Sheet-like member, resin composition for molding, and electronic component device

Abstract

A sheet-like member is obtained by molding a resin composition for molding containing a thermosetting component and an inorganic filler that contains at least one of calcium titanate particles and strontium titanate particles.

Description

Sheet-like member, molding resin composition, and electronic component device

[0001] The present disclosure relates to a sheet-like member, a molding resin composition, and an electronic component device.

[0002] In recent years, with the demand for electronic devices to be more highly functional and lighter, thinner, shorter, and smaller, the integration and even higher density of electronic components have progressed, and the semiconductor packages used in these electronic devices have become smaller than ever before.Furthermore, the radio waves used for communication in electronic devices have become higher in frequency.

[0003] BACKGROUND ART In order to reduce the size of semiconductor packages and to accommodate high frequencies, high-dielectric-constant resin compositions have been proposed for use in encapsulating semiconductor elements.

[0004] JP 2015-036410 A JP 2017-057268 A JP 2018-141052 A

[0005] Examples of materials for encapsulating electronic components such as semiconductor devices include molding resin compositions containing a curable resin and an inorganic filler. When a material with a high dielectric loss tangent is used as the molding resin composition, transmission signals are converted into heat due to transmission loss, which tends to reduce communication efficiency. The amount of transmission loss caused by heat conversion of radio waves emitted for communication in a dielectric is expressed as the product of the square root of the frequency, the dielectric constant, and the dielectric loss tangent. In other words, the transmission signal is more likely to be converted into heat in proportion to its frequency. In particular, in recent years, radio waves used for communication have become higher in frequency to accommodate an increase in the number of channels due to the diversification of information. Therefore, molding resin compositions capable of molding cured products with low dielectric loss tangents are in demand. Meanwhile, a higher dielectric constant allows for smaller substrates and semiconductor packages. Therefore, from the perspective of suppressing transmission loss and miniaturizing substrates, etc., it is desirable to ensure a high dielectric constant and a low dielectric loss tangent.

[0006] An object of the present disclosure is to provide a sheet-like member having a high relative dielectric constant and a low dielectric loss tangent, a molding resin composition capable of molding the sheet-like member, and an electronic component device including the sheet-like member.

[0007] Specific means for solving the above problems include the following aspects. <1> A sheet-like member obtained by molding a molding resin composition containing a thermosetting component and an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles. <2> The sheet-like member according to <1>, wherein the thermosetting component contains at least one selected from the group consisting of maleimide resin, vinyl resin, and (meth)acrylic resin. <3> The sheet-like member according to <1> or <2>, further containing a thermoplastic component. <4> The sheet-like member according to <3>, wherein the thermoplastic component contains at least one selected from the group consisting of thermoplastic resin and thermoplastic elastomer. <5> The sheet-like member according to any one of <1> to <4>, wherein the inorganic filler further contains alumina. <6> The sheet-like member according to any one of <1> to <5>, wherein the content of the inorganic filler is 30% to 90% by volume. <7> The sheet-like member according to any one of <1> to <6>, wherein the thickness is 20 μm to 700 μm. <8> The sheet-like member according to any one of <1> to <7>, for use in embedding an antenna patch for transmitting and receiving data or covering an antenna patch for transmitting and receiving data. <9> A molding resin composition comprising: a thermosetting component; a thermoplastic component; and an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles. <10> The molding resin composition according to <9>, for use in sealing an antenna. <11> An electronic component device comprising: a support member; an electronic component including an antenna arranged on the support member; and the sheet-like member according to any one of <1> to <8>, sealing the electronic component.

[0008] According to the present disclosure, there are provided a sheet-like member having a high relative dielectric constant and a low dielectric loss tangent, a molding resin composition capable of molding the same, and an electronic component device including the same.

[0009] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, each component may contain multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified. In the present disclosure, the "total content of calcium titanate particles and strontium titanate particles" may be read as either "the content of calcium titanate particles" or "the content of strontium titanate particles." In the present disclosure, the "total of calcium titanate particles and strontium titanate particles" may be read as either "calcium titanate particles" or "strontium titanate particles."

[0010] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0011] <Sheet-Shaped Member> The sheet-shaped member of this embodiment is obtained by molding a molding resin composition containing a thermosetting component and an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles.

