Sealing material composition and electronic component device

Abstract

This sealing material composition contains an epoxy resin, a curing agent, and an inorganic filler, and in the composition, the ratio of 14C to 12C (14C / 12C ratio) is 0.05×10-12 to 1.2×10-12.

Description

Encapsulating material composition and electronic component device

[0001] The present disclosure relates to an encapsulant composition and an electronic component device.

[0002] In the field of element encapsulation of electronic component devices such as transistors, integrated circuits (ICs), and large-scale integrations (LSIs), resin encapsulation has traditionally been mainstream from the standpoints of productivity, cost, etc., and encapsulant compositions containing epoxy resins have been widely used. The reason encapsulant compositions containing epoxy resins are used is because epoxy resins have an excellent balance of various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products.

[0003] On the other hand, the use of fossil resources is facing problems such as resource depletion and the carbon dioxide (CO ) generated during incineration. ２ ) is a concern for global warming. Therefore, we must reduce the use of fossil resources and CO2 derived from fossil resources. ２ From the perspective of reducing emissions, there is a growing movement to replace fossil fuel resources with carbon-neutral biomass-derived materials (bioplastics).

[0004] As an example of a biomass-derived material, naturally occurring epichlorohydrin derivatives are known (see, for example, Patent Document 1).

[0005] Special Publication No. 2013-541531

[0006] Encapsulant compositions used for encapsulating elements in electronic component devices have high required physical properties and low tolerance for impurities, which are different from the required characteristics of general-purpose resin materials. However, no encapsulant composition that satisfies these required characteristics and uses a biomass-derived resin has been known. The present disclosure has been made in view of the above-mentioned conventional circumstances, and aims to provide an encapsulant composition that satisfies the required characteristics as an encapsulant and contributes to carbon neutrality, and an electronic component device using the same.

[0007] Specific means for achieving the above object are as follows: <1> A composition containing an epoxy resin, a curing agent, and an inorganic filler,１４ C's １２ Ratio to C ( １４ C / １２ C ratio) is 0.05 × 10 ―１２ ~1.2 × 10 ―１２ <2> The encapsulant composition according to the present invention, １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ <3> The encapsulant composition according to <1>, wherein the content of the epoxy resin in the total epoxy resin is １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ <4> The encapsulant composition according to <1> or <2>, wherein the ratio of the epoxy resin is 50% by mass to 99% by mass. １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ <5> The encapsulant composition according to any one of <1> to <3>, wherein the ratio of the total amount of the curing agent to the total amount of the curing agent is 1 to 2. １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２<6> The encapsulant composition according to any one of <1> to <4>, wherein the ratio of the curing agent is 50% by mass to 99% by mass. <6> The encapsulant composition according to any one of <1> to <5>, wherein the mass-based content of the ammonium salt is 10,000 ppm or less. <7> The encapsulant composition according to any one of <1> to <6>, wherein the mass-based content of the ammonium salt is 100 ppm or more. <8> The encapsulant composition according to any one of <1> to <7>, wherein the mass-based content of the metal cation is 10,000 ppm or less. <9> The encapsulant composition according to any one of <1> to <8>, wherein the mass-based content of the metal cation is 100 ppm or more. <10> The encapsulant composition according to any one of <1> to <9>, wherein the mass-based content of the metal cation is 100 ppm or more. <11> The encapsulant composition according to any one of <1> to <9>, which is solid at 25°C. <12> The encapsulant composition according to any one of <1> to <11>, wherein the content of the inorganic filler is 70% by mass to 90% by mass. <13> The encapsulant composition according to any one of <1> to <11>, wherein the content of the inorganic filler is more than 0% by mass and not more than 70% by mass. <14> An electronic component device comprising a support member, an electronic component placed on the support member, and a cured product of the encapsulant composition according to any one of <1> to <13> that encapsulates the electronic component.

[0008] According to the present disclosure, it is possible to provide an encapsulant composition that satisfies the required properties as an encapsulant and contributes to carbon neutrality, and an electronic component device using the same.

[0009] Hereinafter, embodiments of 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.

