WO2021235277A1 - Composition de résine thermoconductrice et corps moulé la comprenant - Google Patents

Composition de résine thermoconductrice et corps moulé la comprenant Download PDF

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Publication number
WO2021235277A1
WO2021235277A1 PCT/JP2021/017933 JP2021017933W WO2021235277A1 WO 2021235277 A1 WO2021235277 A1 WO 2021235277A1 JP 2021017933 W JP2021017933 W JP 2021017933W WO 2021235277 A1 WO2021235277 A1 WO 2021235277A1
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Prior art keywords
thermally conductive
resin composition
polyamide
heat
thermoplastic resin
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PCT/JP2021/017933
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English (en)
Japanese (ja)
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夕哉 正鋳
渉 大畠
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ユニチカ株式会社
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Priority to CN202180034970.1A priority Critical patent/CN115551951B/xx
Publication of WO2021235277A1 publication Critical patent/WO2021235277A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention contains a thermoplastic resin and a thermally conductive filler, and can produce a molded body having excellent fogging resistance and a thermal conductivity of 2 W / (m ⁇ K) or more in the flow direction. It relates to a resin composition and a molded body made of the resin composition.
  • the thermal conductivity in the flow direction is 2 W / (m), which is 10 times the thermal conductivity of 0.2 W / (m ⁇ K) of a general resin composition. ⁇ K) is required. Therefore, there is a demand for a material having a thermal conductivity of 2 W / (m ⁇ K) or more in the flow direction of the molded product and having good fogging resistance.
  • a resin composition having high thermal conductivity can be obtained by highly filling a resin material with a thermally conductive filler (for example, graphite, copper, aluminum, aluminum oxide, etc.) having high thermal conductivity. Has been done. Molds manufactured using such a resin composition have been studied as members for manufacturing electrical and electronic parts (for example, Patent Documents 1 to 7).
  • a thermally conductive filler for example, graphite, copper, aluminum, aluminum oxide, etc.
  • the degassing during manufacturing becomes insufficient, and the resin composition can be obtained by using the resin composition. It has been found that there arises a problem that the fogging resistance of the molded product is deteriorated.
  • the degassing in the production of the resin composition is performed by simply evacuating from the vent port provided in the vicinity of the most downstream in the extrusion direction in the extruder in the conventional method. At this time, if a large amount of the heat conductive filler is blended in the resin composition, the internal pressure becomes high, and the melt tends to overflow from the vent port and / or the vent port tends to be closed.
  • the present invention provides a resin composition capable of producing a molded body having excellent fogging resistance while having a thermal conductivity of 2 W / (m ⁇ K) or more in the flow direction, and a molded body obtained from the resin composition.
  • the purpose is.
  • the present invention also relates to a resin composition capable of producing a molded product having excellent fogging resistance, bending characteristics and molding fluidity while having a thermal conductivity of 2 W / (m ⁇ K) or more in the flow direction. It is an object of the present invention to provide a more obtained molded product.
  • the thermal conductivity is a property in which heat is easily conducted in a molded product manufactured by using the thermally conductive resin composition.
  • the thermal conductivity may be, for example, a characteristic that the thermal conductivity in the flow direction at the time of manufacturing a molded body (for example, at the time of injection molding) is 2 W / (m ⁇ K) or more.
  • the fogging resistance is a property that the molded product manufactured by using the heat conductive resin composition is less likely to be fogged even in a high temperature environment of 100 ° C. or higher (for example, 125 ° C.).
  • the bending property is a property in which the bending strength and the bending elastic modulus of the molded product manufactured by using the heat conductive resin composition are sufficiently high. Molding fluidity is a characteristic that the resin composition can sufficiently flow when a molded product is produced using the thermally conductive resin composition.
  • Thermal conductivity and fogging resistance are the characteristics of the thermally conductive resin composition of the present invention. Bending characteristics and molding fluidity are not the characteristics that the thermally conductive resin composition of the present invention must have, but the characteristics that the thermally conductive resin composition of the present invention usually has or are preferable to have. Is.
  • the present inventors have solved the above-mentioned problems by strengthening the degassing by the vacuum pump when compounding the thermoplastic resin and the heat conductive filler. We found that and arrived at the present invention.
  • the gist of the present invention is as follows. ⁇ 1> A thermally conductive resin composition containing a thermoplastic resin (A) and a thermally conductive filler (B). The mass ratio of the thermoplastic resin (A) to the thermally conductive filler (B) is 38/62 to 85/15. The haze value of the glass plate after the fogging test at 125 ° C. for 200 hours is 8 or less. A heat conductive resin composition having a heat conductivity of 2 W / (m ⁇ K) or more in the flow direction of a molded body obtained by molding the heat conductive resin composition.
  • the thermally conductive filler (B) is talc, aluminum oxide, magnesium oxide, zinc oxide, magnesium carbonate, silicon carbide, aluminum nitride, boron nitride, silicon nitride, carbon, graphite, silver, copper, aluminum,
  • the thermally conductive resin composition according to ⁇ 1> which is one or more materials selected from the group consisting of titanium, nickel, tin, iron, and stainless steel.