[0012] From the viewpoint of suppressing transmission loss, it is desirable to achieve a low dielectric loss tangent, and from the viewpoint of miniaturizing substrates, semiconductor packages, antennas, etc., it is preferable to achieve a high relative dielectric constant. The sheet-like member of this embodiment has a high relative dielectric constant and a low dielectric loss tangent. Furthermore, the sheet-like member of this embodiment can be suitably used for sealing electronic components such as antennas by techniques such as lamination and hot plate pressing, and more specifically, can be used for embedding or covering antenna patches for data transmission and reception.

[0013] The molding resin composition is molded into a sheet, which is then heated and dried to obtain a sheet-like member. For example, the molding resin composition is applied to a substrate such as a PET film, and the applied resin composition layer is heated and dried to obtain a sheet-like member.

[0014] The components constituting the molding resin composition used to mold the sheet-like member of this embodiment will be described below. The molding resin composition of this embodiment contains a thermosetting component and an inorganic filler, and may also contain other components such as a thermoplastic component as necessary.

[0015] (Thermosetting Component) The molding resin composition contains a thermosetting component. Examples of the thermosetting component include epoxy resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, vinyl resins, polyimide resins such as maleimide resins, polyamide resins, polyamideimide resins, silicone resins, and (meth)acrylic resins. The molding resin composition may contain only one type of thermosetting component, or may contain two or more types.

[0016] The thermosetting component preferably contains at least one selected from the group consisting of maleimide resins, vinyl resins, and acrylic resins, and more preferably contains at least one maleimide resin, at least one vinyl resin, and at least one acrylic resin independently.

[0017] The content of the thermosetting component in the molding resin composition is, for example, 1% by mass to 30% by mass, preferably 2% by mass to 25% by mass, and more preferably 5% by mass to 20% by mass, based on the total solid content.

[0018] The thermosetting component preferably contains a maleimide resin, more preferably a bismaleimide resin, and even more preferably an aromatic bismaleimide resin. For example, the maleimide resin is preferably a maleimide resin represented by the following general formula (A-1):

[0019]

[0020] In general formula (A-1), X Ａ１ is a divalent organic group. Ａ１ may contain a phenylene group having a substituent, or may contain a condensed ring of an alicyclic ring such as an indane ring and an aromatic ring.

[0021] X Ａ１ may be a divalent organic group represented by the following general formula (A-1).

[0022]

[0023] In general formula (A-2), R Ａ２ and R Ａ３ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ａ２ is a divalent organic group. Ａ２ and n Ａ３ are each independently an integer of 0 to 4. * represents a binding site.

[0024] In general formula (A-2), X Ａ２ may be a divalent organic group having one or more condensed rings of an alicyclic ring such as an indene ring and an aromatic ring, and the two *'s represent bonding sites with the two nitrogen atoms in general formula (A-1). The aromatic bismaleimide resin may contain, for example, a compound represented by the following general formula (M1).

[0025]

[0026] In general formula (M1), R Ｍ１ , R Ｍ２ , RＭ３ , and R Ｍ４ R each independently represents a hydrogen atom or an organic group. Ｍ５ and R Ｍ６ each independently represents a hydrogen atom or an alkyl group. Ｍ represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R Ｍ７ and R Ｍ８ are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R Ｍ９ and R Ｍ１０ R each independently represents a hydrogen atom or an alkyl group. Ｍ１１ , R Ｍ１２ , R Ｍ１３ , and R Ｍ１４ each independently represents a hydrogen atom or an organic group, and nx represents an integer of 1 or more and 20 or less.

[0027] The thermosetting component preferably includes a vinyl resin, such as polybutadiene, butadiene copolymers such as acrylonitrile / butadiene / styrene copolymers and butadiene / styrene copolymers, and polyisoprene.

[0028] The thermosetting component preferably contains a (meth)acrylic resin. Examples of the (meth)acrylic resin include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, dimethyloltricyclodecane dimethacrylate, dimethacrylate of an ethylene oxide adduct of bisphenol A, trimethylolpropane trimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecaethylene glycol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol dimethacrylate, Examples of the acrylate include acrylate, 1,6-hexanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, dimethyloltricyclodecane diacrylate, diacrylate of an ethylene oxide adduct of bisphenol A, diacrylate of a propylene oxide adduct of bisphenol A, trimethylolpropane acrylic acid benzoate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethylene oxide-modified isocyanuric acid triacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, ε-caprolactone-modified tris(acryloyloxyethyl)isocyanurate, and phenyl glycidyl ether acrylate urethane prepolymer.

