Thermosetting resin composition and electronic device

Abstract

To provide a thermosetting resin composition excellent in thermal conductivity.SOLUTION: The thermosetting resin composition of the present invention contains an epoxy resin, highly thermally conductive inorganic particles having a thermal conductivity of 20 W / m k or more, and a predetermined phenolic compound. The content of the highly thermally conductive inorganic particles is 50 mass% or more and 99 mass% or less in 100 mass% of the thermosetting resin composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thermosetting resin composition and an electronic device. [Background technology]

[0002] Various developments have been made so far regarding thermosetting resin compositions. For example, the technology described in Patent Document 1 is known as this type of technology. Patent Document 1 describes a sealing material having an inorganic filler containing at least one selected from the group consisting of an epoxy resin, a curing agent, fused silica, silica, alumina, and glass fiber (claims of Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-013920 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, as a result of investigations by the present inventors, it was found that the sealing material described in Patent Document 1 above leaves room for improvement in terms of thermal conductivity. [Means for solving the problem]

[0005] As a result of further investigation, the present inventors found that the thermal conductivity of the cured product can be improved by increasing the filling rate of highly thermally conductive inorganic particles in a thermosetting resin composition and then adding a specified phenolic compound, and thus completed the present invention.

[0006] According to the present invention, there are provided the following thermosetting resin composition and electronic device.

[0007] [1] Epoxy resin, Highly thermally conductive inorganic particles with a thermal conductivity of 20 W / m K or more, A thermosetting resin composition comprising a phenolic compound represented by the following general formula (A): The thermosetting resin composition, wherein the highly thermally conductive inorganic particles account for 50% by mass or more and 99% by mass or less of 100% by mass of the thermosetting resin composition. [ka] (In the above general formula (A), R 1 ~R 4 may be the same or different and may be represented by any one of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted alkyl group, or R 1 ~R 4 Two adjacent groups among these may be bonded to each other to form an aromatic ring or a heterocyclic ring. [2] The thermosetting resin composition according to the above [1], A thermosetting resin composition, wherein the highly thermally conductive inorganic particles contain one or more particles selected from the group consisting of alumina, silicon carbide, aluminum nitride, boron nitride, silicon nitride, magnesium oxide, and beryllium oxide. [3] The thermosetting resin composition according to the above [2], A thermosetting resin composition, wherein the content of alumina in the highly thermally conductive inorganic particles is 50 mass % or more based on 100 mass % of the thermosetting resin composition. [4] The thermosetting resin composition according to any one of the above [1] to [3], A thermosetting resin composition comprising inorganic particles having a thermal conductivity of less than 20 W / m·K. [5] The thermosetting resin composition according to the above [4], The thermosetting resin composition, wherein the inorganic particles having a thermal conductivity of less than 20 W / m·K include silica. [6] The thermosetting resin composition according to any one of the above [1] to [5], A thermosetting resin composition, wherein the phenolic compound represented by the above general formula (A) contains one or more selected from the group consisting of catechol, pyrogallol, 2,3-naphthalenediol, 5,6-dihydroxyindole, protocatechuic acid, and esculetin. [7] The thermosetting resin composition according to any one of the above [1] to [6], A thermosetting resin composition comprising the highly thermally conductive inorganic particles having a phenolic compound represented by the following general formula (A) bonded to at least a portion of the surface thereof. [8] The thermosetting resin composition according to any one of the above [1] to [7], A thermosetting resin composition comprising a coupling agent. [9] The thermosetting resin composition according to the above [8], A thermosetting resin composition, wherein the content of the phenolic compound represented by the general formula (A) and the coupling agent is 0.1% by mass or more and 5% by mass or less, based on 100% by mass of the thermosetting resin composition.

[10] The thermosetting resin composition according to any one of the above [1] to [9], A thermosetting resin composition comprising a curing agent.

[11] The thermosetting resin composition according to the above

[10] , The thermosetting resin composition, wherein the curing agent comprises a phenolic resin-based curing agent.

[12] The thermosetting resin composition according to any one of the above [1] to

[11] , A thermosetting resin composition in granular or tablet form.

[13] The thermosetting resin composition according to any one of the above [1] to

[12] , A thermosetting resin composition used to form an encapsulant for encapsulating electronic components.

[14] A substrate; An electronic component provided on the substrate; and a sealant for sealing the electronic component, The sealing material is composed of a cured product of the thermosetting resin composition according to any one of the above [1] to

[13] . electronic equipment. Effect of the Invention

[0008] According to the present invention, there are provided a thermosetting resin composition having excellent thermal conductivity, and an electronic device using the same. [Brief description of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing an example of a configuration of an electronic device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In all drawings, similar components are given similar reference numerals and their explanations will be omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to the actual dimensional ratios.

