WO2023189778A1 - Feuille de matériau composite - Google Patents

Feuille de matériau composite Download PDF

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Publication number
WO2023189778A1
WO2023189778A1 PCT/JP2023/010754 JP2023010754W WO2023189778A1 WO 2023189778 A1 WO2023189778 A1 WO 2023189778A1 JP 2023010754 W JP2023010754 W JP 2023010754W WO 2023189778 A1 WO2023189778 A1 WO 2023189778A1
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WIPO (PCT)
Prior art keywords
composite material
material sheet
surface layer
inorganic particles
fluid
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PCT/JP2023/010754
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English (en)
Japanese (ja)
Inventor
智也 加藤
哲弥 大塚
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日東電工株式会社
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Publication of WO2023189778A1 publication Critical patent/WO2023189778A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular

Definitions

  • the present invention relates to a composite material sheet.
  • thermosetting resins Conventionally, composite materials containing inorganic materials and thermosetting resins are known.
  • Patent Document 1 describes a composite material including a filler and a binding resin.
  • the filler is a scaly filler made of an inorganic material.
  • the binding resin is a thermosetting resin that binds the filler.
  • This composite material is a foam material formed so that a plurality of voids are dispersed.
  • the filler is accumulated on the inner wall of the void so that the flat surfaces of the filler overlap each other.
  • a slurry-like mixture is prepared by mixing a filler, a polyester resin, and a blowing agent such as ethanol, and the mixture is poured into a mold.
  • a composite material is produced by heating a mixture in a mold to a temperature higher than a curing temperature, foaming a polyester resin, and curing the foamed polyester resin.
  • Patent Document 1 has room for reexamination from the viewpoint of increasing the thermal conductivity in the surface layer of a sheet-like composite material.
  • the present invention provides a composite material sheet that is advantageous from the viewpoint of increasing thermal conductivity in the surface layer.
  • the present invention A skeleton part containing resin, multiple voids, a heat transfer path formed by inorganic particles; having a surface layer in which the resin and the inorganic particles are present; In a plan view of the surface layer, the ratio of the area of the portion where the inorganic particles are present to the area of the surface layer is 10% or more; Provides composite material sheets.
  • the above composite material sheet is advantageous from the viewpoint of increasing thermal conductivity in the surface layer.
  • FIG. 1 is a plan view schematically showing the surface of a composite material sheet in this embodiment.
  • FIG. 2 is a cross-sectional view of the composite material sheet taken along line II-II in FIG. 1.
  • FIG. 3A is a drawing schematically illustrating an example of a method for manufacturing a composite material sheet.
  • FIG. 3B is a drawing schematically illustrating another example of a method for manufacturing a composite material sheet.
  • FIG. 4A is a photograph of the composite material sheet according to Example 1 in plan view.
  • FIG. 4B is a photograph of the cross section of the composite material sheet according to Example 1.
  • FIG. 5A is a photograph of the composite material sheet according to Comparative Example 1 in plan view.
  • FIG. 5B is a photograph of the composite material sheet according to Comparative Example 1.
  • the composite material sheet 1 includes a skeleton portion 11, a plurality of voids 12, and a heat transfer path 15.
  • the skeleton portion 11 contains resin.
  • the heat transfer path 15 is formed by inorganic particles 13.
  • the composite material sheet 1 has a surface layer 1s in which resin and inorganic particles 13 contained in the skeleton portion 11 are present. In a plan view of the surface layer 1s, the ratio S 13 /S 1S of the area S 13 of the portion where the inorganic particles 13 are present to the area S 1S of the surface layer 1s is 10% or more.
  • the ratio S 13 /S 1S is preferably 12% or more, more preferably 15% or more, and still more preferably 20% or more.
  • the ratio S 13 /S 1S is, for example, 80% or less. Thereby, since the skeleton portion 11 occupies a certain amount of volume in the surface layer 1s, the composite material sheet 1 tends to have desired strength.
  • the ratio S 13 /S 1S may be included in any of the ranges determined by all combinations of the lower limit of any one of 10%, 12%, 15%, and 20% and 80%.
  • the inorganic particles 13 form a plurality of scattered aggregates 13a in a plan view of the surface layer 1s. According to such a configuration, variations in thermal conductivity are less likely to occur within the plane of the surface layer 1s.
  • the plurality of aggregates 13a are arranged, for example, to form a sea-island structure.
  • the average diameter of the aggregates 13a in a plan view of the surface layer 1s is not limited to a specific value. Its average diameter is, for example, 600 ⁇ m to 1100 ⁇ m. According to such a configuration, the ratio S 13 /S 1S can be easily adjusted to a desired range, and the thermal conductivity in the surface layer 1s of the composite material sheet 1 can be easily increased.