[0029] When the thermosetting component contains a maleimide resin, the content of the maleimide resin may be 30% by mass to 80% by mass, or 40% by mass to 75% by mass, based on the total amount of the thermosetting component.

[0030] When the thermosetting component contains a vinyl resin, the content of the vinyl resin may be 1% by mass to 50% by mass, or 5% by mass to 40% by mass, based on the total amount of the thermosetting component.

[0031] When the thermosetting component contains an acrylic resin, the content of the acrylic resin may be 5% by mass to 50% by mass, or 15% by mass to 40% by mass, based on the total amount of the thermosetting component.

[0032] (Thermoplastic component) The molding resin composition may contain a thermoplastic component. When the molding resin composition contains a thermoplastic component, a sheet-like member having excellent flexibility can be obtained. Examples of the thermoplastic component include a thermoplastic resin and a thermoplastic elastomer. The molding resin composition may contain only one type of thermoplastic component, or may contain two or more types of thermoplastic components.

[0033] Examples of thermoplastic resins include polyethylene (PE), polypropylene (PP), polycarbonate (PC), polystyrene, polyvinyl chloride, vinyl polymers, saturated polyester, polyamide, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), thermoplastic (meth)acrylic resin, acrylonitrile-ethylene-propylene-diene-styrene copolymer resin (AES resin), styrene-ethylene-butylene-styrene copolymer (SEBS), thermoplastic epoxy resin, and phenoxy resin.

[0034] Examples of the thermoplastic elastomer include styrene-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-isobutylene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene copolymer, and hydrogenated products thereof.

[0035] The content of the thermoplastic component in the molding resin composition is, for example, 1% by mass to 30% by mass, preferably 2% by mass to 25% by mass, and more preferably 5% by mass to 20% by mass, based on the total solid content.

[0036] In the molding resin composition, the mass ratio of the thermoplastic component to the thermosetting component (thermoplastic component / thermosetting component) is preferably 0.05 to 10, more preferably 0.1 to 5, and even more preferably 0.3 to 2.

[0037] (Inorganic Filler) The molding resin composition contains an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles.

[0038] -Calcium titanate particles and strontium titanate- The shape of the calcium titanate particles or strontium titanate is not particularly limited, and examples thereof include spherical, elliptical, and irregular shapes. The calcium titanate particles or strontium titanate particles may be crushed. The calcium titanate particles or strontium titanate particles may be surface-treated. The calcium titanate particles or strontium titanate particles may be a mixture of two or more fillers having different volume average particle sizes.

[0039] The volume average particle size of the calcium titanate particles or the volume average particle size of the strontium titanate may be 0.1 μm to 100 μm, 0.2 μm to 80 μm, 0.5 μm to 30 μm, 0.5 μm to 10 μm, or 0.5 μm to 8 μm. The volume average particle size of the calcium titanate particles and the volume average particle size of the strontium titanate particles can be measured as follows. A molding resin composition is placed in a crucible and left at 800°C for 4 hours to be incinerated. The resulting ash is observed with an SEM, separated by shape, and the particle size distribution is determined from the observed image. From the particle size distribution, the volume average particle size of the calcium titanate particles and the volume average particle size of the strontium titanate particles can be determined as the volume average particle size (D50). The volume average particle size of calcium titanate particles and the volume average particle size of strontium titanate particles may be determined by measurement using a laser diffraction / scattering particle size distribution measuring device (for example, LA920 manufactured by Horiba, Ltd.).

[0040] From the viewpoint of the balance between the dielectric constant and the dielectric loss tangent, the total content of the calcium titanate particles and the strontium titanate particles is preferably 1% by mass to 99% by mass, more preferably 3% by mass to 97% by mass, and even more preferably 5% by mass to 95% by mass, based on the total inorganic filler.

[0041] In the molding resin composition, the total mass ratio of the calcium titanate particles and strontium titanate particles to the total of the thermosetting component and the thermoplastic component (total of the calcium titanate particles and strontium titanate particles / total of the thermosetting component and the thermoplastic component) is preferably 0.5 to 10, more preferably 0.7 to 5, and even more preferably 1 to 4, from the viewpoint of the balance between the dielectric loss tangent and the fluidity.

