WO2019066543A1 - 인조 흑연 분말을 이용한 열전도성 박막의 제조방법 - Google Patents

인조 흑연 분말을 이용한 열전도성 박막의 제조방법 Download PDF

Info

Publication number
WO2019066543A1
WO2019066543A1 PCT/KR2018/011516 KR2018011516W WO2019066543A1 WO 2019066543 A1 WO2019066543 A1 WO 2019066543A1 KR 2018011516 W KR2018011516 W KR 2018011516W WO 2019066543 A1 WO2019066543 A1 WO 2019066543A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
graphite powder
artificial graphite
thermally conductive
conductive thin
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/KR2018/011516
Other languages
English (en)
French (fr)
Korean (ko)
Inventor
김동하
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Indong Electronics Co Ltd
Original Assignee
Indong Electronics 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 Indong Electronics Co Ltd filed Critical Indong Electronics Co Ltd
Priority to JP2020518034A priority Critical patent/JP7279952B2/ja
Priority to CN201880063530.7A priority patent/CN111149442B/zh
Priority to EP18861916.7A priority patent/EP3691426B1/en
Priority to US16/651,775 priority patent/US11737243B2/en
Publication of WO2019066543A1 publication Critical patent/WO2019066543A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
    • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
    • H05K7/20472—Sheet interfaces
    • H05K7/20481—Sheet interfaces characterised by the material composition exhibiting specific thermal properties
    • 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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
    • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
    • H05K7/20472—Sheet interfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material

