Resin composition and method for producing resin composition

Abstract

This resin composition contains a resin component and inorganic particles, and has a value V10 / V1 of 0.7 or more, the value being obtained by dividing the viscosity V10, which is measured at a shear rate of 10S-1 and 130°C, by the viscosity V1, which is measured at a shear rate of 1S-1 and 130°C.

Description

Resin composition and method for producing the resin composition

[0001] The present disclosure relates to a resin composition and a method for producing the resin composition.

[0002] Electronic component devices in which elements such as semiconductor chips are encapsulated with an insulating material called an encapsulant around the elements or between the elements and a substrate are used in various electronic devices. Resin compositions containing a thermosetting resin such as an epoxy resin and inorganic particles such as silica are widely used as encapsulants. One method for manufacturing a semiconductor package using a resin composition as an encapsulant is to heat and melt a resin composition that is solid at room temperature, and then inject the molten resin composition into a mold and allow it to harden (transfer molding).

[0003] Japanese Patent Application Laid-Open No. 2023-082306

[0004] When manufacturing semiconductor packages using transfer molding, variations in the shear rate applied to the resin composition may occur due to the structure inside the mold into which the resin composition is injected. Resin compositions used as encapsulants generally exhibit shear rate dependence, and tend to decrease in viscosity as the shear rate increases. When a resin composition whose viscosity change is highly dependent on shear rate is injected into a mold, variations in the flow state of the resin composition are likely to occur. Variations in the flow state of the resin composition inside the mold may cause abnormalities in the appearance (flow marks) of the cured product obtained by curing the resin composition. In view of these circumstances, the present disclosure aims to provide a resin composition having excellent flow properties when melted and a method for producing the resin composition.

[0005] The means for solving the above problems include the following embodiments: <1> A composition containing a resin component and inorganic particles, and a composition containing a resin component and inorganic particles, the composition being heated at 130°C and a shear rate of 10 s －１ Viscosity V measured at １０ at 130°C and a shear rate of 1 s －１ Viscosity V measured at １ The value V obtained by dividing １０ / V １A resin composition in which the maximum particle size of the inorganic particles is 0.7 or more. <2> The resin composition according to <1>, in which the maximum particle size of the inorganic particles is 9.0 μm or less. <3> The resin composition according to <1> or <2>, in which the content of the inorganic particles is 70 mass% or more of the total resin composition. <4> The resin composition according to any one of <1> to <3>, in which the resin component includes an epoxy resin. <5> The resin composition according to any one of <1> to <4>, in which the resin composition is solid at room temperature and normal pressure. <6> A method for producing the resin composition according to any one of <1> to <5>, comprising preparing a granulated product containing at least a portion of the inorganic particles and at least a portion of the resin component.

[0006] According to the present disclosure, a resin composition having excellent flow properties when melted and a method for producing the resin composition are provided.

[0007] 1 is a graph showing the viscosity measurement results at 130°C of the resin compositions obtained in the examples.

[0008] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention 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 invention.

[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, multiple types of particles corresponding to each component may be contained. 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, unless otherwise specified, solid, solid, liquid, and liquid refer to the state at room temperature and normal pressure (e.g., 25°C and atmospheric pressure).

[0010] <Resin Composition> The resin composition of the present disclosure contains a resin component and inorganic particles, and is heated at 130°C and a shear rate of 10 S －１ Viscosity V when measured １０ at 130°C and a shear rate of 1 S －１ Viscosity V when measured １ The value V obtained by dividing １０ / V １ is 0.7 or more.

[0011] V １０ / V １ indicates the degree of dependency of the viscosity change of the resin composition on the shear rate, and V １０ / V １ The larger the V, the smaller the degree of decrease in viscosity of the resin composition with an increase in shear rate (i.e., the smaller the dependency of viscosity change of the resin composition on shear rate). １０ / V １ Therefore, the resin composition of the present disclosure exhibits excellent flow properties with little variation in the flow state when injected into a mold.

[0012] V of the resin composition １０ / V １ is preferably 0.75 or more, more preferably 0.85 or more, and even more preferably 0.90 or more. １０ / V １ The upper limit of is not particularly limited, and may be, for example, 1.1 or less, or 1.05 or less.

[0013] The resin composition may or may not exhibit dilatancy (a phenomenon in which viscosity increases with increasing shear rate). Resin compositions generally exhibit a tendency for viscosity to decrease with increasing shear rate, but the occurrence of dilatancy may contribute to suppressing the decrease in viscosity that accompanies an increase in shear rate. When a resin composition exhibits dilatancy, it exhibits a tendency for viscosity to decrease at a shear rate of 10 s －１ From 100S －１ Dilatancy may be exhibited within the range.

[0014] V of the resin composition at 130°C １０ and V １ The value of is not particularly limited and can be selected depending on the application of the resin composition. For example, the V １０ and V １ The values ​​of may be independently 2000 Pa s or less, 1500 Pa s or less, or 1000 Pa s or less. For example, the V １０ and V １ may each independently be 10 Pa·s or more, 20 Pa·s or more, or 50 Pa·s or more.

[0015] In the present disclosure, the viscosity of the resin composition at 130°C is measured using a rotational rheometer.

[0016] Each component contained in the resin composition of the present disclosure will be described below. The type of resin component contained in the resin composition is not particularly limited and can be selected depending on the application of the resin composition, etc. For example, when the resin composition is used as a sealing material for electronic component devices, the resin composition may contain a thermosetting resin and a curing agent as resin components.

