 coated on an outer surface of the first conductive portion 52 and including a crack, and a second conductive portion 53 covering an outer surface of the first conductive portion 52.
  • a conductive adhesive layer 200 may be further provided on at least one surface of the conductive fibrous web 110 as shown in FIG. 7.
  • the conductive adhesive layer 200 may be a known conductive adhesive layer. The detailed description is replaced with the description in the first embodiment described above.
  • the flexible electromagnetic shielding material 1200 may have at least some pores of the conductive fibrous web 120 and the plurality of pores H including a plurality of pores H.
  • the first conductive component 300 provided therein may further include a conductive adhesive layer 200 provided on one or both surfaces of the conductive fibrous web 120.
  • the conductive fibrous web 120 has a three-dimensional network structure and includes a plurality of pores (H).
  • the plurality of pores H may be formed by being surrounded by conductive composite fibers 60 forming the conductive fibrous web 120.
  • the porosity of the conductive fibrous web 120 may be 30 to 80%, through which it can be easily implemented as a flexible and flexible electromagnetic shielding material.
  • the conductive fiber web 120 may have an air permeability of 0.01 ⁇ 2cfm, if the air permeability is less than 0.01cfm when forming a conductive adhesive layer on any one surface of the conductive fiber web, the conductive adhesive layer as pores of the fiber web Impregnation of the formation composition may be difficult, and if it exceeds 2cfm, mechanical properties and electromagnetic shielding performance of the conductive fibrous web may be degraded.
  • the conductive fiber web 120 may have a thickness of 5 to 200 ⁇ m, and a basis weight may be 5 to 100 g / m 2. If the thickness of the conductive fibrous web is greater than 200 ⁇ m, it may not be easy to form a metal shell portion of the conductive composite fiber, which is an example of forming the conductive fibrous web 120, on the fibers included in the entire outer and inner regions of the fibrous web. There is a fear that the elastic properties are lowered. In addition, when the thickness is less than 5 ⁇ m the mechanical strength of the conductive fibrous web is lowered, the handling becomes difficult, it may not be easy to manufacture.
  • the conductive fibrous web may be formed by stacking a single conductive fibrous web or a single conductive fibrous web.
  • a conductive adhesive layer for bonding each conductive fibrous web may be further interposed therebetween.
  • the conductive adhesive layer is replaced with the description of the conductive adhesive layer 200 to be described later.
  • the basis weight of the conductive fibrous web 120 is less than 5g / m2 the mechanical strength of the conductive fibrous web is reduced, the handling becomes difficult, may not be easy to manufacture, if the conductive fiber web exceeds 100g / m2 It may not be easy to form the metal shell portion of the fiber in the fiber contained in the entire area outside and inside the fiber web, and there is a fear that the elastic property is lowered.
  • the conductive composite fiber 60 forming the conductive fiber web 120 includes a fiber part 61 including a fiber forming component and a metal shell part coated on the outside of the fiber part 11. And (62).
  • the fiber forming component of the fiber portion 61 is a subject of forming a fiber or a fibrous web in a conductive composite fiber or a conductive fibrous web, and expresses elasticity, flexibility and wrinkle / resilience of the fibrous web, and is usually formed in a fibrous form.
  • Known high molecular compounds that can be used without limitation.
  • the fiber forming component is a fiber part 61 and the conductive fibrous web 120 implemented therein is a fluorine-based compound PVDF and polyurethane to prevent the development of improved elasticity, flexibility, heat resistance, chemical resistance and mechanical strength It may be blended on the use solution and spun.
  • PVDF and polyurethane may be included in a weight ratio of 1: 0.2 to 2, and more preferably 1: 0.4 to 1.5 weight ratio. If the polyurethane weight is less than 0.2 times based on the weight of PVDF, flexibility, elasticity, etc. may be lowered, which may cause tearing when the substrate is provided on the substrate having deformation or step difference in use. It may be difficult to get in close contact with the part where it is, and the damage of the conductive fibrous web may be greater than the initial designed electromagnetic shielding performance. In addition, if the polyurethane weight is included in excess of 2 times based on the PVDF weight, the restoring force due to expansion and contraction is lowered, which may cause permanent deformation of the shape due to failure to restore to the stretched state.
  • the chemical resistance is significantly lowered, and the fiber portion may be damaged during the formation of the metal shell. Accordingly, the mechanical properties such as the fiber part is cut off or the fiber web is torn due to the shape deformation of the conductive fiber web may be stretched or wrinkled. Can be degraded.
  • the metal shell 62 functions to reduce the resistance of the conductive fibrous web to express the electromagnetic shielding performance.
  • the metal shell 62 may be used without limitation in the case of a conventional electrically conductive metal material.
  • the metal shell 62 may be at least one material selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys, and stainless steel.
  • the metal shell portion may be formed of three layers of nickel layer / copper layer / nickel layer, wherein the copper layer may exhibit excellent electromagnetic shielding performance as the conductive fiber web may have low electrical resistance.
  • the nickel layer formed on the copper layer can prevent the degradation of the electromagnetic shielding performance by preventing oxidation of the copper layer.
  • the metal shell portion 62 may have a thickness of 0.1 to 2 ⁇ m, and if the thickness of the metal shell portion exceeds 2 ⁇ m, cracking or peeling occurs when the shape of the conductive composite fiber 60 changes, such as bending. easy to do.
  • the increased thickness of the conductive portion alters the pore structure of the conductive fibrous web, which can make it difficult to achieve a desired level of flexibility, flexibility, and the like.
  • the thickness is less than 0.1 ⁇ m it is not easy to form a thin thickness, it is very easy to crack or peel off it may be difficult to express the electromagnetic shielding performance to the desired level when stretched.
  • the conductive composite fiber 60 may have a diameter of 0.2 to 10 ⁇ m, and when the diameter is less than 0.2 ⁇ m, handleability may decrease, and manufacturing may not be easy. There is a risk of reducing the shielding performance.
  • the first conductive component 300 may be provided in some or all of the plurality of pores H provided in the conductive fibrous web 120 formed of the conductive composite fiber 60.
  • the first conductive component 300 expresses the electromagnetic wave shielding performance together with the conductive fiber web 120 described above, and at the same time, the conductive fiber may be cracked in the metal shell 62 that may occur when the conductive fiber web 120 is stretched or wrinkled. It is possible to prevent the increase in resistance of the web to express the electromagnetic shielding performance to the desired level.
  • the first conductive component 300 may be provided to contact at least a portion of the conductive composite fiber 60 in the pores (H) formed surrounded by the conductive composite fiber (60).
  • the pores H may be in contact with the conductive composite fiber 60. Due to the first conductive component 300 provided, spaced apart gaps due to cracks are electrically connected to each other, thereby minimizing or preventing increase in resistance of the conductive fibrous web 120.
  • the first conductive component 300 may be used without limitation in the case of a known material having electrical conductivity.
  • the first conductive component 300 may be made of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloy, and stainless steel. It may be a material of any one or more of one or more metals and conductive polymer compounds selected from the group. The specific kind of the conductive polymer compound is replaced with the description of the conductive polymer compound in the first embodiment described above.
  • the first conductive component 300 may be a metal particle to prevent the increase in resistance due to cracks that may occur in the metal shell portion 62, and to improve the electromagnetic shielding performance due to the first conductive component itself. have.
  • the metal particles when the metal particles are provided in the pores H, the metal particles may be adjusted to have a particle diameter equal to or smaller than the pore diameter of the pores H so as to contact the metal shell 62. Particles having a particle size of 0.80 to 0.95 times the average pore size can be used as the first conductive component 90% or more of the total metal particles.
