Thermosetting resin composition, resin sheet, and metal matrix composite

Abstract

The thermosetting resin composition of at least a part of the heat dissipation insulating member interposed between the heat generating body and the heat dissipating body of the present invention comprises: (A) an epoxy resin; (B) a thermosetting resin other than the epoxy resin (A); (C) a phenoxy resin having a mesogenic structure in the molecule; (D) a thermally conductive particle; and (E) an organosiloxane compound.

Description

Technical Field

[0001] The present invention relates to a thermosetting resin composition, a resin sheet formed from the composition, and a metal base substrate comprising the resin sheet. Background Technology

[0002] The insulating materials used in electrical / electronic equipment are required to have good heat dissipation properties. Various developments have been made to improve the heat dissipation properties of insulating materials.

[0003] As such a technology, for example, the technology described in Patent Document 1 is known. Patent Document 1 describes a thermosetting resin composition that uses bisphenol A type epoxy resin as the thermosetting resin and uses flake-shaped or spherical boron nitride particles as thermally conductive particles.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-193504 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, the prior art described in Patent Document 1 suffers from high moisture absorption and reduced insulation durability. Furthermore, it has long been known that even the addition of silane coupling agents to thermally conductive particles such as boron nitride particles does not improve adhesion.

[0009] Technical solutions to the problem

[0010] The inventors of this invention discovered that moisture absorption at the interface between resin and thermally conductive particles affects insulation durability, and after studying this, they found that by combining thermally conductive particles with organosiloxane compounds such as silane coupling agents, the moisture absorption rate is reduced and the insulation durability is improved.

[0011] According to the present invention, a thermosetting resin composition is provided, which constitutes at least a portion of a heat-dissipating insulating component between a heat-generating element and a heat-dissipating element, the thermosetting resin composition comprising:

[0012] (A) Epoxy resin;

[0013] (B) Thermosetting resins other than epoxy resin (A);

[0014] (C) Phenoxy resins with a mesocrystalline structure within the molecule;

[0015] (D) Thermally conductive particles; and

[0016] (E) Organosiloxane compounds.

[0017] According to the present invention, a resin sheet is provided, which is formed from the thermosetting resin composition.

[0018] Furthermore, according to the present invention, a metal substrate is provided, comprising, in sequence:

[0019] metal substrate;

[0020] An insulating layer formed by curing the resin sheet; and

[0021] Metal layer.

[0022] Invention Effects

[0023] According to the present invention, a thermosetting resin composition that yields a resin sheet with low moisture absorption, excellent insulation durability, and excellent thermal conductivity and insulation, a resin sheet formed from the composition, and a metal substrate comprising the resin sheet can be provided. Attached Figure Description

[0024] Figure 1 This is a schematic cross-sectional view showing the structure of the metal substrate involved in this embodiment.

[0025] Figure 2 This is a schematic cross-sectional view showing the structure of a semiconductor device using a metal substrate according to this embodiment. Detailed Implementation

[0026] Hereinafter, embodiments of the present invention will be described using the accompanying drawings. Furthermore, in all the drawings, the same reference numerals are used to denote the same constituent elements, and descriptions are appropriately omitted. Also, unless otherwise specified, “~” indicates “above” to “below”.

[0027] The thermosetting resin composition of this embodiment constitutes at least a portion of a heat-dissipating insulating component between a heat-generating element and a heat-dissipating element, comprising: (A) an epoxy resin; (B) a thermosetting resin other than epoxy resin (A); (C) a phenoxy resin having a mesocrystalline structure within the molecule; (D) thermally conductive particles; and (E) an organosiloxane compound.

[0028] Examples of heat-generating components include semiconductor elements, LED elements, substrates containing semiconductor elements or LED elements, central processing units (CPUs), power semiconductors, lithium-ion batteries, and fuel cells.

[0029] Examples of heat sinks include heat sinks, heat spreaders, and cooling fins.

[0030] The heat dissipation and insulation component only needs to be partially composed of the thermosetting resin composition of this embodiment. Specifically, examples include a heat sink formed by curing the thermosetting resin composition, and a laminate containing the heat sink and a substrate (e.g., Figure 1 The substrate can be a metal substrate 100, etc. The substrate is not particularly limited as long as it is a heat-dissipating metal substrate, such as a copper substrate, a copper alloy substrate, an aluminum substrate, or an aluminum alloy substrate, preferably a copper substrate or an aluminum substrate, and more preferably a copper substrate. By using a copper substrate or an aluminum substrate, the heat dissipation performance of the heat-dissipating insulating component can be improved.

[0031] A portion of the heat dissipation and insulation component is composed of a thermosetting resin composition according to this embodiment, and its thermal conductivity is preferably 12 W / m·K or higher, more preferably 15 W / m·K or higher.

[0032] The heat dissipation insulating component and the heat sink can be formed on one side or both sides of the heat-generating body. Furthermore, various substrates or layers can be provided between the heat-generating body and the heat dissipation insulating component, or between the heat dissipation insulating component and the heat sink, within a range that does not affect heat dissipation.

[0033] In this embodiment, the heating element, the heat dissipation and insulation component, and the heat sink can be appropriately combined from the aforementioned components to obtain a laminated structure. This laminated structure can be used in various applications requiring heat dissipation and insulation, including semiconductor devices, smartphones, LED bulbs / lamps, power modules, lithium-ion batteries, fuel cells, wireless base stations, uninterruptible power supplies, and many others.

[0034] The components included in the thermosetting resin composition of this embodiment will be described below.

[0035] (Epoxy Resin (A))

[0036] As the epoxy resin (A), known epoxy resins can be used within the scope of the effects of this invention. Examples include bisphenol A type, F type, S type, AD type glycidyl ethers, hydrogenated bisphenol A type glycidyl ether, phenolic varnish type glycidyl ether, cresol phenolic varnish type glycidyl ether, bisphenol A type phenolic varnish type glycidyl ether, naphthalene type glycidyl ether, biphenol type glycidyl ether, dihydroxypentadiene type glycidyl ether, triphenylmethane type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, hydroquinone type glycidyl ether, etc., and at least one of these can be used.

[0037] As for epoxy resin (A), from the viewpoint of the effects of the present invention, it is preferable to include at least one selected from naphthalene-type glycidyl ether, biphenol-type glycidyl ether, dihydroxypentadiene-type glycidyl ether, and hydroquinone-type glycidyl ether.

[0038] The epoxy resin (A) is preferably an epoxy resin containing a mesocrystalline framework. This further improves the thermal conductivity (heat dissipation) during curing.

[0039] It is believed that during the curing of epoxy resin containing a mesocrystalline framework, a higher-order structure (liquid crystal phase or crystalline phase) is formed from this mesocrystalline framework. Furthermore, it is believed that thermal conductivity (heat dissipation) is further improved through heat transfer within this higher-order structure. The presence of this higher-order structure in the cured product can be investigated using observation with a polarizing microscope.