[0042] -Alumina- The inorganic filler may further contain alumina. One type of alumina particles may be used alone, or two or more types may be used in combination. The alumina particles may be a mixture of two or more types of fillers having different volume average particle sizes.

[0043] The shape of the alumina particles is not particularly limited, and examples thereof include spherical, elliptical, and irregular shapes. The alumina particles may be crushed or surface-treated.

[0044] The content of the alumina particles is preferably 1% by mass to 99% by mass, more preferably 3% by mass to 95% by mass, and even more preferably 5% by mass to 90% by mass, based on the total amount of the inorganic filler.

[0045] The volume average particle size of the alumina particles is not particularly limited. The volume average particle size of the alumina particles is preferably 0.2 μm to 100 μm, more preferably 0.5 μm to 50 μm, and even more preferably 1.0 μm to 10 μm. When the volume average particle size is 0.2 μm or more, the increase in viscosity of the molding resin composition tends to be further suppressed. When the volume average particle size is 100 μm or less, the filling property of the molding resin composition tends to be further improved. The volume average particle size of the alumina particles can be determined by placing the molding resin composition in a crucible and leaving it at 800°C for 4 hours to incinerate it. The resulting ash is observed with an SEM, separated by shape, and the particle size distribution is determined from the observed image. From the particle size distribution, the volume average particle size of the alumina particles can be determined as the volume average particle size (D50). Alternatively, the volume average particle size of the alumina particles may be determined by measurement using a laser diffraction / scattering particle size distribution analyzer (e.g., HORIBA, Ltd., LA920).

[0046] The content of alumina particles and the total content of calcium titanate particles and strontium titanate particles relative to the entire inorganic filler can be determined by the following method. A thin slice sample of the cured molding resin composition is imaged using a scanning electron microscope (SEM). An arbitrary area S is identified in the SEM image, and the total area A of the inorganic fillers contained in area S is determined. Next, an SEM-EDX (energy dispersive X-ray spectrometer) is used to identify the elements of the inorganic filler, thereby determining the total area B of specific particles such as alumina particles, calcium titanate particles, and strontium titanate particles contained within the total area A of the inorganic filler. The total area B of the specific particles is divided by the total area A of the inorganic filler, and converted into a percentage (%), which is the content (volume %) of the specific particles relative to the entire inorganic filler. The content (mass %) of the specific particles can then be calculated from the specific gravity of the specific particles. The area S is set to be sufficiently large relative to the size of the inorganic filler. For example, it is set to be large enough to contain 100 or more inorganic fillers. The area S may be the sum of the areas of a plurality of cut surfaces.

[0047] The total content of alumina, calcium titanate particles, and strontium titanate particles may be 70% by mass to 100% by mass, or 90% by mass to 100% by mass, based on the total amount of the inorganic filler.

[0048] The inorganic filler may include fillers other than alumina particles, calcium titanate particles, or strontium titanate particles.

[0049] -Other Fillers- The inorganic filler may contain fillers other than alumina particles, calcium titanate particles, or strontium titanate. The shape of the other fillers is not particularly limited, and examples include spherical, elliptical, and irregular shapes. The other fillers may also be crushed. The other fillers may also be surface-treated. One type of other filler may be used alone, or two or more types may be used in combination. The other filler may also be a mixture of two or more fillers having different volume average particle sizes.

[0050] The type of other filler is not particularly limited. Specific examples of the material of the other filler include inorganic materials such as silica, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having a flame-retardant effect may also be used as the other filler. Examples of inorganic fillers having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

[0051] The other filler may contain titanium compound particles other than calcium titanate particles or strontium titanate. Examples of titanium compound particles other than calcium titanate particles or strontium titanate include barium titanate particles, potassium titanate particles, magnesium titanate particles, lead titanate particles, aluminum titanate particles, lithium titanate, and titanium oxide particles. However, from the viewpoint of keeping the dielectric tangent of the sheet-shaped member low, the content of barium titanate particles is preferably less than 1% by mass, more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass, relative to the total inorganic filler. In other words, it is preferable that the inorganic filler does not contain barium titanate particles or contains barium titanate particles at the above content. Furthermore, the total content of titanium compound particles other than calcium titanate particles or strontium titanate particles may be less than 1% by mass, less than 0.5% by mass, or less than 0.1% by mass, relative to the total inorganic filler. That is, the inorganic filler may not contain any titanium compound particles other than calcium titanate particles or strontium titanate particles, or may contain any titanium compound particles other than calcium titanate particles or strontium titanate particles in the above content.