[0010] 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. 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, particles corresponding to each component may include 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.

[0011] In the present disclosure, １４ C / １２ The C ratio is a value measured by ASTM 6866 Method B. Specifically, it is as follows: the sample to be measured is chemically converted into carbon dioxide, and the generated carbon dioxide is further reduced to graphite. This graphite is ionized, and １２ C. １３ C and １４ The rate of C is measured by an accelerator. １４ The ratio of C is accurately measured. From the measurement results obtained, １４ C / １２ In the present disclosure, biomass-derived materials such as biomass-derived epoxy resins and biomass-derived curing agents refer to: １４ C's １２ Ratio to C ( １４ C / １２ C ratio) is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ In addition, in the present disclosure, a fossil resource-derived material such as an epoxy resin derived from a fossil resource refers to a material １４ C / １２C ratio is 0.10 x 10 ―１２ This refers to materials that are less than

[0012] <Sealant composition> The encapsulant composition of the present disclosure includes an epoxy resin, a curing agent, and an inorganic filler, １４ C's １２ Ratio to C ( １４ C / １２ C ratio) is 0.05 × 10 ―１２ ~1.2 × 10 ―１２ The encapsulant composition of the present disclosure includes an epoxy resin, a curing agent, and an inorganic filler, １４ C / １２ C ratio is 0.05 x 10 ―１２ ~1.2 × 10 ―１２ This makes it possible to satisfy the required properties as a sealing material and also contribute to carbon neutrality.

[0013] Carbon-neutral biomass-derived materials tend to contain more impurities than fossil-derived materials. However, because encapsulant compositions generally contain a large amount of inorganic filler, the ratio of biomass-derived materials in the encapsulant composition can be kept low, thereby making it possible to reduce the impact of impurities that may be contained in the biomass-derived materials. Therefore, the present inventors attempted to apply biomass-derived materials to encapsulant compositions, and have completed the present invention.

[0014] In the encapsulant composition of the present disclosure, １４ C / １２ C ratio is 0.05 x 10 ―１２ ~1.2 × 10 ―１２ It is said that 0.10 × 10 ―１２ ~1.1 x 10 ―１２ is preferable, and 0.30 × 10 ―１２ ~1.1 x 10 ―１２ More preferably, 0.50 × 10 ―１２ ~1.1 x 10 ―１２ is more preferably 0.70 × 10 ―１２ ~1.1 x 10 ―１２ is particularly preferred.

[0015] In the encapsulant composition of the present disclosure, all of the materials constituting the encapsulant composition may be biomass-derived materials, or only a part of the materials may be biomass-derived materials. In general, the components of the encapsulant composition other than the inorganic filler are mainly composed of an epoxy resin and a curing agent. Therefore, １４ C / １２ C ratio 0.05 x 10 ―１２ ~1.2 × 10 ―１２ To achieve this, it is preferable to use a biomass-derived material for at least one of the epoxy resin and the curing agent, and it is more preferable to use a biomass-derived material for both the epoxy resin and the curing agent.

[0016] The biomass-derived materials that can be included in the sealant composition of the present disclosure are preferably obtained from raw materials that do not compete with food production, such as the Anacardiaceae plant Rhus verniciflua, aphids, onion skins, waste oil, lignin, and pine resin.

[0017] The encapsulant composition of the present disclosure will be described in detail below. The encapsulant composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and may contain other components as needed.

[0018] (Epoxy Resin) The encapsulant composition of the present disclosure contains an epoxy resin. １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ is preferable, and 0.30 × 10 ―１２ ~1.1 x 10 ―１２ More preferably, 0.50 × 10 ―１２ ~1.1 x 10 ―１２ is more preferably 0.70 × 10 ―１２ ~1.1 x 10 ―１２ The epoxy resin may be used alone or in combination of two or more. When two or more epoxy resins are used in combination, the epoxy resin １４ C / １２ The C ratio is the ratio of the epoxy resins in a mixture of two or more types. １４ C / １２Furthermore, when two or more epoxy resins are used in combination, all of the epoxy resins may be biomass-derived epoxy resins, or a biomass-derived epoxy resin may be used in combination with another epoxy resin.