[0040] As a mesocrystalline framework, any framework that facilitates liquid crystallization or crystallinity through intermolecular interactions can be cited. The mesocrystalline framework preferably contains a conjugated structure. Specifically, examples of mesocrystalline frameworks include biphenyl, phenyl benzoate, azobenzene, stilbene, naphthalene, anthracene, chalcone, and phenanthrene frameworks.

[0041] The epoxy resin (A) is particularly preferably composed of a fused polycyclic aromatic hydrocarbon backbone, and especially preferably composed of a naphthalene backbone.

[0042] For example, the biphenyl skeleton (-C6H4-C6H4-) may experience a decrease in liquid crystallinity at high temperatures due to thermal motion causing the central carbon-carbon single bond to "rotate." Similarly, the phenyl benzoate skeleton (-C6H4-COO-C6H4-) may also exhibit ester bond rotation at high temperatures. However, in fused polycyclic aromatic hydrocarbon skeletons such as naphthalene, this decrease in liquid crystallinity caused by rotation is theoretically not present. That is, by including fused polycyclic aromatic hydrocarbon skeletons in epoxy resins, heat dissipation at high temperatures can be easily further improved.

[0043] Furthermore, by employing a naphthalene skeleton as the polycyclic aromatic hydrocarbon skeleton, the aforementioned advantages can be achieved while also suppressing excessive rigidity of the epoxy resin. This is because the naphthalene skeleton is a relatively small mesocrystalline skeleton. The fact that the epoxy resin is not excessively rigid is preferable from the viewpoint of suppressing cracking and other issues caused by the easy relaxation of stress during the curing of the thermosetting resin composition of this embodiment.

[0044] The epoxy resin (A) preferably comprises epoxy resins with two or more functional groups. That is, it is preferable that one molecule of the epoxy resin contains two or more epoxy groups. The number of functional groups in the epoxy resin is preferably 2 to 6, more preferably 2 to 4.

[0045] From the viewpoint of the effects of the present invention, the epoxy resin (A) in this embodiment preferably comprises one or more compounds selected from those represented by the following formula.

[0046]

[0047] The epoxy equivalent of epoxy resin (A) is, for example, 100 to 200 g / eq, preferably 105 to 190 g / eq, and more preferably 110 to 180 g / eq. By using an epoxy resin with an appropriate epoxy equivalent, it is possible to control the curing properties and optimize the physical properties of the cured product.

[0048] As a method, the epoxy resin preferably also includes other epoxy resins that are liquid or semi-solid at room temperature (23°C). Specifically, it is preferred that part or all of the epoxy resin is liquid or semi-solid at 23°C.

[0049] The use of liquid or semi-solid epoxy resins is preferred from the viewpoint that it is easy to form cured products of the desired shape.

[0050] The thermosetting resin composition of this embodiment may contain only one type of epoxy resin, or it may contain two or more types.

[0051] The epoxy resin (A) relative to the resin component (100% by mass) of the thermosetting resin composition that does not contain thermally conductive particles (D) is, for example, 5% to 40% by mass, preferably 7% to 35% by mass, and more preferably 10% to 30% by mass. This ensures sufficient curability and allows for the production of resin sheets with high thermal conductivity and superior insulation.

[0052] The thermosetting resin composition that does not contain thermally conductive particles (D) consists of resin components other than thermally conductive particles (D), including epoxy resin (A) and thermosetting resin (B).

[0053] [Thermosetting resin (B)]

[0054] The thermosetting resin composition of this embodiment includes a thermosetting resin (B). The thermosetting resin (B) does not include epoxy resin (A).

[0055] Examples of thermosetting resins (B) include thermosetting compounds that contain a mesocrystalline structure (mesocrystalline framework) within the molecule or thermosetting compounds that do not contain a mesocrystalline structure within the molecule.

[0056] Examples of thermosetting resins (B) include cyanate resins, maleimide resins, phenolic resins, benzoxazine resins, polyimide resins, unsaturated polyester resins, melamine resins, silicone resins, acrylic resins, and derivatives of phenol, and may include at least one of these.

[0057] In this embodiment, the thermosetting resin (B) preferably includes at least one selected from cyanate resin, bismaleimide resin, phenolic resin and benzoxazine resin, and more preferably includes at least cyanate resin.

[0058] These thermosetting resins can be any monomers, oligomers, or polymers having two or more reactive functional groups within a single molecule, and their molecular weight or molecular structure is not particularly limited.

[0059] (Cyanate ester resin)

[0060] As cyanate ester resins, known cyanate ester resins can be used within the scope of the effects of this invention. Cyanate ester resins may include, for example, one or more selected from phenolic varnish-type cyanate ester resins; bisphenol A-type cyanate ester resins, bisphenol E-type cyanate ester resins, tetramethylbisphenol F-type cyanate ester resins, etc.; naphthol aralkyl-type cyanate ester resins obtained by reacting naphthol aralkyl-type phenolic resins with cyanogen halides; dicyclopentadiene-type cyanate ester resins; and phenol aralkyl-type cyanate ester resins containing a biphenylene skeleton. Among these, from the viewpoint of the effects of this invention, it is more preferable to include at least one of phenolic varnish-type cyanate ester resins and naphthol aralkyl-type cyanate ester resins, and particularly preferably, phenolic varnish-type cyanate ester resins.

[0061] As a phenolic varnish-type cyanate ester resin, for example, a cyanate ester resin represented by the following general formula (I) can be used.

[0062]

[0063] The average repeating unit n of the phenolic varnish-type cyanate ester resin represented by general formula (I) is any integer. The average repeating unit n is not particularly limited, but preferably 1 or more, more preferably 2 or more. If the average repeating unit n is the lower limit value or above, the heat resistance of the phenolic varnish-type cyanate ester resin is improved, and the oligomer release and volatilization during heating can be further suppressed. Furthermore, the average repeating unit n is not particularly limited, but preferably 10 or less, more preferably 7 or less. If n is the upper limit value or below, the increase in melt viscosity can be suppressed, and the moldability of the resin sheet can be improved.

[0064] Furthermore, as the cyanate ester resin, a naphthol aralkyl type cyanate ester resin represented by the following general formula (II) is preferably used. The naphthol aralkyl type cyanate ester resin represented by the following general formula (II) is, for example, a cyanate ester resin obtained by condensing a naphthol aralkyl type phenolic resin with a cyanide halide. This naphthol aralkyl type phenolic resin is obtained by reacting naphthols such as α-naphthol or β-naphthol with p-xylylene glycol, α,α'-dimethoxy-p-xylene, 1,4-bis(2-hydroxy-2-propyl)benzene, etc. The repeating unit n in general formula (II) is preferably an integer of 10 or less. If the repeating unit n is 10 or less, more uniform resin flakes can be obtained. Furthermore, intramolecular polymerization is less likely to occur during synthesis, the separation property during washing is improved, and there is a tendency to prevent a decrease in yield.

[0065]

[0066] In the above general formula (II), R independently represents a hydrogen atom or a methyl group, and n represents an integer greater than 1 and less than 10.