  • the average diameter of the aggregates 13a in a plan view of the surface layer 1s can be determined, for example, by measuring the maximum diameter of 50 or more aggregates 13a in a plan view of the surface layer 1s, and calculating the arithmetic average of the maximum diameters.
  • the average diameter of the aggregates 13a in a plan view of the surface layer 1s may be 650 ⁇ m or more, 700 ⁇ m or more, or 800 ⁇ m or more.
  • the average diameter may be 1050 ⁇ m or less, or 1000 ⁇ m or less.
  • the average diameter of the aggregates 13a in a plan view of the surface layer 1s is determined by all combinations of the lower limit of any one of 600 ⁇ m, 650 ⁇ m, 700 ⁇ m, and 800 ⁇ m and the upper limit of any one of 1100 ⁇ m, 1000 ⁇ m, and 1050 ⁇ m. It may be included in any of the specified ranges.
  • the ratio of the average value of the distance between the centers of the aggregates 13a to the average diameter of the aggregates 13a is not limited to a specific value.
  • the ratio is, for example, 2 or less.
  • the ratio S 13 /S 1S can be easily adjusted to a desired range, and the thermal conductivity in the surface layer 1s of the composite material sheet 1 can be easily increased.
  • the average value of the distance between the centers of the aggregates 13a in a plan view of the surface layer 1s is, for example, the distance between the centers of the aggregates 13a closest to the center of a circle whose diameter is the maximum diameter of 50 or more aggregates 13a in a plan view of the surface layer 1s. It can be determined by measuring the shortest distance to the center of a circle whose diameter is the maximum diameter of the aggregate 13a and finding the arithmetic average of the shortest distances.
  • the ratio of the average distance between the centers of the aggregates 13a to the average diameter of the aggregates 13a may be 1.75 or less, or may be 1.5 or less.
  • the ratio may be 1 or more, 1.1 or more, or 1.2 or more.
  • the ratio is within the range determined by all combinations of the lower limit of any one of 1, 1.1, and 1.2 and the upper limit of any one of 2, 1.75, and 1.5. may be included in
  • the inorganic particles 13 are arranged, for example, along the periphery of the voids 12 in the surface layer 1s. As a result, aggregates 13a are formed.
  • the maximum diameter d2 is larger than the maximum diameter d1.
  • the maximum diameter d1 is the maximum diameter of the surface layer 1s of the void 12 in the thickness direction.
  • the maximum diameter d2 is the maximum diameter in the in-plane direction of the surface layer 1s of the void 12 that is in contact with the surface layer 1s. According to such a configuration, the ratio S 13 /S 1S can be easily adjusted to a desired range, and the thermal conductivity in the surface layer 1s of the composite material sheet 1 can be easily increased.
  • the ratio d2/d1 of the maximum diameter d2 to the maximum diameter d1 in the void 12 in contact with the surface layer 1s is, for example, greater than 1, may be 1.1 or more, or may be 1.2 or more, It may be 1.3 or more, 1.4 or more, or 1.5 or more.
  • the ratio d2/d1 is, for example, 3 or less.
  • the thickness of the composite material sheet 1 is not limited to a specific value.
  • the thickness of the composite material sheet 1 is, for example, 10 mm or less. In this case, the ratio S 13 /S 1S is easily adjusted to a desired range, and the thermal conductivity in the surface layer 1s of the composite material sheet 1 is likely to be high.
  • the thickness of the composite material sheet 1 may be 8 mm or less, 5 mm or less, or 3 mm or less.
  • the thickness of the composite material sheet 1 is, for example, 0.1 mm or more.
  • the thickness of the surface layer 1s is, for example, 0.1 to 10% of the thickness of the composite material sheet 1, and is, for example, 1 ⁇ m to 300 ⁇ m.
  • the thickness of the surface layer 1s may correspond to, for example, the shortest distance from the surface of the composite material sheet 1 to the void 12 in a cross-sectional view of the composite material sheet 1.
  • the resin contained in the skeleton portion 11 is not limited to a specific resin.
  • the resin contained in the skeleton portion 11 is, for example, a thermosetting resin.
  • thermosetting resins are phenolic resins, urea resins, melamine resins, diallyl phthalate resins, polyester resins, epoxy resins, aniline resins, silicone resins, furan resins, polyurethane resins, alkylbenzene resins, guanamine resins, xylene resins, and imides. It is resin.
  • the curing temperature of the thermosetting resin is, for example, 25°C to 160°C.
  • the inorganic particles 13 are not limited to specific particles.
  • the inorganic particles 13 have, for example, a higher thermal conductivity than that of the resin included in the skeleton portion 11.