[0019] Examples of biomass-derived epoxy resins include epoxy resins obtained by epoxidizing biomass-derived alcohols, biomass-derived phenols, biomass-derived carboxylic acids, etc. Examples of biomass-derived alcohols include glucose, sorbitol, glycerin, polyglycerin, propanediol, butanediol, isosorbide, etc. Examples of biomass-derived phenols include tannic acid, quercetin, cardanol, lignin-derived substances, etc. Examples of biomass-derived carboxylic acids include carboxylic acids obtained by oxidizing the above biomass-derived alcohols, etc. Biomass-derived epoxy resins can be obtained by epoxidizing the above alcohols, etc. Methods for epoxidizing the above alcohols, etc. are not particularly limited, and conventionally known methods can be used.

[0020] Specific examples of biomass-derived epoxy resins include Denacol from Nagase ChemteX Corporation. Further examples include various materials that are scheduled to be marketed by Sakata Inx Corporation, Mitsubishi Chemical Corporation, Mitsui Chemicals, Inc., and the like.

[0021] The encapsulant composition of the present disclosure may contain an epoxy resin other than the biomass-derived epoxy resin, such as a so-called fossil resource-derived epoxy resin. Specific examples of such epoxy resins include novolac epoxy resins obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; triphenylmethane epoxy resins obtained by epoxidizing a triphenylmethane phenolic resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst; and copolymers obtained by epoxidizing a novolac resin obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. diphenylmethane-type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins which are diglycidyl ethers of bisphenol S, etc.; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which active hydrogen atoms bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. are substituted with glycidyl groups; and dicyclopentadiene-type epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenolic compound.Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are produced by epoxidizing an intramolecular olefin bond; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include pentadiene-modified epoxy resins, cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins, naphthalene-type epoxy resins which are glycidyl ethers of naphthalene ring-containing phenolic resins, halogenated phenol novolac-type epoxy resins, hydroquinone-type epoxy resins, trimethylolpropane-type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Epoxidized acrylic resins are also suitable as epoxy resins. These other epoxy resins may be used alone or in combination of two or more.

[0022] When a biomass-derived epoxy resin is used in combination with another epoxy resin, the ratio of the biomass-derived epoxy resin to the total epoxy resin is, in one embodiment, preferably 50% by mass to 99% by mass, more preferably 60% by mass to 97% by mass, and even more preferably 70% by mass to 95% by mass, and in another embodiment, preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and even more preferably 20% by mass to 30% by mass.

[0023] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. When two or more epoxy resins are used in combination, the epoxy equivalent of the mixture of two or more epoxy resins preferably falls within the above range. In the present disclosure, the epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0024] When the epoxy resin is solid at 25° C., the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and reflow resistance, the softening point or melting point of the epoxy resin is preferably 40° C. to 180° C., and from the viewpoint of handleability during preparation of the encapsulant composition, it is more preferably 50° C. to 130° C. The melting point or softening point of the epoxy resin is a value measured by differential scanning calorimetry (DSC) or a method in accordance with JIS K 7234:1986 (ring and ball method).

[0025] (Curing Agent) The encapsulant composition of the present disclosure contains a curing agent. Examples of the curing agent include an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, and an active ester compound. １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２ is preferable, and 0.30 × 10 ―１２ ~1.1 x 10 ―１２ More preferably, 0.50 × 10 ―１２ ~1.1 x 10 ―１２ is more preferably 0.70 × 10 ―１２ ~1.1 x 10 ―１２ The curing agent may be used alone or in combination of two or more. When two or more curing agents are used in combination, １４ C / １２ The C ratio is the ratio of the mixture of two or more curing agents. １４ C / １２When two or more curing agents are used in combination, all of the curing agents may be biomass-derived curing agents, or a biomass-derived curing agent may be used in combination with another curing agent. Examples of other curing agents include so-called fossil resource-derived curing agents.