[0067] The cyanate ester resin, relative to the resin content (100% by mass) of the thermosetting resin composition that does not contain thermally conductive particles (D), is, for example, 10% to 70% by mass, preferably 15% to 60% by mass, and more preferably 20% to 50% by mass. This ensures sufficient curability and allows for the production of resin sheets with superior thermal conductivity and insulation.

[0068] (Maleimide resin)

[0069] Maleimide resins are preferably maleimide resins having at least two maleimide groups in the molecule.

[0070] Examples of maleimide resins having at least two maleimide groups within the molecule include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis[4-(4-maleiminophenoxy)phenyl]propane, bis-(3-ethyl-5-methyl-4-maleiminophenyl)methane, 4-methyl-1,3-phenylene bismaleimide, and N,N'-ethylene dimaleimide. Resins containing two maleimide groups in their molecules, such as imine, N,N'-hexamethylene bismaleimide, bis(4-maleimide phenyl) ether, bis(4-maleimide phenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, and bisphenol A diphenyl ether bismaleimide; and resins containing three or more maleimide groups in their molecules, such as biphenyl aralkyl maleimide and polyphenylmethane maleimide.

[0071] (Phenolic resin)

[0072] Examples of phenolic resins include phenolic varnish resins such as phenol, cresol, and bisphenol A varnish resins, as well as methyl phenolic resins. One type of phenolic resin can be used alone, or two or more can be used in combination.

[0073] Among phenolic resins, phenolic varnish resin is preferred.

[0074] (Benzoxazine resin)

[0075] Specifically, examples of benzoxazine resins include o-cresol aniline type benzoxazine resin, m-cresol aniline type benzoxazine resin, p-cresol aniline type benzoxazine resin, phenol-aniline type benzoxazine resin, phenol-methylamine type benzoxazine resin, phenol-cyclohexylamine type benzoxazine resin, phenol-m-toluidine type benzoxazine resin, phenol-3,5-dimethylaniline type benzoxazine resin, bisphenol A-aniline type benzoxazine resin, and bisphenol A-amine type benzoxazine resin. Bisphenol F-aniline type benzoxazine resin, bisphenol S-aniline type benzoxazine resin, dihydroxydiphenyl sulfone-aniline type benzoxazine resin, dihydroxydiphenyl ether-aniline type benzoxazine resin, benzophenone type benzoxazine resin, biphenyl type benzoxazine resin, bisphenol AF-aniline type benzoxazine resin, bisphenol A-methylaniline type benzoxazine resin, phenol-diaminodiphenylmethane type benzoxazine resin, triphenylmethane type benzoxazine resin, and phenolphthalein type benzoxazine resin, etc.

[0076] From the viewpoint of the effects of the present invention, the content of thermosetting resin (B) relative to the resin component (100% by mass) of the thermosetting resin composition that does not contain thermally conductive particles (D) is preferably 0.1% to 70% by mass, more preferably 0.5% to 65% by mass, and even more preferably 1% to 60% by mass.

[0077] [Phenoxy resin (C)]

[0078] The thermosetting resin composition of this embodiment includes a phenoxy resin (C) having an intramolecular mesocrystalline structure.

[0079] As an example of the phenoxy resin containing a mesocrystalline structure, a phenoxy resin comprising a compound having structural units derived from phenolic compounds and structural units derived from epoxy compounds within its molecule, and having a mesocrystalline structure in at least one of these structural units.

[0080] Furthermore, as another example of the phenoxy resin containing a mesocrystalline structure, phenoxy resins that contain structural units derived from phenolic compounds containing a mesocrystalline structure within their molecules can be cited.

[0081] An example of the phenoxy resin containing a mesocrystalline structure can be manufactured using known methods, for example, by reacting a polyfunctional phenolic compound having two or more hydroxyl groups in the molecule with a polyfunctional epoxy compound having two or more epoxy groups in the molecule.

[0082] That is, the phenoxy resin may comprise a reactive compound of a polyfunctional phenolic compound and a polyfunctional epoxy compound. Any or both of these polyfunctional phenolic compounds and polyfunctional epoxy compounds have a mesocrystalline structure.

[0083] Furthermore, other examples of the phenoxy resin containing a mesocrystalline structure can be manufactured using known methods, such as by carrying out an addition polymerization reaction of a phenolic compound containing a mesocrystalline structure having two or more phenolic groups in epichlorohydrin.

[0084] That is, the phenoxy resin may contain an addition polymer of a phenolic compound with a mesocrystalline structure.

[0085] The manufacture of the phenoxy resin can be carried out in the absence of a solvent or in the presence of a reaction solvent. Aprotic organic solvents, such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, sulfolane, and cyclohexanone, are preferably used as the reaction solvent. After the reaction is complete, a resin dissolved in a preferred solvent can be obtained by solvent displacement or similar methods. Furthermore, the phenoxy resin obtained by solvent reaction can be further processed into a solvent-free solid resin by solvent removal treatment using an evaporator or similar apparatus.

[0086] Regarding the reaction catalyst that can be used to manufacture the phenoxy resin, alkali metal hydroxides, tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds, quaternary phosphonium compounds, and imidazole compounds are preferred as conventionally known polymerization catalysts.

[0087] The weight-average molecular weight (Mw) of the phenoxy resin is typically 500 to 200,000. Preferably, it is 1,000 to 100,000, more preferably 2,000 to 50,000. Mw is measured by gel permeation chromatography and represents a value converted using a standard polystyrene calibration curve.

[0088] In this embodiment, the mesocrystalline structure has, for example, the structure represented by the following general formula (1) or general formula (2).

[0089] -A1-x-A2-……(1)

[0090] -x-A1-x-……(2)

[0091] In the general formulas (1) and (2), A1 and A2 each independently represent an aromatic group, a fused aromatic group, an alicyclic group, or an alicyclic heterocyclic group, and x each independently represents a directly bonded or divalent bonded group selected from the group consisting of -O-, -C=C-, -C≡C-, -CO-, -CO-O-, -CO-NH-, -CH=N-, -CH=NN=CH-, -N=N-, and -N(O)=N-.

[0092] Wherein, A1 and A2 are each preferably selected independently from the following groups: a hydrocarbon group having 6 to 12 carbon atoms with a benzene ring, a hydrocarbon group having 10 to 20 carbon atoms with a naphthalene ring, a hydrocarbon group having 12 to 24 carbon atoms with a biphenyl structure, a hydrocarbon group having 12 to 36 carbon atoms with three or more benzene rings, a hydrocarbon group having 12 to 36 carbon atoms with a fused aromatic group, and an alicyclic heterocyclic group having 4 to 36 carbon atoms. A1 and A2 may be unsubstituted or may be derivatives with substituents.

[0093] Specific examples of A1 and A2 in mesocrystalline structures include phenylene, biphenylene, naphthylene, anthraceneylene, cyclohexyl, pyridyl, pyrimidinyl, and thiophenylene. Furthermore, these can be unsubstituted or derivatives with substituents such as aliphatic hydrocarbon groups, halogen groups, cyano groups, and nitro groups.