  • Examples of inorganic materials contained in the inorganic particles 13 include hexagonal boron nitride (h-BN), alumina, crystalline silica, amorphous silica, aluminum nitride, magnesium oxide, carbon fiber, silver, copper, aluminum, and silicon carbide. , graphite, zinc oxide, silicon nitride, silicon carbide, cubic boron nitride (c-BN), beryllia, diamond, carbon black, graphene, carbon nanotubes, carbon fiber, and aluminum hydroxide.
  • the number of types of inorganic particles 13 in the composite material sheet 1 may be only one, or two or more types of inorganic particles 13 may be used in combination in the composite material sheet 1.
  • the shape of the inorganic particles 13 is not limited to a specific shape. Examples of the shape are spherical shape, rod shape (including short fiber shape), scale shape, and needle shape.
  • the aspect ratio of the inorganic particles 13 is not limited to a specific value.
  • the aspect ratio of the inorganic particles 13 is, for example, less than 50, may be 40 or less, or may be 30 or less.
  • the aspect ratio of the inorganic particles 13 may be 1, 2 or more, or 3 or more.
  • the aspect ratio is the ratio of the maximum diameter of the particles to the minimum diameter of the particles (maximum diameter/minimum diameter) when the inorganic particles 13 are viewed from the direction in which the projected area of the inorganic particles 13 is maximized.
  • the average particle diameter of the inorganic particles 13 is not limited to a specific value.
  • the average particle size of the inorganic particles 13 is, for example, 0.05 ⁇ m to 100 ⁇ m, may be 0.1 ⁇ m to 50 ⁇ m, may be 0.1 ⁇ m to 30 ⁇ m, or may be 0.5 to 10 ⁇ m. .
  • the "average particle size" can be determined, for example, by a laser diffraction scattering method.
  • the average particle diameter is determined by the 50% cumulative value (median diameter ) d50 .
  • the shape of the inorganic particles 13 can be determined, for example, by observation using a scanning electron microscope (SEM) or the like.
  • the aspect ratio is 1.0 or more and less than 1.7, particularly 1.0 or more and 1.5 or less, and even 1.0 or more and 1.3 or less, and at least part of the outline
  • the inorganic particles 13 have a spherical shape.
  • the average particle size of the inorganic particles 13 is, for example, 0.1 ⁇ m to 50 ⁇ m, may be 0.1 ⁇ m to 10 ⁇ m, or may be 0.5 ⁇ m to 5 ⁇ m.
  • the average particle size of the inorganic particles 13 is, for example, 0.1 ⁇ m to 20 ⁇ m, and may be 0.5 ⁇ m to 15 ⁇ m.
  • the average thickness of the inorganic particles 13 is, for example, 0.05 ⁇ m to 1 ⁇ m, and may be 0.08 ⁇ m to 0.5 ⁇ m.
  • the average thickness can be determined by measuring the thickness of 50 arbitrary inorganic particles 13 using a SEM and calculating the arithmetic mean value.
  • the minimum diameter (usually short axis length) of the inorganic particles 13 is, for example, 0.01 ⁇ m to 10 ⁇ m, and may be 0.05 ⁇ m to 1 ⁇ m.
  • the maximum diameter (usually the major axis length) of the inorganic particles 13 is, for example, 0.1 ⁇ m to 20 ⁇ m, and may be 0.5 ⁇ m to 10 ⁇ m. If the size of the inorganic particles 13 is within this range, the heat transfer paths 15 are likely to be formed in the thickness direction of the composite material sheet 1 by the plurality of inorganic particles 13.
  • the content of inorganic particles 13 in the composite material sheet 1 is not limited to a specific value.
  • the content of inorganic particles 13 in the composite material sheet 1 is, for example, 10% by mass to 80% by mass, may be 10% by mass to 70% by mass, or may be 10% by mass to 55% by mass.
  • the content of inorganic particles 13 in the composite material sheet 1 is, for example, 1% to 50% by volume, may be 2% to 45% by volume, or may be 5% to 40% by volume, It may be 5% to 30% by volume.
  • the composite material sheet 1 can have high thermal conductivity and desired rigidity.
  • the mass-based content of the inorganic particles 13 in the composite material sheet 1 can be determined, for example, by removing materials other than the inorganic particles 13 from the composite material sheet 1. For example, materials other than the inorganic particles 13 are burned out from the composite material sheet 1.
  • the content of the inorganic particles 13 may be determined using elemental analysis. For example, acid is added to the composite material sheet 1, microwave irradiation is applied, and the composite material sheet 1 is subjected to pressure acid decomposition. Examples of acids that can be used include hydrofluoric acid, concentrated sulfuric acid, concentrated hydrochloric acid, and aqua regia.
  • the solution obtained by pressure acid decomposition is analyzed for elements using inductively coupled plasma optical emission spectroscopy (ICP-AES). Based on the results, the content of inorganic particles 13 on a mass basis in the composite material sheet 1 can be determined.