  • the metal particles having a particle size of less than 0.8 times the average pore size of the pores are included in more than 90% of the total metal particles, even if the metal particles are included in the pores, the metal shell portion 62 of the conductive composite fiber 60 As there is less possibility of contacting with, it may not be possible to minimize or prevent the increase of resistance to the desired level when cracking occurs in the metal shell part by stretching or bending.
  • the metal particles having a particle size of more than 0.95 times the average pore size of the pores are included in more than 90% of the total metal particles, it may be difficult to provide the metal particles in the pores, even if provided Particles are provided only in the pores exposed on the surface of the fibrous web, and metal particles may be difficult to be provided in the inner pores. Therefore, when the crack occurs in the metal shell part by stretching or bending, the resistance increase may not be minimized or prevented. have.
  • the metal particles having a particle size of 0.80 to 0.95 times the average pore size of the pores are less than 90% of the total metal particles, the metal particles are difficult to be disposed in the pores so as to contact the metal shells or the pores themselves. As more metal particles are harder to penetrate, it may not be possible to minimize or prevent an increase in resistance to a desired level when cracking occurs in the metal shell part by stretching or bending.
  • the first conductive component 300 may be provided in an amount of 11 to 900 parts by weight based on 100 parts by weight of the conductive fibrous web 120. If the first conductive component 300 is less than 11 parts by weight with respect to 100 parts by weight of the conductive fibrous web, it is difficult to express a desired level of electromagnetic shielding performance or electrically cracked portions where cracks are generated when metal shells are cracked. It can be difficult to communicate, making it difficult to maintain the designed electromagnetic shielding performance. In addition, if the first conductive component is provided in excess of 900 parts by weight, the porosity of the conductive fibrous web may decrease, the weight may increase, and the elasticity and flexibility may be significantly reduced. In addition, when the electromagnetic shielding material is stretched or wrinkled, the first conductive component may be detached to deteriorate the electromagnetic shielding performance.
  • the electromagnetic shielding material according to one embodiment of the present invention described above may be prepared by including (1) preparing a conductive fibrous web and (2) providing a first conductive component in at least some pores of the manufactured conductive fibrous web. May be, but is not limited thereto.
  • step (1) a step of manufacturing the conductive fibrous web 120 is performed.
  • the conductive fibrous web 120 implements a fibrous web having a three-dimensional network structure with the manufactured conductive composite fiber 60 or (a) spinning a spinning solution containing a fiber-forming component to produce a fibrous web formed of fibrous parts. Step and (b) to form a metal shell to cover the outside of the fiber portion can be produced through the step of producing a conductive fibrous web.
  • the conductive composite fiber spins the spinning solution containing the fiber-forming component through the inner nozzle of the double spinning nozzle, and extrudes a metal paste capable of forming a metal shell through the outer nozzle. It can be prepared by firing the metal paste.
  • the conductive composite fiber may be prepared by forming a metal shell portion on the outer surface of the fiber manufactured through a spinning solution containing a fiber forming component.
  • the spinning solution may further include a solvent appropriately selected according to the spinning method, the type of the fiber-forming component provided, etc. may be a solution in which the fiber-forming component is dissolved or a melt in which the fiber-forming component is melted.
  • the method of spinning the spinning solution may be appropriately selected in consideration of the diameter of the desired conductive fiber and the type of the fiber forming component.
  • the spinning solution may be electrospinning or a method in which the spinning solution is extruded through the spinneret using pressure. .
  • dry spinning or wet spinning can be appropriately selected in consideration of the type of the fiber forming component, the type of the solvent provided in the spinning solution, and the present invention is not particularly limited thereto.
  • the method of forming the metal shell on the outer surface of the manufactured fiber may be performed by a known metal coating method or plating method.
  • the fiber may be subjected to drying and / or sintering after immersing the fiber in a metal paste.
  • the plating may be performed through electroless plating using a known plating method.
  • the conductive composite fiber produced may be a method of manufacturing a known fibrous web, for example, a dry nonwoven fabric such as a chemical bonding nonwoven fabric, a thermal bonding nonwoven fabric, an airlay nonwoven fabric, a wet nonwoven fabric, a spanless nonwoven fabric, a needle punching nonwoven fabric, or a meltblown fabric. Can be made into a conductive fibrous web.
  • a dry nonwoven fabric such as a chemical bonding nonwoven fabric, a thermal bonding nonwoven fabric, an airlay nonwoven fabric, a wet nonwoven fabric, a spanless nonwoven fabric, a needle punching nonwoven fabric, or a meltblown fabric.
  • the conductive fibrous web is another manufacturing method, (a) preparing a fibrous web formed of a fiber portion spun a spinning solution containing a fiber forming component and (b) a metal shell portion to cover the outside of the fiber portion It can be prepared, including the step of forming a conductive fibrous web.
  • the fibrous web may be manufactured by a known spinning method.
  • the fibrous web may be manufactured through a calendering process on a fibrous mat collected and accumulated in a collector by spinning a fiber forming component.
  • it can be prepared by performing the above-described method for producing a known fibrous web for the fibers produced separately.
  • the fiber web prepared in step (a) is a step (b), to form a metal shell portion to cover the fiber portion of the fiber web.
  • the step (b) is to form a metal shell portion on the outer surface of the fiber portion of the manufactured fiber web
  • the metal shell portion can be formed by a known method, for example, metal shell portion deposition, plating, conductivity Coating through a paste; and the like.
  • the metal shell portion may be deposited only on the outside of the fiber portion positioned on the surface portion of the fiber web, and the metal shell portion may be difficult to be provided in the fiber portion located in the center portion of the fiber web, and thus, electromagnetic waves may be at a desired level. It may be difficult to develop masking effects.
  • the surface portion of the fibrous web on which the metal shell is deposited may decrease the elastic properties of the fibrous web as the pores may be closed, and there is a concern that the deposited portion may be easily crushed or peeled off during the stretching.
  • the fibrous portion in the case of coating the fibrous web with a conductive paste, the fibrous portion may be evenly coated on the surface / center portion of the fibrous web, but the elastic properties may be remarkably reduced due to the pore closure, thereby causing the metal shell to break during stretching. Peeling can be serious.
  • the metal shell may be formed through plating on the fibrous web, and more preferably, the plating may be electroless plating.
  • step (2) the step of providing a first conductive component in at least some pores of the prepared conductive fibrous web.
  • the first conductive component may be provided in the pores provided in the conductive fibrous web by appropriately changing a known method for filling the material in the pores of the porous substrate, for example, the application of a conductive solution containing the first conductive component, Known coating methods such as dipping, screen printing, floating printing, bar coating or comma coating can be used, and the listed methods can be carried out by employing the conditions according to the known methods for each. Detailed description thereof will be omitted.
  • the viscosity of the conductive solution, the pore size, the porosity of the conductive fiber web can be adjusted to adjust the content of the conductive solution provided in the conductive fiber web.
  • the conductive solution may be a metal paste including metal particles as a conductive component, and the metal paste may include a binder component.
  • the binder component may be a polymer compound having elasticity and elasticity so as not to inhibit elasticity, flexibility, etc. of the conductive fibrous web, and may be, for example, a urethane-based compound.
  • the flexible electromagnetic shielding material 1200 ′ is a metal shell portion 62 of the conductive composite fiber 60 ′ forming the conductive fiber web 120 ′.
  • Crack (C) is formed at '), and may include a second conductive component 310 provided in the spaced gap of the crack (C). As the second conductive component 310 electrically connects the spaced gaps of the cracks C, the increase in resistance due to the occurrence of the cracks C may be minimized.
  • the crack (C) is intentionally formed in the manufacturing step of the electromagnetic shielding material, to improve the flexibility of the electromagnetic shielding material through the crack (C), and to prevent the degradation of properties due to the generation of the crack (C) after commercialization
  • the second conductive component 310 is interposed in the spaced gap of the crack C, and the resistance decreases due to the crack C through the first conductive component 300 'contacting the portion where the crack C is located. Can be minimized from the commercialization stage to meet the desired initial design properties.