  • the thermally conductive resin composition further contains a non-thermally conductive fibrous reinforcing material (C), and the total of the thermoplastic resin (A) and the thermally conductive filler (B) and the non-thermally conductive filler.
  • the thermoplastic resin (A) is composed of a crystalline polyamide and an amorphous polyamide, and the mass ratio of the crystalline polyamide to the amorphous polyamide is 100/0 to 40/60.
  • the thermally conductive resin composition according to any one of ⁇ 5>. ⁇ 7> The mass ratio of the thermoplastic resin (A) to the thermally conductive filler (B) is 38/62 to 75/25. The heat conductive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the heat conductive filler (B) is graphite. ⁇ 8> The mass ratio of the thermoplastic resin (A) to the thermally conductive filler (B) is 45/55 to 70/30.
  • the thermally conductive filler (B) is scaly graphite having an average particle size of 80 to 270 ⁇ m.
  • the thermally conductive resin composition further contains a non-thermally conductive fibrous reinforcing material (C).
  • the mass ratio of the total of the thermoplastic resin (A) and the thermally conductive filler (B) to the non-thermally conductive fibrous reinforcing material (C) is 100/0 to 75/25, ⁇ 1>.
  • the thermally conductive resin composition according to any one of ⁇ 7>. ⁇ 9> A molded product made of the thermally conductive resin composition according to any one of ⁇ 1> to ⁇ 8>.
  • a resin composition capable of producing a molded body having excellent fogging resistance while having a thermal conductivity of 2 W / (m ⁇ K) or more in the flow direction and a molded body obtained by the resin composition can be produced.
  • a schematic cross-sectional view of an extruder for producing the resin composition of the present invention is shown.
  • the schematic diagram for demonstrating the method of measuring the haze value which defines the resin composition of this invention is shown.
  • the schematic diagram of the air collecting bottle used in the method of measuring the haze value which defines the resin composition of this invention is shown.
  • the thermally conductive resin composition of the present invention contains a thermoplastic resin (A) and a thermally conductive filler (B).
  • thermoplastic resin (A) used in the present invention is not particularly limited, but is, for example, an olefin resin such as polyethylene, polypropylene, an ethylene- ⁇ -olefin copolymer (for example, an ethylene-propylene copolymer, etc.); polymethylpentene.
  • an olefin resin such as polyethylene, polypropylene, an ethylene- ⁇ -olefin copolymer (for example, an ethylene-propylene copolymer, etc.); polymethylpentene.
  • the polyamide resin used in the present invention is a homopolyamide or copolyamide having an amide bond, or a mixture thereof.
  • Homopolyamides and copolyamides having an amide bond can be obtained by polymerizing lactam, aminocarboxylic acid, diamine, dicarboxylic acid and the like.
  • lactam, aminocarboxylic acid and diamine, and dicarboxylic acid constituting the homopolyamide and copolyamide include lactam, aminocarboxylic acid, diamine and dicarboxylic acid which can form the crystalline polyamide and the amorphous polyamide described later, respectively. ..
  • the crystalline (or amorphous) of the polyamide resin is not particularly limited, and the polyamide resin is, for example, crystalline polyamide (A-1-1) alone or crystalline polyamide (A-1-1) and amorphous polyamide. It may be any mixture of (A-1-2). Specifically, the polyamide resin contains a crystalline polyamide (A-1-1) and may or may not further contain an amorphous polyamide (A-1-2).
  • the crystalline polyamide (A-1-1) has a value of heat of fusion measured at a heating rate of 16 ° C./min under a nitrogen atmosphere using a differential scanning calorimeter (DSC) of 1 cal / g or more.
  • DSC differential scanning calorimeter
  • Amorphous polyamide (A-1-2) has a melting heat value of less than 1 cal / g measured at a heating rate of 16 ° C./min under a nitrogen atmosphere using a differential scanning calorimeter (DSC). It means a certain polyamide resin.
  • Examples of the crystalline polyamide (A-1-1) include polytetramethylene isophthalamide (polyamide 4I), polytetramethylene terephthalamide (polyamide 4T), polycapramide (polyamide 6), and polytetramethylene adipamide (polyamide 46). ), Polyhexamethylene adipamide (polyamide 66), polycapramide / polyhexamethylene adipamide copolymer (polyamide 6/66), polyundecamide (polyamide 11), polycapramide / polyundecamide copolymer (polyamide 6/11), polydodecamide.
  • Polyamide 12 polycoupled / polydodecamide copolymer (polyamide 6/12), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116).
  • Polyhexamethylene isophthalamide (Polyamide 6I), Polyhexamethylene terephthalamide (Polyamide 6T), Polycapramide / Polytetramethylene terephthalamide copolymer (Polyamide 6 / 4T), Polycapramido / Polytetramethylene isophthalamide copolymer (Polyamide 6 / 4I) , Polyhexamethylene adipamide / polytetramethylene terephthalamide copolymer (polyamide 66 / 4T), polyhexamethylene adipamide / polytetramethylene isophthalamide copolymer (polyoxide 66 / 4I), polyhexamethylene terephthalamide / polyhexamethylene Isophthalamide copolymer (polyamide 6T / 6I), polycapramide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polycapramide / polyhexamethylene isophthalamide
  • polyamide 6 and / or polyamide 66 is more preferable, and polyamide 6 is more preferable, from the viewpoints of further improvement of thermal conductivity and fogging resistance, and improvement of bending characteristics and molding fluidity.
