WO2023032574A1 - Élément de blindage contre les ondes électromagnétiques - Google Patents

Élément de blindage contre les ondes électromagnétiques Download PDF

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Publication number
WO2023032574A1
WO2023032574A1 PCT/JP2022/029772 JP2022029772W WO2023032574A1 WO 2023032574 A1 WO2023032574 A1 WO 2023032574A1 JP 2022029772 W JP2022029772 W JP 2022029772W WO 2023032574 A1 WO2023032574 A1 WO 2023032574A1
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Prior art keywords
conductive filler
electromagnetic wave
wave shielding
liquid crystalline
shielding member
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PCT/JP2022/029772
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English (en)
Japanese (ja)
Inventor
昭宏 長永
真奈 中村
光博 望月
宏光 青藤
Original Assignee
ポリプラスチックス株式会社
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Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to CN202280058304.6A priority Critical patent/CN117882502A/zh
Priority to JP2023517301A priority patent/JPWO2023032574A1/ja
Priority to KR1020247007368A priority patent/KR20240058096A/ko
Publication of WO2023032574A1 publication Critical patent/WO2023032574A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the present invention relates to electromagnetic shielding members.
  • Liquid crystalline resins represented by liquid crystalline polyester resins, have well-balanced mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and are widely used as high-performance engineering plastics due to their excellent dimensional stability. It's being used. Further, for example, Patent Document 1 discloses a liquid crystal polyester resin composition having excellent moldability, and a molded article obtained by molding the liquid crystal polyester resin composition has excellent electromagnetic wave shielding properties and electrical insulation properties. , it is also disclosed that it is useful for members related to electronic equipment.
  • a liquid crystalline resin composition can be mentioned as a candidate for the conductive material as described above.
  • the conventional liquid crystalline resin compositions do not have sufficient electromagnetic wave shielding properties, and their high melt viscosities lead to insufficient moldability.
  • the present invention has been made to solve the above problems, and its object is to provide an electromagnetic shielding member molded from a liquid crystalline resin composition having excellent moldability and having excellent electromagnetic shielding properties. It is in.
  • a molded body of a liquid crystalline resin composition containing a liquid crystalline resin, a fibrous conductive filler, and a granular conductive filler, and the fibrous conductive filler and the granular conductive filler is within a predetermined range, the mass ratio of the content of the fibrous conductive filler to the content of the granular conductive filler is within a predetermined range, and the predetermined electromagnetic shielding property is within a predetermined range
  • the present invention provides the following.
  • An electromagnetic wave shielding member comprising a molding of a liquid crystalline resin composition containing (A) a liquid crystalline resin, (B) a fibrous conductive filler, and (C) a granular conductive filler.
  • the total content of the (B) fibrous conductive filler and the (C) granular conductive filler is 15 to 60% by mass
  • the mass ratio of the content of the fibrous conductive filler (B) to the content of the granular conductive filler (C) is 0.30 to 22.0
  • the electromagnetic wave shielding member has an electromagnetic wave shielding property of 35 dB or more at a frequency of 100 MHz, as measured according to the KEC method.
  • the total content of the (B) fibrous conductive filler and the (C) granular conductive filler is 20 to 50% by mass;
  • the (B) fibrous conductive filler is carbon fiber, The electromagnetic wave shielding member according to (1) or (2), wherein the (C) granular conductive filler is carbon black.
  • the (D) non-conductive filler is selected from the group consisting of talc, mica, glass flakes, silica, glass beads, glass balloons, potassium titanate whiskers, calcium silicate whiskers, milled glass fibers, and glass fibers.
  • an electromagnetic shielding member that is molded from a liquid crystalline resin composition that is excellent in moldability and that is excellent in electromagnetic shielding properties.
  • the electromagnetic wave shielding member of the present invention comprises a molded body of a liquid crystalline resin composition containing (A) a liquid crystalline resin, (B) a fibrous conductive filler, and (C) a granular conductive filler.