[0094] As the bonding group (linking group) in the mesocrystalline structure, x is preferably directly bonded or selected from the group consisting of -C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH=NN=CH-, -N=N- or -N(O)=N-, a divalent substituent.

[0095] Here, direct bonding refers to the interconnection of single bonds or A1 and A2 in a mesocrystalline structure to form a ring structure. For example, a naphthalene structure can be included in the structure represented by the general formula (1).

[0096] As the polyfunctional phenolic compounds, compounds containing a mesocrystalline structure, represented by the following general formula (A), can be used, for example. These can be used alone or in combination of two or more.

[0097]

[0098] In the general formula (A), R 1 and R 3 Each independently represents a hydroxyl group, R 2 and R 4Each of these terms independently represents one of the following: hydrogen atoms, chain or cyclic alkyl groups with 1 to 6 carbon atoms, phenyl groups, and halogen atoms. a and c are integers from 1 to 3, and b and d are integers from 0 to 2. a+b and c+d are any one of 1 to 3. a+c can be 3 or more.

[0099] As the aforementioned multifunctional epoxy compounds, compounds containing a mesocrystalline structure, represented by the following general formula (B), can be used, for example. These can be used alone or in combination of two or more.

[0100]

[0101] In the general formula (B), R 5 and R 7 Each independently represents a glycidyl ether group, R 6 and R 8 Each of these terms independently represents one selected from hydrogen atoms, chain or cyclic alkyl groups with 1 to 6 carbon atoms, phenyl groups, and halogen atoms, where e and g are integers from 1 to 3, and f and h are integers from 0 to 2. Where e+f and g+h are any one of 1 to 3.

[0102] Furthermore, R in general formulas (A) and (B) respectively represents -A1-x-A2-, -x-A1-x-, or -x-. Additionally, the two benzene rings in general formula (A) can be interconnected to form a fused ring.

[0103] As the R 2 R 4 R 6 and R 8 Specific examples include hydrogen atoms, methyl, ethyl, propyl, butyl, chlorine atoms, and bromine atoms, among which hydrogen atoms and methyl atoms are particularly preferred.

[0104] As the aforementioned multifunctional epoxy compounds containing a mesocrystalline structure, for example, addition polymers of compounds represented by the general formula (B) can be used. These can be used alone or in combination of two or more.

[0105] Among the polyfunctional phenolic compounds and the polyfunctional epoxy compounds, polyfunctional phenolic compounds having three or more hydroxyl groups in the molecule and polyfunctional epoxy compounds having two or more epoxy groups in the molecule can be used.

[0106] That is, the phenoxy resin may contain branched reactive compounds, which are branched reactive compounds consisting of polyfunctional phenolic compounds having three or more hydroxyl groups in the molecule and polyfunctional epoxy compounds having two or more epoxy groups in the molecule.

[0107] As a polyfunctional phenolic compound having three or more hydroxyl groups in the molecule, it may include, for example, polyphenols or polyphenol derivatives.

[0108] The polyphenol is a compound containing three or more phenolic hydroxyl groups within its molecule. Furthermore, the polyphenol preferably possesses the mesocrystalline structure within its molecule. For example, biphenyl skeletons, phenyl benzoate skeletons, azobenzene skeletons, stilbene skeletons, etc., can be used as mesocrystalline structures.

[0109] In addition, polyphenol derivatives include: for polyphenol compounds having three or more phenolic hydroxyl groups and a mesocrystalline structure, compounds in which the positions where substitution is possible are changed to other substituents.

[0110] In this embodiment, the branched reactive compound can be obtained by using one or more of the polyfunctional phenolic compounds, including polyfunctional phenolic compounds having at least three or more hydroxyl groups in the molecule, and one or more of the polyfunctional epoxy resins.

[0111] For example, a combination of a trifunctional phenolic compound and a difunctional epoxide compound, or a combination of a trifunctional phenolic compound, a difunctional phenolic compound, and a difunctional epoxide compound can be used.

[0112] As the trifunctional phenolic compound, resveratrol, represented by the following chemical formula, can be used, for example.

[0113]

[0114] As the difunctional phenolic compound, for example, R can be used. 1 and R 3 A difunctional phenolic compound in which the hydroxyl groups are bonded to the para-position of each benzene ring.

[0115] Furthermore, R can be used as the difunctional epoxy compound. 5 and R 7 A difunctional epoxy compound in which glycidyl ether groups are bonded to the para position of each benzene ring.

[0116] Furthermore, when the difunctional phenolic compound has a naphthalene ring as a fused ring, the R can be used. 1 and R 3 A difunctional phenolic compound in which the hydroxyl group is bonded to any one of the following positions: 1 and 4, 1 and 5, 1 and 6, 2 and 3, 2 and 6, or 2 and 7 of the naphthalene ring. Furthermore, when the difunctional epoxide compound has the naphthalene ring as a fused ring, the R... 5 and R 7 A difunctional epoxy compound in which the glycidyl ether group is bonded to any one of the following positions: 1 and 4, 1 and 5, 1 and 6, 2 and 3, 2 and 6, or 2 and 7 of the naphthalene ring.

[0117] The branched reactive compound (branched phenoxy resin) can be obtained by combining the trifunctional phenolic compound with the difunctional epoxy compound, or by combining the trifunctional phenolic compound, the difunctional phenolic compound and the difunctional epoxy compound as described above.

[0118] On the other hand, difunctional phenolic compounds and difunctional epoxides may also be used among the polyfunctional phenolic compounds and polyfunctional epoxides. These can be used alone or in combination of two or more.

[0119] That is, the phenoxy resin may contain linear reactive compounds, which are linear reactive compounds consisting of a difunctional phenolic compound having two hydroxyl groups in the molecule and a difunctional epoxy compound having two epoxy groups in the molecule.

[0120] As the difunctional phenolic compound, the R can be used 1 and R 3 A difunctional phenolic compound in which hydroxyl groups are bonded to the para-position of each benzene ring. Furthermore, as said difunctional epoxide compound, the R... 5 and R 7 A difunctional epoxy compound in which glycidyl ether groups are bonded to the para position of each benzene ring.

[0121] Furthermore, when the difunctional phenolic compound has a naphthalene ring as a fused ring, the R can be used. 1 and R 3 A difunctional phenolic compound in which the hydroxyl group is bonded to any one of the following positions: 1 and 4, 1 and 5, 1 and 6, 2 and 3, 2 and 6, or 2 and 7 of the naphthalene ring. Furthermore, when the difunctional epoxide compound has the naphthalene ring as a fused ring, the R... 5 and R 7 A difunctional epoxy compound in which the glycidyl ether group is bonded to any one of the following positions: 1 and 4, 1 and 5, 1 and 6, 2 and 3, 2 and 6, or 2 and 7 of the naphthalene ring.

[0122] The linear reactive compound (linear phenoxy resin) can be obtained by combining this difunctional phenolic compound with a difunctional epoxy compound.