  • the second conductive component 310 may be used without limitation when the material is a known material having electrical conductivity.
  • the second conductive component 310 may be aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloy, and stainless steel. It may be any one or more materials of one or more metals and conductive polymer compounds selected from the group consisting of.
  • the second conductive component 310 may be silver particles.
  • the second conductive component 310 may have the same or different material as the first conductive component 120 ′.
  • the second conductive component 310 may be used to adjust the size so that the average particle size is interposed in the spaced gap of the crack, for example, the particle size may be 0.01 ⁇ 0.1 ⁇ m.
  • the method for manufacturing the flexible electromagnetic shielding material having the second conductive component 310 interposed in the spaced apart gap of the crack C will be described. It may be prepared by elongating in the uniaxial or biaxial direction to generate a crack in the metal shell portion and then the second conductive component 310 penetrates the spaced gaps of the crack (C) in the elongated state. .
  • a solution including the second conductive component 310 for example, silver paste is treated to the conductive fibrous web, and the conductive fibrous web is stretched in the uniaxial or biaxial direction to generate cracks in the metal shell.
  • the silver paste may be interposed in the spaced spaces by allowing the pretreated silver paste to penetrate into the spaced spaces of the cracks maintained in the stretched state.
  • the first conductive component is interposed with the second conductive component in the spaced apart gap of the crack and then provided to the pores of the conductive fibrous web in a separate process, or in the process of treating the above-mentioned second conductive component
  • the first conductive component may be included in the solution to be used so that the first conductive component may be provided in the pores of the conductive fibrous web, and the second conductive component may be interposed between the cracks between the cracks of the metal shell.
  • Conductive adhesive layers 200 and 200 ' may be further provided on at least one surface of the conductive fibrous webs 120 and 120' implemented by the aforementioned manufacturing methods.
  • the detailed description of the conductive adhesive layers 200 and 200 ' is replaced with the description of the conductive adhesive layer in the above-described first embodiment.
  • the flexible electromagnetic shielding material 1300 includes a conductive fibrous web 130 formed of the conductive composite fiber 70, and the conductive fibrous web 130 of FIG. It may further include a conductive adhesive layer 200 provided on one side or both sides.
  • the conductive fibrous web 130 has a three-dimensional network structure and includes a plurality of pores.
  • the plurality of pores may be formed by being surrounded by conductive composite fibers 70, which is an example of forming the conductive fibrous web 130.
  • the conductive fiber web 130 may have an air permeability of 0.01 ⁇ 2cfm, if the air permeability is less than 0.01cfm when forming a conductive adhesive layer on any surface of the conductive fiber web, the conductive adhesive layer as pores of the fiber web Impregnation of the formation composition may be difficult, and if it exceeds 2cfm, mechanical properties and electromagnetic shielding performance of the conductive fibrous web may be degraded.
  • the conductive fiber web 130 has a thickness of 5 ⁇ 200 ⁇ m, the basis weight may be 5 ⁇ 100g / m2. If the thickness of the conductive fibrous web exceeds 200 ⁇ m, it may not be easy to form the conductive portion on the outer surface of the fibrous portion located at the center of the fibrous web, and there is a concern that the stretching property is degraded. In addition, when the thickness is less than 5 ⁇ m the mechanical strength of the conductive fibrous web is lowered, the handling becomes difficult, it may not be easy to manufacture.
  • the conductive fibrous web 130 may be formed by stacking a single conductive fibrous web or a single conductive fibrous web.
  • a conductive adhesive layer for adhering each conductive fibrous web may be further interposed therebetween.
  • the conductive adhesive layer is replaced with the description of the conductive adhesive layer 200 to be described later.
  • the basis weight of the conductive fibrous web 130 is less than 5g / m2 the mechanical strength of the conductive fibrous web is lowered, handling becomes difficult, may not be easy to manufacture, if the fiber web exceeds 100g / m2 It may not be easy to form the conductive portion on the outer surface of the fiber portion located in the center of the, and there is a fear that the elastic properties are lowered.
  • the conductive composite fiber 70 is implemented by including a crimped fiber portion 71 and a conductive portion 72 coated on the outside of the fiber portion 71 as shown in FIG.
  • the crimp formed on the fiber portion 71 may be formed in different ways according to the material and the manufacturing method of the fiber portion, and the degree of formation of the crimp is not particularly limited in the present invention as it can be adjusted in consideration of the desired elasticity. However, preferably, after stretching the conductive fibrous web 130 having the conductive portion 72 to be described later 1.2 times in the uniaxial direction, the surface resistance value measured in a state where the stretching force is removed is based on the surface resistance value before stretching. Crimps may be formed in the fiber portion to vary by less than 10%.
  • the elasticity of the conductive fiber web may be determined by factors such as the elongation / restoration force of the fiber portion and / or the elongation / restoration force of the conductive portion, and the structure in which the fiber portion forms the web. have.
  • the conductive part is a material having poor elasticity such as a metal, cracks and peeling may occur in the conductive part due to uniaxial stretching of the conductive fiber web, thereby increasing the surface resistance.
  • the conductive fiber web may not be torn or visually torn when the conductive fiber web is uniaxially stretched. Emissions can greatly increase resistance.
  • the conductive fibrous web formed of the crimped fiber part as in the present invention has excellent elasticity like the spring by the winding fiber part, thereby minimizing the influence of the material of the fiber part, the elastic properties of the material of the conductive part, and the like. Etc. can be significantly increased, and even when stretched, damage or peeling of the conductive portion can be minimized or prevented, thereby preventing a decrease in physical properties that increase from the initial designed resistance value.
  • the conductive fibrous web according to an embodiment of the present invention stretches 1.2 times the uniaxial length in the uniaxial direction and then measures the resistance in the state in which the stretching force is removed, so that the measured surface resistance value extends the conductive fibrous web. As it changes within 10% of the total surface resistance value, the property change can be minimized or prevented despite the expansion. If the resistance value is more than 10% in the state of recovery after extension than the resistance value before extension, the resistance value may be significantly increased than that originally designed due to peeling or damage of the conductive part when adhered to the stepped skin contact surface. Damage to the shielding material may occur.
  • the fiber forming component for implementing the fiber portion 71 is a subject of forming a fiber or a fibrous web in a conductive composite fiber or a conductive fibrous web, to express the elasticity, flexibility and wrinkle / resilience of the fibrous web, and usually in fibrous form
  • the fiber forming component may be a conductive fiber web 130 is a mixture of spinning fluorine-based compound PVDF and polyurethane on the spinning solution for spinning to improve the elasticity, flexibility, heat resistance, chemical resistance and mechanical strength .
  • PVDF and polyurethane may be included in a weight ratio of 1: 0.2 to 2, and more preferably 1: 0.4 to 1.5 weight ratio.
  • the polyurethane weight is less than 0.2 times based on the weight of PVDF, flexibility, elasticity, etc. may be lowered, which may cause tearing when the substrate is provided on the substrate having deformation or step difference in use. It may be difficult to get in close contact with the part where it is, and the damage of the conductive fibrous web may be greater than the initial designed electromagnetic shielding performance.
  • the polyurethane weight is more than 2 times based on the weight of PVDF, the restoring force due to expansion and contraction is lowered, which may cause permanent deformation of the shape due to failure to restore to the state before stretching. Failure to reduce the spacing between cracks can cause degradation of electromagnetic shielding performance.
  • the chemical resistance is significantly lowered, and the fiber portion may be damaged during the formation of the metal shell. Accordingly, the mechanical properties such as the fiber part is cut off or the fiber web is torn due to the shape deformation of the conductive fiber web may be stretched or wrinkled. Can be degraded.