[0011] The thermosetting resin composition of this embodiment will be outlined.

[0012] The thermosetting resin composition contains an epoxy resin, highly thermally conductive inorganic particles having a thermal conductivity of 20 W / m·K or more, and a phenolic compound represented by the following general formula (A), in which the highly thermally conductive inorganic particles account for 50% by mass or more and 99% by mass or less of 100% by mass of the thermosetting resin composition. [ka]

[0013] In the above general formula (A), R 1 ~R 4 may be the same or different and may be represented by any one of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted alkyl group, or R 1 ~R4 Two adjacent groups among these may be bonded to each other to form an aromatic ring or a heterocyclic ring.

[0014] According to the findings of the present inventors, it has been found that the thermal conductivity of the cured product of the thermosetting resin composition can be improved by using a high-filling rate thermally conductive inorganic particle in combination with the phenolic compound represented by the above general formula (A).

[0015] Although the detailed mechanism is unclear, it is believed that the two hydroxyl groups in the aromatic ring of the above-mentioned phenol-based compound form hydrogen bonds with the particle surface of the thermally conductive inorganic particles, improving the compatibility of the thermally conductive inorganic particles with the epoxy resin due to the aromatic ring, thereby suppressing the thermal resistance at the interface between the resin and the filler, thereby further enhancing the thermal conductivity effect of the thermally conductive inorganic particles.

[0016] The thermosetting resin composition of the present embodiment can be used, for example, as a heat dissipation material, an insulating material, or a semiconductor encapsulation material for electric and electronic devices. Examples of the semiconductor encapsulation material include a thermosetting resin composition for forming an encapsulant for encapsulating electronic components such as a semiconductor chip.

[0017] The electric and electronic devices may be, for example, ordinary semiconductor devices (electronic devices having semiconductor elements as electronic components) or power modules (electronic devices having power semiconductor elements as electronic components). Power semiconductor elements use wide band gap materials such as SiC, GaN, Ga2O3, or diamond, and are designed to be used at high voltages and large currents, so they generate more heat than ordinary silicon chips (semiconductor elements), and therefore operate in even higher temperature environments. Power semiconductor elements are required to be used for long periods of time in high temperature operating environments, for example, at 200°C or higher or 250°C or higher. Specific examples of power semiconductor elements include, for example, rectifier diodes, power transistors, power MOSFETs, insulated gate bipolar transistors (IGBTs), thyristors, gate turn-off thyristors (GTOs), and triacs.

[0018] According to the thermosetting resin composition of the present embodiment, a semiconductor encapsulation material that can be used in a power module can be provided.

[0019] The thermosetting resin composition of the present embodiment will be described in detail below.

[0020] The thermosetting resin composition contains at least an epoxy resin, highly thermally conductive inorganic particles, and a phenolic compound represented by the above general formula (A).

[0021] (Epoxy resin) The epoxy resin is a compound having two or more epoxy groups in one molecule, and can be a monomer, oligomer, or polymer in general, and is not particularly limited in molecular weight or molecular structure. These may be used alone or in combination of two or more.

[0022] Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), and bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol group methane type novolac type epoxy resin, tetraphenol group ethene type epoxy resin, and the like. Examples of the epoxy resins include novolac-type epoxy resins such as aryl alkylene-type epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, xylylene-type epoxy resins, biphenyl aralkyl-type epoxy resins, and other aryl alkylene-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene diol-type epoxy resins, bifunctional to tetrafunctional epoxy naphthalene resins, binaphthyl-type epoxy resins, naphthalene aralkyl-type epoxy resins, and other naphthalene-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins. These may be used alone or in combination of two or more.

[0023] The lower limit of the content of the epoxy resin is, for example, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of the solid content of the thermosetting resin composition. This allows the flowability of the thermosetting resin composition during molding to be appropriately controlled. On the other hand, the upper limit of the content of the epoxy resin is, for example, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the solid content of the thermosetting resin composition. This allows the linear expansion coefficient of the thermosetting resin composition to be within an appropriate range, and high thermal conductivity properties can also be expressed, so that a thermosetting resin composition having high reliability and high heat dissipation can be provided.

[0024] In the present embodiment, the solid content of the thermosetting resin composition refers to the total of the components contained in the thermosetting resin composition excluding the solvent. In this specification, the symbol "to" indicates that both the upper and lower limits are included, unless otherwise specified.

[0025] The thermosetting resin composition may or may not contain other thermosetting resins in addition to the epoxy resin. Other thermosetting resins include, for example, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, silicone resins, bismaleimide resins, acrylic resins, and phenol derivatives and their derivatives. As these thermosetting resins, monomers, oligomers, and polymers having two or more reactive functional groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited. These may be used alone or in combination of two or more.