  • the total content of the (B) fibrous conductive filler and the (C) granular conductive filler is 15 to 60% by mass, and the content of the (C) granular conductive filler
  • the mass ratio of the content of the fibrous conductive filler (B) is 0.30 to 22.0, and the electromagnetic wave shielding property at a frequency of 100 MHz, measured according to the KEC method, is 35 dB or more.
  • the electromagnetic wave shielding member according to the present invention is molded from a liquid crystalline resin composition having excellent moldability, and has excellent electromagnetic wave shielding properties.
  • the electromagnetic shielding member according to the present invention has an electromagnetic shielding property of 35 dB or more at a frequency of 100 MHz, which is measured according to the KEC method, and is excellent in electromagnetic shielding property.
  • the electromagnetic shielding property is preferably 37 dB or more, more preferably 38 dB or more.
  • the electromagnetic wave shielding member of the present invention can be suitably used for applications requiring excellent electromagnetic wave shielding properties.
  • audio equipment parts e.g., audio, laser disc (registered trademark), compact disc, digital video disc, etc.
  • Office computer-related parts Office computer-related parts, telephone-related parts, facsimile-related parts, printer/copier-related parts such as print heads and transfer rolls, cleaning jigs, motor parts, microscope parts, binocular parts, camera parts, watch parts, etc.
  • alternator terminals for light dimmers, motor core sealing materials, insulator parts, power seat gear housings, thermostat bases for air conditioners, air conditioner panel switch substrates, Horn terminals, insulating plates for electrical parts, lamp housings, ignition device cases, air pressure sensors, fuse connectors, vehicle speed sensors, and other automotive and vehicle related parts; It can be particularly suitably used for information communication-related parts such as chip antennas, wireless LAN antennas, ETC (Electric Toll Collection System) antennas, and satellite communication antennas.
  • ETC Electronic Toll Collection System
  • the (A) liquid crystalline resin used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase.
  • the anisotropic melt phase properties can be confirmed by conventional polarimetry using crossed polarizers. More specifically, confirmation of the anisotropic molten phase can be carried out by using a Leitz polarizing microscope and observing the molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • a liquid crystalline polymer applicable to the present invention normally transmits polarized light and exhibits optical anisotropy when inspected between crossed polarizers even in a molten state.
  • the type of (A) liquid crystalline resin as described above is not particularly limited, and aromatic polyesters and/or aromatic polyesteramides are preferable. Polyesters that partially contain aromatic polyesters and/or aromatic polyesteramides in the same molecular chain are also within the scope.
  • the liquid crystalline resin is preferably at least about 2.0 dl/g, more preferably 2.0 to 10.0 dl/g when dissolved in pentafluorophenol at 60° C. at a concentration of 0.1% by mass. of logarithmic viscosity (I.V.) is preferably used.
  • the aromatic polyester or aromatic polyester amide as (A) the liquid crystalline resin applicable to the present invention particularly preferably contains a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof. It is an aromatic polyester or an aromatic polyester amide having as a constituent component.
  • Polyester mainly composed of structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof; (2) Mainly (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof A polyester consisting of a structural unit derived from at least one selected from the group consisting of; (3) Mainly (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof and (c) a structural unit derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.
  • Amide; (5) A group consisting mainly of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic hydroxyamines, aromatic diamines, and derivatives thereof (c) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; and (d) and a structural unit derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.
  • a molecular weight modifier may be used in combination with the above constituents, if necessary.
  • Preferred examples of specific compounds constituting (A) the liquid crystalline resin applicable to the present invention include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxy Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I), and compounds represented by the following general formula (II) ; 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and aromatics such as compounds represented by the following general formula (III) dicarboxylic acids; p-aminophenol, p-phenylenediamine, N-acetyl-p-aminophenol and other aromatic amines.
  • X A group selected from alkylene (C 1 to C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—.