  • the fiber portion to form a crimp according to the bi-shrinkage characteristics can be formed by placing in the fiber cross-section so that the two components with different shrinkage characteristics as a fiber forming component is not blended.
  • the two components may be a heterogeneous component having different shrinkage characteristics or a homogeneous component having different viscosity.
  • the conductive portion 72 serves to express the electromagnetic shielding performance by lowering the resistance of the conductive fibrous web.
  • the conductive portion 72 may be used without limitation in the case of a conventional electrically conductive material.
  • the conductive portion 72 may be at least one metal selected from the group consisting of aluminum, nickel, copper, silver, gold, chromium, platinum, titanium alloys, and stainless steel.
  • the conductive portion 72 may be a conductive polymer compound.
  • the conductive polymer compound may be used without limitation in the case of a known polymer compound having electrical conductivity. The specific kind of the conductive polymer compound replaces the description of the conductive polymer compound in the first embodiment.
  • the conductive portion 72 may be a metal in order to express a desired level of electromagnetic shielding performance.
  • the conductive portion may be formed of three layers, that is, a nickel layer / copper layer / nickel layer.
  • the copper layer may exhibit excellent electromagnetic shielding performance as the conductive fiber web may have a low electrical resistance.
  • the nickel layer formed on the copper layer can prevent the degradation of the electromagnetic shielding performance by preventing oxidation of the copper layer.
  • the nickel layer contacting the fiber portion may have a thickness of 0.02 to 0.2 ⁇ m, and the copper layer formed thereon may have a thickness of 0.08 to 1.8 ⁇ m, and the outermost nickel layer may be formed. Silver thickness may be formed to 0.02 ⁇ 0.2 ⁇ m. If the thickness of each layer is out of the above range, the expression of the effect according to each layer may be insignificant or non-expression, and the desired physical properties of the present invention may be insignificant.
  • the conductive part may have a thickness of 0.1 to 2 ⁇ m, and if the thickness of the conductive part exceeds 2 ⁇ m, cracks and peeling may easily occur when the shape of the conductive composite fiber 70 changes, such as bending, and conductivity.
  • the negative material is a conductive polymer compound, it may be difficult to reduce the electrical resistance by increasing the thickness.
  • the increased thickness of the conductive portion alters the pore structure of the conductive fibrous web, which can make it difficult to achieve a desired level of flexibility, flexibility, and the like.
  • the thickness is less than 0.1 ⁇ m it is not easy to form a thin thickness, it is very easy to crack or peel off it may be difficult to express the electromagnetic shielding performance to the desired level when stretched.
  • the conductive composite fiber 70 may have a diameter of 0.2 ⁇ 10 ⁇ m, when the diameter is less than 0.2 ⁇ m the handleability is lowered, may not be easy to manufacture, when the diameter exceeds 10 ⁇ m reduced elasticity As a result, electromagnetic wave shielding performance may be reduced.
  • the conductive adhesive layer 200 may be further provided on at least one surface of the conductive fibrous web 130 including the conductive composite fiber 70 described above as shown in FIG. 13.
  • the description of the conductive adhesive layer 200 is replaced with the description of the conductive adhesive layer in the above-described first embodiment.
  • Electromagnetic shielding material 1300 is a three-dimensional network structure to implement a fibrous web with a crimped conductive composite fiber 70 to produce a conductive fibrous web or (a) fiber formation Spinning the spinning solution containing the component to produce a fiber web through the crimped fiber portion, and (b) forming a conductive portion to cover the outside of the fiber portion to produce a conductive fiber web. .
  • the method of the present invention is a method of implementing a conductive fibrous web through conductive composite fibers prepared after the conductive composite fibers are manufactured.
  • the conductive composite fiber may be manufactured by first manufacturing a fiber part to which crimp is applied and then forming a conductive part on the outside of the fiber part, and simultaneously forming a fiber part and a conductive part.
  • the crimped fiber part may be manufactured through a known method of manufacturing a crimped fiber. Specifically, a method of extruding the molten spinning solution to impart crimping to the spun fiber portion, the method of imparting crimping to the fiber part using the bishrinkage property of the bicomponent polymer, and the physical flammability and heat setting method of the fiber part. Consider how to give crimps.
  • the method of imparting crimping to the fiber part by using the bishrinkage property of the bicomponent polymer is, for example, polyethylene terephthalate having an intrinsic viscosity of 0.6 to 0.8 dl / g as the first component and an intrinsic viscosity of 0.4 to the second component.
  • the polyethylene terephthalate of 0.55 dl / g may be produced by complex spinning such that the spun fiber section cross-sectional shape is appropriately divided into two components in a side-by-side type, an 8-shaped shape, or a circular cross section. In this case, during spinning, it may be manufactured as a stretched yarn through a separate stretching process after high-speed spinning or spinning. Fibers thus produced are latent crimps that have not been crimped and may express the crimps through separate heat treatment before forming the conductive portion, or simultaneously express the crimps through heat applied to form the conductive portion.
  • the method of imparting crimping through the physical flammability and heat setting method to the fiber portion is a combustible-heat fixation-combustion method, a combustible method, a knife edge method, a starting method, a high pressure air spray method, a complex crimping method, and an open horn.
  • Known methods such as islanding, can be suitably employed, and can be manufactured. As the known conditions can be used according to the selected method, the present invention omits specific description thereof.
  • the fiber portion by electrospinning when manufacturing the fiber portion by electrospinning it can be spun so that the crimp is formed on the fiber spun by changing the spinning conditions. For example, there is a method of inducing rapid aggregation by increasing the weight and diameter of the fiber to form a crimp, and a method of shortening the flight time of the fiber at the time of aggregation.
  • the spinning conditions such as reducing the distance between the nozzle and the integrated plate, the fiber can be crimped by spinning differently from the usual electrospinning.
  • the conductive portion can be formed in the fiber portion implemented by the above-described method, the conductive portion can be carried out through a known coating method or plating method for coating a metal or a polymer compound on the outer surface of the fiber produced, for example,
  • the conductive part is a metal
  • the conductive part may be formed by immersing the fiber in the metal paste and then drying and / or sintering the fiber.
  • the conductive portion can be formed through electroless plating by a known plating method.
  • the method of simultaneously forming the fiber portion and the conductive portion to produce a conductive composite fiber is to spin the spinning solution containing the fiber-forming component through the inner nozzle of the double-spinning nozzle, it is possible to form the conductive portion through the outer nozzle After extruding the metal paste, the metal paste may be fired.
  • the discharge rate of the spinning solution radiated from the inner nozzle during electrospinning, an applied voltage and / or humidity between the air gaps Properly adjusted can impart a winding crimp to the spun nanoscale fiber portion.
  • the specific conditions for crimping imparted may be changed according to the degree of crimping to be imparted to the nanofiber part, so the present invention is not particularly limited thereto.
  • the conductive composite fiber produced by the above-described method is a known method of manufacturing a fibrous web, for example, a dry nonwoven fabric such as a chemical bonding nonwoven fabric, a thermal bonding nonwoven fabric, an airlay nonwoven fabric, a wet nonwoven fabric, a span nonwoven fabric, a needle punching nonwoven fabric, or a meltable fabric. It can be made into a conductive fibrous web using a method such as new.
  • the step (a) it is possible to manufacture a fiber web after the crimped fiber part is manufactured through the method of manufacturing the crimped fiber part in the conductive composite fiber manufacturing method described above.
  • the fiber web is produced through a calendering process on a fiber mat collected and accumulated in a collector by spinning a fiber-forming component, or known for the crimped fibers produced separately.