[0026] Specific examples of the amine curing agent include aromatic amine curing agents having one aromatic ring, such as m-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, and 2,4-diaminoanisole; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,4'-diaminodiphenylmethane; aromatic amine curing agents having two aromatic rings, such as 3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolysis condensates of aromatic amine curing agents; aromatic amine curing agents having a polyether structure, such as polytetramethylene oxide di-p-aminobenzoate and polytetramethylene oxide di-para-aminobenzoate; condensates of aromatic diamines and epichlorohydrin; and reaction products of aromatic diamines and styrene.

[0027] Examples of acid anhydride curing agents include phthalic anhydride, maleic anhydride, methyl himic anhydride, himic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride having multiple alkyl groups obtained by Diels-Alder reaction from maleic anhydride and a diene compound, and various cyclic acid anhydrides such as dodecenyl succinic anhydride.

[0028] Examples of phenolic curing agents include novolak resins obtained by condensing or co-condensing at least one selected from the group consisting of phenolic compounds (e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F) and naphthol compounds (e.g., α-naphthol, β-naphthol, and dihydroxynaphthalene) with an aldehyde compound (e.g., formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde) under an acidic catalyst; phenol-aralkyl resins; biphenyl-aralkyl resins; and naphthol-aralkyl resins. Further examples of phenolic curing agents include the biomass-derived phenols described above.

[0029] The type of active ester compound is not particularly limited as long as it has one or more ester groups in the molecule that react with epoxy groups. Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds. Examples of active ester compounds include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds containing an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. Ester compounds containing an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring. Specific examples of active ester compounds include aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group. Among these, aromatic esters are preferred which are obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group, using as raw materials a mixture of an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms on the aromatic ring of benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfonic acid, etc. have been substituted with carboxy groups, a monohydric phenol in which one hydrogen atom on the aromatic ring has been substituted with a hydroxyl group, and a polyhydric phenol in which 2 to 4 hydrogen atoms on the aromatic ring have been substituted with hydroxyl groups. That is, aromatic esters having structural units derived from the aromatic carboxylic acid component, structural units derived from the monohydric phenol, and structural units derived from the polyhydric phenol are preferred.

[0030] The hardener is １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 × 10 ―１２Phenolic curing agents are preferred because these materials are readily available. When a biomass-derived curing agent is used in combination with another curing agent, the ratio of the biomass-derived curing agent to the entire curing agent is, in one embodiment, preferably 50% to 99% by mass, more preferably 60% to 97% by mass, and even more preferably 70% to 95% by mass. In another embodiment, it is preferably 10% to 40% by mass, more preferably 15% to 35% by mass, and even more preferably 20% to 30% by mass. When a biomass-derived phenolic curing agent is used as the curing agent, the ratio of the biomass-derived phenolic curing agent to the entire curing agent is, in one embodiment, preferably 50% to 99% by mass, more preferably 60% to 97% by mass, and even more preferably 70% to 95% by mass. In another embodiment, it is preferably 10% to 40% by mass, more preferably 15% to 35% by mass, and even more preferably 20% to 30% by mass.

[0031] In the encapsulant composition of the present disclosure, the content of the curing agent is not particularly limited, and the ratio of the equivalent number of the functional group of the curing agent (for example, an amino group in the case of an amine-based curing agent, a phenolic hydroxyl group in the case of a phenol-based curing agent, an acid anhydride group in the case of an acid anhydride-based curing agent, or an ester group in the case of an active ester compound) to the equivalent number of the epoxy resin (equivalent number of curing agent / equivalent number of epoxy resin) is preferably set in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and even more preferably in the range of 0.8 to 1.2.

[0032] (Inorganic Filler) The encapsulant composition of the present disclosure contains an inorganic filler. The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as silica, such as fused silica and crystalline silica, glass, alumina, aluminum nitride, boron nitride, talc, clay, mica, calcium titanate, and barium titanate. An inorganic filler having a flame retardant effect may also be used. 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.

[0033] Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. Boron nitride is preferred from the viewpoint of reducing the dielectric loss tangent. One type of inorganic filler may be used alone, or two or more types may be used in combination. The inorganic filler may be in the form of powder, beads obtained by spheroidizing powder, fiber, etc.