Definitions

  • the present invention relates to a method for manufacturing a thermally conductive thin film for protecting an element or the like integrated in an electronic device such as a smart phone from heat. More particularly, the present invention relates to a method for producing a thermally conductive thin film excellent in thermal conductivity and thinness from raw graphite powder.
  • a substrate on which an IC chip is mounted may be made of a metal PCB having good thermal conductivity, And the heat is controlled by using a heat sink.
  • Natural graphite thin films and artificial graphite thin films using carbon-based materials and thermally conductive thin films such as copper plates are mainly used for controlling heat of electronic devices and the like (see Korean Patent Publication No. 1509494).
  • artificial graphite thin films have a higher thermal conductivity than natural graphite thin films, but they are produced by calcining a high-priced polymer film (for example, a polyimide film) at a high temperature of 2000 to 3000 ° C. Resulting in an increase in the final product price, and it is very difficult to manufacture in the form of a roll having a long width (1000 mm).
  • a high-priced polymer film for example, a polyimide film
  • the thermal conductivity and the tensile strength are intermediate between the performances of the natural graphite thin film and the artificial graphite thin film.
  • the thin copper foil has a high cost in manufacturing the thin graphite thin film. .
  • thermoly conductive thin film which is superior in thermal conductivity compared to a conventional natural graphite thin film or a metal thin film by using artificial graphite powder and is manufactured at a lower cost than a synthetic graphite thin film obtained from a conventional polyimide or the like To provide a method to do so.
  • Another object of the present invention is to provide a thermally conductive thin film produced by the above method.
  • the present invention provides a method for producing a graphite powder, comprising the steps of: (1) pretreatment of artificial graphite powder under pressure or reduced pressure; (2) adding an intercalant to the pretreated artificial graphite powder; (3) heat treating the artificial graphite powder to which the intercalating agent is added; And (4) rolling the heat-treated artificial graphite powder.
  • thermoly conductive thin film produced according to the above method.
  • an article comprising the thermally conductive thin film, the article being an electronic device, an electronic device case, a lighting device, a battery, a battery case, or an EMI gasket.
  • the thermally conductive thin film produced in the present invention can remove heat generated in electronic devices such as smart phones, tablet PCs, and the like, in which IC chips are highly integrated.
  • FIG. 1 shows an example of a method for producing a thermally conductive thin film according to the present invention.
  • SEM scanning electron microscope
  • Fig. 3 shows various examples of meshes for selecting a thermally conductive filler.
  • 5 is an SEM image of a cross section of a thin film produced without performing a pretreatment for reduced pressure.
  • Fig. 6 shows an example of the crystal structure and the c-axis value of graphite.
  • lid part 131: lid part, 132: storage part, 200: tablet PC,
  • 300 notebook PC
  • 301 display unit
  • 302 keyboard unit
  • 700 set top box
  • 800 beam projector
  • 900 black box
  • a method for producing a graphite powder comprising the steps of: (1) pretreatment of artificial graphite powder under pressure or reduced pressure; (2) adding an intercalant to the pretreated artificial graphite powder; (3) heat treating the artificial graphite powder to which the intercalating agent is added; And (4) rolling the heat-treated artificial graphite powder.
  • FIG. 1 shows an example of a method for producing a thermally conductive thin film according to the present invention.
  • artificial graphite powder is prepared (S100); After selecting the particle diameters of these powders (S200); A high-temperature pre-pressurization or a high-temperature pre-pressure pre-treatment is performed (S300); An interlayer inserting agent is added to perform interlayer inserting (S300); Treated at a temperature of about 1500 to 2200 ° C to expand the artificial graphite powder (S500); Thinning through the rolling process (S600); A final thermally conductive thin film can be obtained (S700)
  • the artificial graphite powder is pretreated under a pressurized or reduced pressure condition.
  • Artificial graphite is graphitized by artificially treating graphitizable carbon materials, and is distinguished from natural graphite obtained by collecting natural graphite.
  • the artificial graphite powder used as a raw material for the thermally conductive thin film of the present invention is distinguishable from natural graphite powder which has conventionally been conventionally used in the production of graphite thin films. That is, in the present invention, natural graphite powder such as crystalline flake graphite powder or amorphous graphite powder is not used.
  • Artificial graphite refers to graphitized cokes obtained by heat treatment of coke, which is a by-product of petroleum or coal, at a high temperature, although there are various kinds of graphite cokes according to their raw materials and manufacturing process. As such, artificial graphite is superior in terms of purity, crystallinity, electrical conductivity and thermal conductivity as compared with natural graphite because it is generally manufactured by heat treatment at 1,000 to 2,000 DEG C and optionally 2000 to 3,000 DEG C.
  • Kish graphite which is obtained by refining only the graphite component in a mixture of graphite and slag separated on the surface when the molten iron or cast iron is cooled, is also included in a wide range of artificial graphite.
  • Artificial graphite has a hexagonal crystal structure and has a molecular weight of about 12.0 and can have the appearance of black powder. Also, artificial graphite has a specific gravity of about 2.23 to 2.25, a melting point of about 3500 ° C or more, a Mohs hardness of 1 to 2, and a specific heat of about 0.46 cal / g. In addition, the thermal conductivity of the artificial graphite is about 0.4 ⁇ 1.0 cal / cm.s. °C, thermal expansion coefficient of approximately 1.7 ⁇ 10 -6, and a modulus of elasticity of about 3.5 ⁇ 10 5 kg / cm2, the electric resistance is about 0.04 ⁇ 0.08 Cm and a friction coefficient of about 0.1 to 0.2.
  • the artificial graphite powder according to the present invention is preferably selected from spherical, flake or plate artificial graphite powders having thermal conductivity.
  • Examples of the artificial graphite powder include Sungraf, Tenny Carbon And Bai Xing Graphite Co., Ltd.
  • Figure 2 shows an exemplary SEM image of artificial graphite powder (before expansion).