  • the fibrous web may be manufactured by performing the prepared fibrous web.
  • the fiber web prepared in step (a) is performed in step (b) to form a conductive part to cover the fiber part of the fiber web.
  • the step (b) is to form a conductive portion on the outer surface of the fiber portion of the fibrous web state
  • the conductive portion may be formed by a known method, for example, the deposition of the conductive portion, plating, coating method through the conductive paste, etc. This can be.
  • the conductive portion may be deposited only on the outside of the fiber portion positioned in the surface portion of the fibrous web, and the conductive portion may be difficult to be provided in the fibrous portion located in the center portion of the fibrous web. It can be difficult to express.
  • the surface portion of the fibrous web on which the conductive portion is deposited may decrease the elastic properties of the fibrous web as the pores may be closed, and there is a concern that the deposited portion may be easily broken or peeled off during the stretching.
  • the fibrous portion in the case of coating the fibrous web with the conductive paste, the fibrous portion may be evenly coated on the surface / center portion of the fibrous web, but the elastic property may be remarkably decreased due to the pore closure, thereby causing the conductive portion to break. Peeling can be serious.
  • the conductive portion may be formed through plating on the fibrous web, and more preferably, the plating may be electroless plating.
  • a conductive adhesive layer on at least a portion of the conductive fibrous web prepared;
  • the conductive adhesive layer is formed by being treated on at least one surface of a conductive fibrous web in which a conductive adhesive composition including a resin component, a conductive filler, a solvent, and other additives such as a dispersant and a flame retardant, which forms the matrix of the conductive adhesive layer, is formed.
  • a conductive adhesive composition including a resin component, a conductive filler, a solvent, and other additives such as a dispersant and a flame retardant, which forms the matrix of the conductive adhesive layer, is formed.
  • the method of treating the conductive adhesive composition may use a known coating method such as coating, screen printing, floating printing, or comma coating of the conductive adhesive composition, and the enumerated methods employ conditions according to the known methods for each.
  • the viscosity of the conductive adhesive composition, the pore size of the conductive fibrous web, the porosity may be adjusted to prevent the conductive adhesive composition from penetrating into the conductive fibrous web, or may be adjusted to be impregnated into the conductive fibrous web.
  • the electromagnetic shielding materials 1000, 1100, 1200, and 1300 are implemented as the electromagnetic shielding circuit module 2000 as shown in FIG. 15, and specifically, a circuit board 2200 on which the elements 2310 and 2320 are mounted.
  • the electromagnetic shielding material 2100 may be provided on the circuit board 2200 to cover at least the upper and side portions of the elements 2310 and 2320.
  • the circuit board 2200 may be a known circuit board provided in an electronic device.
  • the circuit board 2200 may be a PCB or an FPCB. Since the size and thickness of the circuit board 1200 can be changed according to the internal design of the electronic device to be implemented, the present invention is not particularly limited thereto.
  • the devices 2310 and 2320 may be well-known devices mounted on a circuit board in an electronic device such as a driving chip, and may be devices that generate electromagnetic waves and / or heat or are sensitive to electromagnetic waves to easily malfunction.
  • the electromagnetic shielding material 2100 according to the exemplary embodiment of the present invention, even when a distance between the adjacent elements 2310 and 2320 is narrow or a step occurs due to the thickness of the elements 2310 and 2320 as shown in FIG. As it can be adhered closely, it is advantageous to express more improved electromagnetic shielding performance.
  • a spinning solution was prepared by dissolving 12 g of polyvinylidene fluoride in a weight ratio of dimethylacetamide and acetone at 70:30 using 88 ° C. at 6 ° C. for 6 hours using a magnetic bar. Spherical silver particles having an average particle diameter of 1.3 ⁇ m were added to the spinning solution by mixing polyvinylidene fluoride and silver particles in a volume ratio of 1: 0.2 to account for 16.7% of the total volume of the final fiber, followed by ultrasonic disperser. Dispersed for 12 hours. The spinning solution was introduced into a solution tank of an electrospinning apparatus, the solution was stirred through an impeller, and discharged at a rate of 20 ⁇ l / min / hole.
  • the temperature of the spinning section is 30 °C
  • the humidity is maintained at 50%
  • the distance between the collector and the spinneret tip 20cm using a high voltage generator to apply a voltage of 40kV to the spin nozzle pack (Spin Nozzle Pack) and
  • a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • a nickel metal shell portion was formed on the manufactured fibrous web.
  • nickel electroless plating was performed on the fibrous web.
  • the fibrous web was immersed in a degreasing solution at 60 ° C. for 30 seconds and then washed with pure water, and then immersed in an etching solution (5 M NaOH, pure water) at 60 ° C. for 1 minute. It was washed with pure water. Thereafter, the fibrous web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water.
  • a catalyst solution Pd 0.9%, HCl 20%, pure water
  • the conductive fibrous web was prepared as shown in Table 1 having a thickness of 10 ⁇ , a basis weight of 12 g / m 2, and a porosity of 40%. It was.
  • Example 2 Prepared in the same manner as in Example 1, the content of the conductive filler, the particle diameter was changed as shown in Table 1 or Table 2 to prepare a conductive fiber web as shown in Table 1.
  • Example 2 Prepared in the same manner as in Example 1, but did not include a conductive filler, to prepare a conductive fibrous web as shown in Table 2.
  • the resistance of the conductive fiber web surface was measured by a resistance meter (HIOKI 3540 m ⁇ HITESTER, HIOKI). Based on the measured value of Comparative Example 1 measured as 100, the measured resistance value according to the example was expressed as a relative percentage.
  • the specimen was stretched 1.2 times in the transverse direction using a jig, and then three sets were repeated with one set of 1.2 times in the longitudinal direction.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Conductive Filler Particle size ( ⁇ m) 1.3 1.45 1.6 0.25 0.35 0.75 Content (% by volume) 16.7 16.7 16.7 16.7 16.7 16.7 2nd part diameter (nm) 300 300 300 300 300 300 300 300 300 Second part diameter: conductive filler diameter 1: 4.33 1: 4.83 1: 5.33 1: 0.83 1: 1.17 1: 2.5 Initial electromagnetic shielding performance (%) 89.6 87.4 86.7 99.1 94.2 92.1 Electromagnetic shielding performance change rate (%) 10.7 11.1 23.8 26.6 18.5 14.9 Shape holding power ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Conductive Filler Particle size ( ⁇ m) One 1.3 1.3 1.3 1.3 - Content (% by volume) 16.7 8.5 10.5 49 52 0 2nd part diameter (nm) 300 300 300 300 300 300 300 300 Second part diameter: conductive filler diameter 1: 3.33 1: 4.33 1: 4.33 1: 4.33 1: 4.33 - Initial electromagnetic shielding performance (%) 90.5 98.5 93.2 79.4 78.1 100 Electromagnetic shielding performance change rate (%) 12.0 14.4 11.6 16.6 26.9 41.1 Shape holding power ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 3 the particle size of the conductive filler was outside the preferred range of the present invention, but in Example 11, the content was outside the preferred range of the present invention, the tearing occurred due to elongation due to the decrease in mechanical strength, and thus the variation rate. It can also be confirmed that it was large.
  • Example 3 Prepared in the same manner as in Example 1, but changed the fiber-forming component and solvent of the spinning solution. Specifically, 16 g of the fiber-forming component in which the weight ratio of polyvinylidene fluoride and polyurethane were mixed at 7: 3 was mixed with 84 g of the solvent in which the weight ratio of dimethylacetamide and acetone was mixed at 7: 3. It was dissolved by using to prepare a spinning solution, through which the thickness was 10 ⁇ m, basis weight of 11.6g / m2, porosity of 38% to prepare a conductive fibrous web as shown in Table 3.