[0052] The preferred ranges of the volume average particle diameters of the other fillers are the same as the preferred ranges of the volume average particle diameter of the alumina particles.

[0053] -Content and characteristics of inorganic filler- From the viewpoint of controlling the fluidity and strength of the molding resin composition, the content of the inorganic filler contained in the molding resin composition or the sheet-shaped member is preferably 30% by volume to 90% by volume, more preferably 40% by volume to 90% by volume, and even more preferably 50% by volume to 85% by volume, based on the entire molding resin composition or the sheet-shaped member.

[0054] The content (volume %) of inorganic filler in a molding resin composition can be determined by the following method. A thin section sample of the cured molding resin composition is imaged using a scanning electron microscope (SEM). An arbitrary area S is identified in the SEM image, and the total area A of the inorganic fillers contained in area S is determined. The total area A of the inorganic fillers is divided by area S to convert it to a percentage (%), and this value is used as the content (volume %) of inorganic filler in the molding resin composition. Area S is set to an area sufficiently large relative to the size of the inorganic filler. For example, it is set to a size that contains 100 or more inorganic fillers. Area S may be the sum of multiple cross sections. The inorganic filler may have a bias in its presence in the direction of gravity when the molding resin composition is cured. In this case, when imaging with an SEM, the entire cured product is imaged in the direction of gravity, and the area S containing the entire cured product in the direction of gravity is determined.

[0055] In the molding resin composition, the mass ratio of the inorganic filler to the total of the thermosetting component and the thermoplastic component (inorganic filler / total of the thermosetting component and the thermoplastic component) is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20, from the viewpoint of the balance between the dielectric loss tangent and the fluidity.

[0056] (Initiator) The molding resin composition may contain an initiator as needed. Examples of initiators include radical polymerization initiators that generate free radicals by heat. Specific examples of initiators include inorganic peroxides, organic peroxides, and azo compounds. Examples of inorganic peroxides include potassium persulfate (dipotassium peroxosulfate), sodium persulfate, and ammonium persulfate. Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane, hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide, α,α'-di(t-butylperoxy)diisopropylbenzene, dicumyl peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)cyclohexyl dialkyl peroxides such as dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, diacyl peroxides such as dibenzoyl peroxide and di(4-methylbenzoyl) peroxide, peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate, and peroxyesters such as 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexyl peroxybenzoate, t-butyl peroxybenzoate, and t-butylperoxy 2-ethylhexanoate. Examples of azo compounds include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl.

[0057] When the molding resin composition contains an initiator, the content of the initiator is, for example, 0.1 to 8.0 parts by mass per 100 parts by mass of the thermosetting component, and from the viewpoint of curability, 0.5 to 6.0 parts by mass is more preferable. When the content of the initiator is 8.0 parts by mass or less, volatile matter is less likely to be generated, and the occurrence of voids during curing tends to be further suppressed. Furthermore, when the content of the initiator is 1 part by mass or more, curability tends to be better.

[0058] (Various Additives) In addition to the components described above, the molding resin composition of this embodiment may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, stress relaxation agents, curing accelerators, curing agents, and polymerization inhibitors, as exemplified below, and may also contain solvents such as toluene and methyl ethyl ketone. The molding resin composition of this embodiment may contain various additives known in the technical field as needed, in addition to the additives exemplified below.

[0059] (Coupling Agent) The molding resin composition in this embodiment may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the molding resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate-based compounds, and aluminum / zirconium-based compounds.

[0060] When the molding resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, adhesion to the adherend tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, moldability of the package tends to be further improved.

[0061] (Characteristics of Molding Resin Composition) The relative dielectric constant at 10 GHz of a cured product obtained by molding the molding resin composition of this embodiment under the conditions described in the Examples below may be 10.0 to 30.0, 15.0 to 28.0, or 20.0 to 26.0, from the viewpoint of a balance between antenna miniaturization and a low dielectric loss tangent. The relative dielectric constant may be 30 to 45. The relative dielectric constant is measured at a temperature of 25±3°C using a dielectric constant measuring device (for example, Agilent Technologies, product name "Network Analyzer N5227A").