  • artificial graphite powder has pores and is capable of expanding through intercalation.
  • the artificial graphite powder used in the present invention is not particularly limited as long as it is an expandable artificial graphite powder.
  • the artificial graphite powder may be graphitized coke powder, kish graphite powder, or a mixed powder thereof.
  • Such artificial graphite powders have been conventionally used in the manufacture of electrode materials for steel industry, cathode materials for mobile phones, and moderator for nuclear power.
  • Artificial graphite powder has various properties such as carbon content, interlayer space and density by particle diameter.
  • Average particle diameter (mu m, D50) Carbon content (average, mol%) Tap density (average, g / cm3) pH 3 to 20 90 to 99% 1.1 to 1.3 > 5 20 to 50 90 to 99% 1.0 to 1.2 > 5 50-100 90 to 99% 1.0 to 1.2 > 5 100 to 500 90 to 99% 1.0 to 1.2 > 5 500 to 1000 90 to 99% 0.9-1.1 > 5 1000 ⁇ 2000 90 to 99% 0.9 to 1.0 > 5
  • the artificial graphite powder may have a particle size of 3 to 20 ⁇ m, 20 to 50 ⁇ m, 50 to 100 ⁇ m, 100 to 500 ⁇ m, 500 to 1,000 ⁇ m, or 1,000 to 2,000 ⁇ m.
  • the artificial graphite powder may have a particle size in the range of 50 to 500 ⁇ m, in the range of 50 to 200 ⁇ m, in the range of 100 to 200 ⁇ m, or in the range of 100 to 150 ⁇ m.
  • the intercalating agent is well inserted into the voids of the graphite powder and has a good expansion.
  • Such artificial graphite powder is pretreated under pressure or reduced pressure.
  • the thermal conductivity of the artificial graphite powder or the final thin film can be further improved.
  • heat transfer heat is transferred by free electrons and the movement of molecules, more specifically lattice vibrations, and heat energy is transferred from high energy to low energy.
  • the thermal conductivity is affected by the density. Therefore, the thermal conductivity of the final thin film can be further improved by increasing the density of the intermolecular spacing as narrow as possible.
  • ⁇ is a thermal conductivity (W / mK)
  • ⁇ is the density (g / cm3) a
  • C p is the specific heat (J / gK)
  • ⁇ is thermal diffusivity (m2 / s).
  • Such high density of the thin film can be achieved by pretreating the raw material artificial graphite powder under a pressure or a reduced pressure condition.
  • the artificial graphite powder can be pretreated under a pressurizing condition of 100 to 2000 bar. In this way, at the time of pretreatment under the pressurizing conditions, artificial graphite powders are solidified and hardened, whereby high density can be achieved.
  • the artificial graphite powder can be pretreated under a reduced pressure of 10 -2 to 10 -7 Torr.
  • the space for interlayer insertion in the microstructure of the artificial graphite powder is increased to increase the degree of expansion, and then the thin film having improved interlayer structure can be obtained through rolling, thereby achieving high density .
  • the temperature at the time of the pre-treatment under the pressure or the depressurization condition may be room temperature or high temperature condition.
  • the pre-treatment may be performed at 500 to 3000 ° C, 500 to 2500 ° C, 500 to 2000 ° C, 1500 to 2600 ° C, or 1000 to 3000 ° C.
  • the carbon atoms are rearranged to further grow the graphite crystal structure, thereby further improving the thermal conductivity.
  • the expansion and the particle spacing of the artificial graphite powder can be changed by controlling the temperature condition during the decompression pretreatment (see Table 8).
  • the pretreatment may be a heat treatment of the artificial graphite powder at a temperature of 500 to 3000 ° C. under a pressure of 100 to 2000 bar.
  • the pretreatment may be performed by heat-treating the artificial graphite powder at 500 to 3000 ° C under a reduced pressure of 10 -2 to 10 -5 Torr.
  • the furnace furnace can be an induction furnace furnace or a resistance heating furnace furnace.
  • the pretreatment may be controlled for 30 minutes to 50 hours, 30 minutes to 30 hours, or 30 minutes to 10 hours.
  • a step of screening the artificial graphite powder to a desired particle size range may be carried out, if necessary.
  • the particle size selection of the artificial graphite powder may be performed using a mesh, for example, a grating mesh may be used.
  • a grating mesh having a rectangular hole (i) a grating mesh having a hole in which a square and a rectangle are mixed, or (iii) a grating mesh having a square hole.
  • a grating mesh having a square hole (i) a grating mesh having a rectangular hole, (ii) a grating mesh having a hole in which a square and a rectangle are mixed, or (iii) a grating mesh having a square hole.
  • only one of these meshes may be used, or a combination thereof may be used.
  • the step of selecting the artificial graphite powder includes (i) a step of firstly screening with a grating mesh having the rectangular hole; (ii) a step of secondary selection with a grating mesh having a mixture of a rectangular hole and a square hole; And (iii) tertiary selection with a grating mesh having a square hole.
  • FRP glass fiber reinforced plastic
  • a mixed material thereof As the material of the mesh, steel, stainless steel (SUS), glass fiber reinforced plastic (FRP), or a mixed material thereof can be used. Particularly, among these, FRP materials prepared by mixing unsaturated polyester resin and glass fiber are preferable from the viewpoints of light weight, hardness, durability and economy. In addition, FRP materials have chemical resistance, insulation, and non-magnetic properties, which is beneficial for graphite processing.
  • step (2) an intercalant is added to the pretreated artificial graphite powder.
  • an oxidizing agent may be used.
  • a strong oxidizing agent selected from the group consisting of sulfuric acid, nitric acid, potassium chlorate, potassium nitrate, and mixtures thereof may be used as the first oxidizing agent.
  • a mixture of sulfuric acid, nitric acid, a mixture of sulfuric acid and nitric acid, a mixture of nitric acid and potassium chlorate, or a mixture of sulfuric acid and potassium nitrate may be used as the first oxidizing agent.
  • a compound selected from the group consisting of perchloric acid, hydrogen peroxide, chromic acid, boric acid, and mixtures thereof is further used as the second oxidant (auxiliary oxidant) in the first oxidant treatment.
  • the first oxidizing agent and the second oxidizing agent may each have a concentration of 5 to 60%, for example, 10 to 60%, 20 to 60%, 30 to 60% To 60% can be used.
  • the mixing ratio of the first oxidizing agent to the second oxidizing agent may be 1: 100 to 50: 100, more specifically 1: 100 to 20: 100, and still more preferably 1: 100 to 10: 100.