  • Example 12 The preparation was carried out in the same manner as in Example 12, except that the content ratio of PVDF and polyurethane, which are fiber forming components, was changed as shown in Table 3 to prepare a conductive fiber web as shown in Table 3 below.
  • Example 1 In Example 1 and Examples 12 to 18, the following physical properties were evaluated and shown in Table 2 below.
  • the specimen was stretched 1.4 times in the transverse direction using a jig, and then three sets were repeated with one set of 1.4 times in the longitudinal direction again in a state where the stress was removed.
  • the area (C) of the specimen was calculated after three sets of stretching and recovery in the horizontal and vertical directions.
  • the area variation rate was calculated according to Equation 2 based on the area (D) of the initial specimen before the stretching process.
  • damage occurred such as tearing after 3 sets of expansion
  • Example 1 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Fiber Forming Ingredients PVDF: Polyurethane Weight Ratio 1: 0.0 1: 0.43 1: 1.45 1: 1.6 1: 1.9 1.2.2 1: 0.14 1: 0.22 Electromagnetic shielding performance change rate (%) 26.9 6.9 8.2 11.6 12.8 16.7 15.1 10.3 Shape holding power Damage ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Area variation rate (%) Unmeasured 3.2 6.4 6.8 7.5 Unmeasured Unmeasured 2.1
  • Example 1 containing no polyurethane as the fiber forming component of the fiber part, it was confirmed that the tearing occurred as the elongation ratio was increased than in Experimental Example 1, and it was confirmed that the rate of variation of the electromagnetic shielding performance was also significantly increased.
  • Example 16 the tearing occurred even when the polyurethane was increased was expected as a result of damage to the fiber portion depending on the various solutions applied during the plating process.
  • a spinning solution was prepared by dissolving 12 g of polyvinylidene fluoride in a weight ratio of dimethylacetamide and acetone at 70:30 using 88 ° C. at 6 ° C. for 6 hours using a magnetic bar.
  • the spinning solution was introduced into a solution tank of an electrospinning apparatus and discharged at a rate of 20 ⁇ l / min / hole.
  • the temperature of the radiation section is 30 °C
  • the humidity is maintained at 50%
  • the distance between the collector and the spinneret tip 20cm, using a high voltage generator on the collector the voltage of 40kV to the spin nozzle pack (Spin Nozzle Pack)
  • air pressure of 0.01 MPa per spin pack nozzle was applied to produce PVDF fiber webs having an average diameter of 200 nm.
  • heat and pressure were applied at a temperature of 140 ° C. and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • a first conductive portion that is nickel was formed on the manufactured fibrous web.
  • nickel electroless plating was performed on the fibrous web.
  • the fibrous web was immersed in a degreasing solution at 60 ° C. for 30 seconds and then washed with pure water, and then immersed in an etching solution (5 M NaOH, pure water) at 60 ° C. for 1 minute. It was washed with pure water.
  • the fibrous web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water.
  • the fibrous web After immersing the fibrous web in 50 ° C sulfuric acid solution (H 2 SO 4 85ml / L, pure water) for 30 seconds for catalytic activity and then rinsing with pure water, the fibrous web was immersed in 60 ° C nickel ion solution for 1 minute and then pure The first conductive portion of nickel having a thickness of 0.12 mu m was coated on the fiber portion of the fibrous web.
  • 50 ° C sulfuric acid solution H 2 SO 4 85ml / L, pure water
  • a second conductive part forming solution was prepared to form the second conductive part. Specifically, in order to improve volatilization in a dispersion in which 1 to 1.5 parts by weight of PEDOT is mixed with respect to 100 parts by weight of ultrapure water, 100 parts by weight of the dispersion is used. 50 parts by weight of IPA was mixed and stirred at room temperature for 6 hours. The second conductive part forming solution prepared was spray coated on the fibrous web fixed to the mold and dried in a vacuum oven at 60 ° C.
  • the nanofiber diameter, the thickness of the first conductive portion and / or the second conductive portion was changed as shown in Table 4 to prepare a conductive fiber web as shown in Table 4.
  • Example 19 Prepared in the same manner as in Example 19, except that only the first conductive portion was formed to prepare a conductive fiber web as shown in Table 4 below.
  • the electromagnetic wave shielding materials according to Examples 19 to 26 and Comparative Examples 2 and 3 were evaluated according to Experimental Example 1 described above, and the initial electromagnetic wave shielding performance, the electromagnetic wave shielding performance variation rate, and the shape holding force were evaluated and shown in Table 4.
  • the initial electromagnetic shielding performance is a relative value of the measured resistance value according to Examples 19 to 24 and Comparative Example 3 on the basis of the measured value of Comparative Example 2.
  • Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Comparative Example 2 Comparative Example 3 Nano fiber diameter (nm) 200 200 800 1500 1500 800 800 200 200 200 First conductive part thickness ( ⁇ m) 0.12 0.07 1.0 1.9 2.2 1.5 1.5 0.12 0.12 0 Second conductive part thickness ( ⁇ m) 0.06 0.06 0.05 0.09 0.09 0.95 1.2 0.02 0 1.0 Initial electromagnetic shielding performance (%) 103.5 109.1 81.7 76.4 74.3 78.5 84.8 106.2 100 115.8 Electromagnetic shielding performance variation rate (%) 12.8 16.5 9.6 11.5 15.1 12.4 26.8 16.0 41.1 0.6 Shape holding power ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Comparative Example 2 in which only the first conductive portion, which is a metal, is formed, it can be seen that the electromagnetic wave shielding variation rate is remarkable.
  • Comparative Example 3 in which only the second conductive portion is formed may confirm that the initial electromagnetic shielding performance is not significantly better than the embodiments.
  • Example 20 in which the first conductive portion was made too thin, the initial electromagnetic wave shielding performance was lowered compared to Example 19, which was caused by peeling of the first conductive portion in the stretching process before forming the second conductive portion. It was expected.
  • Example 23 in which the first conductive portion was too thick, it can be seen that the variation rate of the electromagnetic shielding performance was larger than that of Example 22.
  • Example 26 in which the second conductive portion was too thin, the initial electromagnetic shielding performance was lowered in comparison with Example 19, because the second conductive portion was filled in the gaps between the cracks generated so that the electrical connection was weak. was expected as a result.
  • Example 25 in which the second conductive portion was excessively formed, tearing occurred after three sets of extension and recovery, and it can be seen that the variation of the electromagnetic shielding performance was also large.
  • Example 19 Prepared in the same manner as in Example 19, except that the fiber-forming component and the solvent of the spinning solution were changed. Specifically, 16 g of the fiber-forming component in which the weight ratio of polyvinylidene fluoride and polyurethane were mixed at 7: 3 was mixed with 84 g of the solvent in which the weight ratio of dimethylacetamide and acetone was mixed at 7: 3. It was dissolved by using to prepare a spinning solution, through which a thickness of 20 ⁇ m, a basis weight of 11.1g / m2, porosity of 30% to prepare a conductive fibrous web as shown in Table 5.
  • Example 19 Examples 27 to 33, the electromagnetic wave shielding performance variation rate and the shape holding force were evaluated in the same manner as in Experiment 2, and the following physical properties were evaluated and shown in Table 5 below.
  • Example 19 Example 27 Example 28 Example 29 Example 30
  • Example 31 Example 32
  • Electromagnetic shielding performance change rate (%) 23.9 4.8 4.0 7.5 8.7 12.7 11.1 6.4
  • Shape holding power Damage ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Area variation rate (%) Unmeasured 3.0 5.8 6.4 6.9 Unmeasured Unmeasured 2.2
  • Example 19 containing no polyurethane as the fiber forming component of the fiber part, it was confirmed that the tearing occurred as the elongation ratio was increased in Experimental Example 1, and it was confirmed that the variation rate of the electromagnetic shielding performance was also significantly increased.