[0026] (hardening agent) The thermosetting resin composition may contain a curing agent, if necessary. The curing agent is not particularly limited as long as it is selected according to the type of thermosetting resin and reacts with the resin. Specific examples of the curing agent include polyaddition type curing agents, catalyst type curing agents, and condensation type curing agents.

[0027] Specific examples of the polyaddition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA); aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS); polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide; and alicyclic polyamines such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA). Examples of the curing agent include acid anhydrides, such as aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA), phenolic resin-based curing agents such as novolac-type phenolic resins, polyvinylphenols, and aralkyl-type phenolic resins, polymercaptan compounds such as polysulfides, thioesters, and thioethers, isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins. As the polyaddition-type curing agent, one or a combination of two or more of the above specific examples can be used.

[0028] Specific examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30), imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24), and Lewis acids such as BF3 complexes. The catalyst-type curing agent may be one of the above specific examples or a combination of two or more of them.

[0029] Specific examples of the condensation type curing agent include resol type phenol resins, urea resins such as methylol group-containing urea resins, melamine resins such as methylol group-containing melamine resins, etc. As the condensation type curing agent, one or a combination of two or more of the above specific examples can be used.

[0030] The curing agent may include a phenol resin-based curing agent among the above specific examples. As the phenolic resin-based curing agent, a phenolic resin can be used. Specific examples of the phenolic resin-based curing agent include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, naphthol novolac resin, aminotriazine novolac resin, novolac resin, and trisphenylmethane-type phenol novolac resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; and resol-type phenolic resins. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the glass transition temperature and reducing the linear expansion coefficient, novolac type phenolic resins can be used.

[0031] The content of the curing agent can be appropriately set depending on the content of the epoxy resin.

[0032] (Inorganic particles)

[0033] The thermosetting resin composition contains, as inorganic particles, highly thermally conductive inorganic particles having a thermal conductivity of 20 W / m·K or more.

[0034] The highly thermally conductive inorganic particles may contain one or more selected from the group consisting of alumina, silicon carbide, aluminum nitride, boron nitride, silicon nitride, magnesium oxide, and beryllium oxide. These may be used alone or in combination of two or more. Among these, alumina may be used from the viewpoint of thermal conductivity.

[0035] The particle diameter d50 of the highly thermally conductive inorganic particles, at which the cumulative frequency in the volumetric particle size distribution is 50%, is, for example, 0.1 μm to 50 μm, preferably 0.2 μm to 40 μm, and more preferably 0.5 μm to 30 μm. By making it equal to or greater than the lower limit, the melt viscosity of the resin composition can be reduced. By making it equal to or less than the upper limit, the thermal conductivity can be improved.

[0036] The particle size of the inorganic particles can be measured, for example, using a laser diffraction / scattering type particle size distribution measuring device.

[0037] The highly thermally conductive inorganic particles may be surface-treated before being added to the thermosetting resin composition, or may not be surface-treated. The surface treatment means that a coupling agent and / or a phenolic compound represented by the above general formula (A) is chemically, physically, or both bonded to the surface of the highly thermally conductive inorganic particles. That is, one embodiment of the thermosetting resin composition may contain highly thermally conductive inorganic particles to which the phenolic compound represented by the above general formula (A) is bonded, thereby further increasing the thermal conductivity.

[0038] The lower limit of the content of the highly thermally conductive inorganic particles is, for example, preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 80% by mass or more, based on 100% by mass of the solid content of the thermosetting resin composition, which can improve the thermal conductivity of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the content of the highly thermally conductive inorganic particles is, for example, preferably 99% by mass or less, more preferably 98% by mass or less, and more preferably 96% by mass or less, based on the solid content of the thermosetting resin composition, which allows the viscosity of the thermosetting resin composition to be adjusted to a suitable range for carrying out the mixing step.

[0039] The lower limit of the content of alumina in the highly thermally conductive inorganic particles is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 90% by mass or more, which can improve the thermal conductivity of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the content of the highly thermally conductive inorganic particles may be, for example, 99% by mass or less, or 97% by mass or less, based on the solid content of the thermosetting resin composition, which allows the properties of the thermosetting resin composition to be well balanced.

[0040] The thermosetting resin composition may contain, as the inorganic particles, non-thermally conductive inorganic particles having a thermal conductivity of less than 20 W / m·K. Examples of non-thermally conductive inorganic particles include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely powdered silica; metal compounds such as titanium oxide, aluminum hydroxide, and magnesium hydroxide; talc; clay; mica; and glass fiber. These may be used alone or in combination of two or more. Among these, silica may be used.

[0041] The lower limit of the content of the non-thermally conductive inorganic particles is, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 1.0% by mass or more, based on 100% by mass of the solid content of the thermosetting resin composition, which can improve the mechanical properties of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the content of the non-thermally conductive inorganic particles is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less, based on the solid content of the thermosetting resin composition, which can suppress a decrease in thermal conductivity in the cured product of the thermosetting resin composition.