  • the crystalline polyamide resin one of the above may be used alone or in combination.
  • Examples of the amorphous polyamide (A-1-2) include isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane copolymer and terephthalic acid / 2, 2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine copolymer, isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ⁇ -lauro Lactum copolymer, isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymer, isophthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6 -Hexanediamine copolymer, isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine
  • isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane from the viewpoint of further improvement of thermal conductivity and fogging resistance, and improvement of bending characteristics and molding fluidity.
  • Polymer terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine copolymer, isophthalic acid / terephthalic acid / 1,6- Hexadiamine / bis (3-methyl-4-aminocyclohexyl) methane copolymer and terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexane
  • isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymers are preferred, isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl).
  • a methane copolymer and an isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymer are more preferable.
  • the amorphous polyamide resin one of the above may be used alone or in combination.
  • the crystalline polyamide (A-1-1) and the amorphous polyamide (A-1-2) in combination further improvement in fogging resistance can be achieved, for example, the haze value after the fogging test can be further increased. It can be made smaller.
  • the mass ratio of the crystalline polyamide (A-1-1) and the amorphous polyamide (A-1-2) is not particularly limited, and further the thermal conductivity and the fogging resistance are further improved, and the bending characteristics and the molding fluidity are improved. From the viewpoint of the above, it is preferably 100/0 to 40/60, more preferably 100/0 to 55/45, more preferably 100/0 to 70/30, and even more preferably 100/0 to 80/20.
  • the ratio of crystalline polyamide (A-1-1) and amorphous polyamide (A-1-2) is further improved and the mechanical properties (particularly bending characteristics) are maintained. It is possible.
  • the relative viscosity of the thermoplastic resin (A) (particularly the polyamide resin) is not particularly limited, but from the viewpoint of improving mechanical properties (particularly bending properties) and heat resistance, 96% by mass concentrated sulfuric acid is used as a solvent and the temperature is 25.
  • the relative viscosity measured at ° C. and a concentration of 1 g / dL is preferably 1.6 or more (particularly 1.85 or more).
  • the relative viscosity is usually 3.5 or less, especially 3.2 or less.
  • the thermoplastic resin composition used in the present invention needs to contain the heat conductive filler (B) together with the thermoplastic resin (A).
  • the thermally conductive filler (B) include talc (5 to 10), aluminum oxide (36), magnesium oxide (60), zinc oxide (25), magnesium carbonate (15), silicon carbide (160), and the like.
  • Inorganic fillers such as aluminum nitride (170), boron nitride (210), silicon nitride (40), carbon (10 to several hundred), graphite (10 to several hundred), silver (427), copper (398),
  • Metallic fillers such as aluminum (237), titanium (22), nickel (90), tin (68), iron (84), and stainless steel (15) can be mentioned (the numbers in parentheses are representative of thermal conductivity).
  • the average particle size of the heat conductive filler (B) is not particularly limited, and may be, for example, 1 ⁇ m or more, particularly 1 to 500 ⁇ m (preferably 1 to 200 ⁇ m).
  • Examples of the form of graphite include spherical, powdery, fibrous, needle-like, scale-like, whisker-like, microcoil-like, and nanotube-like.
  • scaly graphite is more preferable because it can increase the heat conduction efficiency when blended with the thermoplastic resin (A).
  • the larger the average particle size of scaly graphite the higher the thermal conductivity, but the mechanical properties tend to decrease, and the mechanical properties and thermal conductivity are uniform without causing agglomerates due to poor dispersion.
  • the average particle size of the scaly graphite is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 30 ⁇ m or more. It is particularly preferably 30 to 500 ⁇ m (particularly 30 to 200 ⁇ m), and most preferably 80 to 270 ⁇ m (particularly 80 to 180 ⁇ m).
  • the talc form examples include plate-like, scaly-like, scaly-like, and flaky-like.
  • scaly talc and flaky talc are more preferable because they tend to be oriented in the plane direction when formed into a molded body, and as a result, the thermal conductivity can be increased.
  • the average particle size of the scaly talc is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and more preferably 15 ⁇ m or more for the same reason as the above-mentioned reason for the preferable average particle size of the scaly graphite. It is more preferably 15 to 70 ⁇ m, and particularly preferably 15 to 70 ⁇ m.
  • the thermally conductive filler (B) used in the present invention is a silane-based coupling agent or a titanium-based coupling agent in order to improve the adhesion with the thermoplastic resin (A) as long as the effect of the present invention is not impaired.
  • the surface may be treated with.
  • the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ - (aminoethyl) - ⁇ -aminopropyldimethoxymethyl.
  • Aminosilane-based coupling agents such as silane, and epoxysilane-based cups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Ring agent can be mentioned.
  • the titanium-based coupling agent include isopropyltristearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, tetraisopropylbis (dioctylphosphite) titanate and the like. These may be used alone or in combination of two or more.