[0062] The dielectric loss tangent at 10 GHz of a cured product obtained by molding the molding resin composition of this embodiment under the conditions described in the Examples below may be 0.010 or less, 0.005 or less, or even 0.003 or less, from the viewpoint of reducing transmission loss. The lower limit of the dielectric loss tangent at 10 GHz of the cured product is not particularly limited, and may be, for example, 0.001. The dielectric loss tangent is measured at a temperature of 25±3°C using a dielectric constant measuring device (for example, Agilent Technologies, product name "Network Analyzer N5227A").

[0063] (Uses of Sheet-Like Member and Molding Resin Composition) The sheet-like member and molding resin composition of this embodiment can be applied, for example, to the production of electronic component devices, particularly high-frequency devices, as described below. The molding resin composition of this embodiment may be used to seal electronic components in high-frequency devices. In particular, in recent years, with the spread of fifth-generation mobile communication systems (5G), semiconductor packages (PKGs) used in electronic component devices have become more highly functional and smaller. As PKGs become smaller and more functional, development of antenna-in-package (AiP), which is a PKG with antenna functionality, is also progressing. In AiP, radio waves used for communication are becoming higher in frequency to accommodate the increase in the number of channels associated with the diversification of information, and sealing materials are required to have both a high dielectric constant and a low dielectric loss tangent. As described above, the molding resin composition of this embodiment can provide a sheet-like member that has both a high dielectric constant and a low dielectric loss tangent. Therefore, in high-frequency devices, the molding resin composition is particularly suitable for antenna-in-package (AiP) applications in which an antenna placed on a support member is encapsulated with the molding resin composition. In electronic component devices including an antenna, such as an antenna-in-package, heat is generated by power supply when a power supply amplifier is provided on the opposite side of the antenna. From the viewpoint of improving heat dissipation, the molding resin composition used in manufacturing electronic component devices preferably contains alumina particles as an inorganic filler.

[0064] When the sheet-shaped member of the present disclosure is used to seal electronic components such as antennas, the electronic components may be sealed with the sheet-shaped member by techniques such as lamination, hot plate pressing, etc. The sheet-shaped member of the present disclosure can suitably seal electronic components by techniques such as lamination, hot plate pressing, etc.

[0065] The thickness of the sheet-like member of the present disclosure may be 20 μm to 700 μm, 20 μm to 600 μm, or 100 μm to 500 μm.

[0066] An electronic component device according to an embodiment of the present disclosure includes a support member, an electronic component disposed on the support member, and a sheet-like member of the molding resin composition encapsulating the electronic component. Examples of the electronic component device include a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, on which electronic components (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, and antennas) are mounted, and the resulting electronic component region is encapsulated with the molding resin composition (e.g., a high-frequency device).

[0067] The type of the support member is not particularly limited, and a support member generally used in the manufacture of electronic component devices can be used. The electronic component may include an antenna, or may include an antenna and an element other than an antenna. The antenna is not limited as long as it functions as an antenna, and may be an antenna element or wiring.

[0068] In the electronic component device of the present embodiment, if necessary, another electronic component may be disposed on the surface of the support member opposite to the surface on which the electronic component is disposed. The other electronic component may be encapsulated with the molding resin composition described above, or with another resin composition, or may not be encapsulated.

[0069] (Method for manufacturing an electronic component device) The method for manufacturing an electronic component device according to this embodiment includes the steps of placing electronic components on a support member and sealing the electronic components with the sheet-like member described above. The method for carrying out each of the above steps is not particularly limited, and can be carried out using a general method. Furthermore, the types of support member and electronic components used in manufacturing the electronic component device are not particularly limited, and support members and electronic components commonly used in manufacturing electronic component devices can be used.

[0070] Methods for sealing electronic components using the sheet-like member include lamination, hot plate pressing, etc. By using the sheet-like member, the sealing process can be simplified and the size can be increased.

[0071] The above-described embodiment will be specifically described below using examples, but the scope of the above-described embodiment is not limited to these examples.

[0072] <Preparation of Molding Resin Composition 1> The components shown below were mixed in the blending ratios (parts by mass) shown in Table 1 to prepare molding resin composition 1 of Example 1.

