WO2021049123A1 - 熱伝導性改良剤、熱伝導性改良方法、熱伝導性樹脂組成物および熱伝導性樹脂成形体 - Google Patents
熱伝導性改良剤、熱伝導性改良方法、熱伝導性樹脂組成物および熱伝導性樹脂成形体 Download PDFInfo
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Definitions
- the present invention relates to a thermal conductivity improving agent, a thermal conductivity improving method, a thermal conductive resin composition, and a thermal conductive resin molded body.
- the heat conductive member is typically formed of a resin composition containing a heat conductive filler (see, for example, Patent Documents 1 to 4).
- the above-mentioned heat conductive member is required to have further excellent heat conductivity.
- the present invention has been made to solve the above problems, and one of the objects of the present invention is to provide a resin composition having excellent thermal conductivity.
- a thermally conductive resin composition contains a resin, a first thermally conductive filler having an aspect ratio of 10 or more and a major axis of less than 30 ⁇ m, and a second thermally conductive filler having an aspect ratio of 2 or less.
- the first thermally conductive filler is formed of at least one selected from the group consisting of magnesium oxide, magnesium hydroxide and boron nitride.
- the second thermal conductive filler is formed of at least one selected from the group consisting of magnesium oxide, magnesium hydroxide and aluminum oxide.
- the thickness of the first thermal conductive filler is 10 nm or more and 200 nm or less.
- the major axis of the first thermal conductive filler is 20 ⁇ m or less. In one embodiment, the particle size of the second thermal conductive filler is 2 ⁇ m or more. In one embodiment, the particle size of the second thermally conductive filler is larger than the major axis of the first thermally conductive filler. In one embodiment, the heat conductive resin composition contains 90 parts by weight or more and 700 parts by weight or less of the first heat conductive filler and the second heat conductive filler with respect to 100 parts by weight of the resin. ..
- the ratio of the content of the first heat conductive filler to the content of the second heat conductive filler is , 0.1 or more and 5 or less. In one embodiment, the total volume ratio of the first thermal conductive filler and the second thermal conductive filler in the thermally conductive resin composition is 25% or more and 70% or less.
- a thermally conductive resin molded article is provided.
- This heat conductive resin molded body is formed from the above heat conductive resin composition.
- the thermally conductive resin molded product is in the form of a sheet.
- the sheet-shaped thermally conductive resin molded body has a ratio of the thermal conductivity in the thickness direction (thermal conductivity in the thickness direction / thermal conductivity in the surface direction) to the thermal conductivity in the surface direction. It is 0.5 or more.
- a thermal conductivity improver includes a first thermal conductive filler having an aspect ratio of 10 or more and a major axis of less than 30 ⁇ m, and a second thermal conductive filler having an aspect ratio of 2 or less.
- thermo conductivity improving method uses the above-mentioned thermal conductivity improving agent.
- excellent thermal conductivity is achieved by combining a first thermally conductive filler having an aspect ratio of 10 or more and a major axis of less than 30 ⁇ m and a second thermally conductive filler having an aspect ratio of 2 or less. obtain.
- the definitions of terms in the present specification are as follows. 1.
- Particle size The particle size is the average particle size in the particle size distribution measurement. 2. It is a value measured by a long-diameter scanning electron microscope (SEM) observation, and is an average value of the long-diameters of randomly selected primary particles (for example, L in FIGS. 1A and 1B). The primary particles are the smallest particles observed by SEM and are distinguished from other agglomerated particles (secondary particles).
- Third particles 3.
- Thickness This is a value measured by SEM observation and is an average value of the thicknesses of randomly selected primary particles (for example, T in FIGS. 1A and 1B).
- Aspect ratio (major axis / thickness) It is a value calculated by dividing the thickness from the major axis.
- Thermal conductivity improver in one embodiment of the present invention includes a first thermal conductivity filler and a second thermal conductivity filler.
- A-1. First Thermal Conductive Filler The aspect ratio of the first thermal conductive filler is 10 or more, preferably 30 or more, more preferably 45 or more, still more preferably 55 or more, and particularly preferably 65 or more.
- the second heat conductive filler described later is dispersed between the first heat conductive fillers, and a heat conductive path is easily formed.
- the aspect ratio of the first thermally conductive filler is, for example, 200 or less, preferably 100 or less.
- Such a first heat conductive filler can be easily filled in the resin described later, and can be excellent in processability when producing, for example, the heat conductive resin composition described later.
- the major axis of the first thermal conductive filler is, for example, 0.5 ⁇ m or more, preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more. This is because the heat conduction path can be formed well. On the other hand, the major axis of the first thermal conductive filler is less than 30 ⁇ m, preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less. Such a first heat conductive filler can be easily filled in the resin described later, and can be excellent in processability when producing, for example, the heat conductive resin composition described later.
- the thickness of the first thermally conductive filler is, for example, 10 nm or more, preferably 20 nm or more, and more preferably 50 nm or more.
- a first heat conductive filler can be easily filled in the resin described later, and can be excellent in processability when producing, for example, the heat conductive resin composition described later.
- the thickness of the first thermally conductive filler is, for example, 200 nm or less, preferably 180 nm or less. This is because the heat conduction path can be formed well.
- the first thermally conductive filler may have any suitable shape as long as the above aspect ratio can be satisfied.
- the shape of the first heat conductive filler include scaly shape, plate shape, film shape, fibrous shape, columnar shape, prismatic shape, elliptical shape, and flat shape.
- the scaly shape is adopted. This is because the above aspect ratio can be satisfactorily achieved.
- such a first thermally conductive filler can have isotropic thermal conductivity in the plane direction, excellent thermal conductivity can be achieved.