  • the mass ratio (A / B) of the thermoplastic resin (A) and the heat conductive filler (B) needs to be 38/62 to 85/15. From the viewpoint of further improvement of thermal properties (particularly thermal conductivity) and fogging resistance, and improvement of mechanical properties (particularly bending properties) and molding processability (particularly molding fluidity), 38/62 to 75 are preferable. / 25, more preferably 45/55 to 70/30, still more preferably 48/52 to 65/35. If the amount of the heat conductive filler (B) is too large, the fogging resistance is lowered and the bending property is lowered. If the amount of the heat conductive filler (B) is too small, sufficient heat conductivity may not be obtained.
  • the resin composition used in the present invention can contain a fibrous reinforcing material (C) different from the heat conductive filler.
  • the fibrous reinforcing material (C) is a fibrous reinforcing material having non-thermal conductivity.
  • the fact that the fibrous reinforcing material (C) has non-thermal conductivity means that the substance constituting the fibrous reinforcing material (C) has a thermal conductivity of less than 5 W / (m ⁇ K), particularly 4 W / (m ⁇ K) or less. It means having a rate.
  • non-thermally conductive fibrous reinforcing material examples include inorganic fibers, organic fibers, and fibers made of a mixture thereof.
  • examples of the inorganic fiber include glass fiber and the like.
  • examples of the organic fiber include aramid fiber, high-density polyethylene fiber, other general polyamide, and organic fiber such as polyester.
  • glass fiber is preferable from the viewpoint of being able to more effectively improve the bending characteristics when blended in the composite resin composition of the thermoplastic resin (A) and the heat conductive filler (B).
  • the mass ratio of the total of the thermoplastic resin (A) and the thermally conductive filler (B) to the fibrous reinforcing material (C) is usually 100/0 to 50/50 parts by mass, and has thermal conductivity and fogging resistance. From the viewpoint of further improvement of bending characteristics and molding fluidity, the content is preferably 100/0 to 75/25 parts by mass, and more preferably 90/10 to 75/25 parts by mass.
  • the mass ratio of the total of the thermoplastic resin (A) and the thermally conductive filler (B) to the fibrous reinforcing material (C) is 100/0, which means that the fibrous reinforcing material (C) is not contained. do.
  • the resin composition of the present invention may or may not contain the fibrous reinforcing material (C).
  • the total mass ratio of the polyamide resin (A) and the heat conductive filler (B) to the fibrous reinforcing material (C) is 99 /. It may be 1 to 50/50 parts by mass, particularly 98/2 to 75/25 parts by mass.
  • the glass fiber may be surface-treated with a silane coupling agent, a titanium-based coupling agent, a zirconia-based coupling agent, or the like in order to improve the adhesion and uniform dispersibility with the matrix resin.
  • Fiberglass is usually used in the form of chopped strands.
  • the cross section of the glass fiber may have any shape such as a round shape, a flat shape, a gourd shape, an eyebrows shape, an oval shape, an elliptical shape, a rectangle shape, or a similar product thereof.
  • the average fiber length of the glass fiber is preferably 1 to 10 mm, more preferably 1.5 to 6 mm.
  • the fiber diameter of the glass fiber is preferably 4 to 18 ⁇ m, more preferably 7 to 15 ⁇ m.
  • the fiber cross section is other than round, for example, flat, gourd, eyebrows, oval, elliptical, or rectangular, the long side (for example, maximum length) and short side (for example, maximum length) in the cross-sectional shape.
  • the ratio (that is, the aspect ratio) to the length in the vertical direction is preferably 1.5 to 10, and more preferably 2 to 8.
  • flame retardants additives to the resin composition used in the present invention as long as the effects of the present invention are not impaired.
  • Agents may be added.
  • the flame retardant include halogen-based flame retardants, aluminum hydroxide, magnesium hydroxide, inorganic flame retardants such as antimony trioxide, phosphinates and diphosphinates, and polymers thereof, polyphosphate melamine, cyanurate melamine. , Red phosphorus, phosphoric acid ester, condensed phosphoric acid ester, phosphazene compound and the like.
  • crystal nucleating agent examples include sorbitol compounds, benzoic acid and metal salts of the compounds, and phosphoric acid ester metal salts.
  • compatibilizer examples include ionomer-based compatibilizers, oxazoline-based compatibilizers, elastomer-based compatibilizers, reactive compatibilizers, and copolymer-based compatibilizers.
  • the pigment for example, either an organic type or an inorganic type can be used.
  • the antioxidant include hindered phenol-based, phosphite-based, and thioether-based antioxidants.
  • the weathering agent absorbs and blocks ultraviolet rays to prevent photodegradation of the resin, or captures radicals generated by ultraviolet rays or heat to suppress polymer decomposition.
  • weather resistant agent examples include an ultraviolet blocking agent, a light stabilizer, an ultraviolet absorber, and an antioxidant. These additives may be used alone or in combination of two or more. In the present invention, the method for mixing these additives is not particularly limited.
  • the heat-conducting resin composition of the present invention comprises a thermoplastic resin (A), a heat-conducting filler (B), and, if necessary, various additives, in a general extruder, for example, a uniaxial extruder.
