WO2014193169A1 - Procédé de préparation pour un matériau composite de blindage contre une onde électromagnétique utilisant une fibre de carbone plaquée de cuivre et de nickel préparée par des processus continus anélectrolytique et électrolytique, et matériau composite de blindage contre une onde électromagnétique - Google Patents

Procédé de préparation pour un matériau composite de blindage contre une onde électromagnétique utilisant une fibre de carbone plaquée de cuivre et de nickel préparée par des processus continus anélectrolytique et électrolytique, et matériau composite de blindage contre une onde électromagnétique Download PDF

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Publication number
WO2014193169A1
WO2014193169A1 PCT/KR2014/004789 KR2014004789W WO2014193169A1 WO 2014193169 A1 WO2014193169 A1 WO 2014193169A1 KR 2014004789 W KR2014004789 W KR 2014004789W WO 2014193169 A1 WO2014193169 A1 WO 2014193169A1
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WIPO (PCT)
Prior art keywords
resin
copper
carbon fiber
electroless
weight
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Application number
PCT/KR2014/004789
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English (en)
Korean (ko)
Inventor
이종길
허수형
박민영
강병록
강지훈
Original Assignee
주식회사 불스원신소재
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Priority claimed from KR20130159979A external-priority patent/KR101469683B1/ko
Application filed by 주식회사 불스원신소재 filed Critical 주식회사 불스원신소재
Priority to CN201480030964.9A priority Critical patent/CN105284199B/zh
Priority to JP2016516447A priority patent/JP6341994B2/ja
Priority to US14/894,250 priority patent/US9890280B2/en
Publication of WO2014193169A1 publication Critical patent/WO2014193169A1/fr
Priority to US15/856,237 priority patent/US10385208B2/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding

Definitions

  • the present invention relates to a method for producing an electromagnetic wave shielding composite using copper and nickel plated carbon fibers produced by an electroless and electrolytic continuous process, and to an electromagnetic wave shielding composite. .
  • electromagnetic waves represent a serious hazard directly to the human body.
  • These electromagnetic waves are divided into high frequencies generated by various home appliances such as mobile phones, radars, TVs, and microwave ovens, and low frequencies generated by home and industrial power generation.
  • electromagnetic waves generated in the high frequency band of 100 MHz to several GHz are generated. Hazards caused by humans have been raised.
  • the unit representing the shielding effect of electromagnetic waves is expressed in decibels (dB) and means the electromagnetic field strength ratio before and after shielding.
  • the effect of 20 dB is the amount of electromagnetic waves At 1/10, 40 dB means the amount of electromagnetic waves is reduced to 1/100. In general, it is judged that the shielding effect is good when it is 30 to 40 dB or more.
  • regulations are being strengthened around the world, and each country is strengthening regulations related to EMI.
  • a metal substrate is used for electromagnetic shielding, or a coating or plating having conductivity on the substrate is used.
  • Metal substrates are disadvantageous in that the processing of complex patterns is disadvantageous and weighty.
  • the plating on the substrate is disadvantageous in productivity due to complicated processes such as degreasing, etching, thickening activation, accelerators, metal deposition, activation, and plating 1-3.
  • shielding materials using fillers such as carbon nanotubes, metal powders, flaxes, ferrites, and the like have been reported, but disadvantages such as dispersibility, processability, and electromagnetic shielding efficiency have been reported.
  • the metal layer is applied to the layered material, but the plating method of the conductive powder is difficult, and the productivity and production price are high.
  • an object of the present invention is to provide a method for producing an electromagnetic wave shielding composite using copper and nickel plated carbon fibers in a continuous process of thermoplastic resin and electroless and electrolytic plating. .
  • Another object of the present invention is to provide a method for producing an electromagnetic wave shielding composite using a copper and nickel plated carbon fiber in a continuous process of thermosetting resin and electroless and electrolytic plating.
  • Another object of the present invention is to provide an electromagnetic shielding composite prepared by the method of the present invention described above. "Detailed description of the invention below is a further object and advantage of the present invention become apparent from the claims and the drawings.
  • the present invention provides a method for producing an electromagnetic wave shielding composite comprising the following steps: (a) 50-90 wt% thermoplastic resin and copper and nickel plated in an electroless and electrolytic continuous process; Mixing 10-50% by weight carbon fiber; And (b) injection or extrusion molding the resultant of step (a) to obtain an electromagnetic shielding composite.
  • the present invention provides a method for producing an electromagnetic wave shielding composite, comprising the following steps: (a) 50-90 wt% of a thermosetting resin and copper and nickel plated in an electroless and electrolytic continuous process; Mixing 10-50% by weight of carbon fibers; And (b) ejecting and molding the resultant of step (a) to obtain an electromagnetic shielding composite.
  • the present inventors want to develop a composite having excellent electromagnetic shielding performance I tried.
  • a combination of copper and nickel-plated carbon fibers with thermoplastic or thermosetting resins is produced by injection, extrusion, or ejection molding in an electroless and electrolytic continuous process. It was confirmed that the excellent.
  • the present invention provides the electromagnetic wave shielding composite by largely mixing (i) (i-1) thermoplastic resin or (i-2) thermosetting resin and (ii) copper and nickel plated carbon fiber in a continuous electroless and electrolytic process. do.