- the channels between the fillers are easily connected (the heat conduction path is easily formed), and excellent heat conduction is achieved. Sex can be achieved.
- the first thermally conductive filler typically contains matrix particles.
- the first thermally conductive filler (maternal particle) can be formed of any suitable material.
- the first thermally conductive filler (matrix particle) is formed of an insulating material.
- the material for forming the first thermally conductive filler (matrix particle) include magnesium compounds such as magnesium hydroxide and magnesium oxide, boron nitride, and aluminum hydroxide.
- the first thermally conductive filler (matrix particle) is formed of at least one selected from the group consisting of magnesium oxide, magnesium hydroxide and boron nitride. Of these, magnesium hydroxide is preferable.
- the above major axis and aspect ratio can be satisfactorily achieved.
- particles having the above major axis and aspect ratio can be satisfactorily prepared.
- it is excellent in terms of cost and can contribute to the improvement of flame retardancy.
- the above-mentioned parent particles are surface-treated.
- the matrix particles are surface-treated with any suitable surface treatment agent.
- the surface treatment agent is selected from the group consisting of, for example, higher fatty acids, anionic surfactants, phosphate esters, coupling agents, esters of polyhydric alcohols and fatty acids, acrylic polymers and silicone treatment agents. At least one is used.
- higher fatty acids examples include higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid, and behenic acid, and alkali metal salts of these higher fatty acids.
- anionic surfactant examples include sulfate ester salts of higher alcohols such as stearyl alcohol and oleyl alcohol, sulfate ester salts of polyethylene glycol ether, amide-bonded sulfate ester salts, ester-bonded sulfate ester salts, ester-bonded sulfonates, and amides.
- sulfate ester salts of higher alcohols such as stearyl alcohol and oleyl alcohol
- sulfate ester salts of polyethylene glycol ether examples include bond sulfonates, ether bond sulfonates, ether bond alkylaryl sulfonates, ester bond alkylaryl sulfonates, and amide bond alkylaryl sulfonates.
- phosphoric acid esters examples include phosphoric acid monoesters in which orthophosphoric acid and alcohols such as oleyl alcohol and stearyl alcohol are dehydrated and condensed, phosphoric acid diesters or mixtures thereof, alkali metal salts or amine salts thereof. ..
- Examples of the coupling agent include vinyl ethoxysilane, vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, and beta (3,4-epoxycyclohexyl).
- Silane coupling agents such as ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N) -Titanate-based coupling agents such as aminoethyl-aminoethyl) titanate and isopropyltridecylbenzenesulfonyl titanate; and aluminum-based coupling agents such as acetoalkoxyaluminum diisopropyrate can be mentioned.
- esters of the polyhydric alcohol and the fatty acid examples include glycerin monostearate and glycerin monooleate.
- any appropriate method can be adopted as the surface treatment method for the mother particles.
- a wet method may be adopted, or a dry method may be adopted.
- a method is used in which the surface treatment agent is added in a liquid or dispersion state to a slurry of parent particles and mixed.
- the mixing may be carried out while heating (for example, to 100 ° C. or lower).
- the mixing method is not particularly limited, and may be performed mechanically, for example.
- the dry method for example, while stirring the parent particles (powder) using a mixer such as a Henschel mixer, the above surface treatment agent is added in a liquid, solid or dispersion state and heated.
- a method of mixing without heating is used.
- the amount of the surface treatment agent used is preferably 10% by weight or less of the parent particles, more preferably 1.0% by weight to 8.0% by weight, and particularly preferably 1.0% by weight to 3.0% by weight. Is. According to such a range, for example, the dispersibility can be improved without lowering the thermal conductivity of the filler, and the heat conductive resin molded product described later can be satisfactorily molded.
- the parent particles can be subjected to any other appropriate treatment as needed.
- Other treatments include, for example, washing with water, dehydration, granulation, drying, pulverization, and classification.
- the above surface treatment can also be applied to the matrix particles on which the coating layer described later is formed.
- the surface treatment agent used for the surface treatment is at least selected from the group consisting of higher fatty acids, anionic surfactants, phosphoric acid esters, coupling agents and esters of polyhydric alcohols and fatty acids. One is preferably used.
- the first thermally conductive filler may have a coating layer formed on the surface of the parent particles.
- the coating layer can be formed by applying any suitable coating agent to the parent particles.
- an acid resistant coating layer is formed on the surface of the parent particles.
- the acid resistant coating layer comprises, for example, an oxide or hydroxide of at least one element selected from the group consisting of silicon, aluminum, titanium, zirconia, zinc and boron.
- the acid resistant coating layer comprises an oxide of silicon and / or a hydroxide of silicon.
- a coating layer can be formed by allowing silicic acid and its soluble salts as a coating agent to act on the parent particles.
- the amount of the coating agent used is preferably 2% by weight or less of the parent particles, more preferably 0.01% by weight to 1.5% by weight, and particularly preferably 0.01% by weight to 1.0% by weight. is there.
- A-2. Second Thermal Conductive Filler The aspect ratio of the second thermal conductive filler is 2 or less. Specifically, the aspect ratio of the second thermal conductive filler is 1 or more and 2 or less.
- a second heat conductive filler By using such a second heat conductive filler, it is possible to intervene between the first heat conductive fillers and form a good heat conductive path (for example, in various directions). As a result, excellent thermal conductivity can be achieved. Specifically, excellent thermal conductivity (for example, thermal conductivity in the thickness direction) can be achieved in the thermally conductive resin molded product described later.
- such a second thermally conductive filler can be excellent in filling property into a resin described later, and can be excellent in processability when producing, for example, a thermally conductive resin composition described later.
