WO2019078044A1 - Composition de résine thermoconductrice, objet durci, et procédé de rayonnement thermique - Google Patents

Composition de résine thermoconductrice, objet durci, et procédé de rayonnement thermique Download PDF

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Publication number
WO2019078044A1
WO2019078044A1 PCT/JP2018/037446 JP2018037446W WO2019078044A1 WO 2019078044 A1 WO2019078044 A1 WO 2019078044A1 JP 2018037446 W JP2018037446 W JP 2018037446W WO 2019078044 A1 WO2019078044 A1 WO 2019078044A1
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Prior art keywords
thermally conductive
component
resin composition
conductive resin
mass
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PCT/JP2018/037446
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English (en)
Japanese (ja)
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由智 小野
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株式会社スリーボンド
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Priority to CN201880067861.8A priority Critical patent/CN111247207B/zh
Priority to JP2019549213A priority patent/JPWO2019078044A1/ja
Publication of WO2019078044A1 publication Critical patent/WO2019078044A1/fr
Priority to JP2023029107A priority patent/JP2023078170A/ja

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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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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 thermally conductive resin composition, a cured product obtained by curing the composition, and a heat dissipation method of an electric and electronic component using the composition.
  • a thermally conductive resin is used between a heating element of an electrical / electronic component and a heat dissipation member such as a radiation fin in order to dissipate heat generated from the electrical / electronic component such as a semiconductor to the outside.
  • a heat conductive resin an epoxy resin-based heat conductive resin is often used because it can achieve both adhesiveness and heat conductivity.
  • the conventional epoxy resin-based thermally conductive resin uses dicyandiamide, hydrazide or the like as a curing agent, and therefore, it has been necessary to heat it at over 150 ° C. in order to cure it.
  • plastic materials are known to be susceptible to high temperatures. Therefore, low temperature curability (specifically, curability at 150 ° C. or less) is required for the epoxy resin-based thermally conductive resin.
  • JP 2009-292881 A (corresponding to US Patent Application Publication 2009/298965) includes a low temperature curing property including an amine adduct type latent curing agent and a high thermal conductivity filler.
  • a high thermal conductivity epoxy resin based composition is disclosed.
  • the thermal conductivity of the cured product of the epoxy resin composition disclosed in the experimental example of JP 2009-292881 A is 2.3 W / m. It was K, and its thermal conductivity was not satisfactory. Further, the epoxy resin-based composition disclosed in the experimental example of the above-mentioned publication contains a large amount of aluminum oxide for the purpose of imparting thermal conductivity, and therefore has a problem of high viscosity and poor handling. .
  • an object of the present invention is to provide a thermally conductive resin composition which can form a cured product which is excellent in low-temperature curing properties (curing properties at 150 ° C. or lower) and handling properties and is excellent in thermal conductivity. .
  • the present invention includes the following embodiments.
  • (C) A mixture of the following (C1) to (C3), and the mass ratio of (C1) to (C3) ((C1) A mixture wherein / (C3)) is 0.14 to 1.0, and the mass ratio of (C2) to (C3) ((C2) / (C3)) is 0.25 to 1.5; (C1) thermally conductive powder having an average particle diameter of 0.01 ⁇ m or more and less than 2 ⁇ m (C2) thermally conductive powder having an average particle diameter of 2 ⁇ m or more and less than 20 ⁇ m (C3) thermally conductive powder having an average particle diameter of 20 ⁇ m or more and less than 150 ⁇ m .
  • the components (C1) to (C3) are each independently at least one thermally conductive powder selected from the group consisting of alumina, zinc oxide, aluminum nitride, boron nitride, carbon and diamond.
  • the thermally conductive resin composition as described in [1].
  • [3] The thermally conductive resin composition according to [1] or [2], wherein the shape of the components (C1) to (C3) is spherical or amorphous.
  • the component (C1) is 5 to 60% by mass
  • the component (C2) is 10 to 65% by mass
  • the component (C3) is 100% by mass of the total of (C1), (C2) and (C3)
  • One embodiment of the present invention is a thermally conductive resin composition (hereinafter also referred to as a composition) containing the following components (A) to (C): (A) Epoxy resin (B) Adduct-type latent curing agent which is solid at 25 ° C.