  • thermoplastic resin a process for producing an electromagnetic wave shielding composite using a thermoplastic resin is as follows:
  • thermoplastics with copper and nickel plated carbon fibers (a) Compatibility of thermoplastics with copper and nickel plated carbon fibers
  • the process of the present invention involves mixing 50-90% by weight of thermoplastic resin with 10-50% by weight of copper and nickel plated carbon fibers in an electroless and electrolytic continuous process.
  • the thermoplastic resin is used after drying using various dryers known in the art, such as a hot air dryer (a dryer).
  • a hot air dryer a dryer
  • thermoplastic resin used in the present invention forms a matrix, but when the content thereof is less than 50% by weight, moldability and physical properties are deteriorated, and when the content exceeds 90% by weight, the volume resistivity and the electromagnetic shielding performance are poor. There is a problem falling.
  • the content of the mixture of step (a) is 70-90% by weight of thermoplastic resin and 10-30% by weight of copper and nickel plated carbon fiber, more preferably thermoplastic resin 70-80 20% by weight and 20-30% by weight copper and nickel plated carbon fiber.
  • thermoplastic resin used in the present invention may use a variety of thermoplastic resins known in the art, and preferably, polycarbonate resin, polystyrene resin, polyether resin, polysulfone resin, polyolefin resin, polyimide Resin, fluorine resin, poly (meth) acrylate resin, At least one thermoplastic resin is selected from the group consisting of polyacetal resins, polyamide resins, aromatic vinyl resins, acrylic-butadiene-styrene copolymer resins and polyvinyl chloride resins, more preferably PP (Polypropylene), PA6 (Polyamide6), PC (Polycarbonate) and ABS (acrylonitrile butadiene styrene resin) selected from the group consisting of at least one, more preferably PP, PA6, PC, PC and ABS, or ABS.
  • polycarbonate resin polystyrene resin
  • polyether resin polysulfone resin
  • polyolefin resin polyimide Resin
  • fluorine resin
  • carbon fiber used in the present invention various carbon fibers known in the art may be used, and commercially available ones may be used, or those manufactured from PAN or pitch systems may be used.
  • the average diameter of the high conductivity carbon fiber is 7 ⁇ , including the plating thickness of the 25 m to 9.5 urn, especially the fiber diameter It is not limited to the scope of the present invention.
  • the high conductive carbon fiber produced can be processed in a chopped state as shown in FIG. 4 to increase processability and dispersibility with the resin.
  • the content of the copper and nickel-plated carbon fiber used in the present invention is less than 10% by weight, there is a disadvantage that the electromagnetic shielding performance is lowered, and when the content of more than 50% by weight, the physical properties of the composite, the workability and economical efficiency is reduced.
  • the copper and nickel plated carbon fibers of step (a) are 3 mm to 500 mm in length in chopped form.
  • the result of step (a) additionally comprises a conductive material selected from the group consisting of ferrite and metal plated bars.
  • the conductive material may be included in the electromagnetic shielding composite of the present invention for the purpose of lowering the surface resistance and enhancing the internal conductivity of the composite.
  • the result of step (a) is 40-89.5% by weight of thermoplastic resin, 10-50% by weight of copper and nickel plated carbon fiber. And 0.5-10% by weight of conductive material, and even more preferably 67-89% by weight of thermoplastic resin, 10-30% by weight of copper and nickel plated carbon fiber and 1-3% by weight of conductive material. Include.
  • the metal plated on the graphite is aluminum, iron, crumb, stainless, copper, nickel, block nickel, silver, gold, platinum, palladium, tin, cobalt and two or more alloys thereof At least one metal is selected from the group consisting of, and more preferably at least one metal is selected from the group consisting of aluminum, crumb, copper, nickel, silver, platinum, paralymium, tin, cobalt and two or more alloys thereof. More preferably copper, nickel, palladium or tin, most preferably nickel.
  • the mixing of the step (a) is selected from the group consisting of carbon filler, flame retardant, plasticizer, coupling agent, heat stabilizer, light stabilizer, inorganic filler, mold release agent, dispersant, anti-dropping agent and weathering stabilizer It further comprises one or more additives.
  • the method of the present invention comprises the steps of (a) and (b) (a-1) to prepare the compounding pellets using an extruder for making a pellet using the product of step (a). It further comprises a step.
  • the compounding pellets are prepared using an extruder at conditions of temperature 230-255 ° C and speed 70-150 rpm.
  • the extruder may use an extruder for producing a variety of pellets known in the art, the extrusion conditions are divided into five sections of the temperature section of the extruder 230 ° C, 245 ° C, 245 ° C, 245 ° C and 255 Set at ° C and the speed 8 to 120 rpm conditions are more preferred.
  • step (a) the method of the present invention is subjected to the step of obtaining the electromagnetic shielding composite by injection or extrusion molding the result of step (a).
  • Injection molding of the step (b) is preferably carried out using an injection machine under conditions of temperature 215-275 ° C, speed 40-70 rpm, pressure 40-80 bar and mold cooling time 4-12 seconds, more preferably Divide the temperature section of the injection machine into 5 sections and set it at 215-255 ° C, 220-265 ° C, 220-265 ° C, 220-265 ° C and 230-275 ° C respectively, and the speed 50-60rpm, pressure 50-70 bar and mold engraving time 6–10 seconds.