[0042] (Phenol compounds) The thermosetting resin composition contains one or more phenolic compounds represented by the following general formula (A).

[0043] [ka]

[0044] In the above general formula (A), R 1 ~R 4 may be the same or different and may be represented by any one of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted alkyl group, or R 1 ~R 4 Two adjacent groups among these may be bonded to each other to form an aromatic ring or a heterocyclic ring. Examples of the substituent include an alkyl group, a hydroxy group, a carboxy group, a carbonyl group, an ester group, and an amino group.

[0045] In general formula (A), R 1 ~R 4 may all be hydrogen atoms, or at least one may be a hydroxyl group. For example, R adjacent to the OH group in general formula (A) 1 or R 4 may have a hydroxy group.

[0046] In the general formula (A), the alkyl group may be a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group.

[0047] In general formula (A), R 1 ~R4 At least one of them may be a carboxy group. In the general formula (A), the carboxy group is represented by -COOH or -RCOOH, where R may be, for example, an alkylene group having 1 to 4 carbon atoms.

[0048] The aromatic ring or heterocyclic ring is R 1 ~R 4 Of these, R 1 and R 2 Combination of R 2 and R 3 Combination of, and R 3 and R 4 Among these, R 2 and R 3 A combination of is preferred.

[0049] In the general formula (A), examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Of these, a benzene ring or a naphthalene ring may be used. In the general formula (A), the heterocycle may contain an oxygen atom and / or a nitrogen atom in the ring, and may be any of a 3-membered ring to a 6-membered ring, and preferably a 4-membered ring to a 6-membered ring, and examples thereof include a lactone ring, an oxazole ring, an imidazole ring, a thiazole ring, and a pyridine ring. At least a portion of the aromatic ring or heterocyclic ring adjacent to the benzene ring in the general formula (A) may be substituted with the same type of substituent as the above-mentioned substituent.

[0050] The phenolic compound represented by the above general formula (A) more preferably contains one or more members selected from the group consisting of catechol, pyrogallol, 2,3-naphthalenediol, 5,6-dihydroxyindole, protocatechuic acid, and esculetin.

[0051] The lower limit of the content of the phenolic compound represented by the general formula (A) is, for example, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 0.2% by mass or more, based on 100% by mass of the solid content of the thermosetting resin composition, which can increase the thermal conductivity of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the phenolic compound represented by the general formula (A) is, for example, preferably 5% by mass or less, more preferably 4% by mass or less, and more preferably 3% by mass or less, based on the solid content of the thermosetting resin composition, which allows the physical properties of the cured product of the thermosetting resin composition to be well balanced.

[0052] (Other Ingredients) The thermosetting resin composition may contain, as necessary, one or more of various additives such as a coupling agent, a fluidity imparting agent, a release agent, an ion scavenger, a curing accelerator, a stress reducing agent, an organic filler, a colorant, and a flame retardant.

[0053] (Coupling Agent) The thermosetting resin composition may contain a coupling agent, if necessary. Specific examples of coupling agents include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, and 3-glycidoxypropyl triethoxy silane; styryl silanes such as p-styryl trimethoxy silane; methacryl silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; acryl silanes such as 3-acryloxypropyl trimethoxy silane; N-2-(aminoethyl)-3-amino Examples of the coupling agent include aminosilanes such as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and phenylaminopropyltrimethoxysilane; isocyanurate silane; alkyl silane; ureidosilanes such as 3-ureidopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatepropyltriethoxysilane; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. The coupling agent may be one or more of the above specific examples.

[0054] The lower limit of the content of the phenolic compound represented by the general formula (A) and the coupling agent is, for example, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and more preferably 0.15% by mass or more, based on 100% by mass of the solid content of the thermosetting resin composition, which can increase the thermal conductivity of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the amount of the phenolic compound represented by the general formula (A) and the coupling agent is, for example, preferably 5% by mass or less, more preferably 4% by mass or less, and more preferably 3% by mass or less, based on the solid content of the thermosetting resin composition, which allows the physical properties of the cured product of the thermosetting resin composition to be well balanced.

[0055] (Fluidity imparting agent) The fluidity imparting agent can suppress the reaction of a non-latent curing accelerator, such as a phosphorus atom-containing curing accelerator, during melt-kneading of the resin composition, thereby improving the productivity of the thermosetting resin composition.

[0056] (Release agent) Specific examples of the release agent include natural waxes such as carnauba wax, synthetic waxes such as montan acid ester wax and oxidized polyethylene wax, higher fatty acids and metal salts thereof such as zinc stearate, paraffin, carboxylic acid amides such as erucic acid amide, etc. One or more of the above specific examples can be blended as the release agent.