  • Example 31 the tearing occurred even when the polyurethane was increased was expected as a result of the damage to the fiber portion depending on the various solutions applied during the plating process.
  • a spinning solution was prepared by dissolving 12 g of polyvinylidene fluoride in a weight ratio of dimethylacetamide and acetone at 70:30 using a magnetic bar at 85 ° C. for 6 hours at 80 ° C.
  • the spinning solution was introduced into a solution tank of an electrospinning apparatus and discharged at a rate of 20 ⁇ l / min / hole.
  • the temperature of the radiation section is 30 °C
  • the humidity is maintained at 50%
  • the distance between the collector and the spinneret tip 20cm, using a high voltage generator on the collector the voltage of 40kV to the spin nozzle pack (Spin Nozzle Pack)
  • air pressure of 0.03 MPa per spin pack nozzle was applied to prepare a PVDF fiber web having an average diameter of 400 nm.
  • a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • a nickel metal shell portion was formed on the manufactured fibrous web.
  • nickel electroless plating was performed on the fibrous web.
  • the fibrous web was immersed in a degreasing solution at 60 ° C. for 30 seconds and then washed with pure water, and then immersed in an etching solution (5 M NaOH, pure water) at 60 ° C. for 1 minute. It was washed with pure water. Thereafter, the fibrous web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water. Subsequently, the fibrous web was immersed in 50 ° C.
  • a silver paste containing silver particles having an average particle diameter of 0.58 ⁇ m as a first conductive component and a particle diameter of 92% of all the particles within a range of 0.56 to 0.66 ⁇ m was formed by using a bar coater on the conductive fiber web. Penetrated into the pores of, and the paste that did not penetrate was removed and dried in a vacuum oven at 60 °C to prepare an electromagnetic shielding material as shown in Table 6.
  • Example 33 Prepared in the same manner as in Example 33, except that the particle size of the first conductive component was changed to the following Table 6 to prepare a conductive shield as shown in Table 6.
  • Example 33 Manufactured in the same manner as in Example 33, wherein the conductive fibrous web was uniaxially treated with a silver paste containing silver particles having an average particle diameter of 0.05 ⁇ m as a second conductive component in the conductive fibrous web using a bar coater. 1.2 times elongation caused cracking in the metal shell of the conductive composite fiber. At this time, the stretched state was maintained for 2 hours to allow the second conductive component to penetrate into the spaced apart spaces of the cracked metal shell part, and was dried in a vacuum oven at 60 ° C. after removing the non-penetrated silver paste. Thereafter, the silver paste including the first conductive component according to Example 1 was treated as in Example 1 and dried to prepare an electromagnetic shielding material as shown in Table 6 below.
  • the initial electromagnetic wave shielding performance and the electromagnetic wave shielding performance fluctuation rate were evaluated and shown in Table 6 below.
  • the initial electromagnetic shielding performance is expressed as a relative percentage of the measured resistance value according to the embodiment based on the measured value of Comparative Example 4.
  • Example 33 Example 34 Example 35 Example 36 Example 37 Comparative Example 4 Pore average pore size ( ⁇ m) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 First conductive component Silver Particle Average Particle Size ( ⁇ m) 0.58 0.55 0.49 0.72 0.58 Not included Silver particle size ( ⁇ m) 0.56-0.66 0.56-0.66 0.30-0.52 0.68-0.80 0.56-0.66 Content (%) in the first conductive component 92 87 92 95 92 Second conductive component Silver particle size ( ⁇ m) Not included Not included Not included Not included Not included Not included 0.05 Not included Initial electromagnetic shielding performance (%) 73.2 80.5 89.3 86.6 77.3 100 Electromagnetic shielding performance change rate (%) 6.1 10.2 16.4 19.5 3.0 40.3
  • Example 33 in which the first conductive component is within the preferred range of the present invention, is superior in initial electromagnetic wave shielding performance and performance maintenance degree compared with Examples 34 to 36.
  • the second conductive component is interposed between the cracks generated in the nickel metal layer, but the initial electromagnetic shielding performance in comparison with the electromagnetic shielding material according to Example 33 in which no crack is generated It can be seen that this somewhat reduced. However, it can be seen that the electromagnetic shielding material according to Example 37 is superior to Example 33 in terms of maintaining performance even in external force due to additional expansion / recovery.
  • Example 33 Prepared in the same manner as in Example 33, except that the fiber-forming component and solvent of the spinning solution were changed. Specifically, 16 g of the fiber-forming component in which the weight ratio of polyvinylidene fluoride and polyurethane were mixed at 7: 3 was mixed with 84 g of the solvent in which the weight ratio of dimethylacetamide and acetone was mixed at 7: 3. It was dissolved to use to prepare a spinning solution, through which the thickness is 20 ⁇ m, basis weight is 9.85g / m2, porosity of 49%, the average pore diameter of 0.7 ⁇ m was prepared after the conductive fiber web containing the first conductive component The silver paste was treated to prepare an electromagnetic shielding material as shown in Table 7 below.
  • Example 38 Prepared in the same manner as in Example 38, but changed the content ratio of PVDF and polyurethane as a fiber forming component as shown in Table 7 to prepare an electromagnetic shielding material as shown in Table 7.
  • the electromagnetic wave shielding material according to Examples 33 and 38 to 44 was evaluated in the same manner as in Experiment 2, and the variation rate and shape holding force of the electromagnetic wave shielding performance were evaluated and shown in Table 7 below.
  • Example 33 Example 38 Example 39 Example 40
  • Example 42 Example 43
  • Example 44 Fiber Forming Ingredients PVDF: Polyurethane Weight Ratio 1: 0.0 1: 0.43 1: 1.45 1: 1.6 1: 1.9 1.2.2 1: 0.14 1: 0.22
  • Electromagnetic shielding performance change rate (%) 22.9 5.5 6.1 9.4 10.0 15.7 14.1 10.3 Shape holding power Damage ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Area variation rate (%) Unmeasured 3.0 6.1 6.7 7.0 Unmeasured Unmeasured 2.0
  • Example 33 containing no polyurethane as the fiber forming component of the fiber part, it was confirmed that the tearing occurred as the elongation ratio was increased, and the rate of variation of the electromagnetic shielding performance was also significantly increased.
  • Example 42 the tearing occurred even when the polyurethane was increased was expected as a result of damage to the fiber portion depending on the various solutions applied during the plating process.
  • a spinning solution was prepared by dissolving 15 g of polyvinylidene fluoride in a weight ratio of dimethylacetamide and acetone at 70:30 using a magnetic bar at 85 ° C. for 6 hours at a temperature of 80 ° C.
  • the spinning solution was poured into the solution tank of the electrospinning apparatus and discharged at a rate of 20 ⁇ l / min / hole.
  • the temperature of the spinning section is 32 °C
  • the humidity is 55%
  • the distance between the collector and the spinning nozzle tip is 16cm
  • 40 kV is applied to the spinning nozzle pack using a high voltage generator.
  • a winding crimp was formed on the fiber, and a PVDF fiber web having an average diameter of 500 nm was prepared.
  • a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • nickel, copper, and nickel were sequentially electroless plated onto the manufactured fibrous web to form a metal shell having a three-layer structure.
  • nickel electroless plating was performed on the fibrous web.
  • the fibrous web was immersed in a degreasing solution at 60 ° C. for 30 seconds and then washed with pure water, and then immersed in 60 ° C. etching solution (5M NaOH, pure water) for 1 minute. After washing with pure water. Thereafter, the fibrous web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water.