  • the injection machine used for injection molding may use various injection machines known in the art.
  • the copper and nickel-plated carbon fibers of the step (a) are 3 to 20 ⁇ in chopped form.
  • Preferred, more preferably 3 kPa to 12 kPa in chopped form, even more preferably 3 mm to 9 kPa in chopped form, even more preferably chopped ) Is 5 kPa to 7 kPa in length.
  • the extrusion of the step (b) is preferably carried out using an extruder under the conditions of temperature 230-265 ° C and speed 30-60 rpm, More preferably, the silver section of the extruder is divided into five sections, each of which is set at 230 ° C, 255 ° C, 255 ° C, 255 ° C and 265 ° C, using a T-dice at a speed of 4 and 50 rpm.
  • the extruder used for the extrusion may use various extruders known in the art.
  • the copper and nickel plated carbon fibers of step (a) are preferably 3 kPa to 30 kPa in the chopped form because they are made in film or sheet form. More preferably, the length is 6 mm to 18 mm in the chopped form, and even more preferably the length is 9 mm to 15 mm in the chopped form.
  • electromagnetic shielding composites can be prepared by mixing and molding (i) thermoplastic resins and ( ⁇ ) copper and nickel plated carbon fibers in an electroless and electrolytic continuous process.
  • a process for producing an electromagnetic wave shielding composite using a thermosetting resin is as follows:
  • thermoplastic resin of the present invention The manufacturing process of the electromagnetic wave shielding composite material using the thermoplastic resin of the present invention described above Common contents between the manufacturing process of the electromagnetic wave shielding composite material using the thermosetting resin, for example, additives such as carbon filler, etc. are excessive complexity of the specification according to the repetitive description. In order to avoid, the description thereof is omitted.
  • the process of the present invention involves the step of mixing 50-90% by weight of thermosetting resin with 10-50% by weight of copper and nickel plated carbon fibers in an electroless and electrolytic continuous process.
  • the content of the mixture of step (a) is 70-90% by weight of thermosetting resin and 10-30% by weight of copper and nickel plated carbon fiber, more preferably thermoplastic resin 75-85 Weight percent and 15-25 weight percent copper and nickel plated carbon fibers.
  • thermosetting resin used in the present invention uses a variety of thermosetting resins known in the art, and uses a liquid phase in view of the characteristics of the resin.
  • the thermosetting resin preferably at least one thermosetting resin is selected from the group consisting of polyurethane resins, epoxy resins, phenolic resins, urea resins, melamine resins and unsaturated polyester resins, and more preferably polyurethane based resins. It is resin, an epoxy resin, or a phenol resin, More preferably, it is a polyurethane resin or an epoxy resin.
  • thermosetting resin copper and nickel plated carbon fibers having a length of 3 kPa to 500 kPa in the form of chopped may be used, and a length of 3 kPa to 60 kPa in the form of chopped is more preferable.
  • the copper and nickel plated carbon fibers are preferably 3 kPa to 20 kPa in chopped form, and 3 kPa to 9 kPa in length in chopped form. More preferably, even more preferably in the form of chopped lengths of 5 to 7 mm in length.
  • an epoxy resin and a curing agent preferably ac l anhydride series
  • the copper and nickel plated carbon fiber is preferably 3 mm to 30 mm in chopped form, more preferably 6 mm to 18 mm in length in chopped form, even more preferably 9 to 15 mm long in chopped form.
  • the mixing may be carried out using a variety of mixers known in the art for dispersibility of carbon fibers in the thermosetting resin, preferably for 30-5 minutes at a speed of 500-1500 rpm.
  • the result of step ( a ) further comprises a conductive material selected from the group consisting of ferrite, abyss and metal plated abyss, more preferably the result of step (a) Silver thermosetting resin 40-89.5 weight 3 ⁇ 4>, 10-50% by weight copper and nickel plated carbon fiber and 0.5-10% by weight conductive material ⁇
  • step (a) the method of the present invention is subjected to the ejection molding the result of step (a) to obtain an electromagnetic wave shielding composite.
  • the ejection molding of step (b) comprises (b-1) ejecting the resultant of the step (b) to a mold or a conveyor; (b-2) curing the discharged product of step (b-1); And (b-3) releasing the cured product of step (b-2).
  • step (b-1) it is preferable to perform mold release treatment on the mold before discharging the thermosetting resin and the copper and nickel-plated carbon fiber mixed solution resulting from the step (b) to the mold or the conveyor.
  • the release treatment can be carried out using various release agents known in the art.
  • the curing of the step (b-2) may be carried out by applying heat, pressure or ultraviolet light.
  • electromagnetic shielding composites can be prepared by mixing and molding (i) thermosetting resins and (ii) copper and nickel plated carbon fibers in a continuous electroless and electrolytic process.
  • the present invention provides the following steps Provided is a method of making an electromagnetic shielding composite comprising: (a) injecting copper and nickel plated carbon fibers into a mold or conveyor in an electroless and electrolytic continuous process; And (b) impregnating the carbon fiber of step (a) with a thermosetting resin to impregnate the electromagnetic shielding composite material.