[0057] (Ion scavenger) Specific examples of the ion trapping agent include hydrotalcites such as hydrotalcite and hydrotalcite-like substances, and hydrated oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. One or more of the specific examples above may be blended as the ion trapping agent.

[0058] (Cure accelerator) The curing accelerator may contain one or more of phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; and nitrogen atom-containing compounds such as amidines and tertiary amines, exemplified by 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, and 2-methylimidazole, and quaternary salts of the above amidines and amines. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving the curability. In addition, it is more preferable to contain a compound having latency, such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, or an adduct of a phosphonium compound and a silane compound, from the viewpoint of improving the balance between moldability and curability.

[0059] (Low stress agent) Specific examples of the low stress agent include silicone compounds such as silicone oil and silicone rubber, polybutadiene compounds, and acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyl group-terminated butadiene copolymer compounds. One or more of the above specific examples can be blended as the low stress agent.

[0060] (Coloring agent) Specific examples of the colorant include carbon black, red iron oxide, titanium oxide, etc. One or more of the above specific examples of the colorant may be blended.

[0061] (Flame retardant) Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, carbon black, etc. As the flame retardant, one or more of the above specific examples can be blended.

[0062] A method for producing the thermosetting resin composition according to this embodiment will be described. The method for producing the thermosetting resin composition includes, for example, a mixing step of mixing raw material components such as an epoxy resin, thermally conductive inorganic particles, and a phenolic compound represented by the above general formula (A).

[0063] The timing and amount of the phenolic compound to be added during the production process can be appropriately changed, and for example, it may be added all at once to the other raw material components, or it may be added gradually to a mixture of one or more raw material components, or it may be mixed with another raw material component and then mixed with the other raw material components. The phenolic compound may be used diluted with a solvent such as an alcohol solvent, or it may be used undiluted.

[0064] The mixing step is a step of mixing the raw material components to prepare a mixture. The mixing method is not limited, and a known method can be used depending on the components used. Specifically, in the mixing step, the raw material components contained in the thermosetting resin composition described above are mixed uniformly using a mixer, etc. Then, the mixture is melt-kneaded using a kneading machine such as a roll, a kneader, or an extruder to prepare a mixture.

[0065] The method for producing the thermosetting resin composition may include a molding step of molding the obtained mixture.

[0066] The molding method is not limited, and a known method can be used depending on the shape of the thermosetting resin composition. The shape of the thermosetting resin composition is not limited, and examples thereof include granular, powder, tablet, and sheet shapes. The thermosetting resin composition for semiconductor encapsulation may be, for example, granular or tablet.

[0067] The shape of the thermosetting resin composition can be selected depending on the molding method. The molding process for producing the thermosetting resin composition in the granular form includes, for example, a process of crushing the mixture cooled after melt kneading. For example, the thermosetting resin composition in the granular form may be sieved to adjust the size of the granules. For example, the thermosetting resin composition in the granular form may be treated by a centrifugal milling method or a hot cut method to adjust the degree of dispersion or the flowability. In addition, the molding process for producing a powdered thermosetting resin composition may include, for example, a process of pulverizing a mixture to form a granular thermosetting resin composition, and then further pulverizing the granular thermosetting resin composition. In addition, the molding process for producing a tablet-shaped thermosetting resin composition can be, for example, a process of pulverizing a mixture to form a granular thermosetting resin composition, and then molding the granular thermosetting resin composition into tablets.

[0068] Next, an electronic device using the thermosetting resin composition according to this embodiment will be described.

[0069] The thermosetting resin composition according to this embodiment can be used to form an encapsulant for encapsulating electronic components. The method for forming the encapsulant is not limited, and examples thereof include transfer molding, compression molding, injection molding, etc. By these methods, the encapsulant can be formed by molding and curing the thermosetting resin composition.

[0070] The electronic component is preferably, but not limited to, a semiconductor element. Examples of semiconductor elements include, but are not limited to, integrated circuits, large scale integrated circuits, transistors, thyristors, diodes, and solid-state imaging elements. Among these, the thermosetting resin composition of the present embodiment is useful for semiconductor elements having exposed metal parts. This can suppress corrosion of the metal parts. An example of such a semiconductor element having exposed metal parts is a transistor. Among transistors, the thermosetting resin composition of the present embodiment can be effectively used for sealing MIS transistors having exposed gate electrodes.

[0071] The substrate is not limited to any particular one, but examples thereof include wiring boards such as interposers, lead frames, and the like.

[0072] When an electrical connection between an electronic component and a substrate is required, the electronic component may be connected appropriately. The method of electrical connection is not limited, but examples thereof include wire bonding and flip chip connection. Among these, the semiconductor element for which the thermosetting resin composition of the present embodiment is useful is a semiconductor element having an exposed metal part. This can suppress corrosion of the metal part. An example of an electrical connection method in which such a metal part is exposed is wire bonding.