  • (C) A mixture of the following (C1) to (C3), and the mass ratio of (C1) to (C3) ((C1) A mixture wherein / (C3)) is 0.14 to 1.0, and the mass ratio of (C2) to (C3) ((C2) / (C3)) is 0.25 to 1.5; (C1) thermally conductive powder having an average particle diameter of 0.01 ⁇ m or more and less than 2 ⁇ m (C2) thermally conductive powder having an average particle diameter of 2 ⁇ m or more and less than 20 ⁇ m (C3) thermally conductive powder having an average particle diameter of 20 ⁇ m or more and less than 150 ⁇ m .
  • the heat conductive resin composition can form a cured product excellent in low temperature curability and handling property and excellent in thermal conductivity.
  • low temperature refers to, for example, 150 ° C. or less, preferably 120 ° C. or less, more preferably 100 ° C. or less, and still more preferably 80 ° C. or less.
  • excellent in low-temperature curing property means that when the composition is heated at the above temperature, a cured product without tack (stickiness) on the surface is obtained.
  • excellent in handling properties means that the viscosity of the thermally conductive resin composition is low and the coating operation is easy.
  • thermoplastic resin composition according to the present invention details of the thermoplastic resin composition according to the present invention will be described.
  • the epoxy resin which is the component (A) of the present invention any compound having two or more glycidyl groups in one molecule and not falling under the component (B) can be used without particular limitation.
  • the component (A) for example, an epoxy resin having two glycidyl groups in one molecule (hereinafter also referred to as “bifunctional epoxy resin”), an epoxy resin having three or more glycidyl groups in one molecule (hereinafter And “polyfunctional epoxy resin”).
  • the component (A) is a bifunctional epoxy resin and a multifunctional epoxy resin from the viewpoint of reducing the viscosity of the composition to improve the handling property, and the viewpoint of enhancing the thermal conductivity and / or heat resistance of the cured product. It is preferable to use in combination with At this time, the polyfunctional epoxy resin is more preferably a trifunctional or tetrafunctional epoxy resin, and still more preferably a tetrafunctional epoxy resin.
  • the mass ratio (bifunctional epoxy resin: multifunctional epoxy resin) is preferably in the range of 30:70 to 70:30, and more preferably 40: It is in the range of 60 to 60:40. Within the above range, the handling properties of the composition and the thermal conductivity of the cured product can be highly compatible.
  • the component (A) can be used either liquid or solid at 25 ° C., but is preferably liquid at 25 ° C. from the viewpoint of improving the handling property of the composition.
  • liquid means having fluidity, and specifically, when the component is inclined 45 °, it means that the shape can not be maintained for 10 minutes or more, resulting in a change in shape.
  • the viscosity at 25 ° C. of the component (A) is preferably 1 to 50 Pa ⁇ s, more preferably 3 to 40 Pa ⁇ s, and 5 to 30 Pa Even more preferably s.
  • the viscosity is a value measured by the method described in the examples described later.
  • the epoxy equivalent of the component (A) is preferably 50 to 250 g / eq, more preferably 100 to 200 g / eq.
  • the epoxy equivalent is a value measured in accordance with JIS K 7236: 2001.
  • the bifunctional epoxy resin is not particularly limited.
  • bisphenol A epoxy resin and bisphenol F epoxy resin are preferably used from the
  • the polyfunctional epoxy resin is not particularly limited, but novolac epoxy resin such as phenol novolac epoxy resin and cresol novolac epoxy resin; N, N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylene bis (N And glycidyl amine compounds such as tetraglycidyldiaminodiphenylmethane and tetraglycidyl-m-xylylenediamine; and naphthalene type epoxy resins having four glycidyl groups. These compounds may be used alone or in combination of two or more.
  • the commercial product of the component (A) is not particularly limited.
  • jER registered trademark
  • 828 1001, 801, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000
  • Epiclon registered trademark
  • EP 4920 (made by ADEKA Co., Ltd.); TEPIC (made by Nissan Chemical Industries, Ltd.); KF-101, KF-1001, KF-105, X-22-163B, X-22-9002 (Shin-Etsu Chemical Co., Ltd.) ; Denacol (registered trademark) EX411, 314, 201, 212, 252 (manufactured by Nagase ChemteX Co., Ltd.); DER-331, 332, 334, 431, 542 (manufactured by Dow Chemical Company); YH-434, YH-434L Examples include (manufactured by Nippon Steel Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto.