  • a general extruder for example, a uniaxial extruder.
  • the extruder 10 has a cylinder 1 and a screw 2 arranged in the cylinder 1, for example, as shown in FIG.
  • the material added from the main hopper 3 of the extruder 10 is melted and kneaded while being conveyed in the cylinder 1 by the rotation of the screw 2, and is discharged from the discharge port 4.
  • the extruder 10 usually further has a side feeder 11 in the middle of the extruder 10 in the extrusion direction.
  • at least the thermoplastic resin (A) is usually added from the main hopper 3.
  • the method of adding the heat conductive filler (B) and the fibrous reinforcing material (C) is not particularly limited, but the heat conductive filler (B) and the fibrous reinforcing material (C) are independently added to the hopper (the hopper (). In particular, it may be added from the main hopper 3) or from the side feeder 11.
  • the thermally conductive filler (B) is the main hopper 3 or the side feeder 11 (more preferably the side feeder). 11)
  • the fibrous reinforcing material (C) is added from the side feeder 11.
  • a side vacuum device is used at the time of melting and kneading by an extruder.
  • the side vacuum device is, for example, a side vent device for a twin-screw extruder as shown in Japanese Patent No. 5645480.
  • the side vacuum device is, specifically, as shown in FIG. 1, a device 12 for drawing a vacuum from a hole in a side portion of the extruder 10. More specifically, the side vacuum device 12 has a cylinder (not shown) and a screw (not shown) arranged inside the cylinder, and the rotation of the screw causes the melt from the extruder 10 to rotate. The pressure inside the extruder 10 can be reduced while preventing backflow.
  • the screw of the side vacuum device 12 has a screw main body portion (that is, a screw shaft) and a blade portion (that is, a mountain portion) spirally formed on the surface of the screw main body portion.
  • the blade portion is in close contact with the inner wall of the cylinder at the tip thereof in a cross-sectional view perpendicular to the screw shaft. Therefore, the side vacuum device 12 can reduce the pressure inside the extruder 10 while preventing the backflow of the melt from the extruder 10 by reducing the pressure between the blades while rotating the screw. You can do it.
  • the heat conductive filler (B) since melting and kneading are performed using such a side vacuum device 12, even if the heat conductive filler (B) is highly filled, the heat conductive filler (B) overflows and melts. The depressurization inside the extruder is sufficiently achieved while preventing the backflow of the material. As a result, the gas in the cylinder 1 of the extruder 10 is sufficiently removed, and the residual monomer component and the pyrolyzed product component in the thermoplastic resin (A) can be sufficiently removed from the melt, so that heat conduction is sufficient. It is considered that both resistance and fogging resistance can be achieved at a sufficiently high level.
  • a heat conductive filler is blended like the resin composition of the present invention. If the amount is large, the vent portion will be blocked and gas cannot be sucked efficiently. Therefore, the fogging resistance of the obtained resin composition deteriorates.
  • the installation position X 12 (see FIG. 1) of the side vacuum device 12 is usually 0.5 ⁇ Y to 0 when the extrusion direction distance from the main hopper 3 to the ejection port 4 in the extruder 10 is Y (mm).
  • the position is 9.9 ⁇ Y, preferably 0.6 ⁇ Y to 0.85 ⁇ Y, more preferably 0.65 ⁇ Y to 0.80 ⁇ Y, from the viewpoint of further improving the fogging resistance.
  • the position more preferably the position of 0.65 ⁇ Y to 0.75 ⁇ Y.
  • the installation position of the side vacuum device 12 is usually downstream of the installation position of the side feeder 11 in the extrusion direction.
  • Installation position X 11 of the side feeder 11 when the extrusion direction distance from the main hopper 3 in the extruder 10 to the discharge port 4 was Y (mm), typically, 0.3 ⁇ Y ⁇ 0. It is a position of 7 ⁇ Y, preferably a position of 0.35 ⁇ Y to 0.6 ⁇ Y, and more preferably a position of 0.40 ⁇ Y to 0.55 ⁇ Y from the viewpoint of further improving fogging resistance. , More preferably, the position is 0.40 ⁇ Y to 0.50 ⁇ Y.
  • the extrusion direction distance Y from the main hopper 3 to the ejection port 4 is not particularly limited, and may be, for example, 500 to 50,000 mm, particularly 1000 to 10000 mm, preferably 1000 to 5000 mm.
  • the degree of decompression when the side vacuum device 12 is used is a numerical value of the decompression gauge, preferably ⁇ 0.06 MPa or less, still more preferably ⁇ 0.08 MPa or less, from the viewpoint of further improving the fogging resistance.
  • the thermal conductivity of the resin composition of the present invention needs to be 2.0 W / (m ⁇ K) or more, and is preferably 5.0 W / (m ⁇ K) or more from the viewpoint of further improving the thermal conductivity. More preferably, it is 10.0 W / (m ⁇ K) or more. If the thermal conductivity is less than 2 W / (m ⁇ K), a sufficient heat dissipation effect may not be obtained when the molded product is formed.
  • the upper limit of the thermal conductivity is not particularly limited, and the thermal conductivity is usually 50 W / (m ⁇ K) or less, particularly 45 W / (m ⁇ K) or less.