  • the length is from 30 mm
  • a high-conductivity carbon fiber of 60 mm may be first arranged in a flat mold or a mold, and then a thermosetting resin may be discharged to produce a molded article.
  • Electromagnetic shielding composites produced through these molding processes can be dispersed in a network shape in which the carbon fibers are dispersed with each other-in the molded article, the fibers form a plurality of contact points to connect the fibers and the fibers with each other. Surface resistance and excellent electromagnetic shielding can be obtained.
  • the highly conductive carbon fibers are dispersed in a network in the resin.
  • the electromagnetic wave shielding composite produced by the method of the present invention includes copper and nickel plated carbon fibers in an electroless and electrolytic continuous process, and more electromagnetic waves than those using unplated carbon fibers. The shielding effect is improved.
  • the copper and nickel plated carbon fiber used in the present invention is a highly conductive carbon fiber having excellent electrical conductivity manufactured by the electroless and electrolytic continuous process developed by the present inventors, and manufactured by the following method. '
  • the copper and nickel plated carbon fibers in the electroless and electrolytic continuous process used in the method of the present invention are prepared by a method comprising the following steps: (a) The carbon fibers are subjected to a volume of pure water. Cu-ion 2.5-5.5 g / 1, EDTA 20-55 g / 1, formalin 2.5-4.5 g / 1, TEA (triethanolamine) 2-6 g / 1, concentration 25% NaOH 8-12 ml / 1 and 2,2'-bipiridine containing copper to the carbon fiber for 6 to 10 minutes by passing through an electroless plating solution containing 0.008 ⁇ 0.15 g / 1, pH 12-13 and temperature 36-45 ° C.
  • step (b) the copper plated carbon fiber of step (a).
  • the method of the present invention undergoes electroless plating of metals on carbon fibers.
  • the electroless plating solution when plating copper on carbon fibers, includes pure water, copper metal salts, complexing agents, reducing agents, stabilizers, and pH adjusting agents.
  • the copper metal salt contained in the electroless plating solution supplies copper ions for imparting conductivity to the carbon fiber
  • the reducing agent uses formalin, EDTA as a complexing agent, TEA (triethane amine) as a stabilizer, and 2,2'-.
  • Bipiridine and NaOH with a concentration of 25> were used as a pH adjusting agent.
  • the plating rate was increased as the concentration of formalin, a reducing agent included in the electroless plating solution, and NaOH, a pH adjusting agent, increased, but the life of the plating solution was shortened. The content of was adopted.
  • the content of the copper silver and the complexing agent increases in the same ratio as a result of the plating rate and liquid stability test by controlling the content of the reducing agent, the control of the concentration of copper ions and formalin, reducing agent Plating speed and degree .
  • the thickness of the gold layer can be adjusted, and the specific gravity, strength, elastic modulus and strain can be adjusted by adjusting the thickness of the plating layer.
  • the specific gravity increases, and the strength, elasticity and strain As the strain is lowered, electrolytic plating is carried out together with the concentration control of copper ions and formalin, which is a reducing agent, thereby improving conductivity to a thin thickness, thereby solving the above problems, which is the reason for adopting the electroless and electrolytic continuous process in the present invention. .
  • the electroless plating of step (a) is based on the volume of the carbon fiber, based on the volume of pure water, Cu ions 2.5-3.5 g / 1, EDTA 25-35 g / 1, formalin 2.5-3.5 g / 1, TEA (triethanolamine) 2-3 g / 1, containing 25% NaOH 8-12 ml / 1 and 2,2 1 bipi ridine 0.008-0.01 g / l, passed through an electroless plating solution having a pH of 12-13 and silver of 36-4 CTC It is characterized by plating copper on carbon fiber for 6-10 minutes.
  • the electroless plating step of step (a) is based on the volume of the carbon fiber pure water (cu-ion 2.5-3.5 g / 1, EDTA 20-30 g / 1, formalin 2.5-3.5 g / 1, TEA 2-3 g / 1, concentration 25% NaOH 8-12 ml / 1 and 2,2'-bipiridine 0.008-0.01 g It is characterized by plating copper on carbon fiber for 6-10 minutes by passing through an electroless plating solution containing / l and having a pH of 12-13 and a temperature of 36-40 ° C.
  • the electroless plating step of step (a) is based on the volume of the carbon fiber pure water (pure water) 4.5-5.5 g / 1, EDTA 30-40 g / 1 , Formalin 2.5-3.5 g / 1, TEA (triethane to amine) 4-6 g / 1, concentration 25% NaOH 8-12 ml / 1 and 2,2'-bipiridine 0.01-0.15 g / It comprises 1, characterized in that the copper is plated on the carbon fiber for 6-10 minutes by passing through an electroless plating solution having a pH of 12-13 and a temperature of 40-45 ° C.