  • the intercalating agent may comprise a first oxidizing agent selected from the group consisting of sulfuric acid, nitric acid, potassium chlorate, potassium nitrate, and mixtures thereof in a concentration of 40-60%.
  • the intercalating agent further comprises a second oxidizing agent selected from the group consisting of perchloric acid, hydrogen peroxide, chromic acid, boric acid, and mixtures thereof, wherein the first oxidizing agent and the second oxidizing agent are mixed at a ratio of 1: 100 to 50 : 100 by weight.
  • the artificial graphite powder to which the intercalating agent is added is heat-treated.
  • the artificial graphite powder can be expanded.
  • the heat treatment may be performed at a temperature of about 1000 to 3000 ° C, and more specifically, 1000 to 2500 ° C, 1500 to 3000 ° C, 1500 to 2500 ° C, 1200 to 2200 ° C, 1500 to 2200 ° C, ≪ / RTI >
  • conventional natural graphite powders generally undergo expansion at a temperature in the range of 700 to 800 ° C.
  • the thermal conductivity can be further improved by heat treatment in the above-mentioned preferable temperature range.
  • the heat-treated artificial graphite powder may have an expansion degree of 120 to 500%, specifically 120 to 195%, 130 to 170%, or 150 to 300%.
  • the degree of expansion may be defined as the percentage of the c-axis value after expansion based on the c-axis value before expansion in the graphite crystal structure.
  • the graphite crystal structure of the graphite layer is formed by connecting rings of six carbon atoms.
  • the c-axis value (twice the interlayer spacing) is about 6.67 ⁇ and the inter-carbon bond length is about 1.42 ⁇ .
  • the unit cell of graphite contains 4 carbon atoms and the lattice constant is about 2.456 ANGSTROM.
  • the graphite expanded in this manner can be mixed with the binder resin (pressure-sensitive adhesive) added for aggregation of the expanded graphite before rolling.
  • the binder resin may be added or not depending on the thickness of the target graphite thin film, and even if the same thickness is used, it can be used for producing a high density thin film.
  • the reduction rate can be further increased in the subsequent rolling step, so that a thin film having improved thermal conductivity can be obtained.
  • the binder resin a conventional adhesive resin can be used.
  • the binder resin include a cellulose resin, an epoxy resin, an acrylic resin (e.g., methyl methacrylate, acrylic acid alkyl ester monomer polymer), a phenol resin (resole, novolac, (Polyamides, polyesters, polyurethanes, etc.), amines (such as polyvinyl alcohol, polyvinyl alcohol, polyvinyl butyral, nitrile rubber, chloroprene and nylon) Based, melamine-based, acetic acid-based, polyisocyanate-based, and the like.
  • the binder resin further includes a UV curable resin, so that it is possible to improve the ease of curing and the improvement of the tensile force in the production of a thin film in a plate form.
  • a UV curable resin a urethane acrylate resin can be used.
  • the amount of the UV curable resin added may be less than 1% by weight of the final product. If the amount of the UV curable resin is less than 1% by weight, the tensile strength of the product may be improved.
  • the graphite to which the UV curing resin is added may be further subjected to the UV curing process.
  • the UV curing may be performed at a wavelength ranging from 315 nm to 400 nm, and more specifically, at a wavelength ranging from 350 to 380 nm.
  • an arc discharge lamp can be used, for example, a gallium lamp, a mercury lamp, a metal lamp, and the like. Considering the characteristics of the graphite thin film, the use of a gallium lamp may be more advantageous for curing.
  • the artificial graphite powder subjected to the heat treatment is rolled.
  • the rolling may be performed by, for example, passing through the pressure roller 1 to 5 times and pressing.
  • the pressing condition and the number of repetition times at the time of rolling can be determined according to the desired thin film thickness.
  • the thickness of the thin film can be controlled through the rolling, and the density, thermal conductivity and tensile strength can be improved.
  • the thin film thus obtained can be used as a thermally conductive thin film by itself.
  • the thermally conductive thin film may be combined with another functional layer to form a composite sheet.
  • the thermally conductive thin film may be bonded to the adhesive layer to impart the adhesive property.
  • the adhesive layer may include a thermally conductive filler to further improve the thermal conductivity.
  • the adhesive layer may include a carbon-based filler, a metal-based filler, or a composite filler thereof.
  • the adhesive layer includes a composite filler including a carbon-based filler and a metal-based filler; Binder resin; And a pressure-sensitive adhesive.
  • the heat-treated artificial graphite powder is coated on at least one side of the adhesive layer and rolled to obtain a thermally conductive thin film combined with the adhesive layer.
  • a thermally conductive thin film having a high packing ratio of the thermally conductive filler and excellent in tensile strength and flexibility can be easily manufactured.
  • a part of the adhesive component of the adhesive layer may penetrate into the filler layer in the course of coating and rolling the solid powder-like filler on both sides of the adhesive layer, thereby enhancing the interlayer bonding force.
  • it may further include laminating the thermally conductive thin film on at least one side of the adhesive layer.
  • the artificial graphite powder of the step (1) has a particle size of 50 to 200 mu m;
  • the pretreatment is a heat treatment of the artificial graphite powder at 500 to 3000 ⁇ ⁇ under a reduced pressure of 10 -2 to 10 -5 Torr;
  • said intercalating agent comprises a first oxidizing agent selected from the group consisting of sulfuric acid, nitric acid, potassium chlorate, potassium nitrate, and mixtures thereof in a concentration of 40-60%;
  • the heat treatment of step (3) is performed at a temperature of 1500 to 3000 ° C;
  • the thermally conductive thin film may have a thickness of 50 to 1000 ⁇ m, a density of 1.5 to 2.0 g / cm 3, and a horizontal thermal conductivity of 300 to 700 W / mK.
  • thermoly conductive thin film produced according to the above method.
  • the thermally conductive thin film is formed by rolling expanded artificial graphite powder.
  • the thermally conductive thin film is obtained by intercalating an intercalating agent into an artificial graphite powder, heating and expanding it, and then rolling.
  • FIG. 4 is a SEM image of a cross section of a thermally conductive thin film manufactured according to an embodiment of the present invention.
  • the thermally conductive thin film according to the present invention has excellent thickness, density and thermal conductivity.