  • the fibrous web After immersing the fibrous web in 50 ° C sulfuric acid solution (H 2 SO 4 85ml / L, pure water) for 30 seconds for catalytic activity and then rinsing with pure water, the fibrous web was immersed in 60 ° C nickel ion solution for 1 minute and then pure It washed with and formed the nickel layer of 0.03 micrometer in thickness. After washing, immersed in a 40 °C copper ion solution for 3 minutes and then washed with pure water to form a copper layer having a thickness of 1.0 ⁇ m.
  • nickel is difficult to be plated on top of copper
  • copper-plated nanoweb is applied to nickel ion solution, soaked for 30 seconds, washed with pure water to form a nickel layer having a thickness of 0.04 ⁇ m, and then a final layer of nickel / copper / nickel.
  • the metal shell of the structure was coated on the fiber portion of the fibrous web, and the final thickness was 20 ⁇ m, and the basis weight was 16.3 g / m 2, and the conductive fiber web having a porosity of 45% was prepared as shown in Table 8 below.
  • Example 45 Prepared in the same manner as in Example 45 except that 12 g of polyvinylidene fluoride was dissolved in 85 g of a magnetic bar at a temperature of 80 ° C. for 6 hours at a weight ratio of 70:30 of dimethylacetamide and acetone. did.
  • the spinning solution was introduced into a solution tank of an electrospinning apparatus and discharged at a rate of 20 ⁇ l / min / hole.
  • the temperature of the radiation section is 30 °C
  • the humidity is maintained at 50%
  • an air pressure of 0.03 MPa per spin pack nozzle was applied to produce a PVDF fibrous web having an average diameter of 400 nm and no crimp.
  • a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • the resistance of the surface of the electromagnetic shielding material was measured by a resistance meter (HIOKI 3540 m ⁇ HITESTER, HIOKI). Based on the measured value of Comparative Example 1 measured as 100, the measured resistance value according to the example was expressed as a relative percentage.
  • the specimen was stretched in the horizontal direction and visually observed.
  • the force applied when the electromagnetic shielding material was torn or damaged was expressed by the ratio of the initial length in the horizontal direction to the initial length in the horizontal direction.
  • Example 45 Example 46 Comparative Example 5 Air gap (cm) 15 17 20 Air pressure (MPa) 0.01 0.02 0.03 Crimp has exist has exist none Initial electromagnetic shielding performance (%) 99.9 100 100 Electromagnetic shielding performance change rate (%) 4 8 27.5 Mechanical strength according to elongation (times) 1.67 1.53 1.29
  • Example 45 Prepared in the same manner as in Example 45, but changed the fiber-forming component and solvent of the spinning solution. Specifically, 16 g of the fiber-forming component in which the weight ratio of polyvinylidene fluoride and polyurethane were mixed at 7: 3 was mixed with 84 g of the solvent in which the weight ratio of dimethylacetamide and acetone was mixed at 7: 3. It was dissolved by using to prepare a spinning solution, the spinning solution was put in the solution tank of the electrospinning apparatus, and was discharged at a rate of 20 ⁇ m / min / hole.
  • the temperature of the spinning section is 32 °C
  • the humidity is 55%
  • the distance between the collector and the spinning nozzle tip is 16cm
  • 40 kV is applied to the spinning nozzle pack using a high voltage generator.
  • Example 47 Prepared in the same manner as in Example 47, but changed the content ratio of PVDF and polyurethane as a fiber forming component as shown in Table 9 to prepare an electromagnetic shielding material as shown in Table 9.
  • the electromagnetic wave shielding materials according to Examples 45 and 47 to Example 53 were evaluated in the electromagnetic shielding performance retention and shape holding force as shown in Experiment 2, and are shown in Table 2 below. In this case, in the case of maintaining the electromagnetic shielding performance, three sets of stretching were performed in a set of stretching the transverse and vertical by 1.8 times differently from Experimental Example 2.
  • Example 45 Example 47
  • Example 48 Example 49
  • Example 50 Example 51
  • Example 52 Example 53 Fiber Forming Ingredients PVDF: Polyurethane Weight Ratio 1: 0.0 1: 0.43 1: 1.45 1: 1.6 1: 1.9 1.2.2 1: 0.14 1: 0.22
  • Electromagnetic shielding performance change rate (%) 24.8 2.5 3.1 11.4 12.0 20.7 23.1 10.3 Shape holding power Damage ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Area variation rate (%) Unmeasured 1.8 2.6 3.5 3.6 Unmeasured Unmeasured 2.9
  • Example 45 without polyurethane as a fiber forming component of the fiber part, it was confirmed that the tearing occurred as the elongation ratio was increased in Experimental Example 1, and it was confirmed that the variation rate of the electromagnetic shielding performance was also significantly increased.
  • Example 51 the tearing occurred even when the polyurethane was increased was expected as a result of the damage to the fiber portion depending on the various solutions applied during the plating process.
  • a conductive adhesive layer 7 parts by weight of nickel particles having an average particle diameter of 3 ⁇ m was mixed with respect to 100 parts by weight of the conductive adhesive composition including an acrylic adhesive forming component, and then a mixed solution was prepared using a mixing mixer.
  • the prepared mixed solution is coated on a release PET film using a bar coater, and then the conductive fibrous web prepared according to Example 1 is laminated on the coated surface, and then the mixed solution is coated thereon, then laminated with a release PET film, followed by a calendering process.
  • the laminated conductive shielding was thermally cured at 120 ° C. for 24 hours to cure the adhesive adhesive layer. Through this, the conductive adhesive layer was formed to a predetermined thickness on both sides of the conductive fiber web, and the remaining conductive adhesive layer was rested. The part produced an electromagnetic shielding material disposed inside the conductive fibrous web.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un matériau souple de blindage contre les ondes électromagnétiques. Un matériau de blindage contre les ondes électromagnétiques, selon un mode de réalisation de la présente invention, comprend : une bande de fibres conductrices comprenant des fibres composites conductrices comprenant une partie d'enveloppe métallique revêtue sur l'extérieur d'une partie de fibres pour former une pluralité de pores ; et un premier composant conducteur disposé dans au moins certains des pores. En raison de ces caractéristiques, étant donné que le matériau de blindage contre les ondes électromagnétiques présente d'excellentes propriétés d'élasticité et de plissage/récupération, il est possible d'en modifier librement la forme selon les besoins et de fixer le matériau de blindage contre les ondes électromagnétiques pour qu'il adhère complètement à une surface même si la surface sur laquelle doit être disposé le matériau a une forme courbée telle qu'une surface irrégulière ou étagée, et il est ainsi possible d'obtenir une excellente performance de blindage contre les ondes électromagnétiques. De plus, l'invention permet d'empêcher une dégradation de la performance de blindage contre les ondes électromagnétiques même avec diverses modifications de forme. En outre, même lorsque des parties sont montées avec une haute densité dans une zone étroite, le matériau de blindage contre les ondes électromagnétiques peut être disposé pour adhérer complètement aux parties montées tout en surmontant des intervalles d'espacement serrés et des étages entre les parties, ce qui permet d'adopter facilement le matériau souple de blindage contre les ondes électromagnétiques pour un dispositif électronique compact ou flexible.
PCT/KR2017/014552 2016-12-12 2017-12-12 Matériau souple de blindage contre les ondes électromagnétiques, module de circuit de type à blindage contre les ondes électromagnétiques le comprenant et dispositif électronique équipé de ce dernier Ceased WO2018110941A1 (fr)

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US16/468,801 US10945358B2 (en) 2016-12-12 2017-12-12 Flexible electromagnetic wave shielding material, electromagnetic wave shielding type circuit module comprising same and electronic device furnished with same

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CN115465568A (zh) * 2022-10-08 2022-12-13 苏州盛达飞智能科技股份有限公司 一种软质电磁屏蔽包装材料

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