[0073] ・Epoxy resin 1: biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq ・Epoxy resin 2: biphenyl type epoxy resin, epoxy equivalent 192 g / eq ・Curing agent 1: active ester compound, DIC Corporation, product name "EXB-8" ・Curing agent 2: phenolic curing agent, aralkyl type phenolic resin, hydroxyl group equivalent 170 g / eq ・Curing agent 3: melamine-modified phenolic resin, reactive group equivalent 120 g / eq ・Stress relaxation agent 1: indene-styrene-coumarone copolymer ・Stress relaxation agent 2: triarylphosphine oxide ・Curing accelerator: trialkylphosphine / 1,4-benzoquinone adduct ・Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane ・Mold release agent: montan acid ester wax ・Colorant: carbon black Inorganic filler 1: calcium titanate particles, volume average particle size: 23.0 μm, shape: irregular Inorganic filler 2: calcium titanate particles, volume average particle size: 0.2 μm, shape: irregular Inorganic filler 3: calcium titanate particles, volume average particle size: 4.0 μm, shape: irregular Inorganic filler 4: alumina particles, volume average particle size: 5.7 μm, shape: spherical Solvent: MEK (methyl ethyl ketone)

[0074]

[0075] <Preparation of molding resin composition 2> The components shown below were mixed in the blending ratios (parts by mass) shown in Table 2, and the mixture was applied to one side of a 50 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name "Purex A53") in a thickness such that the thickness of the resin layer after drying would be 200 μm. This was then heated and dried at 105°C for 5 minutes, thereby preparing molding resin composition 2 of Example 2. (Thermosetting components) Thermosetting component 1: Aromatic bismaleimide resin containing an indane ring: number average molecular weight = 1,300 (MEK solution, N.V. value 64.2) Thermosetting component 2: 1,2-polybutadiene (number average molecular weight = 1,200, vinyl group content = 85% or more) Thermosetting component 3: 1,12-dodecanediol dimethacrylate (Thermoplastic components) Thermoplastic component 1: Hydrogenated styrene-based thermoplastic elastomer (toluene solution, N.V. value 31.9) (Initiators) Initiator 1: 1,3-di(t-butylperoxyisopropyl)benzene Initiator 2: Isocyanate masked imidazole, Daiichi Kogyo Seiyaku Co., Ltd., product name "G-8009L" (MEK solution, N.V. value 50) Coupling agent: 3-methacryloxypropyltrimethoxysilane Inorganic filler 1: calcium titanate particles, volume average particle size: 23.0 μm, shape: irregular Inorganic filler 2: calcium titanate particles, volume average particle size: 0.2 μm, shape: irregular Inorganic filler 3: calcium titanate particles, volume average particle size: 4.0 μm, shape: irregular Inorganic filler 4: alumina particles, volume average particle size: 5.7 μm, shape: spherical

[0076]

[0077] <Preparation of molding resin composition 3> The components shown below were mixed in the blending ratios (parts by mass) shown in Table 3 to prepare molding resin composition 1 of the comparative example.

[0078] ・Epoxy resin 1: biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq ・Epoxy resin 2: biphenyl type epoxy resin, epoxy equivalent 192 g / eq ・Curing agent 1: active ester compound, DIC Corporation, product name "EXB-8" ・Curing agent 2: phenolic curing agent, aralkyl type phenolic resin, hydroxyl group equivalent 170 g / eq ・Curing agent 3: melamine-modified phenolic resin, reactive group equivalent 120 g / eq ・Stress relaxation agent 1: indene-styrene-coumarone copolymer ・Stress relaxation agent 2: triarylphosphine oxide ・Curing accelerator: trialkylphosphine / 1,4-benzoquinone adduct ・Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane ・Mold release agent: Montan acid ester wax ・Colorant: carbon black ・Inorganic filler 5: silica, volume average particle size: 10.6 μm, shape: spherical Inorganic filler 6: silica, volume average particle size: 0.75 μm, shape: spherical Solvent: MEK (methyl ethyl ketone)

[0079]

[0080] The volume-average particle size of each inorganic filler was a value obtained by the following measurement. Specifically, the inorganic filler was first added to a dispersion medium (water) in an amount ranging from 0.01% by mass to 0.1% by mass, and the mixture was dispersed in a bath-type ultrasonic cleaner for 5 minutes. Five milliliters of the resulting dispersion was poured into a cell, and the particle size distribution was measured at 25°C using a laser diffraction / scattering particle size distribution analyzer (HORIBA, Ltd., LA920). The particle size at an integrated value of 50% (volume basis) in the resulting particle size distribution was taken as the volume-average particle size.