- the particle size of the second thermal conductive filler is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
- the particle size of the second thermally conductive filler is larger than the major axis of the first thermally conductive filler.
- the particle size of the second thermal conductive filler is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less.
- Such a second heat conductive filler is excellent in filling property into the resin described later, and can be excellent in processability when producing, for example, the heat conductive resin composition described later.
- the second thermal conductive filler may have any suitable shape as long as the above aspect ratio can be satisfied.
- the shape of the second thermal conductive filler include spherical shape, agglomerate shape, scaly shape, plate shape, film shape, columnar shape, prismatic shape, elliptical shape, and flat shape.
- a spherical shape is adopted.
- the second thermally conductive filler typically contains matrix particles.
- the second thermally conductive filler (maternal particle) can be formed of any suitable material.
- the second thermally conductive filler (matrix particle) is formed of an insulating material.
- the material for forming the second heat conductive filler (matrix particle) include magnesium compounds such as magnesium hydroxide, magnesium oxide and magnesium carbonate, aluminum compounds such as aluminum oxide and aluminum nitride, boron nitride and silica.
- the second thermal conductive filler (matrix particle) is formed of at least one selected from the group consisting of magnesium hydroxide, magnesium oxide and aluminum oxide. Of these, magnesium oxide and aluminum oxide are preferable, and magnesium oxide is more preferable. This is because it is suitable for interposing between the first thermally conductive fillers (for example, the above-mentioned shape can be satisfactorily achieved), and excellent thermal conductivity can be achieved. In addition, these materials can be excellent in terms of cost.
- the base particles of the second heat conductive filler may be surface-treated. Further, a coating layer may be formed. The details of the surface treatment and the coating layer are as described above.
- the ratio of the content of the first thermal conductive filler to the content of the second thermally conductive filler is preferably 0.1 or more. According to such a content ratio, in the heat conductive resin molded body described later, the channels of the first heat conductive filler and the second heat conductive filler are easily connected, and excellent heat conductivity (for example, in the thickness direction). Thermal conductivity) can be achieved.
- the content ratio is preferably 0.2 or more, more preferably 0.3 or more.
- the ratio of the content of the first thermal conductive filler to the content of the second thermal conductive filler is preferably 5 or less. According to such a content ratio, in the thermally conductive resin molded body described later, a channel of the second thermally conductive filler connecting the first thermally conductive filler is sufficiently formed, and excellent thermal conductivity (for example, for example) is obtained. Thermal conductivity in the thickness direction) can be achieved. In addition, the heat conductive resin molded body described later can be molded satisfactorily. In one embodiment, the content ratio is preferably 0.8 or less, more preferably 0.6 or less.
- the above thermal conductivity improver may contain other components.
- As the other component for example, an optional component described later is adopted.
- the method for improving thermal conductivity in one embodiment of the present invention uses the above-mentioned thermal conductivity improving agent.
- the object for which the thermal conductivity is to be improved contains the thermal conductivity improving agent.
- the above thermal conductivity improving agent is contained in the resin.
- the heat conductive resin composition containing the resin and the heat conductivity improving agent will be described.
- the thermally conductive resin composition according to one embodiment of the present invention includes a resin, the first thermally conductive filler and the second thermally conductive filler.
- Resin Any suitable resin can be selected as the above resin, for example, depending on the use of the obtained heat conductive resin composition and the like.
- the resin include ethylene- ⁇ -olefin copolymers such as polyethylene, polypropylene, and ethylene-propylene copolymers, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and ethylene-vinyl acetate copolymers.
- ABS acrylonitrile-butadiene-styrene copoly
- a styrene-based thermoplastic elastomer such as a styrene-butadiene copolymer and its hydrogenated polymer, a styrene-isoprene block copolymer and its hydrogenated polymer, an olefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, and a polyester.
- a polyurethane-based thermoplastic elastomer a polyurethane-based thermoplastic elastomer, and a polyamide-based thermoplastic elastomer.
- silicone rubber, acrylic rubber, butyl rubber, fluororubber, nitrile rubber, hydrogenated nitrile rubber can be mentioned. These can be used alone or in combination of two or more.
- silicone rubber is preferably used as the resin. This is because when the thermally conductive resin composition is used as a molded product, it can be excellent in flexibility, shape followability, adhesion (for example, adhesion to a heating element such as an electronic component) and heat resistance.
- the thermally conductive resin composition may contain a cross-linking agent for the resin.
- the resin may be a crosslinked product crosslinked with a crosslinking agent.
- the cross-linking of the polymer (silicone) having a silicone skeleton may be a cross-linking with a peroxide or an addition reaction type cross-linking. From the viewpoint of obtaining excellent heat resistance, cross-linking with a peroxide is preferably adopted.
- peroxide examples include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, and t-butyl peroxide.
- Benzoyl peroxide can be mentioned. These can be used alone or in combination of two or more.
- the amount of the cross-linking agent used is, for example, 0.5 parts by weight to 5 parts by weight with respect to 100 parts by weight of the resin.
- a cross-linking accelerator or a cross-linking accelerator can be used in combination.
- the total content of the first thermal conductive filler and the second thermal conductive filler in the thermally conductive resin composition is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight. % Or more. According to such a range, extremely excellent thermal conductivity can be achieved. On the other hand, the total content ratio is preferably 95% by weight or less, more preferably 90% by weight or less. According to such a range, the processability at the time of producing the thermally conductive resin composition can be excellent.