  • ICP-AES inductively coupled plasma optical emission spectroscopy
  • the volume-based content of inorganic particles 13 in the composite material sheet 1 can be determined from the mass and density of the inorganic particles 13 contained in the composite material sheet 1 and the volume and porosity of the composite material sheet 1. Specifically, the volume A of the inorganic particles 13 in the composite material sheet 1 is calculated from the mass and density of the inorganic particles 13. Separately, the volume B of the composite material sheet 1 excluding the volume of voids is calculated based on the porosity of the composite material sheet 1. The volume-based content of inorganic particles 13 in the composite material sheet 1 can be determined based on the relationship (A/B) ⁇ 100.
  • the density of the inorganic particles 13 can be determined, for example, by heating the composite material sheet 1 at high temperature in an electric furnace to burn off the organic material, and then determining the density of the remaining inorganic particles 13 according to Japanese Industrial Standards (JIS) R 1628:1997 or JIS Z 2504:2012. You can ask for it in compliance.
  • JIS Japanese Industrial Standards
  • the method for manufacturing the composite material sheet 1 is not limited to a specific method.
  • the composite material sheet 1 can be manufactured using, for example, a manufacturing apparatus 100 shown in FIG. 3A.
  • the fluid 2 is subjected to a predetermined process to manufacture the composite material sheet 1.
  • the fluid 2 contains a thermosetting resin 2b and inorganic particles 13.
  • the fluid 2 is heated and the thermosetting resin 2b is cured. Thereby, a composite material sheet 1 is obtained.
  • the thickness t1 and the thickness t2 are not limited to specific values as long as the relationship t1>t2 is satisfied.
  • the thickness t1 is, for example, 0.5 mm or more, may be 1 mm or more, or may be 3 mm or more.
  • the thickness t1 is, for example, 30 mm or less, may be 20 mm or less, or may be 10 mm or less.
  • the thickness t2 is, for example, 0.1 mm or more, may be 0.5 mm or more, or may be 1 mm or more.
  • the thickness t2 is, for example, 20 mm or less, may be 10 mm or less, or may be 5 mm or less.
  • the thickness of the composite material sheet 1 is, for example, the same as the thickness t2.
  • the thickness of the composite material sheet 1 may be 90% to 110% of the thickness t2.
  • the temperature around the fluid 2 is maintained at a temperature higher than the curing temperature of the thermosetting resin 2b.
  • the heating time of the fluid 2 is not limited to a specific value as long as the thermosetting resin 2b can be cured.
  • the heating time of the fluid 2 depends on the type and additives of the thermosetting resin 2b, but is, for example, 10 seconds or more and 1 hour or less.
  • the method for preparing the fluid 2 is not limited to a specific method.
  • the fluid 2 is obtained by kneading the thermosetting resin 2b and the inorganic particles 13.
  • the fluid 2 may be obtained by infiltrating the thermosetting resin 2b into the gaps between the inorganic particles 13. Therefore, the inorganic particles 13 are uniformly dispersed in the fluid 2. Thereby, the thermal conductivity of the composite material sheet 1 is less likely to vary within the plane of the composite material sheet 1.
  • the fluid 2 contains, for example, a porosity agent 2p.
  • a plurality of voids 12 are formed in the composite material sheet 1 by the porosity forming agent 2p, and the composite material sheet 1 has a porous structure.
  • the pore-forming agent 2p is not limited to a specific porosity-forming agent as long as it can form a plurality of voids 12 in the composite material sheet 1.
  • the porosity-forming agent 2p is dissolved in a specific solvent.
  • the porosity agent 2p may be evaporated, softened, or thermally decomposed by heating.
  • the porosity agent 2p may be shrunk or removed.
  • the porosity agent 2p can be shrunk or removed by contact with a specific solvent or by heating. The shrunken porosity agent 2p may remain in the composite material sheet 1.
  • the pore-forming agent 2p may have a hollow structure or a solid structure.
  • the pore-forming agent 2p may be hollow resin particles.
  • the heat treatment softens the resin constituting the resin particles, causing the hollow portion to disappear or shrink, and voids 12 may be formed accordingly.
  • the porosity forming agent 2p may be solid resin particles. In this case, when the porosity-forming agent 2p comes into contact with a specific solvent, the porosity-forming agent 2p is dissolved in the solvent, and voids 12 can be formed.
  • resins contained in hollow or solid resin particles include polystyrene (PS), polyethylene (PE), polymethyl methacrylate (PMMA), ethylene vinyl acetate copolymer (EVA), polyethylene (PE), These are polyvinyl chloride (PVC), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-propylene-diene rubber (EPDM), thermoplastic elastomer (TPE), and polyvinyl alcohol (PVA).