  • the component (B) used in the present invention is an adduct type latent curing agent which is solid at 25 ° C.
  • a solid refers to a thing which does not have fluidity, and when an ingredient is inclined 45 degrees, it says that the shape can be maintained for 10 minutes or more specifically ,.
  • the mixture of the components (A) and (B) is stable without heating (for example 25 ° C.), but by heating to 70 to 170 ° C. (preferably 70 to 150 ° C.), the component (B) is stabilized. Acts as a curing agent to cure the component (A).
  • the adduct type refers to, for example, a compound in which an epoxy resin and an amine compound react to an intermediate stage, or a compound in which an amine compound and an isocyanate compound or a urea compound react to an intermediate stage.
  • the component (B) is selected and combined with the components (C1) to (C3) to be described later to handle the handling of the composition and the heat of the cured product. It can be compatible with conductivity.
  • the component (B) is not contained, the viscosity of the composition becomes high and the handling property is poor, and / or the thermal conductivity of the cured product becomes insufficient (see Comparative Examples 1 to 3).
  • the average particle diameter of the component (B) is preferably in the range of 0.1 to 100 ⁇ m, more preferably in the range of 1 to 30 ⁇ m, and still more preferably 2 to 15 ⁇ m. And even more preferably in the range of 3 to 10 ⁇ m, particularly preferably more than 5 ⁇ m and less than 10 ⁇ m.
  • the average particle size of the component (B) is the particle size (D50) at a cumulative volume ratio of 50% in the particle size distribution determined by the laser diffraction scattering method.
  • the upper limit of the softening temperature of the component (B) is, for example, 170 ° C. or less, preferably 160 ° C. or less, more preferably 150 ° C. or less, particularly preferably 145 ° C. or less .
  • the lower limit of the softening temperature of the component (B) is, for example, 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 110 ° C. or higher from the viewpoint of handling. is there.
  • the measuring method of the said softening temperature is calculated
  • the component (B) is not particularly limited, but a reaction product obtained by reacting an amine compound and an isocyanate compound or a urea compound (urea adduct type latent curing agent) or a reaction product of an amine compound and an epoxy compound Resin amine adduct type latent curing agents are preferred. These may be used in combination. Among them, an epoxy resin amine adduct type latent curing agent is preferable from the viewpoint of achieving a high degree of compatibility between the handling property of the composition and the thermal conductivity of the cured product.
  • the softening temperature is preferably 110 ° C. or higher, more preferably 120 ° C., from the viewpoint of reducing the viscosity of the composition and enhancing the handling property. It is the above, still more preferably 130 ° C or more, and particularly preferably 135 ° C or more.
  • the method of measuring the softening temperature is the same as described above.
  • the commercial product of the component (B) is not particularly limited.
  • the urea adduct type latent curing agent for example, Fujicure (registered trademark, the same in the following) FXE-1000, FXR-1020, FXR-1030, FXB- 1050 (above, T & K TOKA Co., Ltd. product) etc. are mentioned.
  • epoxy resin amine adduct type latent curing agent for example, AMICURE (registered trademark, the same as the following) PN-23, AMICURE PN-H, AMICURE PN-31, AMICURE PN-40, AMICURE PN-50, AMICURE PN-F Amicure PN-23J, Amicure PN-31J, Amicure PN-40J, Amicure MY-24, Amicure MY-25, Amicure MY-R, Amicure PN-R (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like. Also, these may be used alone or in combination.
  • the compounding amount of the component (B) in the present invention is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the component (A), and still more preferably 15 to 30 parts by mass.
  • the component (A) can be sufficiently cured when the amount of the component (B) is 5 parts by mass or more, and the heat resistance of the cured product of the thermally conductive resin composition can be 50 parts by mass or less Is excellent.
  • the component (C) of the present invention is (C1) thermally conductive powder having an average particle diameter of 0.01 ⁇ m or more and less than 2 ⁇ m, (C2) thermally conductive powder having an average particle diameter of 2 ⁇ m or more and less than 20 ⁇ m, (C3) average particle It is a mixture of thermally conductive powder having a diameter of 20 ⁇ m or more and less than 150 ⁇ m.