- the thermally conductive resin composition it is preferable to contain 90 parts by weight or more of the first thermally conductive filler and the second thermally conductive filler with respect to 100 parts by weight of the resin, more preferably 140 parts by weight or more, still more preferably. Is 200 parts by weight or more, particularly preferably 250 parts by weight or more. On the other hand, it is preferable that 700 parts by weight or less of the first heat conductive filler and the second heat conductive filler are contained in 100 parts by weight of the resin, and more preferably 600 parts by weight or less. It should be noted that one of the features of the present invention is that excellent thermal conductivity can be achieved even when the filling rate for the resin is low (for example, 300 parts by weight or less).
- the total volume ratio of the first heat conductive filler and the second heat conductive filler in the heat conductive resin composition is preferably 25% or more, more preferably 40% or more, and particularly preferably 45% or more. According to such a range, extremely excellent thermal conductivity can be achieved. On the other hand, the total volume ratio is preferably 70% or less, more preferably 65% or less. According to such a range, the processability at the time of producing the thermally conductive resin composition can be excellent.
- the content ratio of the first heat conductive filler and the second heat conductive filler in the heat conductive resin composition is the same as the content ratio in the above-mentioned heat conductivity improving agent.
- the content ratio of the first heat conductive filler in the heat conductive resin composition is preferably 5% by weight or more. According to such a range, the first thermal conductivity filler can be well oriented to achieve excellent thermal conductivity. For example, channels between fillers are easily connected, and excellent thermal conductivity (for example, thermal conductivity in the thickness direction) can be achieved. On the other hand, the content ratio of the first heat conductive filler in the heat conductive resin composition is preferably 50% by weight or less. According to such a range, the processability at the time of producing the thermally conductive resin composition can be excellent.
- the first heat conductive filler is contained in an amount of 20 parts by weight or more, more preferably 70 parts by weight or more, based on 100 parts by weight of the resin.
- the first thermal conductive filler is contained in 100 parts by weight of the resin, and more preferably 110 parts by weight or less.
- the content ratio of the second heat conductive filler in the heat conductive resin composition is preferably 20% by weight or more. According to such a range, the channels between the fillers are easily connected, and excellent thermal conductivity (for example, thermal conductivity in the thickness direction) can be achieved. On the other hand, the content ratio of the second thermal conductive filler is preferably 70% by weight or less. According to such a range, it is possible to sufficiently secure the content of the first thermal conductive filler and achieve excellent thermal conductivity.
- the second heat conductive filler is contained with respect to 100 parts by weight of the resin, and more preferably 100 parts by weight or more.
- the second thermal conductive filler is contained in an amount of 500 parts by weight or less, more preferably 450 parts by weight or less, based on 100 parts by weight of the resin.
- the thermally conductive resin composition may contain optional components such as a cross-linking agent, a cross-linking accelerator, and a cross-linking accelerator aid.
- the thermally conductive resin composition is an optional component such as a reinforcing agent, a filler, a softening agent, a plasticizer, an antiaging agent, a tackifier, an antistatic agent, a kneaded adhesive, a flame retardant, and a coupling agent. May include.
- the content ratio of the optional component in the heat conductive resin composition is, for example, 0.05% by weight to 10% by weight.
- the thermally conductive resin molded article according to one embodiment of the present invention is formed from the above-mentioned thermally conductive resin composition.
- the heat conductive resin molded product contains the above resin, the above first heat conductive filler, and the above second heat conductive filler.
- the shape (form) of the heat conductive resin molded body is not particularly limited, but is typically a sheet shape (heat dissipation sheet).
- the thickness of the heat radiating sheet is, for example, 200 ⁇ m or more, and typically 200 ⁇ m to 3 mm.
- the thermal conductivity in the thickness direction may be regarded as important. According to the present invention, excellent thermal conductivity in the thickness direction can be achieved.
- the ratio of the thermal conductivity in the thickness direction (thermal conductivity in the thickness direction / thermal conductivity in the surface direction) to the thermal conductivity in the surface direction of the heat dissipation sheet is preferably 0.5 or more, more preferably 0.5 or more. It is 0.7 or more.
- the thermal conductivity of the heat radiating sheet in the thickness direction is, for example, 0.70 W / m ⁇ K or more, preferably 0.85 W / m ⁇ K or more, and more preferably 1.00 W / m ⁇ K or more. , Especially preferably 1.20 W / m ⁇ K or more.
- the thermal conductivity obtained by mixing (kneading) the resin, the first thermal conductive filler, the second thermal conductive filler, and if necessary, the optional component.
- the resin composition is pressed to obtain a heat radiating sheet.
- the resin, the first thermal conductive filler, the second thermal conductive filler, and, if necessary, the optional components are supplied to an extruder to be melt-kneaded and kneaded.
- a heat dissipation sheet is obtained by extruding from an extruder.
- One of the features of the present invention is that excellent thermal conductivity can be achieved regardless of the molding method of the molded product (method of manufacturing the heat radiating sheet).
- the measurement method for each characteristic is as follows. 1.
- Particle size The particle size was measured by a laser diffraction / scattering method (device: Microtrack Bell Co., Ltd., Microtrack MT3000).
- the sample for measurement was prepared by adding 70 mL of a sodium hexametaphosphate solution (0.2%) to 0.7 g of the filler and then sonicating at 280 ⁇ A for 3 minutes.
- Major axis The major axis was calculated by SEM observation.
- the major axis of 10 primary particles randomly selected from SEM photographs of fillers (particles) was measured, and the arithmetic mean (average major axis) of the obtained measured values was obtained.
- the magnification of the major axis SEM observation was 2,000 times for the first heat conductive filler and 500 times for the second heat conductive filler.
- 3. 3. Thickness The thickness was calculated by SEM observation. Specifically, the thicknesses of 10 primary particles randomly selected from SEM photographs of fillers (particles) were measured, and the arithmetic mean (average thickness) of the obtained measured values was obtained.