  • the thermally conductive thin film may have a thickness in the range of 20 to 3000 mu m, more specifically in the range of 30 to 2000 mu m, or in the range of 50 to 1000 mu m.
  • the thermally conductive thin film may have a density in the range of 1.0 to 2.5 g / cm 3, more specifically in the range of 1.3 to 2.2 g / cm 3, or in the range of 1.5 to 2.0 g / cm 3.
  • the thermally conductive thin film may have a thermal conductivity in the range of 200 to 1000 W / mK with respect to the horizontal direction, more specifically in the range of 300 to 900 W / mK, 300 to 800 W / mK, or 300 to 700 W / mK. < / RTI >
  • the thermally conductive thin film may have a thickness of 50 to 1000 ⁇ m, a density of 1.5 to 2.0 g / cm 3, and a horizontal thermal conductivity of 300 to 700 W / mK.
  • the thermally conductive thin film may further include at least one functional layer on at least one side thereof.
  • the thermally conductive thin film may further include an adhesive layer.
  • the adhesive layer may contain a thermally conductive filler.
  • the adhesive layer may contain a carbon-based filler, a metal-based filler, or a composite filler thereof.
  • the thermally conductive thin film may further include an adhesive layer on at least one surface thereof.
  • the thermally conductive thin film has an adhesive layer on both sides thereof, and the adhesive layer may include a carbon-based filler, a metal-based filler, or a composite filler thereof.
  • the thermally conductive thin film having the adhesive layer as described above can be excellent in tensile strength.
  • the thermally conductive thin film having the adhesive layer may have a tensile strength of 20 to 50 kg / mm 2.
  • the thermally conductive thin film is provided with the adhesive layer on both sides thereof and the thermally conductive filler is contained in the adhesive layer as described above, the filler filling rate can be further improved.
  • an article comprising the thermally conductive thin film.
  • the article to which the present invention is directed may be an electronic device, an electronic device case, a lighting device, a battery, a battery case, or an EMI gasket.
  • the electronic device may be a mobile phone, a desktop PC, a notebook PC, a tablet PC, a virtual reality (VR) device, a set-top box, a portable game machine, an external hard disk, an MP3 player, a beam projector, A car navigation system, a communication device, a power converter, a power supply device, or a medical electronic device.
  • a mobile phone a desktop PC, a notebook PC, a tablet PC, a virtual reality (VR) device, a set-top box, a portable game machine, an external hard disk, an MP3 player, a beam projector, A car navigation system, a communication device, a power converter, a power supply device, or a medical electronic device.
  • a VR virtual reality
  • the lighting device may also be an LED lighting device or a light bulb.
  • the article may have a heat source that generates heat by electrical, electronic, or chemical action.
  • the electronic device may include an electronic device, a circuit board, or a light source.
  • the thermally conductive thin film may be attached directly to the surface of the heat source, attached to the surface of the heat sink closely adhering to the heat source, or attached to the casing of the article adjacent to the heat source.
  • the article is an electronic device, a lighting device or a battery including a heat source;
  • the thermally conductive thin film may be attached directly to the surface of the heat source, attached to the surface of the heat sink closely adhering to the heat source, or attached to the casing of the article adjacent to the heat source.
  • 9A and 9B are respectively a sectional view of a direct-lighting type and an edge-type flat panel lighting to which a thermally conductive thin film is applied; 10 shows a bulb-type lamp to which a thermally conductive thin film is applied; 11 is a cross-sectional view of an LED illumination to which a thermally conductive thin film is applied; 12 is a view of an electric vehicle to which a thermally conductive thin film is applied and an enlarged view of the battery cell of the electric vehicle.
  • the thermally conductive thin film 1 may be disposed adjacent to the display portion 113 of the cellular phone or the chipset substrate 115.
  • the thermally conductive thin film 1 may be attached to a portion corresponding to the heat source 11 in the casing 13 of the electronic apparatus (see FIG. 7B) (See FIG. 7C), or directly on the surface of the heat source 11 (see FIG. 7D).
  • the thermally conductive thin film 1 is attached to the rear surface of the LED element 20 of the direct-type flat panel illumination, or to the rear surface of the heat sink 12 brought into close contact with the LED element; As shown in FIGS. 8B and 9B, the thermally conductive thin film 1 can be attached to a position adjacent to the edge portion where the LED element 20 is provided in the edge type flat panel illumination, that is, the side surface of the casing.
  • the thermally conductive thin film may be attached to the inner wall of the casing member 13 such as a bulb type lamp.
  • FIG. 11 is a cross-sectional view of a typical LED lighting.
  • the thermally conductive thin film 1 may be attached to one surface of the substrate 50 provided with the LED element 20 and one surface of the heat sink 12.
  • FIG. 11 is a cross-sectional view of a typical LED lighting.
  • the thermally conductive thin film 1 may be attached to one surface of the substrate 50 provided with the LED element 20 and one surface of the heat sink 12.
  • thermally conductive thin film 1 may be attached to the surface of the battery cell to protect the battery cell 60 of the electric vehicle shown in FIG. 12 from a high temperature.
  • 13A to 15E show an example in which the thermally conductive thin film is applied to various articles in more detail.
  • the thermally conductive thin film 1 is attached to the front face F or the back face B of the battery 111, which is one of the components with the highest heat generation in the cellular phone 110; And may be attached to the front surface (F) or the back surface (B) of the battery case (112) of the cell phone (110)
  • the thermally conductive thin film 1 may be attached to the cell phone case in addition to the cell phone main body to emit heat of the cell phone.
  • the thermally conductive thin film 1 may be attached to the front face F or back face B of the open cell phone case 120;
  • the thermally conductive thin film 1 is attached to the front face F or the back face B of the lid part 131 of the folding cellular phone case 130;
  • the open cell phone case 120 and the folding cell phone case 130 may include a material selected from the group consisting of polymer resin, natural leather, artificial leather, metal, rubber, cubic, and combinations thereof.