  • PS polystyrene
  • PE polyethylene
  • PMMA polymethyl methacrylate
  • EVA ethylene vinyl acetate copolymer
  • PVC polyvinyl chloride
  • PP polypropylene
  • ABS acrylonitrile-butadiene-styrene copolymer
  • EPDM ethylene-propylene-diene rubber
  • TPE thermoplastic elastomer
  • PVA polyvinyl alcohol
  • the inorganic particles 13 form hollow aggregates in the fluid 2, for example.
  • the pores 2h are formed inside the aggregate of the inorganic particles 13.
  • the inorganic particles 13 are aggregated around the holes 2h so as to cover the holes 2h. For example, a plurality of aggregates are dispersed in the fluid 2.
  • the inorganic particles 13 are aggregated around the pore-forming agent 2p so as to cover the outer surface of the porosity-forming agent 2p. Therefore, the inorganic particles 13 can be arranged along the periphery of the voids 12 in the composite material sheet 1 .
  • the manufacturing apparatus 100 includes, for example, a pair of members 20.
  • the pair of members 20 are arranged at a predetermined interval.
  • the fluid 2 is sandwiched between a pair of members 20 and formed to have a second thickness t2.
  • the distance between the pair of members 20 may or may not be constant.
  • the interval between the pair of members 20 may narrow or widen as the fluid 2 passes, as long as the fluid 2 can be formed to have the second thickness t2.
  • the fluid 2 is formed to have a second thickness t2 in a state where it can flow in the plane of the fluid 2 between the pair of members 20.
  • the thickness of the fluid 2 decreases while the fluid 2 flows in the plane of the fluid 2, so that the inorganic particles 13 aggregate along the flat surface in the surface layer 1s of the composite material sheet 1. It is easy to become in a state of
  • the pair of members 20 is not limited to a specific member as long as the fluid 2 can flow so that the fluid 2 has the second thickness t2.
  • the manufacturing apparatus 100 includes, for example, a transport device 40.
  • the conveyance device 40 conveys the fluid 2 so that the fluid 2 passes between the pair of members 20 .
  • the productivity of the composite material sheet 1 tends to be high.
  • the manufacturing apparatus 100 includes, for example, a heater 30.
  • the heater 30 heats the fluid 2 when the fluid 2 is between the pair of members 20 or after the fluid 2 passes between the pair of members 20. Thereby, the fluid 2 is heated in a state where the fluid 2 has the second thickness t2, and the thermosetting resin 2b can be cured.
  • the pair of members 20 includes, for example, a conveying belt 22.
  • the fluid 2 can be heated by a belt 22, for example.
  • the heater 30 is placed in contact with the belt 22.
  • the belt 22 is heated by the heater 30, and the belt 22 further heats the fluid 2.
  • the heater 30 is arranged inside the belt 22, for example.
  • the belt 22 may be made of metal or resin.
  • the molding machine including the belt 22 is, for example, a double belt press machine.
  • the double belt press machine may be a sliding shoe type double belt press machine or a roller type double belt press machine.
  • a pressure block with a built-in heater is placed inside the belt. This pressurizes and heats the belt.
  • the pressure block is fixed and a belt slides on the pressure block.
  • the sliding shoe type double belt press machine may include a plurality of pressure blocks. The temperatures of the plurality of pressure blocks may be the same or different. Some of the plurality of pressure blocks may be used as pressure blocks for cooling.
  • pressure is applied from the inside of the belt using multiple rollers. In this case, the roller itself may have a built-in heater, or the belt may be indirectly heated by another heater.
  • the manufacturing apparatus 100 includes, for example, a supply device 10.
  • the supply device 10 supplies the fluid 2.
  • the fluid 2 having the first thickness t1 is supplied.
  • a fluid 2 is placed on a substrate 3.
  • the fluid 2 is conveyed together with the base material 3 between the pair of members 20 .
  • the feeder 10 feeds the fluid 2 toward the substrate 3, and the fluid 2 is placed on the substrate 3.
  • the pair of members 20 deform the fluid 2 so that it has a second thickness t2 that is smaller than the first thickness t1 when the fluid 2 is supplied from the supply device 10.
  • the fluid 2 is continuously placed on the base material 3 that is unwound from a rolled body (not shown). Thereby, continuous production of the composite material sheet 1 is possible, and the productivity of the composite material sheet 1 tends to be high.
  • a laminate 5 may be formed by disposing the fluid 2 between the base material 3 and the release sheet 4.
  • the laminate 5 is conveyed between a pair of members 20.
  • the composite material sheet 1 can be protected by the base material 3 and the release sheet 4.
  • the fluid 2 may be placed between the pair of members 20 in a state where it is in contact with at least one of the members 20 .
  • the supply device 10 is not limited to a specific supply device as long as it can supply the fluid 2.