  • the thermal conductivity of the resin composition is the thermal conductivity of the molded product produced by using the resin composition. Specifically, the thermal conductivity of the resin composition is calculated from the thermal diffusivity ⁇ , the density ⁇ and the specific heat Cp in the flow direction (that is, the injection direction) in the test piece manufactured by the injection molding method in accordance with ASTM D790. The value corresponding to " ⁇ ⁇ ⁇ ⁇ Cp" is used.
  • the thermal diffusivity ⁇ may be measured by using any device as long as it can measure the thermal diffusivity in the flow direction of the molded body. For example, the laser flash method (particularly the heat constant measuring device TC-7000 (Albac Riko)) It can be measured using (manufactured by the company)).
  • the density ⁇ may be measured using any device as long as it can measure the density of the molded body, and can be measured using, for example, an electronic hydrometer ED-120T (manufactured by Mirage Trading Co., Ltd.).
  • the specific heat Cp may be measured by any device as long as it can measure the specific heat of the molded body, and is elevated by using, for example, a differential scanning calorimetry method (for example, DSC-7 (manufactured by PerkinElmer)). It can be measured under the condition of a temperature rate of 10 ° C./min.
  • the haze value of the resin composition of the present invention needs to be 8.0 or less, and is preferably 7.5 or less, more preferably 6.5 or less, from the viewpoint of further improving the thermal conductivity. When the haze value exceeds 8.0, sufficient fogging resistance cannot be obtained when the molded product is formed.
  • the lower limit of the heat haze value is not particularly limited, and the haze value is usually 0.1 or more, particularly 0.5 or more.
  • the haze value of the resin composition is the haze value of the glass plate when the molded product produced by using the resin composition is subjected to a fogging test.
  • the haze value of the resin composition is 200 in a high temperature environment of 125 ° C. in an air collecting bottle covered with a glass plate of 12 test pieces having a size of 50 mm ⁇ 15 mm ⁇ 2 mm manufactured by an injection molding method.
  • the increase in the haze value on the glass plate when subjected to the time-retaining fogging test is used.
  • the haze value may be measured using any device as long as it can measure the haze value of the glass plate.
  • the haze value can be measured using a haze meter (Haze Meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). can.
  • the resin composition of the present invention can be molded into a desired shape by using a commonly known melt molding method such as injection molding, compression molding, extrusion molding, transfer molding, sheet molding and the like to obtain a molded product.
  • Bending strength and flexural modulus Measured in accordance with ISO standard 178.
  • the evaluation criteria for bending strength and flexural modulus are as follows.
  • Thermal conductivity thermal conductivity of molded product
  • the thermal conductivity ⁇ was calculated by the following formula as the product of the thermal diffusivity ⁇ , the density ⁇ and the specific heat Cp obtained by the following methods.
  • ⁇ ⁇ Cp ⁇ : Thermal conductivity (W / m ⁇ K)
  • ⁇ Thermal diffusivity (m 2 / sec)
  • ⁇ Density (g / m 3 )
  • Cp Specific heat (J / g ⁇ K)
  • the thermal diffusivity ⁇ was specifically measured by the following method.
  • test pieces manufactured according to ASTM D790 are hot-pressed at a temperature above the melting point of the resin using a special die having a cavity with the same width and length (length in the longitudinal direction) as the bending test piece. It was glued together. This laminated material was cut out so that the width (thickness) direction of the obtained test piece was parallel to the flow direction at the time of injection molding, and the width of the obtained test piece was 1 mm to 1.5 mm. ..
  • the resin flow direction was measured by a thermal constant measuring device TC-7000 (manufactured by ULVAC Riko Co., Ltd.) based on a laser flash method.
  • test pieces are manufactured by an injection molding method.
  • the density ⁇ was measured using an electron hydrometer ED-120T (manufactured by Mirage Trading Co., Ltd.) and a bending test piece prepared according to ASTM D790.
  • the specific heat Cp was measured at a heating rate of 10 ° C./min using a bending test piece prepared according to a differential scanning calorimeter DSC-7 (manufactured by PerkinElmer) and ASTM D790.
  • the thermal conductivity in the flow direction was calculated by the above method. For each of ⁇ , ⁇ and Cp, an average value based on the measured values of 10 test pieces was used.
  • the same method as the above-mentioned method for calculating the thermal conductivity in the flow direction is used, except that a sample is prepared so as to have a thickness of 1 mm to 1.5 mm using a bending test piece prepared in accordance with ASTM D790.
  • the thermal conductivity in the thickness direction was calculated.
  • the thermal conductivity in the flow direction was evaluated based on the following criteria. ⁇ : 10.0 or more (best); ⁇ : 5.0 or more and less than 10.0 (good); ⁇ : 2.0 or more and less than 5.0 (no problem in practical use); ⁇ : Less than 2.0 (there is a problem in practical use).
  • the thermal conductivity in the flow direction and the thickness direction is obtained, but the thermal conductivity in the thickness direction is obtained only for reference, and in the present invention, the thermal conductivity is the flow direction. It suffices if the thermal conductivity of is within the above range.