  • the thermally conductive thin film 1 may be applied to a mobile device other than a mobile phone, for example, attached to the back surface B of the tablet PC 200 (see FIG. 14A); Attached to the back surface B of the display portion 301 of the notebook PC 300 or the front or rear surface of the keyboard portion 302 (see Fig. 14B); Attached to the back surface B of the portable game machine 400 (see Fig. 14C); And may be attached to the back surface B of the MP3 player 500 to exhibit a heat radiating effect (see Fig. 14D).
  • the thermally conductive thin film 1 may be applied to various electronic apparatuses other than those illustrated above.
  • the thermally conductive thin film 1 may be attached to the front surface F or the back surface B of the external hard disk 600 (see FIG. 15A) ; 15B) or attached to the upper surface U or the lower surface L of the beam projector 800 (see Fig. 15C), or may be attached to the upper surface U, the lower surface L and the side surface S of the set top box 700 Reference); Or may be attached to the front face F or back face B of the vehicle black box 900 to exhibit a heat radiating effect (see Fig. 15D).
  • the thermally conductive thin film 1 may also be applied to an article for suppressing electromagnetic interference (EMI), for example, attached to a surface of an EMI gasket 950, and then mounted on a case 960 15e).
  • EMI electromagnetic interference
  • Powder of spherical artificial graphite powder (Sungraf Co.) was firstly selected by using a mesh with a particle diameter of 50 to 500 ⁇ , and secondary powders having a particle size of 100 to 300 ⁇ were selected therefrom.
  • the average particle size of the finally selected artificial graphite powder was 100 to 200 ⁇ .
  • the selected artificial graphite powder was pretreated under decompression conditions. Specifically, artificial graphite powder was put into a decompression chamber (HT-VH-RF-2000, manufactured by POLYNANOTEK Co., Ltd.) and heat-treated at a reduced pressure of about 10 -2 torr at about 2000 ° C.
  • a decompression chamber HT-VH-RF-2000, manufactured by POLYNANOTEK Co., Ltd.
  • the pretreated artificial graphite powder was filled in advance of the input portion of the reactor and treated by adding an intercalant. Specifically, 50% sulfuric acid H 2 SO 4 as a strong oxidizing agent as a first oxidizing agent was added to the reactor, and perchloric acid having a concentration of 50% as a secondary oxidizing agent was further added as a second oxidizing agent. The weight ratio of the first oxidant and the second oxidant was 60:40. After mixing in the reactor, it was washed and dried.
  • the reactor in which the artificial graphite powder treated with the intercalating agent was disposed was heated to 1500 DEG C to expand the artificial graphite powder by heat treatment.
  • the expanded graphite was collected and rolled to form a plate, and the thickness was adjusted.
  • the rolled graphite was rolled 3 to 5 times using a pressure roller to prepare a thin film.
  • the obtained thin film was wound into a roll shape while controlling its length.
  • Test Example 1 Evaluation of density change by pre-pressurization
  • the pre-pressurization was carried out at a pressure of 100 to 2000 bar at 500 to 2000 ° C as shown in Table 3 below, in which artificial graphite powder was put in a pressure chamber (Model KCIP 120, equiaxial extruder,
  • Test Example 2 Evaluation of density change according to decompression pretreatment
  • artificial graphite powder was put into a decompression chamber (high-temperature vacuum hydrogen reduction reactor, HT-VH-RF-2000, manufactured by POLYNANOTEK Co., Ltd.) and subjected to pressure reduction under a pressure of 10 -1 to 10 -5 Torr at a temperature of 500 to 2000 ° C .
  • a decompression chamber high-temperature vacuum hydrogen reduction reactor, HT-VH-RF-2000, manufactured by POLYNANOTEK Co., Ltd.
  • Test Example 3 Evaluation of degree of expansion according to pretreatment under reduced pressure and pretreatment temperature
  • Example 1 The procedure of Example 1 was carried out using artificial graphite powder (particle size: 50 to 200 ⁇ ⁇ ), and in Step 1.3., The degree of pre-decompression pretreatment and pretreatment temperature were varied before expansion. The degree of expansion of the artificial graphite powder was calculated according to the following equation (2) and is summarized in Table 8 below.
  • Expansion degree of artificial graphite powder (%) (c-axis value after expansion in graphite crystal structure / c-axis value before expansion) x 100
  • the degree of expansion of the artificial graphite powder was improved when the pretreatment was performed before the expansion, and the expansion degree was also improved according to the pretreatment temperature.
  • Test Example 4 Evaluation according to concentration of intercalant
  • the degree of expansion of the artificial graphite powder was calculated according to the above-mentioned formula (2) by observing with a scanning electron microscope (SEM) after expanding the concentration of the intercalating agent by changing the concentration of the intercalating agent to 20 to 50% Respectively.
  • SEM scanning electron microscope
  • the graphite powder was subjected to various temperature / pressure conditions as shown in Table 10 below, and then the expanded artificial graphite powder was observed by SEM and the results were summarized.
  • the heat treatment temperature is 800 ⁇ 1500 °C
  • the crystal structure is not well developed because the gap is narrow.
  • thermally conductive thin films having various thicknesses were prepared according to the procedure of Example 1, and the thermal conductivity and density thereof were measured and summarized in Table 11 below.
  • the thermal conductivity was measured by LFA (Laser Flash Analysis) method.
  • the thermally conductive thin film of the example made from artificial graphite powder according to the present invention has greatly improved thermal conductivity and thermal diffusivity compared to the conventional natural graphite thin film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)
  • Cooling Or The Like Of Electrical Apparatus (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/KR2018/011516 2017-09-29 2018-09-28 인조 흑연 분말을 이용한 열전도성 박막의 제조방법 Ceased WO2019066543A1 (ko)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020518034A JP7279952B2 (ja) 2017-09-29 2018-09-28 合成グラファイト粉末を用いる熱伝導性薄膜の生成方法
CN201880063530.7A CN111149442B (zh) 2017-09-29 2018-09-28 使用合成石墨粉末生产导热薄膜的方法
EP18861916.7A EP3691426B1 (en) 2017-09-29 2018-09-28 Method for producing thermally conductive thin film using synthetic graphite powder
US16/651,775 US11737243B2 (en) 2017-09-29 2018-09-28 Method for producing thermally conductive thin film using synthetic graphite powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0127267 2017-09-29
KR1020170127267A KR101835385B1 (ko) 2017-09-29 2017-09-29 인조 흑연 분말을 이용한 열전도성 박막의 제조방법