- the magnification of SEM observation of the thickness was 20,000 times for the first heat conductive filler and 500 times for the second heat conductive filler. 4.
- Aspect ratio The aspect ratio was calculated by SEM observation. Specifically, the aspect ratio was calculated by dividing the average major axis by the average thickness.
- Example 1 1st thermal conductive filler (major axis 4 ⁇ m, thickness 57 nm, scaly magnesium hydroxide particles with aspect ratio 70) 90 per 100 parts by weight of silicone rubber (“TSE-201” manufactured by Momentive Performance Materials) Parts by weight, 2nd thermal conductivity filler (“Pyroxma 3320” manufactured by Kyowa Chemical Industry Co., Ltd., spherical magnesium oxide particles with particle size 20 ⁇ m and aspect ratio 1) 210 parts by weight and cross-linking agent (Momentive Performance Materials Co., Ltd. A resin composition was obtained by mixing using a small twin-screw plastomill (manufactured by Brabender) at a ratio of 2 parts by weight of "TC-8" manufactured by Japan.
- TSE-201 manufactured by Momentive Performance Materials
- 2nd thermal conductivity filler (“Pyroxma 3320” manufactured by Kyowa Chemical Industry Co., Ltd., spherical magnesium oxide particles with particle size 20 ⁇ m and aspect ratio 1) 210 parts
- Example 2 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the first heat conductive filler was 30 parts by weight and the blending amount of the second heat conductive filler was 270 parts by weight.
- Example 3 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the first heat conductive filler was 120 parts by weight and the blending amount of the second heat conductive filler was 180 parts by weight.
- Example 4 The resin composition was prepared in the same manner as in Example 1 except that magnesium oxide particles having a particle size of 3 ⁇ m and an aspect ratio of 1 (“Pyroxma 5301” manufactured by Kyowa Chemical Industry Co., Ltd.) were used as the second thermal conductive filler. Obtained.
- Example 5 A resin composition was obtained in the same manner as in Example 1 except that spherical magnesium oxide particles having a particle size of 50 ⁇ m and an aspect ratio of 1 were used as the second thermal conductive filler.
- Example 6 A resin composition was obtained in the same manner as in Example 1 except that scaly magnesium hydroxide particles having a major axis of 1.6 ⁇ m, a thickness of 32 nm, and an aspect ratio of 50 were used as the first thermally conductive filler.
- Example 7 A resin composition was obtained in the same manner as in Example 1 except that scaly magnesium hydroxide particles having a major axis of 9 ⁇ m, a thickness of 150 nm, and an aspect ratio of 60 were used as the first thermally conductive filler.
- Example 8 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the first heat conductive filler was 100 parts by weight and the blending amount of the second heat conductive filler was 400 parts by weight.
- Example 9 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the first heat conductive filler was 50 parts by weight and the blending amount of the second heat conductive filler was 50 parts by weight.
- Example 10 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the first heat conductive filler was 100 parts by weight and the blending amount of the second heat conductive filler was 50 parts by weight.
- Example 11 The resin composition was the same as in Example 1 except that spherical aluminum oxide particles having a particle size of 20 ⁇ m and an aspect ratio of 1 (“AS-20” manufactured by Showa Denko KK) were used as the second thermal conductive filler. I got something.
- Example 1 A resin composition was obtained in the same manner as in Example 1 except that the amount of the first thermally conductive filler compounded was 150 parts by weight without blending the second thermally conductive filler.
- Example 2 A resin composition was obtained in the same manner as in Example 1 except that the amount of the second thermally conductive filler compounded was 300 parts by weight without blending the first thermally conductive filler.
- Comparative Example 4 A resin composition was obtained in the same manner as in Comparative Example 2 except that spherical magnesium oxide particles having a particle size of 50 ⁇ m and an aspect ratio of 1 were used as the second thermal conductive filler.
- Comparative Example 5 A resin composition was obtained in the same manner as in Comparative Example 2 except that the blending amount of the second heat conductive filler was 100 parts by weight.
- Comparative Example 7 The resin composition was the same as in Comparative Example 2 except that spherical aluminum oxide particles having a particle size of 20 ⁇ m and an aspect ratio of 1 (“AS-20” manufactured by Showa Denko KK) were used as the second thermal conductive filler. I got something.
- the thermal conductivity of the resin compositions obtained in each Example and Comparative Example was measured by ISO / CD 22007-2. Specifically, the obtained resin composition is press-molded (primary cross-linking treatment) at 170 ° C., 15 MPa for 10 minutes to form a disk having a thickness of 7.5 mm ⁇ 30 mm ⁇ , and then placed in a gear oven. The mixture was heated at 200 ° C. for 4 hours (secondary cross-linking treatment) to obtain a disk-shaped measurement sample having a thickness of 7.5 mm ⁇ 30 mm ⁇ .
- the thermal conductivity in the thickness direction and the surface direction in the air at room temperature was measured using a hot disk method thermal conductivity measuring device (“TPS-2500S” manufactured by Kyoto Electronics Industry Co., Ltd.). A 6 mm ⁇ sensor was used for the measurement.
- TPS-2500S manufactured by Kyoto Electronics Industry Co., Ltd.
- the measurement results (the ratio of the thermal conductivity in the thickness direction, the thermal conductivity in the surface direction, and the thermal conductivity in the surface direction to the thermal conductivity in the thickness direction (thermal conductivity in the thickness direction / thermal conductivity in the surface direction)) are shown. It is summarized in 1 and Table 2.
- Example 1-3 has a higher thermal conductivity not only in the surface direction but also in the thickness direction as compared with Comparative Example 2.