  • the step (a) is based on the volume of the carbon fiber pure water (pure water) 4.5-5.5 g / 1, EDTA 30-40 g / 1 , Formalin 2.5-3.5 g / 1, TEA (triethane to amine) 4-6 g / 1, concentration 25% NaOH 8-12 ml / 1 and 2,2'-bipiridine
  • the electroless plating step of (a) uses carbon fibers based on the volume of pure water with Cu ions 4.5-5.5 g / 1, EDTA 45-55 g / 1, formalin 3.5-4.5 g / 1, TEA ( Triethane to amine) 4-6 g / 1, 25% NaOH 8-12 ml / 1 and 2,2'-bipiridine 0.01-0.15 g / 1, pH 12-13 and temperature It is characterized by plating copper on carbon fiber for 6-10 minutes by passing it through an electroless plating solution at 4 ° C.
  • the method of the present invention is to plate the carbon fiber in the electroless plating process of copper, and then to continuously plate the nickel in the electrolytic plating process Go through the steps.
  • One of the features of the present invention is that the electroless plating process followed by the nickel electroplating process improves the electrical conductivity of the carbon fiber.
  • Ni (NH 2 SO 3 ) 2 and NiCl 2 are used as nickel metal salts, and H 3 B0 3 is used as a pH buffer.
  • the electrical resistance value is reduced by about 32-37 times compared to the carbon fiber which is not plated through the electroless and electrolytic continuous process, and the electrical conductivity is improved by about 2 times compared to the comparative example. .
  • the electroplating process of step (b) is performed by applying a constant voltage (CV, 5-15 Volt).
  • the electrolytic plating process is carried out by applying a constant voltage (CV) of 5-10 Volt, more preferably by adding 6-8 Volt.
  • CV constant voltage
  • the advantages of electroless and electrolytic plating are excellent electrical conductivity, and are effective in adhesion and ductility, and attach an electrolytic metal to a space of metals produced by electroless plating, thereby forming an alloy layer having a thin thickness and excellent conductivity. In addition, it has the effect of evenly plating the carbon fibers.
  • the carbon fiber of step ( a ) is characterized in that it is pre-treatment by a method comprising the following steps: (?
  • step U Degreasing and softening the carbon fibers by passing them through an aqueous solution comprising a nonionic surfactant; (ii) the resulting carbon fibers of step U) are converted to sodium bisulfite (NaHS0 3 ), sulfuric acid (S0 4 ), Persulfate Performing an etching process for passing through an aqueous solution comprising ammonium persulfate (NH 4 ) 2 S 2 O 8 ) and pure water for quenching, cleaning and conditioning; (iii) performing a sensitizing process by passing the carbon fiber resulting from step (ii) through an aqueous PdCl 2 solution; And (iv) passing the resultant carbon fiber of step (iii) through an aqueous solution of sulfuric acid (H 2 SO 4 ) to perform an activating process.
  • NaHS0 3 sodium bisulfite
  • S0 4 sulfuric acid
  • Persulfate Performing an etching process for passing through an aqueous solution compris
  • Pretreatment of carbon fibers in the process of the present invention first passes through the carbon fibers through an aqueous solution comprising a surfactant, an organic solvent and a nonionic surfactant to degrease and soften the carbon fibers.
  • the aqueous solution containing the surfactant, the organic solvent and the nonionic surfactant performs a degreasing action to remove the epoxy or urethane sized on the carbon fiber, and at the same time swells and softens the fiber surface.
  • the aqueous solution of step (i) is a surfactant (pure water) and NaOH in a weight ratio of 40-49: 1-10, 15-35% by weight, an organic solvent 50-80% by weight of diethyl propanediol and 5-15% by weight of dipropylene glycol methyl ether, and 400-600 ppm of a non-ionic surfactant, even more preferably 20-30% by weight of a mixture of pure water and NaOH in a weight ratio of 45-48: 2-5 as a surfactant, 58-72% of diethyl propanediol 3 ⁇ 4> and dipropylene glycol as an organic solvent Dipropylene glycol methyl ether 8-12% by weight, and 450-550 ppm nonionic surfactant.
  • a surfactant pure water
  • NaOH in a weight ratio of 40-49: 1-10, 15-35% by weight
  • the nonionic surfactants include various nonionic surfactants known in the art, but preferably ethoxylated linear alcohol, ethoxylated linear a 1 ky 1 ⁇ pheno 1) or ethoxylated linear thiol, and more preferably ethoxylated linear alcohol.
  • (i) is carried out for 1-5 minutes at a temperature of 40-60 ° C, more preferably Carry out 1-3 minutes at 45-55 ° C.
  • pretreatment of the carbon fiber neutralizes the strong alkali component, and performs an etching process to assist the cleaning operation and to condition for the next process, the sensitizing process.
  • Aqueous solutions for the etching process include sodium bisulfite (NaHS0 3 ), sulfuric acid (3 ⁇ 4S0 4 ), ammonium persulfate (NH 4 ) 2 S 2 0 8 ) and pure water do.
  • the aqueous solution of step (ii) is sodium bisulfite (NaHS0 3 ) 0.1-10 weight 3 ⁇ 4>, sulfuric acid (H 2 SO 4 ) 0.1-3% by weight, ammonium persulfate (a ⁇ onium persulfate) (NH 4 ) 2 S2 () 8 ) 5-25 wt% and pure water 62-94.8 wt%, even more preferably sodium bisulfite (NaHS0 3 ) 0.8-2 wt% %, Sulfuric acid (3 ⁇ 4SO 4 ) 0.3-1 weight%, ammonium persulfate (NH 4 ) 2 0 8 ) 10-20 weight% and pure water 77-88.9 weight 3 ⁇ 4>.