Publications (1)

Publication Number Publication Date
WO2019066543A1 true WO2019066543A1 (ko) 2019-04-04

Family

ID=61727742

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/011516 Ceased WO2019066543A1 (ko) 2017-09-29 2018-09-28 인조 흑연 분말을 이용한 열전도성 박막의 제조방법

Country Status (6)

Country Link
US (1) US11737243B2 (https=)
EP (1) EP3691426B1 (https=)
JP (1) JP7279952B2 (https=)
KR (1) KR101835385B1 (https=)
CN (1) CN111149442B (https=)
WO (1) WO2019066543A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021125196A1 (ja) * 2019-12-17 2021-06-24 宇部興産株式会社 黒鉛－銅複合材料、それを用いたヒートシンク部材、および黒鉛－銅複合材料の製造方法
JP2023536272A (ja) * 2020-07-30 2023-08-24 エヌティーエス・カンパニー・リミテッド 黒鉛廃棄物を用いた放熱シートを製造する方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102589247B1 (ko) 2018-12-20 2023-10-12 엘지디스플레이 주식회사 디스플레이 장치
KR102014486B1 (ko) 2019-05-23 2019-08-26 유성운 태양전지 패널의 방열시트용 조성물.
KR102014491B1 (ko) 2019-05-23 2019-08-26 유성운 태양전지 패널의 방열시트용 조성물.
KR102026975B1 (ko) 2019-05-23 2019-09-30 유성운 태양광 발전용 태양전지 패널.
CN111805987A (zh) * 2020-07-15 2020-10-23 杭州中家尚实业有限公司 一种凉感面料及其制备方法、应用
KR20230077420A (ko) 2021-11-25 2023-06-01 자화전자(주) 열전도성 박막 시트 제조방법 및 그 방법에 의해 제조된 열전도성 박막 시트
US12082977B2 (en) * 2022-01-25 2024-09-10 GE Precision Healthcare LLC Thermally conductive shock absorbers for medical imaging probes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006137860A (ja) * 2004-11-12 2006-06-01 Hitachi Chem Co Ltd 熱伝導シート
KR101509494B1 (ko) 2013-08-30 2015-04-08 주식회사 서환이지 흑연을 이용한 전자기기용 방열시트
JP2015084431A (ja) * 2008-10-08 2015-04-30 日立化成株式会社 熱伝導シート、及びその熱伝導シートの製造方法
KR101550445B1 (ko) * 2014-08-22 2015-09-04 고영신 팽창흑연을 이용한 엘이디 방열판의 제조방법
KR101642052B1 (ko) * 2015-10-01 2016-07-22 주식회사 이노폴이 열전도성 조성물, 열전도성 점착 시트 및 이의 제조방법
KR101722069B1 (ko) * 2016-06-17 2017-03-31 주식회사 이노폴이 열전도성 박막 시트 및 이의 제조방법

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050175838A1 (en) * 2001-12-26 2005-08-11 Greinke Ronald A. Thermal interface material
US20050155743A1 (en) * 2002-06-28 2005-07-21 Getz George Jr. Composite heat sink with metal base and graphite fins
US7303005B2 (en) 2005-11-04 2007-12-04 Graftech International Holdings Inc. Heat spreaders with vias
WO2007087090A2 (en) 2006-01-25 2007-08-02 Advanced Energy Technology Inc. Heat spreaders with vias
JP5295631B2 (ja) * 2008-01-18 2013-09-18 株式会社カネカ 多層グラファイトフィルムおよびその製造方法、電子機器、ディスプレイならびにバックライト
JP5343477B2 (ja) * 2008-09-18 2013-11-13 パナソニック株式会社 グラファイト複合シートおよびその製造方法
KR101446638B1 (ko) * 2009-05-06 2014-10-02 가부시키가이샤 인큐베이션 얼라이언스 탄소 재료 및 그 제조 방법
US8747623B2 (en) * 2011-10-11 2014-06-10 Nanotek Instruments, Inc. One-step production of graphene materials
KR101282125B1 (ko) * 2012-01-18 2013-07-04 주식회사 지앤씨에스 백라이트 어셈블리 및 그를 포함하는 표시 장치
CN102807213B (zh) * 2012-08-30 2015-09-09 中国科学院苏州纳米技术与纳米仿生研究所 电化学制备石墨烯的方法
JP5725635B1 (ja) 2013-12-17 2015-05-27 グラフェンプラットフォーム株式会社 グラフェン粉体の製造方法及びその製造方法により製造されるグラフェン粉体
JP5563175B1 (ja) * 2014-03-05 2014-07-30 清二 加川 高熱伝導率の放熱シート及びその製造方法
US20160141225A1 (en) * 2014-11-17 2016-05-19 Sgl Carbon Se Latent heat storage devices
CN106832926B (zh) * 2017-01-19 2020-03-10 祝巧凤 用于导热的石墨混合物、石墨膜及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006137860A (ja) * 2004-11-12 2006-06-01 Hitachi Chem Co Ltd 熱伝導シート
JP2015084431A (ja) * 2008-10-08 2015-04-30 日立化成株式会社 熱伝導シート、及びその熱伝導シートの製造方法
KR101509494B1 (ko) 2013-08-30 2015-04-08 주식회사 서환이지 흑연을 이용한 전자기기용 방열시트
KR101550445B1 (ko) * 2014-08-22 2015-09-04 고영신 팽창흑연을 이용한 엘이디 방열판의 제조방법
KR101642052B1 (ko) * 2015-10-01 2016-07-22 주식회사 이노폴이 열전도성 조성물, 열전도성 점착 시트 및 이의 제조방법
KR101722069B1 (ko) * 2016-06-17 2017-03-31 주식회사 이노폴이 열전도성 박막 시트 및 이의 제조방법