  • a sufficiently dried resin composition was molded into a plate molded product having a thickness of 50 mm ⁇ 90 mm ⁇ 2 mm using an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd .: NEX110-12E). The two obtained compacts were cut into 6 equal parts (15 mm width) to obtain sample pieces. As shown in FIG. 2A, the sample piece 21 is placed in the air collecting bottle 22, and the sample piece 21 is placed in an oil bath 24 containing the silicone oil 23 heated to 125 ° C. in the height direction of the air collecting bottle. It was installed so that it could be used up to a height of about 80%, and the mouth of the air collecting bottle was covered with a glass plate 25 having a thickness of 2 mm.
  • the glass plate had dimensions of 80 mm ⁇ 80 mm ⁇ 2 mm in thickness.
  • the air collecting bottle had dimensions of a bottom surface diameter of 85 mm, a height of 150 mm, and an inner diameter of the mouth portion of 50 mm.
  • the glass plate is not particularly limited as long as it has a size that completely covers the mouth of the air collecting bottle. Further, grease may be applied to the mouth portion of the air collecting bottle in order to improve the adhesion. After leaving it in this state for 200 hours, the glass plate was removed from the air collecting bottle and cooled sufficiently.
  • haze values at any 10 points in the portion where the air collecting bottle of the glass plate was covered were measured with a haze meter (Haze Meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The average value of these measured values was defined as the haze value A.
  • the average value of the haze values of any 10 points on the glass plate before being used as a lid was 0.1, and this average value was defined as the haze value B.
  • the value of "haze value A-haze value B" was evaluated based on the following criteria. ⁇ : 6.5 or less (best); ⁇ : More than 6.5 and 7.5 or less (good); ⁇ : More than 7.5 and less than 8.0 (no problem in practical use); ⁇ : Over 8.0 (there is a problem in practical use).
  • Thermoplastic resin (A) -PA6 Polyamide 6 (relative viscosity 2.6, density 1.13 g / cm 3 , heat of fusion 18 cal / g)
  • -PA6x Polyamide 6 obtained by polymerization of ⁇ -caprolactam (relative viscosity 1.9, density 1.13 g / cm 3 ), heat of fusion 18 cal / g)
  • PA66 Polyamide 66 resin (relative viscosity 2.8, density 1.14 g / cm 3 ) obtained by polymerization of hexamethylenediamine and adipic acid, heat of fusion 21 cal / g
  • Amorphous PA Amorphous polyamide (isophthalic acid / terephthalic acid / 1,6-hexamethylenediamine cocondensate, G21 manufactured by EMS, density 1.18 g / cm 3 , heat of
  • Fibrous filler (C) -GF Glass fiber (T-262H manufactured by Nippon Electric Glass Co., Ltd., average fiber diameter 11 ⁇ m, average fiber length 3 mm)
  • -GFx Glass fiber (manufactured by Owens Corning, average fiber diameter 10 ⁇ m, average fiber length 3 mm, density 2.50 g / cm 3 )
  • AR1 Copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber (Technora manufactured by Teijin Techno Products Co., Ltd., average fiber diameter 12 ⁇ m, average fiber length 3 mm)
  • PA6 polyamide 6 resin
  • GaA scaly graphite
  • the degree of decompression in the side vacuum device 12 was ⁇ 0.07 MPa as the value of the decompression gauge.
  • the installation position X 12 (see FIG. 1) of the side vacuum device 12 is a position of 0.70 ⁇ Y when the extrusion direction distance from the main hopper 3 to the ejection port 4 in the extruder 10 is Y (mm). rice field.
  • the melt was sufficiently melted and kneaded, extruded into strands to be cooled and solidified, and then cut with a pelletizer to obtain pellets of the resin composition.
  • the obtained pellets were molded into the above-mentioned predetermined shape by a molding machine (NEX110-12E) manufactured by Nissei Resin Co., Ltd. Pellets of resin composition were used for other evaluations and measurements.
  • Example 2 to 16 and Comparative Examples 1 to 8 The same operation as in Example 1 was carried out except that the resin composition, kneading conditions, molding conditions and side vacuum apparatus (presence / absence) were changed as shown in Table 1, to obtain pellets of the resin composition.
  • the fibrous reinforcing material (C) was supplied, the fibrous reinforcing material (C) was supplied by a side feeder (“11” in FIG. 1) during melting and kneading.
  • Installation position X 11 of the side feeder 11 (see FIG. 1), the extrusion direction distance from the main hopper 3 in the extruder 10 to the discharge port 4 when the Y (mm), was a position of 0.45 ⁇ Y ..
  • the installation position X 12 of the side vacuum device 12 (see FIG. 1) in the extrusion direction of the extruder 10, a downstream side of the installation position X 11 of the side feeder, detail was a position of 0.70 ⁇ Y when the extrusion direction distance from the main hopper 3 to the ejection port 4 in the extruder 10 was Y (mm).
  • a general standard-equipped vacuum device without a screw was installed at the vent port 5 and used.
  • Examples 1 to 16 Since the resin compositions of Examples 1 to 16 satisfy the requirements of the present invention, it is possible to obtain a molded product having a thermal conductivity of 2 W / (m ⁇ K) or more and excellent fogging resistance. rice field.