[0034] The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 50 μm, and more preferably 0.5 μm to 30 μm. When the volume average particle diameter is 0.2 μm or more, an increase in viscosity of the encapsulant composition tends to be further suppressed. When the volume average particle diameter is 50 μm or less, the ability to fill narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler refers to the value measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution analyzer.

[0035] The volume average particle diameter of the inorganic filler in the encapsulant composition or its cured product can be measured by a known method. For example, the inorganic filler is extracted from the encapsulant composition or cured product using an organic solvent, nitric acid, aqua regia, or the like, and then thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer. Alternatively, the cured product can be embedded in a transparent epoxy resin or the like, polished, and the resulting cross-section observed using a scanning electron microscope to obtain a volume-based particle size distribution. Furthermore, the volume average particle diameter of the inorganic filler can also be measured by continuously observing two-dimensional cross-sections of the cured product using an FIB device (focused ion beam SEM) or the like, followed by three-dimensional structural analysis.

[0036] From the viewpoint of the flowability of the encapsulant composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably wide.

[0037] The content of the inorganic filler is not particularly limited and is set appropriately depending on the application of the encapsulant composition. When the encapsulant composition of the present disclosure is solid at 25°C, the content of the inorganic filler may be 70% by mass to 90% by mass. When the encapsulant composition of the present disclosure is liquid at 25°C, the content of the inorganic filler may be more than 0% by mass and not more than 70% by mass.

[0038] (Mold Release Agent) The encapsulant composition of the present disclosure may contain a mold release agent from the viewpoint of obtaining good releasability from the mold during molding. There are no particular limitations on the mold release agent, and conventionally known ones can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. One type of mold release agent may be used alone, or two or more types may be used in combination. The mold release agent may be a biomass-derived release agent or a fossil resource-derived release agent.

[0039] When the encapsulant composition of the present disclosure contains a release agent, the content of the release agent is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 25 parts by mass, and even more preferably 7 parts by mass to 20 parts by mass, per 100 parts by mass of the epoxy resin. When the amount of the release agent is 1 part by mass or more per 100 parts by mass of the epoxy resin, sufficient release properties tend to be obtained. When the amount is 30 parts by mass or less, better adhesion tends to be obtained. The content of the release agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent combined. When the amount of the release agent is 0.01 parts by mass or more per 100 parts by mass of the epoxy resin and the curing agent combined, sufficient release properties tend to be obtained. When the amount is 10 parts by mass or less, better adhesion tends to be obtained.

[0040] (Curing Accelerator) The encapsulant composition of the present disclosure may contain a curing accelerator as needed. The type of curing accelerator is not particularly limited and can be selected depending on the type of epoxy resin, the desired properties of the encapsulant composition, etc. The curing accelerator may be a biomass-derived curing accelerator or a fossil resource-derived curing accelerator.

[0041] Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and the addition of maleic anhydride to these compounds, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone. compounds having intramolecular polarization obtained by adding a compound having a π bond, such as a quinone compound or diazophenylmethane; cyclic amidinium compounds such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;Organic phosphines such as primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, and tertiary phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, and tris(benzyl)phosphine; phosphine compounds such as complexes of the organic phosphines with organic borons; and the organic phosphines or the phosphine compounds, which may be combined with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone. quinone compounds such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, and compounds having intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as 1-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl with the halogenated phenol compound, followed by a dehydrohalogenation step;Examples of the curing accelerator include tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenolic compounds; salts of tetraalkylphosphonium with partial hydrolysates of aromatic carboxylic acid anhydrides; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0042] Among these, the curing accelerator is preferably a curing accelerator containing an organic phosphine. Examples of the curing accelerator containing an organic phosphine include the above-mentioned organic phosphines, phosphine compounds such as complexes of the above-mentioned organic phosphines and organoborons, and compounds having intramolecular polarization formed by adding a compound having a π bond to the above-mentioned organic phosphines or the above-mentioned phosphine compounds. Among these, particularly suitable curing accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound.