[0123] The branched and linear phenoxy resins may have epoxy or hydroxyl groups at the molecular ends or inside the molecule. The presence of epoxy groups at the ends or inside the molecule enables cross-linking reactions, thus improving heat resistance.

[0124] Furthermore, the heat dissipation characteristics can be improved by using rigid and electronically conjugated linear structural units.

[0125] The phenoxy resin (C) relative to the resin content (100% by mass) of the thermosetting resin composition that does not contain thermally conductive particles (D) is, for example, 5% to 60% by mass, preferably 10% to 50% by mass, and more preferably 15% to 40% by mass. This allows for the production of resin sheets with superior thermal conductivity and insulation.

[0126] [Thermal Conductivity Particles (D)]

[0127] The thermosetting resin composition of this embodiment contains thermally conductive particles (D).

[0128] The thermally conductive particles (D) may, for example, comprise highly thermally conductive inorganic particles having a thermal conductivity of 20 W / m·K or higher. These highly thermally conductive inorganic particles may include, for example, at least one selected from silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, silicon carbide, and magnesium oxide. These may be used alone or in combination of two or more.

[0129] The boron nitride may comprise monodisperse particles, agglomerated particles, or mixtures thereof in the form of flake-like boron nitride. Flake-like boron nitride can be granulated into particulate form. Thermal conductivity can be further improved by using agglomerated particles of flake-like boron nitride. The agglomerated particles can be sintered or non-sintered particles.

[0130] The thermally conductive particles (D) (100% by mass) may contain 60% by mass or more, preferably 65% ​​by mass or more, and more preferably 70% by mass or more of the boron nitride. The upper limit is not particularly limited, but may be set to 100% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less.

[0131] It has always been known that even when a silane coupling agent is added to boron nitride particles, the adhesion is not improved. However, by using the organosiloxane compound (E) of this embodiment, even when the thermally conductive particles (D) contain boron nitride particles in the above-mentioned amount, a resin sheet with low moisture absorption, excellent insulation durability, and excellent thermal conductivity and insulation can be obtained.

[0132] The content of thermally conductive particles (D) relative to the resin component (100% by mass) of the thermosetting resin composition is 100% to 400% by mass, preferably 150% to 350% by mass, and more preferably 200% to 330% by mass. Setting this content above the lower limit improves thermal conductivity. Setting it below the upper limit suppresses a decrease in processability.

[0133] [Organosiloxane compounds (E)]

[0134] The thermosetting resin composition of this embodiment contains an organosiloxane compound (E).

[0135] It has long been known that even with the addition of silane coupling agents to thermally conductive particles such as boron nitride particles, the adhesion does not improve, and therefore the effect of such additions has not been studied until now. This time, an organosiloxane compound (E) was added to the thermally conductive particles (D), and the results clearly showed that a resin sheet with low moisture absorption, excellent insulation durability, high thermal conductivity, and excellent insulation can be obtained, thus completing this invention. The mechanism is not yet clear, but it is hypothesized as follows: Due to the addition of the organosiloxane compound, slight lattice defects at the end faces or in-planes of the thermally conductive particles eliminate the influence of polar functional groups that worsen the affinity between the resin and the thermally conductive particles, thereby improving the affinity or hydrophobicity at the interface between the resin and the thermally conductive particles. As a result, the interfacial thermal resistance decreases, and the moisture absorption characteristics further decrease.

[0136] The organosiloxane compound (E) is an aliphatic hydrocarbon compound having a Si-OQ bond (Q being an alkyl group) at one end of its molecular chain. More preferably, the organosiloxane compound (E) has at least one group selected from epoxy, glycidyl ether, amino, isocyanate, phenyl, carboxyl, hydroxyl, alkyl, vinyl, mercapto, and azirhexacyclopentyl groups at the other end. This allows for the production of resin sheets with lower moisture absorption and superior insulation durability.

[0137] Organosiloxane compounds (E) may include compounds represented by the following general formula (1).

[0138]

[0139] In general formula (1), R independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two Rs are alkoxy groups having 1 to 3 carbon atoms. All Rs are preferably alkoxy groups having 1 to 3 carbon atoms, and more preferably alkoxy groups having 1 to 2 carbon atoms.

[0140] L represents a straight-chain or branched alkylene group with 2 to 12 carbon atoms.

[0141] X represents an epoxy group, glycidyl ether group, amino group, isocyanate group, phenyl group, carboxyl group, hydroxyl group, alkyl group, vinyl group, or mercapto group. From the viewpoint of the effects of the present invention, X is preferably an epoxy group, glycidyl ether group, amino group, isocyanate group, alkyl group having 1 to 3 carbon atoms, phenyl group, or mercapto group. From the viewpoint of the pot life of the thermosetting resin composition, epoxy group, phenyl group, glycidyl ether group, phenyl group, or methyl group is more preferred.

[0142] Examples of compounds represented by general formula (1) include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltriethoxysilane, glycidoxyoctyltriethoxysilane, glycidoxyoctyltrimethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, and phenyltrimethoxysilane.

[0143] The thermosetting resin composition of this embodiment contains an organosiloxane compound (E) in an amount of 0.01 to 0.5 parts by mass, preferably 0.02 to 0.3 parts by mass, and more preferably 0.03 to 0.2 parts by mass relative to 100 parts by mass of the thermally conductive particles (D). This results in a resin sheet with further low moisture absorption and superior insulation durability.

[0144] (Cure Accelerator (F))

[0145] The thermosetting resin composition of this embodiment may include a curing accelerator (F) as needed.

[0146] The type or amount of curing accelerator (F) is not particularly limited. Appropriate curing accelerators can be selected from the perspectives of reaction rate or reaction temperature, storage properties, etc.

[0147] Examples of curing accelerators (F) include imidazoles, organophosphorus compounds, tertiary amines, phenolic compounds, and organic acids. These can be used alone or in combination of two or more. From the viewpoint of improving heat resistance, nitrogen-containing compounds such as imidazoles are preferred.

[0148] Examples of the imidazole class include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazole ontium trimellitate.

[0149] Examples of such tertiary amines include triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo(5,4,0)undecene-7.

[0150] Examples of the phenolic compounds include phenolic resins, bisphenol A, nonylphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, allylphenol, etc.

[0151] Examples of organic acids include acetic acid, benzoic acid, salicylic acid, and p-toluenesulfonic acid.

[0152] The content of the curing accelerator (F) relative to 100% by mass of the total thermosetting resin can be 0.01% by mass to 10% by mass, 0.02% by mass to 5% by mass, or 0.05% by mass to 1.5% by mass.

[0153] The thermosetting resin composition of this embodiment may contain other components besides those described above. Examples of such other components include antioxidants and leveling agents.

[0154] As a method for manufacturing the thermosetting resin composition of this embodiment, there is, for example, the following method.