  • Examples 4 to 6, Examples 8 to 10 and Examples 13 to 16 contained glass fiber as a fibrous reinforcing material, and the blending amount was appropriate, so that the bending characteristics were excellent.
  • Examples 8 to 10 contained amorphous polyamide, the haze value by the fogging test was smaller than that of Example 4 which did not contain amorphous polyamide.
  • Example 10 Comparing Examples 8 to 9 with Example 10, it can be seen that the molding fluidity of Example 10 is reduced due to the large mass ratio of the amorphous polyamide.
  • Example 14 contained a large amount of fibrous reinforcing material, the bending characteristics were high, but the molding fluidity was lowered.
  • Comparative Example 2 since the mass ratio of the thermally conductive filler was larger than the range of the present invention, the haze value after the fogging test was high and the molding fluidity was also lowered. In Comparative Example 3, the mass ratio of the thermally conductive filler was smaller than the range of the present invention, so that sufficient thermal conductivity could not be obtained.
  • molded body obtained by molding the resin composition of the present invention include electrical and electronic parts such as sockets, relay parts, coil bobbins, optical pickups, oscillators, and computer-related parts; VTRs, televisions, irons, and the like.
  • Household electrical appliances such as air conditioners, stereos, copiers, refrigerators, rice cookers, and lighting fixtures; heat dissipation members for releasing heat from electronic parts such as heat dissipation sheets, heat sinks, and fans; lamp sockets, lamp reflectors, lamps Lighting equipment parts such as housings; Audio product parts such as compact discs, laser discs (registered trademarks), speakers; Communication equipment parts such as ferrules for optical cables, mobile phones, fixed phones, facsimiles, modems; Separation claws, heater holders, etc.
  • Copier / printing machine related parts Mechanical parts such as impellers, fan gears, gears, bearings, motor parts and cases, and mechanical parts for automobiles; Automotive parts such as engine parts, engine room parts, electrical parts, interior parts, etc.; Cooking utensils such as microwave cooking pots and heat-resistant tableware; parts for space equipment and sensor parts in aircraft and spacecraft.
  • Cylinder 2 Screw 3: Main hopper 4: Discharge port 5: Vent port 10: Extruder 11: Side feeder 12: Side vacuum device 21: Sample piece 22: Air collecting bottle 23: Silicone oil 24: Oil bath 25: Glass plate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine qui peut produire un corps moulé ayant une conductance thermique d'au moins 2 W/(m·K) dans la direction d'écoulement et une excellente résistance à la condensation. La présente invention porte sur une composition de résine thermoconductrice contenant une résine thermoplastique (A) et un matériau de remplissage thermoconducteur (B). Le rapport en masse entre la résine thermoplastique (A) et le matériau de remplissage thermoconducteur (B) est de 3,8/62 à 85/15 et la valeur du voile d'une plaque de verre n'étant pas supérieure à 8 après un essai de condensation pendant 200 heures à 125 °C. La conductivité thermique d'un corps moulé, moulé à partir de la composition de résine thermoconductrice, est d'au moins 2 W/(m·K) dans le sens de l'écoulement.
PCT/JP2021/017933 2020-05-20 2021-05-11 Composition de résine thermoconductrice et corps moulé la comprenant WO2021235277A1 (fr)

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WO2014171363A1 (fr) * 2013-04-16 2014-10-23 東洋紡株式会社 Composition de résine polyamide renforcée de fibres de verre
JP2015147316A (ja) * 2014-02-05 2015-08-20 ユニチカ株式会社 ガスバリア性積層体
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WO2017043070A1 (fr) * 2015-09-09 2017-03-16 株式会社カネカ Composition de résine thermoconductrice
JP2017190407A (ja) * 2016-04-14 2017-10-19 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる成形体
WO2018216770A1 (fr) * 2017-05-25 2018-11-29 東洋紡株式会社 Composition de résine polyamide renforcée de fibres de verre
WO2019074038A1 (fr) * 2017-10-13 2019-04-18 東洋紡株式会社 Composition de résine de polyamide présentant une excellente résistance aux intempéries

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JP2007182551A (ja) * 2005-11-15 2007-07-19 Asahi Kasei Chemicals Corp 耐熱性に優れる樹脂組成物
WO2014171363A1 (fr) * 2013-04-16 2014-10-23 東洋紡株式会社 Composition de résine polyamide renforcée de fibres de verre
JP2015147316A (ja) * 2014-02-05 2015-08-20 ユニチカ株式会社 ガスバリア性積層体
JP2017039901A (ja) * 2015-08-21 2017-02-23 ユニチカ株式会社 筐体
WO2017043070A1 (fr) * 2015-09-09 2017-03-16 株式会社カネカ Composition de résine thermoconductrice
JP2017190407A (ja) * 2016-04-14 2017-10-19 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる成形体
WO2018216770A1 (fr) * 2017-05-25 2018-11-29 東洋紡株式会社 Composition de résine polyamide renforcée de fibres de verre
WO2019074038A1 (fr) * 2017-10-13 2019-04-18 東洋紡株式会社 Composition de résine de polyamide présentant une excellente résistance aux intempéries

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