[0043] When the encapsulant composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined. When the amount of the curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the epoxy resin and curing agent combined, the composition tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the epoxy resin and curing agent combined, the curing speed is not too fast, and a good molded product tends to be obtained.

[0044] (Stress Relaxant) The encapsulant composition of the present disclosure may contain a stress relaxation agent. By including a stress relaxation agent, warpage of the package and the occurrence of package cracks can be further reduced. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexibilizers). Specific examples include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; indene-styrene-coumarone copolymers; triphenylphosphine oxide; and organic phosphorus compounds such as phosphate esters; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress relaxation agent may be derived from biomass or fossil resources. One type of stress relaxation agent may be used alone, or two or more types may be used in combination. Examples of silicone-based stress relaxation agents include those having an epoxy group, those having an amino group, and polyether-modified versions of these, with silicone compounds such as epoxy-group-containing silicone compounds and polyether-based silicone compounds being more preferred.

[0045] From the viewpoint of the dielectric loss tangent, the stress relaxation agent preferably contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide.

[0046] When the encapsulant composition contains a stress relaxation agent, the amount thereof is, for example, preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass, relative to 100 parts by mass of the epoxy resin and the curing agent in total. When the stress relaxation agent contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide, the amount thereof is, for example, preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass, relative to 100 parts by mass of the epoxy resin and the curing agent in total.

[0047] From the viewpoint of dielectric loss tangent, the content of the silicone-based stress relaxation agent is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less, and extremely preferably 0.5% by mass or less, relative to the entire encapsulant composition. The lower limit of the content of the silicone-based stress relaxation agent is not particularly limited, and may be 0% by mass or 0.1% by mass.

[0048] [Various Additives] In addition to the components described above, the encapsulant composition of the present disclosure may contain various additives such as coupling agents, ion exchangers, flame retardants, colorants, etc., as exemplified below. The encapsulant composition of the present disclosure may contain various additives known in the technical field, as needed, in addition to the additives exemplified below.

[0049] (Coupling Agent) The encapsulant composition of the present disclosure may contain a coupling agent. From the viewpoint of improving the adhesion between the epoxy resin and the curing agent and the inorganic filler, the encapsulant 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.

[0050] When the encapsulant 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, adhesiveness 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.

[0051] (Ion Exchanger) The encapsulant composition of the present disclosure may contain an ion exchanger. The encapsulant composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an encapsulated electronic component. The ion exchanger is not particularly limited, and conventionally known ion exchangers can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchangers may be used alone or in combination of two or more. Among these, hydrotalcites represented by the following general formula (A) are preferred:

[0052] Mg （１－Ｘ） Al Ｘ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O ……(A) (0<X≦0.5, m is a positive number)

[0053] When the encapsulant composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions, etc. For example, the content of the ion exchanger is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the epoxy resin and curing agent in total.

[0054] (Flame Retardant) The encapsulant composition of the present disclosure may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0055] When the encapsulant composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, the amount of the flame retardant is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined.

[0056] (Colorant) The encapsulant composition of the present disclosure may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. One type of colorant may be used alone, or two or more types may be used in combination.

[0057] (Organic Solvent) The encapsulant composition of the present disclosure can be blended with an organic solvent as needed to reduce viscosity. In particular, when using an epoxy resin and curing agent that are solid at 25°C, it is preferable to blend an organic solvent in order to obtain a encapsulant composition that is liquid at 25°C. The organic solvent is not particularly limited, and examples thereof include alcohol-based solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ketone-based solvents such as acetone and methyl ethyl ketone; glycol ether-based solvents such as ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate; lactone-based solvents such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amide-based solvents such as dimethylacetamide and dimethylformamide; and aromatic solvents such as toluene and xylene. These organic solvents may be used alone or in combination. The organic solvent may be a biomass-derived organic solvent or a fossil-derived organic solvent. Among these, organic solvents having a boiling point of 170° C. or higher are preferred from the viewpoint of avoiding the formation of bubbles due to sudden evaporation when the encapsulant composition in a liquid state at 25° C. is cured.