  • the average particle diameter of the component (C1) is 0.01 ⁇ m or more to 2 ⁇ m (2.0 ⁇ m) from the viewpoint of obtaining a cured product having high thermal conductivity while reducing the viscosity of the thermally conductive resin composition to improve the handling property.
  • the average particle diameter of the component (C2) is 2 ⁇ m (2.0 ⁇ m) or more from the viewpoint of obtaining a cured product having high thermal conductivity while reducing the viscosity of the thermal conductive resin composition to improve the handling property.
  • the average particle diameter of the component (C3) is preferably 20 ⁇ m or more and 150 ⁇ m or less from the viewpoint of obtaining a cured product with high thermal conductivity while reducing the viscosity of the thermally conductive resin composition to enhance handling. 23 micrometers or more and 100 micrometers or less are more preferable, 25 micrometers or more and 70 micrometers or less are still more preferable, and 30 micrometers or more and less than 50 micrometers are especially preferable.
  • the average particle diameter of the components (C1) to (C3) is the particle diameter (D50) at a cumulative volume ratio of 50% in the particle size distribution determined by the laser diffraction scattering method.
  • the mass ratio ((C1) / (C3)) of the component (C1) to the component (C3) is 0.14 to 1.0.
  • (C1) / (C3) is less than 0.14, the composition has a high viscosity and poor handleability, and the thermal conductivity of the formed cured product is also insufficient (see Comparative Example 4).
  • (C1) / (C3) exceeds 1.0, the composition has a very high viscosity and handling is difficult, and the formation of a cured product becomes difficult (see Comparative Examples 6 and 7).
  • (C1) / (C3) is preferably 0.16 to 0.90, more preferably 0.18 to 0.80, and still more preferably 0. It is preferably from 20 to 0.70, particularly preferably from 0.25 to 0.65.
  • the mass ratio ((C2) / (C3)) of the component (C2) to the component (C3) is 0.25 to 1.5.
  • (C2) / (C3) is less than 0.25, the composition has a high viscosity and poor handleability, and the thermal conductivity of the formed cured product is also insufficient (see Comparative Example 5).
  • (C2) / (C3) exceeds 1.5, the composition has a very high viscosity and handling is difficult, and the formation of a cured product becomes difficult (see Comparative Examples 6 and 8).
  • (C2) / (C3) is preferably 0.27 to 1.2, more preferably 0.30 to 1.0, and still more preferably 0. 40 to 0.95.
  • (C1) / (C3) is 0.14 to 1.0 and (C2) / (C3) is 0.25 to 1.5.
  • (C1) / (C3) is preferably 0.16 to 0.9 (0.90) and (C2) / (C3) is 0.27 to 1.2, and more preferably (C1) / (C1) C3) is 0.18 to 0.8 (0.80) and (C2) / (C3) is 0.3 (0.30) to 1.0.
  • the content of the component (C3) is preferably 30 to 85% by mass, that of the component (C1) is preferably 5 to 30% by mass, the component (C2) is 10 to 50% by mass, and the component (C3) is 30 It is more preferable that the content is 80 to 80% by mass, that of 7 to 28% by mass of the component (C1), 15 to 40% by mass of the component (C2), and 40 to 70% by mass of the component (C3). preferable.
  • the mixing ratio of the components (C1) to (C3) is within the above range, both the handling property and the thermal conductivity of the cured product can be well achieved.
  • the content of the component (C1) is preferably 80 to 300 parts by mass, more preferably 120 to 250 parts by mass with respect to 100 parts by mass of the component (A). is there.
  • the content of the component (C2) is preferably 150 to 400 parts by mass, more preferably 180 to 350 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of the component (C3) is preferably 250 to 500 parts by mass, and more preferably 300 to 450 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of the component (C) (that is, the total content of the components (C1) to (C3)) is not particularly limited, but, for example, 55 to 99 mass with respect to the entire thermally conductive resin composition of the present invention % Is preferable, 60 to 95% by mass is more preferable, 70 to 93% by mass is more preferable, 75 to 90% by mass is still more preferable, and 80 to 86% by mass is particularly preferable. If it is 55 mass% or more, the heat conduction performance is sufficient, and if it is 99 mass% or less, both the workability (handling property of the composition) and the thermal conductivity of the cured product can be achieved.
  • the components (C1) to (C3) are each independently at least one thermally conductive powder selected from the group consisting of alumina, zinc oxide, aluminum nitride, boron nitride, carbon and diamond.