  • the supply device 10 is, for example, a die coater.
  • the fluid 2 is placed on the substrate 3 by die coating. According to such a configuration, the fluid 2 can be placed on the base material 3 with a uniform thickness.
  • the manufacturing apparatus 100 can be modified from various viewpoints. For example, after molding the fluid 2 having a first thickness t1 to have a second thickness t2 smaller than the first thickness t1, the fluid 2 may be heated to harden the thermosetting resin 2b.
  • the inorganic particles 13 tend to aggregate along the flat surface in the surface layer 1s of the composite material sheet 1, and the inorganic particles 13 tend to be arranged at a high density in the surface layer 1s of the composite material sheet 1. Therefore, the thermal conductivity of the surface layer 1s of the composite material sheet 1 tends to increase, and the thermal conductivity of the composite material sheet 1 also tends to increase.
  • the manufacturing apparatus 100 may further include a partition having a dimension equal to or larger than the distance between the pair of members 20, if necessary. Such a partition facilitates suppressing deformation of a portion of the fluid 1 along the gap between the pair of members 20.
  • the manufacturing apparatus 100 may be modified, for example, to a manufacturing apparatus 200 shown in FIG. 3B.
  • the manufacturing apparatus 200 is configured in the same manner as the manufacturing apparatus 100 except for parts that are specifically explained. Components of the manufacturing apparatus 200 that are the same as or correspond to those of the manufacturing apparatus 100 are given the same reference numerals, and detailed description thereof will be omitted. The description regarding the manufacturing apparatus 200 also applies to the manufacturing apparatus 100 unless technically contradictory.
  • the pair of members 20 includes a first pair of rollers 24 and a second pair of rollers 25.
  • the fluid 2 is conveyed by a pair of members 20.
  • the second pair of rollers 25 is arranged downstream of the first pair of rollers 24 in the transport direction of the fluid 2.
  • the distance between the rollers in the second pair of rollers 25 is less than or equal to the distance between the rollers in the first pair of rollers 24.
  • the distance between the rollers is the shortest distance between the rollers.
  • the fluid 2 having the first thickness t1 is made to have the second thickness t2 by passing between the first pair of rollers 24 and between the second pair of rollers 25. molded.
  • the distance between the rollers in the second pair of rollers 25 may be smaller than the distance between the rollers in the first pair of rollers 24.
  • the heater 30 is arranged downstream of the second pair of rollers 25, for example. According to such a configuration, the fluid 2 is heated after passing between the pair of members 20.
  • the fluid 2 may be heated by at least one of the first pair of rollers 24 and the second pair of rollers 25, or may not be heated by the first pair of rollers 24 and the second pair of rollers 25. .
  • the composite material sheet 1 may be manufactured using a device other than the manufacturing device 100 and the manufacturing device 200.
  • the composite material sheet 1 may be manufactured, for example, by a method including the following (i), (ii), and (iii).
  • (ii) A predetermined plate is placed on the fluid 2 with a spacer placed between the plate and the base material, and a weight is placed on the plate so that the fluid 2 has the second thickness t2. Let it flow.
  • the laminate of the base material, fluid 2, plate, and weight prepared in (ii) is placed in a heating furnace to harden the thermosetting resin 2b of the fluid 2, thereby obtaining a composite material sheet 1.
  • the reaction solution was heated to 120° C. over 30 minutes. Thereafter, the reaction solution was kept at 120° C. for 1 hour to prepare a styrene resin particle-containing solution. After the liquid containing styrene resin particles was cooled to 95° C., 2 parts by weight of cyclohexane and 7 parts by weight of butane were pressurized into the autoclave as blowing agents. Thereafter, the temperature of this solution was raised to 120°C again. Thereafter, the solution was kept at 120° C. for 1 hour, and then cooled to room temperature to obtain a slurry. Expandable styrene resin particles were obtained by dehydrating, washing, and drying this slurry.
  • the expandable styrene resin particles were sieved to obtain expandable styrene resin particles having a particle diameter of 0.2 mm to 0.3 mm.
  • the expandable styrene resin particles were foamed using a pressure foaming machine (BHP) manufactured by Daikai Kogyo Co., Ltd. to obtain spherical expanded polystyrene beads having an average diameter of 650 ⁇ m to 1200 ⁇ m.
  • the expanded polystyrene beads were passed through a JIS test sieve with nominal openings (JIS Z 8801-1:2019) of 1.18 mm and 1 mm.
  • Example 1 A silicone resin precursor was prepared by mixing agents A and B of DOWSIL SE 1896 FR A/B manufactured by Dow Corporation at a weight ratio of 1:1 as an impregnant. 11.3 parts by weight of this silicone resin precursor was prepared for 1 part by weight of expanded polystyrene beads. Separately, 20 parts by weight of scale-like boron nitride (aspect ratio 20) was prepared for 1 part by weight of expanded polystyrene beads.