[0073] An electronic device can be obtained by forming an encapsulating resin layer that encapsulates electronic components using a thermosetting resin composition. The electronic device is not limited to, but is preferably a semiconductor device obtained by molding a semiconductor element. Specific types of semiconductor devices include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB.

[0074] An example of an electronic device using the thermosetting resin composition according to this embodiment will be described below. FIG. 1 is a cross-sectional view showing an electronic device 100 according to the present embodiment.

[0075] The electronic device 100 in FIG. 1 includes a base material 30, an electronic component 20 provided on the base material 30, and a sealing material (sealing resin layer 50) that seals the electronic component 20. The sealing resin layer 50 is composed of a cured product of the above-mentioned thermosetting resin composition. The electronic component 20 may be electrically connected to the outside world by bonding wires 40 .

[0076] Specifically, the electronic component 20 is fixed onto the substrate 30 via the die attachment material 10, and the electronic device 100 has an outer lead 34 connected via a bonding wire 40 to an electrode pad (not shown) provided on the electronic component 20. The bonding wire 40 can be set in consideration of the electronic component 20 to be used, and may be, for example, a Cu wire.

[0077] A method for producing an electronic device using the thermosetting resin composition according to this embodiment will be described below. The method for manufacturing an electronic device according to this embodiment includes, for example, a manufacturing step of obtaining a thermosetting resin composition by the above-described method for manufacturing a thermosetting resin composition, a step of mounting electronic components on a substrate, and a step of encapsulating the electronic components using the thermosetting resin composition.

[0078] The electronic device 100 is formed, for example, in the following manner. First, an electronic component is mounted on a substrate. Specifically, an electronic component 20 is fixed onto a die pad 32 (base material 30) using a die attachment material 10, and the die pad 32 (base material 30), which is a lead frame, is connected by a bonding wire 40. This forms an object to be sealed. The object to be sealed is sealed with a thermosetting resin composition to form a sealing resin layer 50, thereby manufacturing the electronic device 100. The electronic device 100 in which the electronic component 20 is sealed is, if necessary, mounted on an electronic device after the thermosetting resin composition has been cured at a temperature of about 80°C to 200°C for about 10 minutes to 10 hours.

[0079] The electronic device 100 uses the above-mentioned thermosetting resin composition as the sealing resin layer 50, and has sufficient adhesion between the sealing resin layer 50 and the electronic components 20, the bonding wires 40, the electrode pads 22, etc., and also has excellent high-temperature storage properties. Even when a Cu wire is used for the bonding wire 40, sufficient high-temperature storage properties and the like can be exhibited.

[0080] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0081] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the description of these examples.

[0082] (Highly thermally conductive inorganic particles) Alumina 1: Alumina particles (Denka, DAB-30FC, average particle diameter d50: 13.2 μm, thermal conductivity: 20-36 W / m K) Alumina 2: Alumina particles obtained by surface-treating Alumina 1 with 2,3-naphthalenediol according to the following procedure: 2,3-Naphthalenediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 1-methoxy-2-propanol (manufactured by Fuji Film Co., Ltd.) to prepare a surface treatment agent with a 2,3-naphthalenediol concentration of 0.01 mol / L. The resulting surface treatment agent was mixed with the above-mentioned alumina 1 and placed in a bottle, and the sealed bottle was rotated at room temperature of 25° C. for 12 hours to mix them. The resulting mixture was filtered, washed with 1-methoxy-2-propanol, and then dried under reduced pressure for 24 hours to obtain alumina 2 surface-treated with 2,3-naphthalenediol.

[0083] The average particle size D that is the cumulative 50% of the inorganic particles by volume 50 The particle size distribution of the particles was measured on a volume basis using a commercially available laser diffraction particle size distribution measuring device (Shimadzu Corporation, SALD-7000), and the cumulative 50% particle size was calculated.

[0084] (Coupling Agent) Coupling agent 1: N-phenylaminopropyltrimethoxysilane (Toray Dow Corning, CF-4083) Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Chisso Corporation, S810)

[0085] (catalyst) Catalyst 1: Triphenylphosphine, manufactured by K.I. Chemicals, product name: PP-360 Catalyst 2: Tetraphenylphosphonium tetrakis(1-naphthyloxy)borate(1-), synthesized by the following procedure: (Synthesis procedure of catalyst 2) 3375 parts by weight of methanol and 167 parts by weight of tetraphenylphosphonium bromide were charged into a reaction vessel, and dissolved under stirring and maintained at 55°C. 280 parts by weight of sodium tetrakis(1-naphthyloxy)borate and 941 parts by weight of acetone were charged into another reaction vessel, and after dissolving at 20°C, 10% NaOH aqueous solution was added until the pH of the acetone solution of sodium tetrakis(1-naphthyloxy)borate became 15. The acetone solution of sodium tetrakis(1-naphthyloxy)borate thus prepared was dropped into the methanol solution of tetraphenylphosphonium bromide over 4 hours. It was confirmed that crystals of the reaction product were precipitated during the dropwise addition. After the dropwise addition was completed, the mixture was cooled to 30°C, and the precipitated crystals were separated by filtration, washed with 3600 parts by weight of methanol, and further dried by heating in vacuum to obtain 363 parts by weight of tetraphenylphosphonium tetrakis(1-naphthyloxy)borate.