  • the liquid crystalline resin (A) used in the present invention can be prepared by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers), and usually a melt polymerization method. , a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or a combination of two or more thereof is used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used.
  • the above-mentioned compounds having ester-forming ability may be used for polymerization as they are, or may be modified from precursors to derivatives having said ester-forming ability in the pre-polymerization stage.
  • catalysts can be used in these polymerizations, and representative ones include potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris ,4-pentanedionato)cobalt (III), and organic compound catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.
  • the amount of catalyst used is generally about 0.001 to 1% by weight, preferably about 0.01 to 0.2% by weight, based on the total weight of the monomers.
  • Polymers produced by these polymerization methods can be further increased in molecular weight by solid phase polymerization in which heating is performed under reduced pressure or in an inert gas, if necessary.
  • the melt viscosity of (A) the liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 3 Pa ⁇ s or more and 500 Pa ⁇ s or less at a shear rate of 1000 sec ⁇ 1 can be used. However, if the viscosity is too high per se, the fluidity will be greatly deteriorated, which is not preferable.
  • the liquid crystalline resin (A) may be a mixture of two or more liquid crystalline resins.
  • the content of (A) the liquid crystalline resin is preferably 40 to 85% by mass, more preferably 50 to 80% by mass, and even more preferably 60.5 to 80% by mass. It is 79.5% by mass.
  • the content of component (A) is within the above range, it is preferable in terms of fluidity, heat resistance, and the like.
  • the liquid crystalline resin composition according to the present invention contains a fibrous conductive filler.
  • a fibrous conductive filler can be used individually by 1 type or in combination of 2 or more types.
  • the average fiber length of the fibrous conductive filler is not particularly limited, and from the viewpoint of conductivity, it may be, for example, 50 ⁇ m or more and 10 mm, 80 ⁇ m or more and 8 mm, or 100 ⁇ m or more and 7 mm.
  • the average fiber length of the fibrous conductive filler is obtained by taking 10 stereomicroscopic images of the fibrous conductive filler from a CCD camera into a PC and using an image measuring device to perform image processing. Therefore, the average of the values obtained by measuring the fiber lengths of 100 fibrous conductive fillers, that is, a total of 1000 fibrous conductive fillers, is adopted for each stereoscopic microscope image.
  • the average fiber length of the fibrous conductive filler (B) in the liquid crystalline resin composition is the fibrous conductive filler remaining after incineration by heating the liquid crystalline resin composition at 500 ° C. for 4 hours. Measured by applying the method.
  • the fiber diameter of the fibrous conductive filler is not particularly limited, and from the viewpoint of conductivity, it may be, for example, 0.2 to 15 ⁇ m, 0.25 to 13 ⁇ m, or 0.3 to 11 ⁇ m.
  • the fiber diameter of the fibrous conductive filler (B) is determined by observing the fibrous conductive filler with a scanning electron microscope and determining the fiber diameter of 30 fibrous conductive fillers. Take the average of the measured values.
  • the fiber diameter of the (B) fibrous conductive filler in the liquid crystalline resin composition is determined by the above method for the fibrous conductive filler remaining after incineration by heating the liquid crystalline resin composition at 500 ° C. for 4 hours. is measured by applying
  • fibrous conductive fillers examples include carbon fibers; conductive fibers such as metal fibers; inorganic fibrous substances, etc., coated with metals such as nickel and copper to impart conductivity. , carbon fiber is preferable from the viewpoint of conductivity.
  • carbon fibers examples include PAN-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from pitch.
  • metal fibers examples include fibers made of mild steel, stainless steel, steel and its alloys, copper, brass, aluminum and its alloys, titanium, lead, and the like. These metal fibers may be coated with other metals to provide further conductivity if required due to their conductivity.
  • inorganic fibrous substances examples include glass fiber, milled glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, calcium silicate whisker ( fibrous wollastonite) and the like.