- the thermal conductivity in the thickness direction can be greatly improved. It can be said that it is an unexpectedly excellent effect.
- Example 8 in which the filler was highly blended, the thermal conductivity in the thickness direction was higher than the thermal conductivity in the surface direction.
- ⁇ SEM observation> SEM observation (2000 times) of a cross section of a molded product molded using the resin composition of Example 1 was performed. The result (image of the resin cross section) is shown in FIG.
- a measurement sample for cross-section SEM observation the molded body after the thermal conductivity measurement was used.
- the molded product was cut using a cross-section sample preparation device (“IB-09010CP” manufactured by JEOL Ltd.). Specifically, in an argon gas atmosphere, the molded product was irradiated with an ion beam at an output of 5.5 kV for 4 hours to cut out a cross section.
- the arrow shown in FIG. 2 indicates the pressing direction during molding of the measurement sample.
- the measurement sample is a molded product formed by pressing from top to bottom in FIG. 2. It can be seen that the scaly filler is oriented in various directions around the spherical filler having a large particle size regardless of the pressing direction. When only the scaly filler is used (for example, in Comparative Example 1), the scaly filler is oriented in the lateral direction (pressed surface).
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Abstract
Description
1つの実施形態においては、上記第1熱伝導性フィラーは、酸化マグネシウム、水酸化マグネシウムおよび窒化ホウ素からなる群から選択される少なくとも1つで形成される。
1つの実施形態においては、上記第2熱伝導性フィラーは、酸化マグネシウム、水酸化マグネシウムおよび酸化アルミニウムからなる群から選択される少なくとも1つで形成される。
1つの実施形態においては、上記第1熱伝導性フィラーの厚みは10nm以上200nm以下である。
1つの実施形態においては、上記第1熱伝導性フィラーの長径は20μm以下である。
1つの実施形態においては、上記第2熱伝導性フィラーの粒径は2μm以上である。
1つの実施形態においては、上記第2熱伝導性フィラーの粒径は上記第1熱伝導性フィラーの長径よりも大きい。
1つの実施形態においては、上記熱伝導性樹脂組成物は、上記樹脂100重量部に対し、上記第1熱伝導性フィラーおよび上記第2熱伝導性フィラーを90重量部以上700重量部以下含有する。
1つの実施形態においては、上記第2熱伝導性フィラーの含有量に対する上記第1熱伝導性フィラーの含有量の比(第1熱伝導性フィラーの重量/第2熱伝導性フィラーの重量)は、0.1以上5以下である。
1つの実施形態においては、上記熱伝導性樹脂組成物における、上記第1熱伝導性フィラーおよび上記第2熱伝導性フィラーの合計体積比率は、25%以上70%以下である。
1つの実施形態においては、上記熱伝導性樹脂成形体はシート状である。
1つの実施形態においては、上記シート状の熱伝導性樹脂成形体は、面方向の熱伝導率に対する厚み方向の熱伝導率の比(厚み方向の熱伝導率/面方向の熱伝導率)が0.5以上である。
本明細書における用語の定義は、下記の通りである。
1.粒径
粒径は、粒度分布測定における平均粒径である。
2.長径
走査型電子顕微鏡(SEM)観察により測定した値であり、無作為に選んだ1次粒子の長径(例えば、図1Aおよび図1BのL)の平均値である。なお、一次粒子とは、SEMにより観察される最小の粒子であって、その他凝集している粒子(二次粒子)とは区別される。
3.厚み
SEM観察により測定した値であり、無作為に選んだ1次粒子の厚み(例えば、図1Aおよび図1BのT)の平均値である。
4.アスペクト比(長径/厚み)
上記長径から上記厚みを除して算出した値である。
本発明の1つの実施形態における熱伝導性改良剤は、第1熱伝導性フィラーおよび第2熱伝導性フィラーを含む。
上記第1熱伝導性フィラーのアスペクト比は、10以上であり、好ましくは30以上、より好ましくは45以上、さらに好ましくは55以上、特に好ましくは65以上である。例えば、第1熱伝導性フィラー間に後述の第2熱伝導性フィラーが分散して、熱伝導パスが形成されやすいからである。一方、第1熱伝導性フィラーのアスペクト比は、例えば200以下であり、好ましくは100以下である。このような第1熱伝導性フィラーは、後述の樹脂に充填しやすく、例えば、後述の熱伝導性樹脂組成物を作製する際の加工性に優れ得る。
上記第2熱伝導性フィラーのアスペクト比は、2以下である。具体的には、第2熱伝導性フィラーのアスペクト比は、1以上2以下である。このような第2熱伝導性フィラーを用いることにより、上記第1熱伝導性フィラー間に介在し、良好に(例えば、様々な方向に)熱伝導パスを形成し得る。その結果、優れた熱伝導性を達成し得る。具体的には、後述の熱伝導性樹脂成形体において、優れた熱伝導性(例えば、厚み方向の熱伝導性)を達成し得る。また、このような第2熱伝導性フィラーは、後述の樹脂への充填性に優れ、例えば、後述の熱伝導性樹脂組成物を作製する際の加工性に優れ得る。