[0058] The content of volatile components including organic solvents and the like is not particularly limited as long as it is to an extent that bubbles are not formed when the liquid encapsulant composition is cured, and is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, based on the total mass of the liquid encapsulant composition. In the present disclosure, the volatile content of the encapsulant composition is calculated based on the difference in weight before and after heating the encapsulant composition at 180°C for 30 minutes.

[0059] (Other Components) In the encapsulant composition of the present disclosure, １４ C / １２ C ratio 0.05 x 10 ―１２ ~1.2 × 10 ―１２ In order to achieve the above range, biomass-derived materials are used as part or all of the epoxy resin, curing agent, etc. Therefore, the sealing material composition of the present disclosure may contain impurities that may be contained in the biomass-derived material. Examples of impurities that may be contained in the biomass-derived material include ammonia salts and metal cations. When the sealing material composition of the present disclosure contains an ammonia salt, the mass-based content of the ammonia salt in the sealing material composition is preferably 10,000 ppm or less in order to reduce the impact on the properties of the cured product. In order to reduce the cost increase associated with the removal of impurities that may be contained in the biomass-derived material, the mass-based content of the ammonia salt in the sealing material composition may be 100 ppm or more. Furthermore, when the sealing material composition of the present disclosure contains a metal cation, the mass-based content of the metal cation in the sealing material composition is preferably 10,000 ppm or less in order to reduce the impact on the properties of the cured product. In order to reduce the cost increase associated with the removal of impurities that may be contained in the biomass-derived material, the mass-based content of the metal cation in the sealing material composition may be 100 ppm or more.

[0060] (Method for Preparing Encapsulant Composition) The method for preparing the encapsulant composition is not particularly limited. When the encapsulant composition is solid at 25°C, a common method includes thoroughly mixing predetermined amounts of components using a mixer or the like, melt-kneading the mixture using a mixing roll, extruder, or the like, cooling, and pulverizing the mixture. More specifically, a method includes stirring and mixing predetermined amounts of the components, kneading the mixture using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, cooling, and pulverizing the mixture. When the encapsulant composition is liquid at 25°C, the encapsulant composition can be obtained, for example, by stirring, melting, mixing, dispersing, or the like predetermined amounts of the components, either collectively or separately, while optionally applying a heat treatment. The apparatus for mixing, stirring, dispersing, or the like of the components is not particularly limited, and examples thereof include a mortar and pestle mill equipped with a stirrer, a heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like.

[0061] (Physical properties of encapsulant composition) The encapsulant composition of the present disclosure may be liquid or solid at 25°C. When the encapsulant composition of the present disclosure is solid at 25°C, from the viewpoint of reducing wire sweep when encapsulating an electronic component device, the viscosity of the encapsulant composition is preferably 200 Pa·s or less at 175°C, more preferably 150 Pa·s or less, even more preferably 100 Pa·s or less, particularly preferably 70 Pa·s or less, and extremely preferably 50 Pa·s or less. The lower limit of the viscosity of the encapsulant composition is not particularly limited, and may be, for example, 2 Pa·s or more at 175°C. The viscosity of the encapsulant composition at 175°C can be measured using a high-speed flow tester (for example, manufactured by Shimadzu Corporation).

[0062] When the encapsulant composition of the present disclosure is liquid at 25° C., from the viewpoint of high fluidity, the viscosity of the encapsulant composition is preferably 0.1 Pa·s to 50.0 Pa·s, more preferably 0.1 Pa·s to 20.0 Pa·s, and even more preferably 0.1 Pa·s to 10.0 Pa·s at 25° C. The viscosity of the encapsulant composition at 25° C. is measured at 25° C. using an E-type viscometer (cone angle 3°, rotation speed 10 rpm).

[0063] Furthermore, when the encapsulant composition is used as an underfill material or the like, the viscosity at 110° C. is preferably 0.20 Pa s or less, and more preferably 0.15 Pa s or less, as an index of ease of filling a narrow gap of several tens to several hundreds of μm with the encapsulant composition at around 100° C. to 120° C. The viscosity of the encapsulant composition at 110° C. is measured using a rheometer AR2000 (manufactured by TA Instruments, aluminum cone 40 mm, shear rate 32.5 / sec).