  • the liquid crystalline resin composition according to the present invention contains a granular conductive filler.
  • Granular conductive fillers can be used singly or in combination of two or more.
  • the median diameter of the particulate conductive filler is not particularly limited, and from the viewpoint of conductivity, it may be, for example, 10 nm or more and 50 ⁇ m or less, 15 nm or more and 20 ⁇ m or less, or 18 nm or more and 10 ⁇ m or less.
  • the median diameter refers to the volume-based median value measured by a laser diffraction/scattering particle size distribution measurement method.
  • Granular conductive fillers include carbon black, granular metal powders (e.g., aluminum, iron, copper), granular conductive ceramics (e.g., zinc oxide, tin oxide, indium tin oxide) and the like. Carbon black is preferred from the viewpoint of properties. Carbon black is not particularly limited as long as it is generally available for coloring resins. Generally, carbon black contains lumps formed by agglomeration of primary particles. A large number of bumps (fine bumpy projections (fine irregularities) formed by agglomeration of carbon black) are less likely to occur on the surface of the molded product. When the content of particles having a particle size of 50 ⁇ m or more is 20 ppm or less, the smoothness of the surface of the molded article tends to be high. A preferable content is 5 ppm or less.
  • the total content of (B) the fibrous conductive filler and (C) the granular conductive filler is 15 to 60% by mass, preferably 20 to 50% by mass, in the liquid crystalline resin composition of the present invention. %, more preferably 20.5 to 39.5% by mass.
  • the total content is 15% by mass or more, it is easy to obtain a molded article with improved electromagnetic wave shielding properties.
  • the total content is 60% by mass or less, the fluidity of the liquid crystalline resin composition is likely to be improved, and a liquid crystalline resin composition having excellent moldability can be easily obtained.
  • the mass ratio of the content of the fibrous conductive filler (B) to the content of the granular conductive filler (C) is 0.30 to 22.0, preferably 0.40 to 21.0. Yes, more preferably 0.50 to 20.0.
  • the mass ratio is 0.30 or more, the fluidity of the liquid crystalline resin composition is likely to be improved, and a liquid crystalline resin composition having excellent molding processability is easily obtained, and a molded article having improved electromagnetic wave shielding properties is obtained. Easy to get.
  • the mass ratio is 20.0 or less, it is easy to obtain a molded article with improved electromagnetic wave shielding properties.
  • the liquid crystalline resin composition according to the present invention may contain a non-conductive filler.
  • a non-conductive filler can be used individually by 1 type or in combination of 2 or more types.
  • Non-conductive fillers include, for example, plate-shaped non-conductive fillers, granular non-conductive fillers, and fibrous non-conductive fillers.
  • the median diameter of the plate-shaped non-conductive filler is not particularly limited, and may be, for example, 10 to 100 ⁇ m, 12 to 50 ⁇ m, or 14 to 30 ⁇ m. From the viewpoint of electromagnetic wave shielding properties, the electromagnetic wave shielding member according to the present invention has a volume resistivity that is an index of conductivity, regardless of the thickness of the molded body, even if it is composed of a molded body having a complicated shape. is preferably small.
  • the plate-shaped non-conductive filler has a median diameter of 10 to 100 ⁇ m, the thickness dependence of the electrical conductivity of the molded article is likely to be reduced, and a molded article having a small variation in volume resistivity regardless of the thickness is easily obtained.
  • Plate-shaped non-conductive fillers include, for example, talc, mica, glass flakes, and the like.
  • the median diameter of the granular non-conductive filler is not particularly limited, and may be, for example, 0.3 to 50 ⁇ m, 0.4 to 25 ⁇ m, or 0.5 to 5.0 ⁇ m.
  • the median diameter of the granular non-conductive filler is 0.3 to 50 ⁇ m, the thickness dependence of the conductivity of the molded body is likely to be reduced, and the molded body with small fluctuations in volume resistivity is easily obtained regardless of the thickness. .