上記熱伝導性改良剤において、上記第2熱伝導性フィラーの含有量に対する上記第1熱伝導性フィラーの含有量の比(第1熱伝導性フィラーの重量/第2熱伝導性フィラーの重量)は、0.1以上であることが好ましい。このような含有比によれば、後述の熱伝導性樹脂成形体において、第1熱伝導性フィラーと第2熱伝導性フィラーとのチャンネルが繋がりやすく、優れた熱伝導性(例えば、厚み方向の熱伝導性)を達成し得る。1つの実施形態においては、上記含有比は、好ましくは0.2以上、さらに好ましくは0.3以上である。
上記熱伝導性改良剤は、その他の成分を含み得る。その他の成分としては、例えば、後述の任意成分が採用される。
本発明の1つの実施形態における熱伝導性改良方法は、上記熱伝導性改良剤を用いる。具体的には、熱伝導性を向上させたい対象物に上記熱伝導性改良剤を含有させる。例えば、上記熱伝導性改良剤を樹脂に含有させる。以下、樹脂と熱伝導性改良剤を含有する熱伝導性樹脂組成物について説明する。
本発明の1つの実施形態における熱伝導性樹脂組成物は、樹脂、上記第1熱伝導性フィラーおよび上記第2熱伝導性フィラーを含む。
上記樹脂は、例えば、得られる熱伝導性樹脂組成物の用途等に応じて、任意の適切な樹脂が選択され得る。樹脂としては、例えば、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体等のエチレン-α-オレフィン共重合体、ポリメチルペンテン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、エチレン-酢酸ビニル共重合体、ポリビニルアルコール、ポリアセタール、ポリフッ化ビニリデンやポリテトラフルオロエチレン等のフッ素系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリスチレン、ポリアクリロニトリル、スチレン-アクリロニトリル共重合体、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)樹脂、ポリフェニレンエーテル、変性ポリフェニレンエーテル、脂肪族ポリアミド類、芳香族ポリアミド類、ポリアミドイミド、ポリメタクリル酸又はそのエステル、ポリアクリル酸又はそのエステル、ポリカーボネート、ポリフェニレンスルフィド、ポリサルホン、ポリエーテルサルホン、ポリエーテルニトリル、ポリエーテルケトン、ポリケトン、液晶ポリマー、シリコーン樹脂、アイオノマーが挙げられる。また、例えば、スチレン-ブタジエン共重合体およびその水添ポリマー、スチレン-イソプレンブロック共重合体およびその水添ポリマー等のスチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、塩化ビニル系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマーが挙げられる。さらには、例えば、シリコーンゴム、アクリルゴム、ブチルゴム、フッ素ゴム、ニトリルゴム、水素化ニトリルゴムが挙げられる。これらは、単独で、または、2種以上を組み合わせて用い得る。
上記熱伝導性樹脂組成物における上記第1熱伝導性フィラーのおよび上記第2熱伝導性フィラーの合計含有割合は、好ましくは50重量%以上、さらに好ましくは60重量%以上、特に好ましくは70重量%以上である。このような範囲によれば、極めて優れた熱伝導性を達成し得る。一方、上記合計含有割合は、好ましくは95重量%以下、さらに好ましくは90重量%以下である。このような範囲によれば、熱伝導性樹脂組成物を作製する際の加工性に優れ得る。
上記熱伝導性樹脂組成物は、上述したように、架橋剤、架橋促進剤、架橋促進助剤等の任意成分を含み得る。また、上記熱伝導性樹脂組成物は、補強剤、充填剤、軟化剤、可塑剤、老化防止剤、粘着付与剤、帯電防止剤、練り込み接着剤、難燃剤、カップリング剤等の任意成分を含み得る。熱伝導性樹脂組成物における任意成分の含有割合は、例えば0.05重量%~10重量%である。
本発明の1つの実施形態における熱伝導性樹脂成形体は、上記熱伝導性樹脂組成物から形成される。具体的には、熱伝導性樹脂成形体は、上記樹脂、上記第1熱伝導性フィラーおよび上記第2熱伝導性フィラーを含む。
1.粒径
レーザー回析散乱法(装置:マイクロトラック・ベル株式会社製、マイクロトラックMT3000)により粒径を測定した。測定用試料は、フィラー0.7gにヘキサメタリン酸ナトリウム溶液(0.2%)を70mL加えた後、280μAで3分間超音波処理を施すことにより調製した。
2.長径
SEM観察により長径を算出した。具体的には、フィラー(粒子)のSEM写真の中から無作為に選んだ10個の1次粒子の長径を測定し、得られた測定値の算術平均(平均長径)を求めた。なお、長径のSEM観察の倍率は、第1熱伝導性フィラーについては2,000倍、第2熱伝導性フィラーについては500倍とした。
3.厚み
SEM観察により厚みを算出した。具体的には、フィラー(粒子)のSEM写真の中から無作為に選んだ10個の1次粒子の厚みを測定し、得られた測定値の算術平均(平均厚み)を求めた。なお、厚みのSEM観察の倍率は、第1熱伝導性フィラーについては20,000倍、第2熱伝導性フィラーについては500倍とした。
4.アスペクト比
SEM観察によりアスペクト比を算出した。具体的には、上記平均長径を上記平均厚みで除してアスペクト比を算出した。
シリコーンゴム(モメンティブ・パフォーマンス・マテリアルズ社製の「TSE-201」)100重量部に対し、第1熱伝導性フィラー(長径4μm、厚み57nm、アスペクト比70の鱗片状の水酸化マグネシウム粒子)90重量部、第2熱伝導性フィラー(協和化学工業株式会社製の「パイロキスマ3320」、粒径20μm、アスペクト比1の球状の酸化マグネシウム粒子)210重量部および架橋剤(モメンティブ・パフォーマンス・マテリアルズ社製の「TC-8」)2重量部の割合で、小型2軸プラストミル(Brabender社製)を用いて混合し、樹脂組成物を得た。