[0086] (Release material) Release material 1: Synthetic wax (Clariant Chemicals, WE-4) Release material 2: Oxidized polyethylene wax (Clariant Japan, Licowax PED191)

[0087] (Ion catcher) Ion catcher 1: Magnesium aluminum hydroxide carbonate hydrate (Kyowa Chemical Industry Co., Ltd., DHT-4H)

[0088] (Non-thermally conductive inorganic particles) Silica 1: Fused spherical silica (Admatechs Co., Ltd., SC-2500SQ, average particle size d50: 0.5 μm, thermal conductivity: 1.3 W / m K)

[0089] (Low stress material) Low stress material 1: Silicone oil (Toray Dow Corning, FZ3730)

[0090] (Coloring agent) Colorant 1: Carbon black (Mitsubishi Chemical, Carbon #5)

[0091] (Phenol compounds) Phenolic compound 1: Catechol (Tokyo Chemical Industry Co., Ltd.) Phenolic compounds 2: 2,3-naphthalenediol (Tokyo Chemical Industry Co., Ltd.) Phenolic compound 3: Pyrogallol (Tokyo Chemical Industry Co., Ltd.)

[0092] (Epoxy resin) Epoxy resin 1: Tetramethylbiphenyl type epoxy resin (bifunctional epoxy compound, Mitsubishi Chemical Corporation, YX-4000)

[0093] (Phenol Resin) Phenolic resin 1: Phenol novolac resin (Sumitomo Bakelite Co., Ltd., PR-55617)

[0094] <Preparation of Thermosetting Resin Composition> The components in the amounts shown in Table 1 below were dry-blended at room temperature using a mixer, and then heated and kneaded for about 15 minutes using a kneader at a temperature of about 80 to 100° C. The mixture was then cooled to room temperature and pulverized to prepare a powdered thermosetting resin composition.

[0095] [Table 1]

[0096] The obtained thermosetting resin composition was evaluated for the following items.

[0097] (Thermal Conductivity) - Preparation of composite compacts The obtained thermosetting resin composition was molded and cured using a compression molding machine under conditions of 180° C., 15 minutes, and 2 MPa, and then heat-treated in an oven at 180° C. for 3 hours to obtain a composite molded product.

[0098] - Specific gravity of composite compact The specific gravity was measured in accordance with JIS K 6911 (general test method for thermosetting plastics). Test pieces were cut from the composite molded body to have dimensions of 2 cm length × 2 cm width × 2 mm thickness. The unit of specific gravity (SP) is g / cm. 3 Let us assume that.

[0099] -Specific heat of composite compact The specific heat (Cp) of the obtained composite compact was measured by DSC method.

[0100] -Measurement of thermal conductivity of composite moldings The obtained composite molded body was surface-polished to a diameter of 10 mm and a thickness of 0.8 mm to prepare a test piece. Next, the thermal diffusion coefficient (α) in the thickness direction of the plate-shaped test piece was measured by the laser flash method using a Xe flash analyzer TD-1RTV manufactured by ULVAC. The measurement was performed under the condition of air and 25°C. For each of the composite molded bodies, the thermal conductivity was calculated from the measured values ​​of the thermal diffusion coefficient (α), specific heat (Cp), and specific gravity (SP) according to the following formula. Thermal conductivity [W / m K]=α[m 2 / s]×Cp[J / kg K]×Sp[g / cm 3 ]

[0101] (Spiral Flow:SF) Using a low-pressure transfer molding machine ("KTS-15" manufactured by Kotaki Seiki Co., Ltd.), the obtained thermosetting resin composition was injected into a metal mold for spiral flow measurement conforming to EMMI-1-66 under conditions of a metal mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds, and the spiral flow (unit: cm) was measured.

[0102] (Gel Time:GT) The obtained thermosetting resin composition was melted on a hot plate heated to 175° C., and then the time until the composition hardened while being kneaded with a spatula, that is, the gel time (unit: seconds), was measured.