[0081] <Evaluation of Molding Resin Compositions> The molding resin compositions of Examples 1 and 2 and Comparative Example 1 were evaluated as follows.

[0082] (Measurement of Thermal Expansion Coefficient) The molding resin compositions of Examples 1 and 2 and Comparative Example 1 were molded under conditions of 180°C / 2 MPa to obtain plate-shaped cured products. The obtained cured products were processed using a precision cutter to a size of 5 mm length, 5 mm width, and 1 mm thickness. The thermal expansion coefficients of the processed cured products were measured using a TMA tester (Seiko Instruments Inc., SS6100). Measurements were performed in tensile mode at 30 to 300°C, with a heating rate of 5°C / min and a load of 4 g. The thermal expansion coefficient (ppm / °C) between 30°C and 120°C was designated CTE α1, and the thermal expansion coefficient (ppm / °C) between 200°C and 260°C was designated CTE α2. The results are shown in Table 4.

[0083] (Glass Transition Temperature) TMA (thermomechanical analysis) was performed on the cured product prepared in the same manner as in the measurement of the thermal expansion coefficient using a TMA tester (Seiko Instruments Inc., SS6100). The intersection of the tangent lines before and after the inflection point of the obtained chart was taken as the glass transition temperature. The heating rate was 5°C / min. The results are shown in Table 4.

[0084] (Flexural Modulus) Using the molding resin compositions of Examples 1 and 2 and Comparative Example 1, plate-shaped cured products (80 mm long, 10 mm wide, 4 mm thick) were obtained in the same manner as in the measurement of the thermal expansion coefficient. The flexural modulus values ​​of the cured products were calculated by performing three-point bending measurement based on JIS K7171 (2016). The evaluation device used was an Instron 5948 (manufactured by Instron Corporation). The results are shown in Table 4.

[0085] (Relative permittivity and dielectric dissipation factor) Using the molding resin compositions of Examples 1 and 2 and Comparative Example 1, plate-shaped cured products (70 mm long, 30 mm wide, 0.3 mm thick) were obtained in the same manner as in the measurement of the thermal expansion coefficient. Using these plate-shaped cured products as test specimens, the relative permittivity and dielectric dissipation factor were measured at a temperature of 25±3°C and 10 GHz using a dielectric constant measuring device (Agilent Technologies, product name "Network Analyzer N5227A" and SPDR dielectric resonator). The results are shown in Table 4 ("Relative permittivity" and "Dielectric dissipation factor" in the table).

[0086] The evaluation results of Examples 1 and 2 and Comparative Example 1 are shown in Table 4.

[0087]

[0088] As shown in Table 4, the molding resin compositions of Examples 1 and 2 tended to give cured products having a higher relative dielectric constant and a reduced dielectric loss tangent to the same extent as the molding resin composition of Comparative Example 1. Furthermore, Example 2 gave a softer sheet having a lower flexural modulus than Example 1 and Comparative Example 1.

[0089] The disclosure of Japanese Patent Application No. 2023-196157, filed on November 17, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A sheet-like member obtained by molding a molding resin composition containing: a thermosetting component; and an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles.

2. The sheet-like member according to claim 1, wherein the thermosetting component contains at least one resin selected from the group consisting of maleimide resins, vinyl resins and (meth)acrylic resins.

3. The sheet-like member according to claim 1, further comprising a thermoplastic component.

4. The sheet-like member according to claim 3, wherein the thermoplastic component includes at least one selected from the group consisting of a thermoplastic resin and a thermoplastic elastomer.

5. The sheet member according to claim 1, wherein the inorganic filler further contains alumina.

6. The sheet-like member according to claim 1, wherein the content of the inorganic filler is 30% by volume to 90% by volume.

7. The sheet-like member according to claim 1, which has a thickness of 20 μm to 700 μm.

8. The sheet-like member according to claim 1, for use in embedding an antenna patch for transmitting and receiving data or for covering an antenna patch for transmitting and receiving data.

9. A molding resin composition comprising: a thermosetting component; a thermoplastic component; and an inorganic filler containing at least one of calcium titanate particles and strontium titanate particles.

10. The molding resin composition according to claim 9, which is used for sealing an antenna.

11. An electronic component device comprising: a support member; an electronic component including an antenna arranged on the support member; and a sheet-like member according to any one of claims 1 to 8 that encapsulates the electronic component.

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