  • at least one heat conductive powder is particularly preferably selected from the group consisting of alumina, aluminum nitride and boron nitride, because they are excellent in thermal conductivity.
  • at least one of the components (C1) to (C3) is preferably alumina, and it is particularly preferable that all of the components (C1) to (C3) are alumina.
  • the component (C) may be surface-treated. Also, these may be used alone or in combination.
  • the shapes of the components (C1) to (C3) are preferably spherical or indeterminate.
  • spherical includes not only perfect spheres but also shapes such as approximately spheres and ovals. More specifically, “spherical” means that the average circularity is 0.4 or more.
  • indeterminate refers to a shape having corners other than a spherical shape (eg, needle shape, fiber shape, scaly shape, dendritic shape, flat shape, crushed shape, etc.). More specifically, "amorphous” means that the average circularity is less than 0.4. Furthermore, when the component (C) is a mixture containing a spherical thermally conductive powder and an amorphous thermally conductive powder, a cured product with further improved thermal conductivity can be obtained.
  • the degree of circularity is obtained by, for example, acquiring a particle projection image using a flow type particle image analyzer FPIA-3000 (manufactured by Malvern Co., Ltd.), and X,
  • grain projection image is set to Y, it is a value represented by X / Y.
  • the average circularity is calculated by summing the circularity of each particle and dividing by the total number of particles.
  • the shape of the component (C1) is preferably spherical.
  • the shape of the component (C1) is preferably indeterminate.
  • the shape of the component (C2) is preferably spherical.
  • the shape of the component (C3) is preferably spherical. Therefore, in one embodiment of the present invention, the (C2) and (C3) components are spherical thermally conductive powders.
  • the thermally conductive resin composition of the present invention may further contain any additive component as long as the properties of the composition are not impaired.
  • the components include plasticizers, solvents, diluents, adhesion-improving components such as silane coupling agents, dispersants, leveling agents, wetting agents, surfactants such as antifoaming agents, antistatic agents, surface lubrication Agents, rust inhibitors, preservatives, viscoelastic modifiers, rheology modifiers, colorants, anti-aging agents such as UV absorbers, non-heat conductive fillers, and the like.
  • the thermally conductive resin composition of the present invention may contain a polymer material such as polyester resin, polycarbonate resin, polyacrylic resin, polyurethane resin, polyvinyl resin or the like for the purpose of adjusting the viscoelasticity and the like.
  • the thermally conductive resin composition of the present invention can be produced by a conventionally known method. For example, after blending the above-mentioned components (A), (B), (C1), (C2) and (C3), and optional components as required, using a known mixing means such as a mixer It can be prepared by mixing preferably at a temperature of 10 to 70 ° C., preferably for 0.1 to 5 hours.
  • the thermally conductive resin composition of the present invention is preferably liquid at 25 ° C.
  • the viscosity at 25 ° C. is preferably less than 250 Pa ⁇ s (lower limit: For example, 0.5 Pa ⁇ s or more).
  • the viscosity is a value measured by the method described in the examples described later.
  • the thermally conductive resin composition of the present invention is excellent in low-temperature curing property and handling property, and can form a cured product excellent in thermal conductivity, so that it can be used in electronic parts such as circuit boards made of plastic materials.
  • a cured product can be formed on an electrical and electronic component by applying the heat conductive composition of the present invention to the electrical and electronic component and heat treating it. Since the formed cured product is excellent in thermal conductivity, the heat generated from the electric and electronic component can be dissipated to the outside through the cured product. It does not restrict
  • the heat treatment conditions are not particularly limited, but in the case of a plastic electric / electronic component, the heat treatment is performed, for example, at 150 ° C. or less (eg, 40 to 120 ° C.) for 5 to 120 minutes.
  • heat dissipation of electrical and electronic components is achieved by radiating the heat generated from the electrical and electronic components to the outside by applying the above-described heat conductive composition to the electrical and electronic components.
  • a method is provided.
  • curing said heat conductive resin composition is provided.
  • ⁇ (A) component> a1 Bisphenol F-type bifunctional epoxy resin (jER (registered trademark) 806, made by Mitsubishi Chemical Corporation, viscosity 15 to 25 Pa ⁇ s (25 ° C.), epoxy equivalent 160 to 170 g / eq) liquid at 25 ° C.