[0155] The resin varnish (a varnish-like thermosetting resin composition) can be prepared by dissolving, mixing, and stirring the above-mentioned components in a solvent. Various mixers can be used for this mixing, such as ultrasonic dispersion, high-pressure impact dispersion, high-speed rotary dispersion, bead milling, high-speed shear dispersion, and rotation-revolutionary dispersion. Furthermore, from the viewpoint of the effects of the present invention, it is preferable to premix the thermally conductive particles (D) and the organosiloxane compound (E), and it is also preferable to prepare a resin varnish other than the organosiloxane compound (E) and mix the organosiloxane compound (E) as an additive into the resin varnish.

[0156] The solvents mentioned above are not particularly limited and can include acetone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosol, carbitol, anisole, and N-methylpyrrolidone, etc.

[0157] [Resin Sheet]

[0158] The resin sheet of this embodiment is formed by curing the thermosetting resin composition. Specifically, the resin sheet includes a carrier substrate and a resin layer formed from the thermosetting resin composition of this embodiment disposed on the carrier substrate.

[0159] The aforementioned resin sheet can be obtained, for example, by solvent removal treatment of a coating film (resin layer) obtained by applying a varnish-like thermosetting resin composition onto a carrier substrate. The solvent content in the resin sheet can be set to 10% by mass or less relative to the overall thermosetting resin composition. For example, the solvent removal treatment can be performed at 80°C to 200°C for 1 to 30 minutes.

[0160] The resin sheet (resin layer) in this embodiment is in the B-order state, and the thermosetting resin composition that does not contain thermally conductive particles (D) and serves as an adhesive preferably has the following curing behavior.

[0161] Specifically, a thermosetting resin composition without thermally conductive particles (D) was pre-dried for 12 minutes at 115°C to form a B-order sheet. The curing torque of the B-order sheet was measured over time using a cone-plate rheometer at a measurement temperature of 180°C. The time required from the start of the measurement to the maximum torque is denoted as T. max The time T from the start of measurement until 50% of the maximum torque value is reached. 50 The ratio (T) 50 / T max The preferred value is 0.1 to 1.0, more preferably 0.2 to 0.8, and even more preferably 0.25 to 0.75.

[0162] As a cone-plate rheometer, for example, the "MCR-301" rheometer manufactured by Anton Paar GmbH in Austria can be used. Furthermore, the measurement frequency can be set to 1 Hz, and the swing angle can be set to 1%.

[0163] By measuring the curing behavior (ratio (T) of the filler-free thermosetting resin composition of this embodiment) 50 / T max Within the above range, the cycle time during stamping can be kept within an appropriate range, and the occurrence of forming defects such as voids can be suppressed, thus improving the productivity of metal substrates and the like described later.

[0164] Furthermore, in this embodiment, the carrier substrate can be, for example, a polymer film or a metal foil. The polymer film is not particularly limited; examples include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as silicone sheets, fluorinated resins, and heat-resistant thermoplastic resin sheets such as polyimide resins. The metal foil is also not particularly limited; examples include copper and / or copper alloys, aluminum and / or aluminum alloys, iron and / or iron alloys, silver and / or silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, and tin and tin alloys.

[0165] The resin substrate in this embodiment is a resin substrate having an insulating layer formed by the cured product of the above-described thermosetting resin composition. This resin substrate can be used as a material for printed circuit boards used to mount electronic components such as LEDs and power modules.

[0166] (Metal base substrate)

[0167] according to Figure 1 The metal substrate (heat dissipation resin component) 100 of this embodiment will be described.

[0168] Figure 1This is a schematic cross-sectional view showing an example of the structure of the metal substrate 100.

[0169] like Figure 1 As shown, the aforementioned metal substrate 100 may include a metal substrate 101, an insulating layer 102 disposed on the metal substrate 101, and a metal layer 103 disposed on the insulating layer 102. The insulating layer 102 may be composed of a resin layer formed from the aforementioned thermosetting resin composition, a cured thermosetting resin composition, and a laminate. These resin layers and laminates may be composed of a thermosetting resin composition (resin sheet) in a B-order state before circuit processing of the metal layer 103, and may be cured bodies formed by curing the composition after circuit processing.

[0170] The metal layer 103 is a circuit-processed layer disposed on the insulating layer 102. Examples of metals constituting the metal layer 103 include one or more selected from copper, copper alloys, aluminum, aluminum alloys, nickel, iron, and tin. Among these, the metal layer 103 is preferably a copper layer or an aluminum layer, and particularly preferably a copper layer. By using copper or aluminum, the circuit processability of the metal layer 103 is improved. The metal layer 103 can be a metal foil that can be obtained in sheet form or in roll form.

[0171] The minimum thickness of the metal layer 103 is, for example, 0.01 mm or more, and preferably 0.035 mm or more, which makes it suitable for applications requiring high current.

[0172] Furthermore, the upper limit of the thickness of the metal layer 103 is, for example, 10.0 mm or less, preferably 5 mm or less. If it is below such a value, the circuit fabrication capability can be improved, and the overall substrate can be made thinner.

[0173] The metal substrate 101 serves to dissipate heat accumulated in the metal base substrate 100. The metal substrate 101 is not particularly limited as long as it is a heat-dissipating metal substrate; for example, it can be a copper substrate, a copper alloy substrate, an aluminum substrate, or an aluminum alloy substrate, with a copper substrate or an aluminum substrate being preferred, and a copper substrate being more preferred. By using a copper substrate or an aluminum substrate, the heat dissipation performance of the metal substrate 101 can be improved.

[0174] The thickness of the metal substrate 101 can be appropriately set as long as it does not impair the purpose of the present invention.

[0175] The upper limit of the thickness of the metal substrate 101 is, for example, 20.0 mm or less, preferably 5.0 mm or less. This improves the machinability of the metal substrate 100 during shape processing or cutting processes when the thickness is below this value.

[0176] Furthermore, the minimum thickness of the metal substrate 101 is, for example, 0.01 mm or more, preferably 0.6 mm or more. By using a metal substrate 101 with a thickness of 0.01 mm or more, the heat dissipation of the metal substrate 100 as a whole can be improved.

[0177] In this embodiment, the metal substrate 100 can be used for various substrate applications, but from the perspective of excellent thermal conductivity and heat resistance, it can be used as a printed substrate for LEDs or power modules.

[0178] The metal substrate 100 may have a metal layer 103 that has been circuit-processed by etching patterns or the like. In this metal substrate 100, a solder resist (not shown) may be formed on the outermost layer, and the electrode portions for connection may be exposed by exposure / development so that electronic components can be mounted.

[0179] (Semiconductor devices)

[0180] The metal substrate (heat dissipation insulating component) 100 of the embodiment can be used for various applications requiring heat dissipation and insulation, such as for semiconductor devices.

[0181] Figure 2 This is a schematic cross-sectional view showing an example of a semiconductor device using a metal substrate 100.

[0182] A semiconductor element 201 is mounted on the metal layer 103 of the metal substrate 100 via an adhesive layer 202 (chip bonding material). The semiconductor element 201 is connected to the connection electrode portion formed on the metal substrate 100 via bonding wires 203 and is mounted on the metal substrate 100.