  • Granular non-conductive fillers include, for example, silica, quartz powder, glass beads, glass balloons, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, silicates such as wollastonite; , titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide; silicon nitride;
  • the average fiber length of the fibrous non-conductive filler is not particularly limited, and may be, for example, 50 ⁇ m to 10 mm, 80 ⁇ m to 7 mm, or 100 ⁇ m to 4 mm.
  • the fiber diameter of the fibrous non-conductive filler is not particularly limited, and may be, for example, 0.2 to 15 ⁇ m, 0.25 to 13 ⁇ m, or 0.3 to 11 ⁇ m.
  • the fiber diameter of the fibrous non-conductive filler is 0.2 to 15 ⁇ m, the thickness dependence of the conductivity of the molded article is easily reduced, and a molded article with small volume resistivity fluctuation regardless of the thickness can be obtained.
  • the average fiber length of the fibrous non-conductive filler and the fiber diameter of the fibrous non-conductive filler are each the values measured in the same manner as described above for (B) the fibrous conductive filler. Take the average.
  • fibrous non-conductive fillers examples include glass fiber, milled glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, silica
  • fibrous non-conductive fillers include glass fiber, milled glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, silica
  • inorganic fibrous substances such as calcium acid whiskers (fibrous wollastonite).
  • the (D) non-conductive filler is preferably talc, because the thickness dependence of the conductivity of the molded body is more likely to be reduced, and a molded body with small fluctuations in volume resistivity is more likely to be obtained regardless of the thickness.
  • the content of the non-conductive filler in the liquid crystalline resin composition of the present invention is preferably 2 to 8% by mass, more preferably 2.3 to 7.7% by mass, and still more It is preferably 2.5 to 7.5% by mass.
  • the content is 2 to 8% by mass, the fluidity of the liquid crystalline resin composition is likely to be improved, and a liquid crystalline resin composition having excellent moldability can be easily obtained.
  • the liquid crystalline resin composition of the present invention may contain other polymers, other fillers, and known substances generally added to synthetic resins, such as antioxidants and ultraviolet absorbers, as long as they do not impair the effects of the present invention.
  • Other ingredients such as stabilizers such as agents, antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants, crystallization accelerators, crystal nucleating agents, release agents, etc. may be added as appropriate according to the required performance. can be done.
  • Other components may be used singly or in combination of two or more.
  • polymers include, for example, epoxy group-containing copolymers. Other polymers may be used singly or in combination of two or more.
  • fillers refer to fillers other than (B) fibrous conductive fillers, (C) granular conductive fillers, and (D) non-conductive fillers, for example, (B) components and ( C) Conductive fillers other than the component can be mentioned. Other fillers may be used singly or in combination of two or more. Examples of conductive fillers other than components (B) and (C) include plate-like conductive fillers.
  • the method for preparing the liquid crystalline resin composition of the present invention is not particularly limited.
  • the components (A) to (C), optionally the component (D), and optionally at least one of the other components are blended, and these are melted using a single-screw or twin-screw extruder.
  • the liquid crystalline resin composition is prepared by kneading.
  • the liquid crystalline resin composition of the present invention obtained as described above preferably has a melt viscosity of 180 Pa ⁇ sec or less, more preferably 145 Pa ⁇ sec or less, from the viewpoint of fluidity when melted and moldability. and more preferably 140 Pa ⁇ sec or less.
  • the melt viscosity is a value obtained by a measurement method according to ISO 11443 under the conditions of a cylinder temperature 10 to 20° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁇ 1 .
  • the stirring torque reached a predetermined value, nitrogen was introduced to increase the pressure from reduced pressure to normal pressure to pressurized state, the polymer was discharged from the bottom of the polymerization vessel, and the strand was pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300° C. for 2 hours in a nitrogen stream to obtain the desired polymer.