  • jER registered trademark
  • a2 Glycidylamine type tetrafunctional epoxy resin (tetraglycidyl diaminodiphenylmethane, YH-434 L, made by Nippon Steel Sumikin Chemical Co., Ltd., liquid at 25 ° C., viscosity 6 to 9 Pa ⁇ s (25 ° C.), epoxy equivalent 115 to 119 g / eq ) ⁇ (B) component>
  • b1 Urea adduct type latent curing agent which is solid at 25 ° C., has an average particle diameter of 7 ⁇ m and a softening temperature of 140 ° C.
  • b'2 1,3-bis (hydrazino carbonoethyl) -5-isopropyl hydantoin (Amicure VDH manufactured by Ajinomoto Fine Techno Co., Ltd.)
  • b'3 3-phenyl-1,1-dimethylurea (Omicure 94 manufactured by Pyi T I Japan Co., Ltd.)
  • b'4 Dicyandiamide having an average particle diameter of 4 ⁇ m (Omicure DDA-5 manufactured by Pyi T I Japan Co., Ltd.) ⁇ (C) component>
  • c1-1 Amorphous alumina powder with an average particle diameter of 1.0 ⁇ m (manufactured by Showa Denko KK, average circularity less than 0.4)
  • c1-2 Spherical alumina powder having an average particle diameter of 1.0 ⁇ m (manufactured by Sumitomo Chemical Co., Ltd., average circularity of 0.4 or more)
  • c2 Spherical alumina powder having an average
  • ⁇ Viscosity measurement> The viscosity of the thermally conductive resin composition of the Example of Table 1 and a comparative example was evaluated.
  • the viscosity (Pa ⁇ s) was measured at 25 ° C. using an EHD viscometer (TV-33 manufactured by Toki Sangyo Co., Ltd.).
  • the measurement conditions are as follows. The lower the viscosity, the better the coating workability and the better the handling property.
  • the viscosity of the composition is preferably less than 250 Pa ⁇ s, more preferably less than 220 Pa ⁇ s, from the viewpoint of the handling property of the composition.
  • "*" indicates that the viscosity was too high to be measured: [Measurement condition] Corn rotor: 3 ° ⁇ R14 Rotation speed: 0.5 rpm.
  • the thermally conductive resin compositions of the examples and comparative examples in Table 1 are applied on a fluorine resin plate to a thickness of 0.5 mm, and heated at 80 ° C. for 1 hour to cure the composition. , Test pieces were made.
  • the thermal conductivity is measured using a thermal conductivity meter (QTM-D3 manufactured by Kyoto Denshi Kogyo Co., Ltd.).
  • the thermal conductivity (W / (m ⁇ K)) of the surface on which the cured product of the test piece is formed is 25 Measured in ° C.
  • the cured product is preferable because the larger the thermal conductivity, the easier it is for heat to be transmitted.
  • the thermal conductivity of the cured product is preferably 3.8 W / (m ⁇ K) or more from the viewpoint of the thermal conductivity of the cured product. It is suggested that there is a significant difference in the performance of radiating heat generated from the electric / electronic component to the outside between the case where the lower limit value is satisfied and the case where the value is not satisfied.
  • the thermal conductivity of the cured product is preferably 4.0 W / (m ⁇ K) or more.
  • the thermally conductive resin compositions according to the examples in Table 1 all have low temperature curability because heat treatment at 80 ° C. for 1 hour yielded a cured product without tack (stickiness) on the surface. Was admitted. Moreover, in Table 1, "**" represents that the viscosity of the composition was too high to form a cured product.
  • thermally conductive resin composition of the present invention can form a cured product excellent in low temperature curability and handling properties and excellent in thermal conductivity.
  • the compositions of Comparative Examples 1 and 3 are compared with the composition of the example (C) It was confirmed that the heat conductivity of the cured product formed was inferior despite the fact that it contained a large amount of components. Moreover, it was confirmed that the composition of Comparative Example 2 has high viscosity and poor handling.
  • composition containing components (C1) to (C3) of the present invention wherein (C1) / (C3) is less than 0.14, or (C2) / (C3) is less than 0.25 Comparative Examples 4 and 5) were confirmed to be inferior in both the handling property and the thermal conductivity of the formed cured product.