  • the fluid according to Example 1 was obtained by adding the above thermosetting resin to a container containing the above composite particles and filling the spaces between the composite particles with the thermosetting resin.
  • a coating film of this fluid was formed by die coating on a base material which is a PET film SS4A (thickness: 50 ⁇ m) manufactured by Nipper Co., Ltd. The thickness of this coating film was 5.0 mm.
  • the above-mentioned PET film was layered on top of the coating film to obtain a laminate.
  • the fluid in the laminate was made to flow to a thickness of 3.0 mm using a sliding shoe type double belt press, and the temperature of the belt of the double belt press was adjusted to 100°C to release the thermosetting resin in the fluid. hardened.
  • the heating time of the fluid was 5 minutes. Peel the cured product of the fluid from the base material and release sheet, cut the cured product into predetermined dimensions, and immerse it in acetone for 30 minutes to dissolve the polyethylene beads in the composite particles and remove the polystyrene beads from the cured product. did. Thereafter, the cured product was heated at 90° C. to volatilize acetone to obtain a composite material sheet according to Example 1.
  • the thickness of the composite material sheet according to Example 1 was 3.05 mm.
  • Example 2 A composite material sheet according to Example 2 was produced in the same manner as in Example 1, except that a roller type double belt press machine was used instead of the sliding shoe type double belt press machine. The fluid in the laminate was fluidized using a roller type double belt press to have a thickness of 3.0 mm. The thickness of the composite material sheet according to Example 2 was 3.0 mm.
  • Example 3 Instead of a sliding shoe type double belt press machine, multiple pairs of rollers are used to flow the fluid in the laminate to a thickness of 3.0 mm, and then the fluid is heated in a heating furnace to form the fluid.
  • a composite material sheet according to Example 3 was produced in the same manner as in Example 1, except that the thermosetting resin in Example 3 was cured. In molding using multiple pairs of rollers, the fluid passed between the rollers in the multiple pairs of rollers. The distance between the rollers in the most upstream pair of rollers was 3.5 mm, and the distance between the rollers in another pair of most downstream rollers was 3.0 mm. During heating in the heating furnace, the temperature inside the heating furnace was adjusted to 100°C. The heating time of the fluid was 5 minutes. The thickness of the composite material sheet according to Example 3 was 2.9 mm.
  • thermosetting resin was added to this plastic case and defoamed under reduced pressure.
  • the pressure at this time was -0.08 MPa to -0.09 MPa in gauge pressure.
  • This operation was repeated three times to impregnate the thermosetting resin between the polystyrene beads.
  • the silicone resin was cured by heating at 80° C. for 2 hours to obtain a resin molded product containing polystyrene beads.
  • This resin molded product was cut into predetermined dimensions. By immersing this in acetone for 30 minutes, the polystyrene beads were dissolved and removed from the resin molded product.
  • a composite material sheet according to Comparative Example 1 was produced by heating the resin molded product at 90° C. to volatilize acetone. In the composite material sheet according to Comparative Example 1, the surface layer (skin layer) was not cut.
  • the thickness of the composite material sheet according to Comparative Example 1 was 3.5 mm.
  • ⁇ Thermal conductivity> In accordance with the American Society for Testing and Materials standard (ASTM) D5470-01 (one-way steady heat flow method), a heat flow meter method was used using a single test specimen and a symmetric configuration method using a thermal conductivity measuring device TCM1001 manufactured by Resca. The thermal conductivity in the thickness direction of the composite material sheets according to each Example and Comparative Example 1 was measured. Each composite material sheet having a thickness t was cut into a square shape with a side length of 20 mm in plan view to obtain a test piece. Silicone grease SCH-20 manufactured by Sunhayato Co., Ltd. was applied to both main surfaces of the test piece so that the thickness of the silicone grease layer was 100 ⁇ m.
  • the thermal conductivity of the silicone grease was 0.84 W/(m ⁇ K).
  • an upper rod with a heating block adjusted to 110°C and a lower rod with a cooling block adjusted to 20°C was used.
  • a block made of oxygen-free copper was used as the test block.
  • a measurement sample was prepared by sandwiching the test piece between oxygen-free copper blocks with a silicone grease layer in between. This measurement sample was sandwiched between an upper rod and a lower rod. Heat was applied in the thickness direction of the test piece.
  • the temperature difference ⁇ T S between the upper and lower surfaces of the test piece was determined according to the following formulas (1) and (2).
  • ⁇ T C is the temperature difference between the top and bottom surfaces of the oxygen-free copper block (test block).