[0103] <Fabrication of electronic devices> A semiconductor chip was mounted on a lead frame, and the electrode pads of the semiconductor chip were wire-bonded to the lead frame using copper wires to obtain a structure. The obtained structure was encapsulated using the thermosetting resin composition of the example obtained using a transfer molding machine under conditions of a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 2 minutes, and then post-cured at 175°C for 4 hours to obtain an electronic device (semiconductor package). It was confirmed that an electronic device with excellent heat dissipation properties was obtained in practical use.

[0104] The thermosetting resin compositions of Examples 1 to 5 showed improved thermal conductivity compared to Comparative Example 1. In addition, the thermosetting resin compositions of Examples 1 to 5 were able to increase the spiral flow and gel time, which allowed for low-pressure molding and high loading of thermally conductive filler. The thermosetting resin composition of such an embodiment can be suitably used as a thermosetting resin composition for sealing electronic components, and thus an electronic device having excellent heat dissipation properties can be obtained. [Explanation of symbols]

[0105] 100 Electronic equipment 10 Die Attach Material 20 Electronic elements 30 Base material 32 Die pad 34 Outer lead 40 Bonding Wire 50 Sealing resin layer

Claims

1. Epoxy resin, Highly thermally conductive inorganic particles having a thermal conductivity of 20 W / m·K or more; A phenolic compound represented by the following general formula (A), A thermosetting resin composition comprising: The highly thermally conductive inorganic particles account for 50% by mass or more and 99% by mass or less in 100% by mass of the thermosetting resin composition, the content of the phenolic compound represented by the general formula (A) and the coupling agent is 0.7% by mass or more and 5% by mass or less in 100% by mass of the thermosetting resin composition, The highly thermally conductive inorganic particles have a particle diameter d50 at which the cumulative frequency in a volume-based particle size distribution is 50% of 0.5 μm to 30 μm; A thermosetting resin composition, wherein the epoxy resin comprises one or more selected from the group consisting of bisphenol-type epoxy resins, novolac-type epoxy resins, biphenyl-type epoxy resins, aryl alkylene-type epoxy resins, naphthalene-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, and fluorene-type epoxy resins (excluding a resin composition comprising (A) an epoxy resin having a biphenyl skeleton, (B) an epoxy resin that is liquid at room temperature, (C) a phenolic resin, and (D) an inorganic filler, containing alumina as the (D) inorganic filler, the content of the (D) inorganic filler being 75 mass% or more of the total solid content, and the oil absorption of the entire (D) inorganic filler contained being 7.5 ml / 100 g or less). 【Chemistry 1】 (In the above general formula (A), R １ ~R ４ may be the same or different, and may be represented by any one of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted alkyl group, or R １ ~R ４ Two adjacent groups among these may be bonded to each other to form an aromatic ring or a heterocyclic ring.

2. The thermosetting resin composition according to claim 1, The thermosetting resin composition, wherein the highly thermally conductive inorganic particles contain one or more particles selected from the group consisting of alumina, silicon carbide, aluminum nitride, boron nitride, silicon nitride, magnesium oxide, and beryllium oxide.

3. The thermosetting resin composition according to claim 2, A thermosetting resin composition, wherein the content of alumina in the highly thermally conductive inorganic particles is 50 mass% or more based on 100 mass% of the thermosetting resin composition.

4. The thermosetting resin composition according to any one of claims 1 to 3, A thermosetting resin composition comprising inorganic particles having a thermal conductivity of less than 20 W / m·K.

5. The thermosetting resin composition according to claim 4, The thermosetting resin composition, wherein the inorganic particles having a thermal conductivity of less than 20 W / m·K contain silica.

6. The thermosetting resin composition according to any one of claims 1 to 5, A thermosetting resin composition, wherein the phenolic compound represented by the general formula (A) contains one or more selected from the group consisting of catechol, pyrogallol, 2,3-naphthalenediol, 5,6-dihydroxyindole, protocatechuic acid, and esculetin.

7. The thermosetting resin composition according to any one of claims 1 to 6, A thermosetting resin composition comprising highly thermally conductive inorganic particles having a phenolic compound represented by general formula (A) bonded to at least a portion of the surface of the highly thermally conductive inorganic particles.

8. The thermosetting resin composition according to any one of claims 1 to 7, A thermosetting resin composition comprising a curing agent.

9. The thermosetting resin composition according to claim 8, The thermosetting resin composition, wherein the curing agent comprises a phenolic resin-based curing agent.

10. The thermosetting resin composition according to any one of claims 1 to 9, A thermosetting resin composition in granular or tablet form.

11. The thermosetting resin composition according to any one of claims 1 to 10, A thermosetting resin composition used to form an encapsulant for encapsulating electronic components.

12. A substrate; An electronic component provided on the substrate; and a sealant for sealing the electronic component. The sealing material is composed of a cured product of the thermosetting resin composition according to any one of claims 1 to 10. electronic equipment.

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