  • the composition (C1) / (C3) exceeds 1.0 or / and (C2) / (C3) exceeds 1.5 ( In Comparative Examples 6 to 8), the viscosity was so high that handling was difficult, and a cured product could not be formed.
  • the thermally conductive resin composition of the present invention is excellent in low-temperature curing property and handling property, and can form a cured product excellent in thermal conductivity, so that it is used for heat radiation of electronic parts such as circuit boards made of plastic materials. Etc. are applicable to a wide range of fields.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermoconductrice comprend les composants suivants (A) à (C) : (A) une résine époxy, (B) un durcisseur latent de type adduit qui est solide à 25 °C, et (C) un mélange des ingrédients suivants (C1) à (C3), dans lequel le rapport en masse de l'ingrédient (C1) à l'ingrédient (C3) est de 0,14 à 1,0 et le rapport en masse de l'ingrédient (C2) à l'ingrédient (C3) est de 0,25 à 1,5. (C1) une poudre thermiquement conductrice ayant un diamètre moyen de particule de 0,01 µm ou plus mais inférieure à 2 µm ; (C2) une poudre thermiquement conductrice ayant un diamètre moyen de particule de 2 µm ou plus mais inférieure à 20 µm ; et (C3) une poudre thermiquement conductrice ayant un diamètre moyen de particule de 20 µm ou plus mais inférieure à 150 µm. La composition de résine thermoconductrice de la présente invention est excellente en termes d'aptitude au durcissement à basse température et de maniabilité et peut former des objets durcis ayant une excellente conductivité thermique.
PCT/JP2018/037446 2017-10-18 2018-10-05 Composition de résine thermoconductrice, objet durci, et procédé de rayonnement thermique WO2019078044A1 (fr)

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CN201880067861.8A CN111247207B (zh) 2017-10-18 2018-10-05 导热性树脂组合物、固化物以及散热方法
JP2019549213A JPWO2019078044A1 (ja) 2017-10-18 2018-10-05 熱伝導性樹脂組成物、硬化物および放熱方法
JP2023029107A JP2023078170A (ja) 2017-10-18 2023-02-28 熱伝導性樹脂組成物、硬化物および放熱方法

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JP2012188632A (ja) * 2011-03-14 2012-10-04 Sekisui Chem Co Ltd 絶縁材料及び積層構造体
WO2014115637A1 (fr) * 2013-01-22 2014-07-31 東レ株式会社 Composition adhésive et feuille adhésive et matériau durci et dispositif semi-conducteur les utilisant
JP2016050301A (ja) * 2014-08-28 2016-04-11 スリーボンドファインケミカル株式会社 熱伝導性樹脂組成物
WO2016125664A1 (fr) * 2015-02-05 2016-08-11 味の素株式会社 Composition de résine

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CN102459394B (zh) * 2009-06-12 2015-01-21 兆科学公司 环氧组合物用的潜硬化剂
KR101852230B1 (ko) * 2012-03-29 2018-04-25 스미또모 베이크라이트 가부시키가이샤 수지 조성물 및 반도체 장치
JP2017128637A (ja) * 2016-01-19 2017-07-27 東レ株式会社 接着剤組成物、接着剤シートならびにそれを有する積層版、基板およびｌｅｄモジュール

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Publication number Priority date Publication date Assignee Title
JP2005206725A (ja) * 2004-01-23 2005-08-04 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
JP2007246861A (ja) * 2006-03-20 2007-09-27 Nippon Steel Chem Co Ltd 樹脂組成物、並びにこの樹脂組成物を用いて得たワニス、フィルム状接着剤及びフィルム状接着剤付き銅箔
JP2012188632A (ja) * 2011-03-14 2012-10-04 Sekisui Chem Co Ltd 絶縁材料及び積層構造体
WO2014115637A1 (fr) * 2013-01-22 2014-07-31 東レ株式会社 Composition adhésive et feuille adhésive et matériau durci et dispositif semi-conducteur les utilisant
JP2016050301A (ja) * 2014-08-28 2016-04-11 スリーボンドファインケミカル株式会社 熱伝導性樹脂組成物
WO2016125664A1 (fr) * 2015-02-05 2016-08-11 味の素株式会社 Composition de résine

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JP2023078170A (ja) 2023-06-06
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