[0183] Furthermore, the semiconductor element 201 is sealed together on the metal substrate 100 by the sealing resin layer 205.

[0184] A heat sink 207 is provided on the metal substrate 101 side of the metal substrate 100 via a thermally conductive layer 206 (thermal interface material (TIM)). The heat sink 207 is made of a material with excellent thermal conductivity, such as aluminum, iron, or copper.

[0185] The embodiments of the present invention have been described above, but these are merely examples of the present invention. Various configurations other than those described above can be used without impairing the effects of the present invention.

[0186] [Example]

[0187] The present invention will be further described in detail below with reference to embodiments, but the present invention is not limited thereto.

[0188] <Examples 1-13, Comparative Example 1 (Preparation of thermosetting resin composition (varnish-like))>

[0189] A varnish-like thermosetting resin composition was obtained by stirring the components and solvent according to the mixing ratios listed in Table 1. In Table 1, the content of thermally conductive particles is expressed as a percentage by volume of the resin component relative to the thermosetting resin composition without thermally conductive fillers.

[0190] The detailed information for each component in Table 1 is as follows. Additionally, the quantities of each component in Table 1 are in parts by mass.

[0191] (Epoxy resin)

[0192] • Epoxy Resin 1: The epoxy resin represented by the following structural formula, manufactured by DIC Corporation, product number "EPICLON HP-4700".

[0193]

[0194] • Epoxy Resin 2: The epoxy resin represented by the following structural formula, manufactured by DIC Corporation, product number "EPICLON 830".

[0195]

[0196] (Cyanate ester resin)

[0197] • Cyanate ester resin 1: Manufactured by Lonza, Primaset "PT-30".

[0198] (Phenoxy resins with intramolecular mesocrystalline structures)

[0199] • Phenoxy resin 1: A phenoxy resin with an intramolecular mesocrystalline structure obtained by the following synthesis steps.

[0200] 70.1 parts by mass of epoxy resin (4,4'-dihydroxybiphenyl diglycidyl ether with a mesocrystalline structure, synthesized by our company, described below), 23.5 parts by mass of bisphenol compound (a difunctional phenol with a mesocrystalline structure, manufactured by Ueno FINECHEMICALS INDUSTRY.LTD., HQPOB), 0.06 parts by mass of triphenylphosphine (TPP), and 6.3 parts by mass of solvent (methyl ethyl ketone) were added to a reactor. The reaction was then carried out at 150°C while removing the solvent. The target molecular weight was confirmed by GPC, and the reaction was stopped. Through this process, phenoxy resin 1 with a molecular weight of 4500 was obtained.

[0201]

[0202] • Phenoxy resin 2: A phenoxy resin with an intramolecular mesocrystalline structure obtained by the following synthetic steps.

[0203] 77.1 parts by mass of an epoxy resin (with a mesocrystalline structure, synthesized by our company, 4,4'-dihydroxybiphenyl diglycidyl ether), 18.0 parts by mass of a bisphenol compound (with a mesocrystalline structure, a difunctional phenol with the following structure, manufactured by Yamada Chemical Co., Ltd., 2,7-DHN), 0.08 parts by mass of triphenylphosphine (TPP), and 4.8 parts by mass of solvent (methyl ethyl ketone) were added to a reactor. The reaction was then carried out at 150°C while removing the solvent. The target molecular weight was confirmed by GPC, and the reaction was stopped. Through this process, phenoxy resin 2 with a molecular weight of 5200 was obtained.

[0204]

[0205] • Phenoxy resin 3: A phenoxy resin with an intramolecular mesocrystalline structure obtained by the following synthetic steps.

[0206] 72.8 parts by mass of an epoxy resin (with a mesocrystalline structure, manufactured by Mitsubishi Chemical Corporation, YX-4000), 21.4 parts by mass of a bisphenol compound (with a mesocrystalline structure, a difunctional phenol with the following structure, synthesized by our company, 4,4'-dihydroxychalcone), 0.07 parts by mass of triphenylphosphine (TPP), and 5.7 parts by mass of solvent (methyl ethyl ketone) were added to a reactor. The reaction was then carried out at a temperature of 120–150°C while removing the solvent. The target molecular weight was confirmed by GPC, and the reaction was stopped. Through this process, phenoxy resin 3 with a molecular weight of 4300 was obtained.

[0207]

[0208] • Phenoxy resin 4: A phenoxy resin with an intramolecular mesocrystalline structure obtained by the following synthetic steps.

[0209] 75.5 parts by mass of an epoxy resin (with a mesocrystalline structure, manufactured by DIC Corporation, HP-4032D), 19.3 parts by mass of a bisphenol compound (with a mesocrystalline structure, a difunctional phenol with a mesocrystalline structure, manufactured by Yamada Chemical Co., Ltd., 2,7-DHN), 0.09 parts by mass of triphenylphosphine (TPP), and 5.1 parts by mass of solvent (methyl ethyl ketone) were added to a reactor. The reaction was then carried out at 150°C while removing the solvent. The target molecular weight was confirmed by GPC, and the reaction was stopped. A phenoxy resin 4 with a molecular weight of 5400 was obtained.

[0210]

[0211] (Curing accelerator)

[0212] • Curing accelerator 1: Phenolic varnish type phenolic compound (PR-51470, manufactured by Sumitomo Bakelite Co., Ltd.).

[0213] (organosiloxane compounds)

[0214] • Organosiloxane 1:3-glycidoxypropyltriethoxysilane.

[0215] • Organosiloxane 2:3-glycidoxypropyltrimethoxysilane.

[0216] • Organosiloxane 3: 3-Mercaptopropyltriethoxysilane.

[0217] • Organosiloxane 4:3-isocyanate-propyltriethoxysilane.

[0218] · Organosiloxane 5: 3-aminopropyltriethoxysilane.

[0219] • Organosiloxane 6: glycidoxyoctyltrimethoxysilane.

[0220] · Organosiloxane 7: Decyltriethoxysilane.

[0221] · Organosiloxane 8: 2,2-Dimethoxy-1-phenyl-1-aza-2-silazane.

[0222] (thermally conductive particles)

[0223] • Thermally conductive particle 1: Condensed boron nitride (manufactured by Mizushima Ferroalloy Co., TLD., HP40).

[0224] <Measurement of Curing Behavior of Thermosetting Compositions in the B-Stage State>

[0225] A thermosetting resin composition without thermally conductive particles was pre-dried at 115°C for 12 minutes to form a B-order sheet. The curing torque of the B-order sheet was measured over time at a measurement temperature of 180°C using a cone-plate viscometer (MCR-301 rheometer manufactured by Anton Paar GmbH, Austria). The time at which the maximum curing torque value was reached was set as T. max Let T be the time from the start of the measurement until the torque reaches 50% of the maximum torque value. 50 When, T is calculated from the measurement results. 50 / T max .