第1熱伝導性フィラーの配合量を30重量部とし、第2熱伝導性フィラーの配合量を270重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーの配合量を120重量部とし、第2熱伝導性フィラーの配合量を180重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径3μm、アスペクト比1の酸化マグネシウム粒子(協和化学工業株式会社製の「パイロキスマ5301」)を用いたこと以外は実施例1と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径50μm、アスペクト比1の球状の酸化マグネシウム粒子を用いたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーとして、長径1.6μm、厚み32nm、アスペクト比50の鱗片状の水酸化マグネシウム粒子を用いたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーとして、長径9μm、厚み150nm、アスペクト比60の鱗片状の水酸化マグネシウム粒子を用いたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーの配合量を100重量部とし、第2熱伝導性フィラーの配合量を400重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーの配合量を50重量部とし、第2熱伝導性フィラーの配合量を50重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーの配合量を100重量部とし、第2熱伝導性フィラーの配合量を50重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径20μm、アスペクト比1の球状の酸化アルミニウム粒子(昭和電工株式会社製の「AS-20」)を用いたこと以外は実施例1と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーを配合せずに、第1熱伝導性フィラーの配合量を150重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第1熱伝導性フィラーを配合せずに、第2熱伝導性フィラーの配合量を300重量部としたこと以外は実施例1と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径3μm、アスペクト比1の酸化マグネシウム粒子(協和化学工業株式会社製の「パイロキスマ5301」)を用いたこと以外は比較例2と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径50μm、アスペクト比1の球状の酸化マグネシウム粒子を用いたこと以外は比較例2と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーの配合量を100重量部としたこと以外は比較例2と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーの配合量を150重量部としたこと以外は比較例2と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーとして、粒径20μm、アスペクト比1の球状の酸化アルミニウム粒子(昭和電工株式会社製の「AS-20」)を用いたこと以外は比較例2と同様にして、樹脂組成物を得た。
第2熱伝導性フィラーを配合せずに、第1熱伝導性フィラーの配合量を200重量部としたこと以外は実施例1と同様にして、樹脂組成物の作製を試みた。しかしながら、良好に作製することはできなかった。
各実施例および比較例で得られた樹脂組成物について、ISO/CD 22007-2により、熱伝導率を測定した。具体的には、得られた樹脂組成物を、170℃、15MPa、10分間の条件でプレス成形(1次架橋処理)して厚み7.5mm×30mmφの円盤状に成形した後、ギアオーブンにて200℃、4時間の条件で加熱(2次架橋処理)し、厚み7.5mm×30mmφの円盤状の測定用試料を得た。
実施例1の樹脂組成物を用いて成形した成形体の断面のSEM観察(2000倍)を行った。その結果(樹脂断面の画像)を図2に示す。なお、断面SEM観察の測定用試料として、上記熱伝導率測定後の成形体を使用した。成形体の切断は、断面試料作製装置(日本電子株式会社製の「IB-09010CP」)を用いて行った。具体的には、アルゴンガス雰囲気の中、成形体に対して5.5kVの出力で4時間イオンビームを照射して断面を切り出した。
T.厚み
Claims (15)
- 樹脂と、
アスペクト比が10以上で、長径が30μm未満の第1熱伝導性フィラーと、
アスペクト比が2以下の第2熱伝導性フィラーと
を含む、熱伝導性樹脂組成物。 - 前記第1熱伝導性フィラーが、酸化マグネシウム、水酸化マグネシウムおよび窒化ホウ素からなる群から選択される少なくとも1つで形成される、請求項1に記載の熱伝導性樹脂組成物。
- 前記第2熱伝導性フィラーが、酸化マグネシウム、水酸化マグネシウムおよび酸化アルミニウムからなる群から選択される少なくとも1つで形成される、請求項1または2に記載の熱伝導性樹脂組成物。
- 前記第1熱伝導性フィラーの厚みが10nm以上200nm以下である、請求項1から3のいずれかに記載の熱伝導性樹脂組成物。
- 前記第1熱伝導性フィラーの長径が20μm以下である、請求項1から4のいずれかに記載の熱伝導性樹脂組成物。
- 前記第2熱伝導性フィラーの粒径が2μm以上である、請求項1から5のいずれかに記載の熱伝導性樹脂組成物。
- 前記第2熱伝導性フィラーの粒径が前記第1熱伝導性フィラーの長径よりも大きい、請求項1から6のいずれかに記載の熱伝導性樹脂組成物。
- 前記樹脂100重量部に対し、前記第1熱伝導性フィラーおよび前記第2熱伝導性フィラーを90重量部以上700重量部以下含有する、請求項1から7のいずれかに記載の熱伝導性樹脂組成物。
- 前記第2熱伝導性フィラーの含有量に対する前記第1熱伝導性フィラーの含有量の比(第1熱伝導性フィラーの重量/第2熱伝導性フィラーの重量)が、0.1以上5以下である、請求項1から8のいずれかに記載の熱伝導性樹脂組成物。
- 前記第1熱伝導性フィラーおよび前記第2熱伝導性フィラーの合計体積比率が、25%以上70%以下である、請求項1から9のいずれかに記載の熱伝導性樹脂組成物。
- 請求項1から10のいずれかに記載の熱伝導性樹脂組成物から形成される、熱伝導性樹脂成形体。
- シート状である、請求項11に記載の熱伝導性樹脂成形体。
- 面方向の熱伝導率に対する厚み方向の熱伝導率の比(厚み方向の熱伝導率/面方向の熱伝導率)が0.5以上である、請求項12に記載の熱伝導性樹脂成形体。
- アスペクト比が10以上で、長径が30μm未満の第1熱伝導性フィラーと、
アスペクト比が2以下の第2熱伝導性フィラーと
を含む、熱伝導性改良剤。 - 請求項14に記載の熱伝導性改良剤を用いる、熱伝導性改良方法。
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