  • q 1 is the heat flux [W/m 2 ] determined by the temperature gradient calculated based on the temperature difference at multiple temperature measurement points on the upper rod
  • q 2 is the heat flux [W/m 2 ] determined by the temperature gradient calculated based on the temperature difference at multiple temperature measurement points on the upper rod. It is the heat flux [W/m 2 ] determined by the temperature gradient calculated based on the temperature difference at the temperature measurement point.
  • t b is the sum of the thicknesses of the oxygen-free copper blocks.
  • k b is the thermal conductivity of the block made of oxygen-free copper.
  • the average diameter dBN of the boron nitride aggregates in the surface layer in plan view and the average value D S of the distance between the centers of the aggregates were determined.
  • the average diameter dBN was determined by measuring the maximum diameter of 50 or more boron nitride aggregates in a plan view of the surface layer of each composite material sheet, and calculating the arithmetic average of the maximum diameters.
  • the average value D S is the maximum diameter of the boron nitride aggregates closest to the center of a circle whose diameter is the maximum diameter of 50 or more boron nitride aggregates in a plan view of the surface layer of each composite material sheet.
  • the diameter was determined by measuring the shortest distance from the center of the circle and finding the arithmetic average of the shortest distances. The results are shown in Table 1.
  • the thermal conductivity in the thickness direction of the composite material sheet according to the example was higher than the thermal conductivity in the thickness direction of the composite material sheet according to Comparative Example 1.
  • the ratio S BN /S 1S in the composite material sheet according to the example was higher than the ratio S BN /S 1S in the composite material sheet according to Comparative Example 1.
  • the first aspect of the present invention is A skeleton part containing resin, multiple voids, a heat transfer path formed by inorganic particles; having a surface layer in which the resin and the inorganic particles are present; In a plan view of the surface layer, the ratio of the area of the portion where the inorganic particles are present to the area of the surface layer is 10% or more; Provides composite material sheets.
  • the second aspect of the present invention is The inorganic particles form a plurality of scattered aggregates in a plan view of the surface layer, A composite material sheet according to the first aspect is provided.
  • the third aspect of the present invention is In a plan view of the surface layer, the ratio of the average value of the distance between the centers of the aggregates to the average diameter of the aggregates is 2 or less, A composite material sheet according to the second aspect is provided.
  • the fourth aspect of the present invention is The average diameter of the aggregates in a plan view of the surface layer is 600 ⁇ m to 1100 ⁇ m, A composite material sheet according to the second side or the third side is provided.
  • the fifth aspect of the present invention is The inorganic particles are arranged along the periphery of the void in the surface layer to form the aggregate,
  • the maximum diameter of the void in contact with the surface layer in the in-plane direction of the surface layer is larger than the maximum diameter of the void in the thickness direction of the surface layer.
  • a composite material sheet according to any one of the second to fourth sides is provided.
  • the sixth aspect of the present invention is The thickness of the composite material sheet is 10 mm or less, A composite material sheet according to any one of the first side to the fifth side is provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

Feuille de matériau composite (1) comprenant une partie squelette (11), une pluralité d'interstices (12) et une voie de transfert de chaleur (15). La partie squelette (11) inclut d'une résine. Le chemin de transfert de chaleur (15) est constitué de particules inorganiques (13). La feuille de matériau composite (1) présente une couche superficielle (1s) dans laquelle se trouvent la résine incluse dans la partie de squelette (11) et les particules inorganiques (13). Le rapport S13/S1S de la surface S13 de la section dans laquelle les particules inorganiques (13) sont présentes à la surface S1S de la couche de surface 1s dans la vue en plan de la couche de surface 1s est supérieur ou égal à 10 %.
PCT/JP2023/010754 2022-03-29 2023-03-17 Feuille de matériau composite WO2023189778A1 (fr)

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JP2022053252 2022-03-29

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007320988A (ja) * 2006-05-30 2007-12-13 Futamura Chemical Co Ltd 封入物を有する連通多孔構造体及びその製法
JP2013014716A (ja) * 2011-07-06 2013-01-24 Nitto Denko Corp 無機粒子含有発泡体
JP2018109101A (ja) * 2016-12-28 2018-07-12 トヨタ自動車株式会社 複合材料およびその製造方法
WO2021201065A1 (fr) * 2020-03-31 2021-10-07 日東電工株式会社 Matériau composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007320988A (ja) * 2006-05-30 2007-12-13 Futamura Chemical Co Ltd 封入物を有する連通多孔構造体及びその製法
JP2013014716A (ja) * 2011-07-06 2013-01-24 Nitto Denko Corp 無機粒子含有発泡体
JP2018109101A (ja) * 2016-12-28 2018-07-12 トヨタ自動車株式会社 複合材料およびその製造方法
WO2021201065A1 (fr) * 2020-03-31 2021-10-07 日東電工株式会社 Matériau composite

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