[0226] <Measurement of physical properties of resin molded articles of thermosetting resin compositions>

[0227] (thermal conductivity)

[0228] • Fabrication of resin molded parts

[0229] The obtained thermosetting resin composition containing thermally conductive filler was clamped and fixed with 0.018 μm copper foil and compressed at 10 MPa and 180°C for 90 minutes to obtain a resin molded body (sample 1 for thermal conductivity measurement). A 10 mm diameter sample for thermal diffusivity measurement was cut from the obtained molded body and used for thermal diffusivity measurement.

[0230] Specific gravity of resin molded parts

[0231] Specific gravity was measured in accordance with JIS K 6911 (General Test Methods for Thermosetting Plastics). The test pieces were sheets cut from the aforementioned resin molded body, measuring 2 cm in length and 2 cm in width. Specific gravity (SP) was measured in g / cm³.

[0232] Specific heat of resin molded parts

[0233] The specific heat (Cp) of the obtained resin molded articles was measured by DSC.

[0234] Measurement of thermal conductivity of resin molded parts

[0235] A sheet with a diameter of 10 mm was cut from the obtained resin molded body as a test piece for thickness direction measurement. Next, the thermal diffusivity (α) in the thickness direction of the sheet-shaped test piece was measured using a ULVAC Xe Flash Analyzer TD-1RTV and an unsteady-state method. The measurement was performed under atmospheric conditions at 25°C.

[0236] For resin molded articles, thermal conductivity is calculated from the obtained measurements of thermal diffusivity (α), specific heat (Cp), and specific gravity (SP) according to the following formula.

[0237] Thermal conductivity [W / m·K]=α[m 2 / s]×Cp[J / kg·K]×Sp[g / cm 3 ]

[0238] In Table 1, the thermal conductivity of the resin molded body is set as "thermal conductivity".

[0239] (Volume resistivity)

[0240] Measurements were performed in accordance with JIS C 2139.

[0241] Specifically, a measured solidified material of appropriate size was placed in an oven at 30°C, and the volume resistivity at the target temperature (i.e., 30°C) was measured.

[0242] (Moisture absorption rate)

[0243] The copper foil was removed from the obtained resin molded body by etching, and the moisture absorption rate (%) was calculated from the weight change before and after treatment when placed at 30°C / 90%RH for 48 hours.

[0244] (Insulation durability)

[0245] Specifically, making one side has A resin-molded body with a ring electrode on one side and a copper foil on the other was placed at 85°C / 85%RH with the ring electrode side as the anode and the copper foil side as the cathode. The time taken until conduction was achieved when a DC voltage of 2kV was applied was measured. The results were evaluated using the following criteria.

[0246] (Evaluation Criteria)

[0247] ○: No connection was established even after more than 100 hours.

[0248] ×: It was connected in less than 100 hours.

[0249]

[0250] The application claims priority based on Japanese Patent Application No. 2019-222223, filed on December 9, 2019, and all its disclosures are incorporated herein by reference.

[0251] Explanation of reference numerals in the attached figures

[0252] 100 metal base substrate

[0253] 101 metal substrate

[0254] 102 Insulation layer

[0255] 103 Metal Layer

[0256] 200 Semiconductor Devices

[0257] 201 Semiconductor Components

[0258] 202 Adhesive Layer

[0259] 203 Joint Line

[0260] 205 Sealing Resin Layer

[0261] 206 Thermal Conductive Layer

[0262] 207 Heatsink.

Claims

1. A thermosetting resin composition, wherein, It constitutes at least a portion of a heat-dissipating insulating component located between a heating element and a heat sink, wherein the thermosetting resin composition comprises: (A) Epoxy resin; (B) Thermosetting resins other than epoxy resin (A); (C) Phenoxy resins with intramolecular mesocrystalline structures; (D) Thermally conductive particles; and (E) Organosiloxane compounds, The thermally conductive particles (D) contain more than 60% by mass of boron nitride. The thermosetting resin composition comprises 0.01 to 1 part by mass of the organosiloxane compound (E) relative to 100 parts by mass of the thermally conductive particles (D). Epoxy resin (A) contains epoxy resin comprising a mesocrystalline framework. The epoxy resin containing a mesocrystalline framework comprises a mesocrystalline framework selected from biphenyl framework, phenyl benzoate framework, azobenzene framework, stilbene framework, naphthalene framework, anthracene framework, chalcone framework, and phenanthrene framework. The content of phenoxy resin (C) is 15% by mass or more and 40% by mass or less relative to 100% by mass of the resin component of the thermosetting resin composition that does not contain thermally conductive particles (D).

2. The thermosetting resin composition according to claim 1, wherein, The thermal conductivity of the heat dissipation and insulation component is above 12 W / m·K.

3. The thermosetting resin composition according to claim 1 or 2, wherein, The thermally conductive particles (D) contain the boron nitride. The boron nitride includes monodisperse particles, particulate particles, aggregated particles, or mixtures thereof of flake boron nitride.

4. The thermosetting resin composition according to claim 1 or 2, wherein, The organosiloxane compound (E) has at least one group selected from epoxy, glycidyl ether, amino, isocyanate, phenyl, carboxyl, hydroxyl, alkyl, vinyl, mercapto and azirsilcyclopentyl.

5. The thermosetting resin composition according to claim 1 or 2, wherein, Phenoxy resins (C) contain structural units derived from phenolic compounds and structural units derived from epoxy compounds.

6. The thermosetting resin composition according to claim 1 or 2, wherein, The phenoxy resin (C) has the mesocrystalline structure selected from the biphenyl skeleton, phenyl benzoate skeleton, azobenzene skeleton, stilbene skeleton, naphthalene skeleton, anthracene skeleton, chalcone skeleton and phenanthrene skeleton.

7. The thermosetting resin composition according to claim 1 or 2, wherein, Thermosetting resin (B) includes at least one selected from cyanate resin, maleimide resin, phenolic resin and benzoxazine resin.

8. The thermosetting resin composition according to claim 1 or 2, wherein, The thermosetting resin composition further comprises a curing accelerator (F).

9. The thermosetting resin composition according to claim 1 or 2, wherein, The ratio T is calculated under the following conditions. 50 / T max The value ranges from 0.1 to 1.

0. condition: A thermosetting resin composition without thermally conductive particles (D) was pre-dried at 115°C for 12 minutes to form a B-order sheet. The curing torque of the B-order sheet was measured over time at a measurement temperature of 180°C using a cone-plate viscometer rheometer. The time of the maximum curing torque value was set as T. max Let T be the time from the start of the measurement until the torque reaches 50% of the maximum torque value. 50 Calculate the ratio, i.e., T 50 / T max .

10. A resin sheet, wherein, It is formed from the thermosetting resin composition according to any one of claims 1 to 9.

11. The resin sheet according to claim 10, wherein, It is a B-order state.

12. A metal-based substrate, wherein, It has the following features in sequence: metal substrate; An insulating layer formed by curing the resin sheet as described in claim 10 or 11; and Metal layer.

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