  • the step ( ⁇ ) is carried out for 1-5 minutes at temperature 20- 25 ° C, and still more preferably for a period of 1-3 minutes at a temperature of 20-25 ° C .
  • step (ii) the carbon fiber, which is the result of step (ii), is passed through an aqueous PdCl 2 solution to undergo a sensitizing process.
  • the sensitizing process is to allow metal ions to adsorb to the surface of the surface-modified carbon fiber.
  • the concentration of the aqueous Pd ci 2 solution is 10-30%, even more preferably 15-25%.
  • the step (iii) is carried out for 1-5 minutes at a temperature of 20-40 ° C, even more preferably for 1 ⁇ 3 minutes at a temperature of 25-35 ° C. do.
  • the carbon fiber pretreatment method passes the resulting carbon fiber through the aqueous solution of concentrated sulfuric acid (H 2 SO 4 ) to perform an activating process. Conduct .
  • the activation process is described as being performed after the sensitizing process, it is also included in the scope of the present invention to perform in conjunction with the sensitizing process.
  • the activation process is carried out to remove colloidal Sn to prevent oxidation of Pd.
  • the concentration of aqueous sulfuric acid (H 2 SO 4 ) solution is 5-15%.
  • step (iv) is carried out for 1-5 minutes at a temperature of 40-60 ° C., and more preferably for 1-3 minutes at a temperature of 45-55 ° C. .
  • the carbon fibers can be pretreated, and the pretreated carbon fibers can be plated with metals copper and nickel in an electroless and electrolytic continuous process.
  • the present invention provides an electromagnetic shielding composite prepared by the method of the present invention described above.
  • the electromagnetic wave shielding composite material of the present invention is manufactured by the method for producing the electromagnetic wave shielding composite material of the present invention described above, common contents between the two are omitted in order to avoid excessive complexity of the specification according to the repeated description.
  • the electromagnetic wave shielding composite material of the present invention may be inserted into a mobile phone cover or a mobile phone pouch and used to block electromagnetic waves, and may be applied to an LCD protective bracket of a portable display product.
  • the present invention provides a method for producing an electromagnetic wave shielding composite and an electromagnetic shielding composite produced by the method.
  • the present invention can provide an electromagnetic wave shielding composite having excellent conductivity and low surface resistance, suitable for EMI shielding, and having high productivity and economical efficiency by using a highly conductive carbon fiber manufactured by an electroless and electrolytic continuous process.
  • FIG. 1 is a block diagram showing a process for manufacturing the electromagnetic shielding composite material according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional photograph of a highly conductive carbon fiber plated in an electroless and electrolytic continuous process.
  • FIG. 3 is a photograph showing a surface in which a highly conductive carbon fiber in a chopped form is dispersed in a network shape having contacts.
  • FIG. 4 is a photograph of a highly conductive carbon fiber plated in a chopped form in an electroless and electrolytic continuous process.
  • FIG. 5 is a graph showing the electromagnetic shielding effect of the molded article using the carbon fiber produced by a continuous process.
  • FIG. 6 is a view of a specimen for an electromagnetic shielding test.
  • FIG. 7 is a block diagram showing a process of manufacturing an electromagnetic wave shielding composite using a thermosetting resin according to another embodiment of the present invention.
  • FIG 8 shows a surface treatment apparatus for a carbon fiber used in the present invention.
  • (C) as a carbon fiber was used Cu-Ni-plated carbon fiber prepared by applying the electroless and electrolytic continuous process manufactured by Bulls New Materials. The carbon fiber was chopped at 6 mm, 12 mm and 30 mm3. Nickel-plated nickel as another additive was used by Novamet.
  • thermoplastic resin PP grade BJ 700, melt index 25, density 0.91 g / cm 3 , heat distortion temperature 105 ° C, Samsung Total
  • melt index 22 Density 1.2 g / cm 3 , heat deflection temperature 147 ° C., LG Chem
  • ABSCgrade ABS XR401 melt index 9, density 1.05 g / cm 3 , heat deflection temperature 105:, LG Chem
  • thermoplastic resins were then mixed in the amounts shown in Table 1 below. Then, the mixture was injected into a twin injection machine (Wujin, Korea, GT-1 9300) and injected into a mold mold of the standard specified by ASTM D4935.
  • the temperature range was divided into five sections and set at 215 ° C, 220 ° C, 220 ° C, 2201 and 230 ° C, respectively, and 55 rpm, 60 bar, and mold cooling time of 8 seconds.
  • PC and ABS common compound the temperature was set to 255 ° C, 265 'C, 265 ° C, 265' C and 275 ° C, 55 rpm, it was working mold cooling time 8 60 bar, in seconds, the same machine.
  • the fabricated sheet was subjected to electromagnetic shielding experiment and showed the result (Table 1).
  • the components were prepared by injection and extrusion processes in Tables 2 and 3, respectively, and tested for electromagnetic shielding performance.
  • the injection molded parts of Table 2 were prepared by drying PP (grade BJ 700, melt index 25, density 0.91 g / cm 3 , heat deflection temperature 105 ° C, Samsung Total) for 6 hours in an 80 ° C vacuum oven.