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021125196A1 (ja) * 2019-12-17 2021-06-24 宇部興産株式会社 黒鉛－銅複合材料、それを用いたヒートシンク部材、および黒鉛－銅複合材料の製造方法
JPWO2021125196A1 (https=) * 2019-12-17 2021-06-24
JP7165341B2 (ja) 2019-12-17 2022-11-04 Ｕｂｅ株式会社 黒鉛－銅複合材料、それを用いたヒートシンク部材、および黒鉛－銅複合材料の製造方法
US12534372B2 (en) 2019-12-17 2026-01-27 Ube Corporation Graphite-copper composite material, heat sink member using the same, and method for producing graphite-copper composite material
JP2023536272A (ja) * 2020-07-30 2023-08-24 エヌティーエス・カンパニー・リミテッド 黒鉛廃棄物を用いた放熱シートを製造する方法
US20230303903A1 (en) * 2020-07-30 2023-09-28 Nts Co., Ltd Method for manufacturing heat dissipation sheet using waste graphite
EP4190746A4 (en) * 2020-07-30 2024-01-24 NTS Co., Ltd. METHOD FOR PRODUCING A HEAT DISSIPATION FILM USING WASTE GRAPHITE

Also Published As

Publication number Publication date
CN111149442A (zh) 2020-05-12
EP3691426A4 (en) 2021-07-07
EP3691426C0 (en) 2025-08-13
KR101835385B1 (ko) 2018-03-09
EP3691426B1 (en) 2025-08-13
EP3691426A1 (en) 2020-08-05
US11737243B2 (en) 2023-08-22
JP2020535662A (ja) 2020-12-03
US20200260614A1 (en) 2020-08-13
CN111149442B (zh) 2022-10-11
JP7279952B2 (ja) 2023-05-23

Similar Documents

Publication Publication Date Title
WO2019066543A1 (ko) 인조 흑연 분말을 이용한 열전도성 박막의 제조방법
WO2013009133A2 (ko) 표면 처리용 수지 조성물 및 이에 의해 코팅된 강판
WO2012018242A2 (ko) 탄소소재를 이용한 고효율 방열도료 조성물
WO2017217759A1 (ko) 열전도성 박막 시트 및 이를 포함하는 물품
WO2015093903A1 (ko) 방열성이 우수한 금속 봉지재, 그 제조방법 및 상기 금속 봉지재로 봉지된 유연전자소자
WO2023013834A1 (ko) 방열 도료 조성물, 이의 제조방법, 이로부터 형성된 방열 코팅막 및 이를 포함하는 히트씽크
WO2023080349A1 (ko) 일액형 우레탄 방열 도료 조성물 및 이의 제조방법
WO2015147449A1 (ko) 전자기파 차폐시트, 및 이의 제조방법
WO2012111963A2 (ko) 기재 필름 및 그의 제조방법
WO2017209473A1 (ko) 편광자 보호 필름, 이를 포함하는 편광판, 및 이를 구비한 표시 장치
WO2017014402A1 (ko) 디스플레이용 양면 점착 테이프 및 제조방법
WO2019135533A1 (ko) 전자파 차폐 필름의 제조 방법
WO2015126088A1 (en) Touch window and display with the same
WO2018021866A1 (ko) 함질소 고리 화합물, 이를 포함하는 색변환 필름, 및 이를 포함하는 백라이트 유닛 및 디스플레이 장치
WO2020076138A1 (ko) 복합 코팅액, 이를 이용하여 제조된 금속 기판 구조체, 및 그 제조 방법
WO2020085868A1 (ko) 플렉서블 디스플레이 장치의 커버 윈도우 및 디스플레이 장치
WO2020204361A1 (ko) 전자파의 차폐 및 흡수 기능이 우수한 복합 자성체 차폐시트 및 자성체시트의 제조 방법
WO2018135916A1 (ko) 충격흡수용 복합시트
WO2022145643A1 (ko) 실리콘 점착 코팅용 조성물 및 이를 포함하는 점착 필름
WO2021075899A1 (ko) 경화성 조성물
WO2021091303A1 (ko) 저주파 안테나용 방열 시트, 이의 제조방법 및 이를 포함하는 전자기기
WO2019112175A1 (ko) 접착제 키트, 이를 포함하는 접착필름 및 봉지재, 및 유기전자장치의 봉지방법
WO2018117315A1 (ko) 박육성형이 가능한 고열전도도 및 고강도 다이캐스팅용 알루미늄합금 조성물 및 그 제조방법
WO2021230717A1 (ko) 봉지 필름
WO2023085512A1 (ko) 항균 대전방지 조성물 및 이를 포함하는 방청 필름

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18861916

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020518034

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018861916

Country of ref document: EP

Effective date: 20200429

WWG Wipo information: grant in national office

Ref document number: 2018861916

Country of ref document: EP