[0064] Furthermore, the encapsulant composition preferably has a thixotropic index [(viscosity at 1.5 rpm) / (viscosity at 10 rpm)], which is the ratio of the viscosity at a rotation speed of 1.5 rpm to the viscosity at a rotation speed of 10 rpm, measured at 25°C using an E-type viscometer, of 0.5 to 1.5, more preferably 0.8 to 1.2. When the thixotropic index is within the above range, the fillet formability in underfill material applications is further improved. The viscosity and thixotropic index of the encapsulant composition can be adjusted to the desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, etc.

[0065] The electronic component device of the present disclosure includes a support member, an electronic component disposed on the support member, and a cured product of the encapsulant 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, an organic substrate, etc., on which electronic components (active elements such as semiconductor chips, transistors, diodes, thyristors, etc., passive elements such as capacitors, resistors, coils, etc., antennas, etc.) are mounted, and the resulting electronic component region is encapsulated with the encapsulant composition (e.g., a high-frequency device).

[0066] In the electronic component device of the present disclosure, 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 encapsulant composition described above, may be encapsulated with another resin composition, or may not be encapsulated.

[0067] (Method for manufacturing electronic component device) The method for manufacturing an electronic component device of the present disclosure includes a step of placing electronic components on a support member and a step of encapsulating the electronic components with the encapsulant composition described above. The method for carrying out each of the above steps is not particularly limited, and can be carried out by 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.

[0068] Methods for encapsulating electronic components using an encapsulant composition that is solid at 25°C include low-pressure transfer molding, injection molding, and compression molding. Among these, low-pressure transfer molding is common. When an encapsulant composition that is liquid at 25°C is used, a post-injection method may be used in which, after the electronic component and a support member are connected, the encapsulant composition penetrates into the gap between the electronic component and the support member by utilizing capillary action. Alternatively, a pre-application method may be used in which the encapsulant composition is first applied to the support member, and then, when the electronic component is connected to the support member by thermocompression bonding, the connection of the electronic component and the support member and the curing reaction of the encapsulant composition are carried out all at once.

Claims

1. Contains an epoxy resin, a hardener, and an inorganic filler; １４ C's １２ Ratio to C ( １４ C / １２ C ratio) is 0.05 x 10 ―１２ ~1.2 x 10 ―１２ The encapsulant composition according to claim 1, 2. About the epoxy resin １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 x 10 ―１２ The encapsulant composition according to claim 1 , 3. Percentage of total epoxy resin １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 x 10 ―１２ The sealing material composition according to claim 1, wherein the ratio of the epoxy resin is 50% by mass to 99% by mass.

4. About the hardener １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 x 10 ―１２ The encapsulant composition according to claim 1 , 5. Percentage of the total hardener １４ C / １２ C ratio is 0.10 x 10 ―１２ ~1.2 x 10 ―１２ The encapsulant composition according to claim 1, wherein the ratio of the curing agent is 50% by mass to 99% by mass.

6. The sealing material composition according to claim 1, wherein the mass-based content of the ammonium salt is 10,000 ppm or less.

7. The sealing material composition according to claim 1, wherein the mass content of the ammonium salt is 100 ppm or more.

8. The sealing material composition according to claim 1, wherein the mass-based content of metal cations is 10,000 ppm or less.

9. The sealing material composition according to claim 1, wherein the mass-based content of the metal cation is 100 ppm or more.

10. The sealing material composition according to claim 1, which has a viscosity at 25° C. of 0.1 Pa·s to 50.0 Pa·s.

11. The encapsulant composition according to claim 1, which is solid at 25°C.

12. The encapsulant composition according to claim 1, wherein the content of the inorganic filler is 70% by mass to 90% by mass.

13. The encapsulant composition according to claim 1, wherein the content of the inorganic filler is greater than 0 mass % and not more than 70 mass %.

14. An electronic component device comprising a support member, an electronic component placed on the support member, and a cured product of the encapsulant composition according to any one of claims 1 to 13 that encapsulates the electronic component.