  • the mixture was injected into an injection molding having a size specified by ASTM D4935 under the same conditions as in Example 1 to prepare a sheet.
  • Table 2 Table 2
  • the manufacture of the extrusion molded product of Table 3 below was carried out in an 80 ° C vacuum oven for PA6 (grade KOPA KN120, melting point 222 ° C, density 1.14 g / cm 3 , relative viscosity (RV) 2.75, K0L0N Ltd) for 6 hours. Dried. The dried PA6 was mixed with PA6 and copper and nickel plated carbon fibers (12 ms) in the amounts shown in Table 3 below, respectively.
  • PA6 grade KOPA KN120, melting point 222 ° C, density 1.14 g / cm 3 , relative viscosity (RV) 2.75, K0L0N Ltd
  • the mixture was introduced into a pellet manufacturing extruder (twin screw compounding extruder; Bautech, Korea, ⁇ -11) and divided into 5 sections of temperature sections, 230 ° C, 245 ° C, 245 ° C, 245 ° C and It was set to 255 ° C and discharged at 100 rpm to undergo a water cooling process to prepare a composite pellet (pellet).
  • the pellets produced were 0.7 mm thick using T-Dies at 45 rpm at 23 ° C, 255 ° C, 255 ° C, 255 ° C, and 265 ° C in the silver section on a sheet-making extruder manufactured by EcoGreen. A phase molding was obtained.
  • Table 4 is a representative resin of the thermosetting resin using a polyurethane resin and an epoxy resin to impregnate the high-conductive carbon fibers plated with Cu and Ni to prepare a sheet, and measured the electromagnetic shielding performance.
  • Polyurethane PlKgrade UP 395, viscosity 1500 cps, specific gravity 1, one-component urethane, Korea, Kukdo Chemical) and copper and nickel plated carbon fiber (6 mm chop) were weighed in a beaker at a weight ratio of 80: 20, and then at 1000 rpm in a blender. Mixing was carried out for minutes to prepare a mixture solution. The prepared mixture was released (released on a 5 ⁇ glass plate).
  • Epoxy resin is first mixed with (KBR-1753, viscosity 800 cps, Korea, Kukdo Chemical) and hardener (hardener, BH-1089, Acid Anhydride series, Korea, Kukdo Chemical) at an increase ratio of 100: 92.
  • (epoxy) solution was prepared.
  • the mixed solution and copper and nickel plated carbon fiber (12 mm chop) were quantified in a beaker at a weight ratio of 80:20, and then mixed at a mixer at 1000 rpm for 1 minute to prepare a mixed solution.
  • the prepared mixed solution was formed into a sheet form by taking 20 g of a release-treated glass plate and pushing it to a thickness of 0.7 mm with a glass rod.
  • the molded glass substrates were dried and cured for 24 hours in a 150 ° C. oven to obtain the final molded product.
  • Comparative Example 1 the shielding performance was measured by injection molding and extrusion molding the uncoated carbon fibers. Specifically, the carbon fiber 6 or 12 chop chop untreated was molded in the same conditions as in Examples 1 and 2 to the content of the following Table 5 to obtain a molded article. In the case of extrusion molding, pellets were prepared first, followed by drying the pellets in a drying furnace to prepare a continuous sheet having a thickness of 0/7 mm in an extruder.
  • Examples 1, 2 and 3 it can be seen that the electromagnetic shielding performance is different depending on the content of the highly conductive carbon fiber regardless of the type of the resin.
  • the addition of nickel-coated graphite (Ni-coated graphite) to the composition ratio having the same high-conductivity carbon content shows a slight increase in the electromagnetic shielding effect.
  • the increase in the shielding efficiency was slightly higher than that of the injection molding.
  • the surface of the molded product has integral skin.
  • Example 3 In the case of Example 3, a small shielding efficiency increased compared with the injection molded article using a thermoplastic resin, because the mutual contact of carbon fiber was formed more stably than the injection molded article.
  • Comparative Example 1 the injection and extrusion molded products using the non-metal plated carbon fiber showed half the electromagnetic shielding efficiency compared to the same content of the highly conductive carbon fiber.
  • the present invention has been shown to be very effective in shielding electromagnetic waves when containing a certain amount of highly conductive carbon fibers prepared by the electroless and electrolytic continuous process.
  • Cu-Ni double-coated carbon fiber is applied to the electroless to electrolytic continuous process manufactured by Bulls won new material used in Examples 1 to 3 is pre-treated and manufactured through the following process.
  • Example 4 Pretreatment of Carbon Fiber
  • an epoxy solvent and a urethane were removed from the carbon fiber by using an organic solvent, and at the same time, the surface of the fiber was swelled to soften it.
  • Sand or Taekwang (TK)) to perform the degreasing and softening process. Degreasing and softening process takes 2 minutes at a temperature of 50 ° C. Was carried out.
  • the carbon fiber subjected to the etching process was treated with PdCl 2 at a concentration of 2OT at a temperature of 30 ° C. for 2 minutes to carry out a sensitizing process.
  • the sensitizing process is carried out to adsorb metal ions on the surface of the surface modified carbon fiber.