  • the obtained polymer had a melting point of 336° C. and a melt viscosity at 350° C. of 19.0 Pa ⁇ s.
  • the melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described below.
  • HBA 4-hydroxybenzoic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • TA 1,4-phenylene dicarboxylic acid
  • BP 4,4'-dihydroxybiphenyl
  • APAP N-acetyl-p-aminophenol
  • Metal catalyst potassium acetate catalyst
  • 110 mg Acylating agent acetic anhydride
  • the temperature of the reaction system was raised to 140° C., and the reaction was carried out at 140° C. for 1 hour. After that, the temperature was further raised to 360°C over 5.5 hours, and the pressure was reduced to 5 Torr (that is, 667 Pa) over 20 minutes to distill off acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reaches a predetermined value, nitrogen is introduced to increase the pressure from reduced pressure to normal pressure to pressurized state, the polymer is discharged from the bottom of the polymerization vessel, and the strand is pelletized to obtain the target polymer as pellets.
  • Talc Crown talc PP (manufactured by Matsumura Sangyo Co., Ltd., talc, median diameter 14.6 ⁇ m) ⁇ Mica: AB-25S (manufactured by Yamaguchi Mica Co., Ltd., mica, median diameter 25.0 ⁇ m)
  • Silica Denka fused silica FB-5SDC (manufactured by Denka Co., Ltd., silica, median diameter 4.0 ⁇ m)
  • ⁇ Glass fiber ECS03T-786H (man
  • compositions of Examples have low melt viscosities and high fluidity, so it is confirmed that they are excellent in moldability. It was confirmed that the molded article obtained was excellent in electromagnetic wave shielding properties.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un élément de blindage contre les ondes électromagnétiques ayant d'excellentes propriétés de blindage contre les ondes électromagnétiques, qui est constitué d'une composition de résine cristalline liquide ayant une excellente aptitude au moulage.　Cet élément de blindage contre les ondes électromagnétiques est constitué d'une composition de résine cristalline liquide comprenant une résine cristalline liquide (A), une charge conductrice fibreuse (B) et une charge conductrice granulaire (C), la teneur totale en charge conductrice fibreuse (B) et en charge conductrice granulaire (C) étant de 15 à 60 % en masse, le rapport massique de la teneur en charge conductrice fibreuse (B) à la teneur en charge conductrice granulaire (C) étant de 0,30 à 22,0, et l'élément de blindage contre les ondes électromagnétiques ayant une propriété de blindage contre les ondes électromagnétiques d'au moins 35 dB à une fréquence de 100 MHz, telle que mesurée selon la méthode KEC.
PCT/JP2022/029772 2021-08-31 2022-08-03 Élément de blindage contre les ondes électromagnétiques WO2023032574A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202280058304.6A CN117882502A (zh) 2021-08-31 2022-08-03 电磁波屏蔽构件
JP2023517301A JPWO2023032574A1 (fr) 2021-08-31 2022-08-03
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JPH0987417A (ja) * 1995-09-22 1997-03-31 Kobe Steel Ltd 導電性薄肉樹脂成形品
JPH09279003A (ja) * 1996-04-10 1997-10-28 Teijin Chem Ltd 導電性樹脂組成物および成形品
JP2001316572A (ja) * 2000-05-08 2001-11-16 Teijin Ltd 電磁波シールド用樹脂組成物
JP2002158487A (ja) * 2000-11-20 2002-05-31 Nok Corp グロメット
JP2004035826A (ja) * 2002-07-05 2004-02-05 Yuka Denshi Co Ltd 高導電性樹脂成形品
JP2011192714A (ja) * 2010-03-12 2011-09-29 Aisin Chemical Co Ltd 電磁波シールド材
JP2011207981A (ja) * 2010-03-29 2011-10-20 Mitsubishi Chemicals Corp 電磁波シールド性ポリアミド樹脂組成物及びその成形品
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