  • the electroless nickel plating was performed on the carbon fiber pretreated in Example 4 using the plating apparatus of FIG. 8 attached below with the composition and conditions of the following Table 8, and electrolytic nickel at the composition and conditions of the following Table 9 in a continuous process.
  • a plating process was carried out to produce copper and nickel plated carbon fibers:
  • the electroplated copper plating was performed on the carbon fiber pretreated in Example 4 using the plating apparatus of FIG. A plating process was carried out to produce copper and nickel plated carbon fibers:
  • Optimization conditions for electroless and electrolytic plating were set by adjusting the concentration of NaOH to adjust pH and the concentration of HCH0 to assist Cu reduction reaction among the compositions and conditions for preparing the copper and nickel plated carbon fibers of Example 7. . .

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

L'invention porte sur un procédé de préparation pour un matériau composite de blindage contre une onde électromagnétique et sur le matériau composite de blindage contre une onde électromagnétique préparé par le procédé. La présente invention utilise une fibre de carbone très conductrice préparée par des processus continus anélectrolytique et électrolytique, et est ainsi adaptée pour un blindage EMI en raison du fait qu'elle possède une excellente conductivité et une faible résistance de surface, et est apte à fournir le matériau composite de blindage contre une onde électromagnétique ayant une excellente productivité et une excellente valeur économique. En outre, le matériau composite de blindage contre une onde électromagnétique selon la présente invention peut être utilisé pour bloquer des ondes électromagnétiques en étant inséré dans un revêtement de téléphone cellulaire et une pochette de téléphone cellulaire, et peut également être appliqué à un support pour protéger un LCD d'un produit d'affichage portable.
PCT/KR2014/004789 2013-05-31 2014-05-29 Procédé de préparation pour un matériau composite de blindage contre une onde électromagnétique utilisant une fibre de carbone plaquée de cuivre et de nickel préparée par des processus continus anélectrolytique et électrolytique, et matériau composite de blindage contre une onde électromagnétique WO2014193169A1 (fr)

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CN201480030964.9A CN105284199B (zh) 2013-05-31 2014-05-29 利用通过无电解及电解连续工序制备的镀敷有铜及镍的碳纤维的电磁波屏蔽复合材料的制备方法及电磁波屏蔽复合材料
JP2016516447A JP6341994B2 (ja) 2013-05-31 2014-05-29 無電解及び電解連続工程によって製造された銅及びニッケルメッキ炭素繊維を用いた電磁波遮蔽複合材の製造方法及び電磁波遮蔽複合材
US14/894,250 US9890280B2 (en) 2013-05-31 2014-05-29 Preparation method for electromagnetic wave shield composite material using copper- and nickel-plated carbon fiber prepared by electroless and electrolytic continuous processes, and electromagnetic wave shield composite material
US15/856,237 US10385208B2 (en) 2013-05-31 2017-12-28 Preparation method for electromagnetic wave shield composite material using copper- and nickel-plated carbon fiber prepared by electroless and electrolytic continuous processes, and electromagnetic wave shield composite material

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KR10-2013-0062962 2013-05-31
KR20130062962 2013-05-31
KR20130159979A KR101469683B1 (ko) 2013-05-31 2013-12-20 무전해 및 전해 연속 공정에 의해 제조된 구리 및 니켈 도금 탄소 섬유를 이용한 전자파 차폐 복합재의 제조 방법 및 전자파 차폐 복합재
KR10-2013-0159979 2013-12-20

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US15/856,237 Division US10385208B2 (en) 2013-05-31 2017-12-28 Preparation method for electromagnetic wave shield composite material using copper- and nickel-plated carbon fiber prepared by electroless and electrolytic continuous processes, and electromagnetic wave shield composite material

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202015106301U1 (de) 2015-11-20 2015-12-04 Stefan Horvath elektromagnetisch abgeschirmte Aufbewahrungstasche

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KR100656858B1 (ko) * 2006-04-20 2006-12-15 이상대 전자파 차폐용 전자제품 케이스와 이의 제조방법
JP2009266953A (ja) * 2008-04-23 2009-11-12 Fujimori Kogyo Co Ltd 電磁波遮蔽材ロール体、電磁波遮蔽シート及びその製造方法
KR20110007826A (ko) * 2009-07-17 2011-01-25 엘에스엠트론 주식회사 굴곡성이 우수한 전해 동박 및 그 제조 방법
KR20120034538A (ko) * 2010-08-26 2012-04-12 제일모직주식회사 고강성 전자파 차폐 조성물 및 그 성형품

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KR100656858B1 (ko) * 2006-04-20 2006-12-15 이상대 전자파 차폐용 전자제품 케이스와 이의 제조방법
JP2009266953A (ja) * 2008-04-23 2009-11-12 Fujimori Kogyo Co Ltd 電磁波遮蔽材ロール体、電磁波遮蔽シート及びその製造方法
KR20110007826A (ko) * 2009-07-17 2011-01-25 엘에스엠트론 주식회사 굴곡성이 우수한 전해 동박 및 그 제조 방법
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Publication number Priority date Publication date Assignee Title
DE202015106301U1 (de) 2015-11-20 2015-12-04 Stefan Horvath elektromagnetisch abgeschirmte Aufbewahrungstasche

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