[0017] (Thermosetting Resin) The type of thermosetting resin contained in the resin composition is not particularly limited. Specific examples of thermosetting resins include epoxy resins, phenolic resins, urea resins, melamine resins, urethane resins, silicone resins, and unsaturated polyester resins. In the present disclosure, those that exhibit both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups, are included in the term "thermosetting resin." The thermosetting resin may be solid or liquid, and is preferably solid. The thermosetting resin may be used alone or in combination of two or more types.

[0018] The thermosetting resin preferably includes an epoxy resin. Specific examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acidic catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acidic catalyst, the above-mentioned phenolic compound and naphthol compound with an aldehyde compound. stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins which are diglycidyl ethers of bisphenol S; 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 bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins in which a co-condensation resin of dicyclopentadiene and a phenolic compound is epoxidized.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 the epoxy resin 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. The epoxy resins may be used alone or in combination of two or more.

[0019] When the thermosetting resin is an epoxy resin, 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, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. The epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0020] When the thermosetting resin is solid at 25° C., the melting point or softening point of the thermosetting resin is not particularly limited. From the viewpoint of blocking resistance, the melting point or softening point of the thermosetting resin is preferably 40° C. or higher, and more preferably 50° C. or higher. From the viewpoint of suppressing thickening of the resin composition due to kneading, the melting point or softening point of the thermosetting resin is preferably 150° C. or lower, more preferably 140° C. or lower, and even more preferably 130° C. or lower.

[0021] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content of the thermosetting resin is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass, relative to the total mass of the resin composition.

[0022] (Curing Agent) The resin composition may contain a curing agent to be used in combination with the thermosetting resin. Examples of curing agents to be used in combination with the epoxy resin include phenolic curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. From the viewpoint of improving heat resistance, the curing agent is preferably a phenolic curing agent (a curing agent containing a phenolic hydroxyl group as a functional group that reacts with an epoxy group). The curing agent may be solid or liquid at room temperature and normal pressure (for example, 25°C, atmospheric pressure), and is preferably solid.

[0023] Specific examples of the phenolic curing agent include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolak-type phenolic resins 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, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, under an acidic catalyst; and copolymers of the above phenolic compounds with dimethoxyparaxylene, bis(methoxymethyl)biphenol, and the like. Examples of suitable phenolic curing agents include aralkyl phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenyl or the like; paraxylylene and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerization of two or more of these. The phenolic curing agents may be used alone or in combination of two or more.

[0024] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenolic curing agent, and active hydrogen equivalent in the case of an amine curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the curing agent is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0025] The hydroxyl equivalent weight in the case of a phenolic curing agent is a value calculated based on the hydroxyl value measured in accordance with JIS K0070:1992, and the active hydrogen equivalent weight in the case of an amine curing agent is a value calculated based on the amine value measured in accordance with JIS K7237:1995.

[0026] When the curing agent is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the curing agent is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance when the resin composition is used for an encapsulant, and more preferably 50°C to 130°C from the viewpoint of handleability during production of the resin composition.

[0027] The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0028] The equivalent ratio of the thermosetting resin to the curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the thermosetting resin (number of functional groups in the curing agent / number of functional groups in the thermosetting resin), is not particularly limited. In order to minimize the amount of unreacted components, the equivalent ratio of the thermosetting resin to the curing agent is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability, it is even more preferable that the equivalent ratio of the thermosetting resin to the curing agent be set in the range of 0.8 to 1.2.

[0029] (Inorganic Particles) The material of the inorganic particles contained in the resin composition is not particularly limited. Specific examples of the material of the inorganic particles include inorganic materials such as silica (e.g., fused silica, crystalline silica), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic particles having a flame-retardant effect may also be used. Examples of inorganic particles having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides (e.g., composite hydroxide of magnesium and zinc), and zinc borate. Among inorganic particles, silica (e.g., fused silica) is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. The inorganic particles contained in the resin composition may be of one type or two or more types.

[0030] The maximum particle size of the inorganic particles contained in the resin composition is preferably 9.0 μm or less. When the maximum particle size of the inorganic particles is 9.0 μm or less, the resin composition can be easily sintered at a high shear rate (for example, 10 s －１ The decrease in viscosity at V １０ / V １ The maximum particle size of the inorganic particles is not particularly limited as long as it is 9.0 μm or less, and may be, for example, 8.0 μm or less, 7.0 μm or less, 6.0 μm or less, 5.0 μm or less, less than 5.0 μm, 4.5 μm or less, 4.0 μm or less, or 3.5 μm or less.

[0031] The volume average particle diameter of the inorganic particles is not particularly limited. From the viewpoint of suppressing a decrease in viscosity at high shear rates, the volume average particle diameter of the inorganic particles is preferably 4.0 μm or less, more preferably 3.5 μm or less, and even more preferably 3.0 μm or less. From the viewpoint of suppressing aggregation of the inorganic particles, the volume average particle diameter of the inorganic particles is preferably 0.1 μm or more, more preferably 0.15 μm or more, and even more preferably 0.2 μm or more. The volume average particle diameter of the inorganic particles can be measured as the particle diameter (D50) at which the cumulative total from the small diameter side reaches 50% in the volume-based particle size distribution measured using a laser scattering diffraction particle size distribution measuring device.

[0032] The specific surface area of ​​the inorganic particles as measured by the BET method is not particularly limited. From the viewpoint of suppressing a decrease in viscosity at a high shear rate, the specific surface area of ​​the inorganic particles as measured by the BET method is preferably 0.1 m ２ / g or more, and 0.5m ２ / g or more, and more preferably 1.0m ２ From the viewpoint of suppressing aggregation of the inorganic particles, the specific surface area of ​​the inorganic particles measured by the BET method is more preferably 50 m / g or more. ２ / g or less, and ２ / g or less is more preferable, and 20m ２ It is more preferable that the SiO2 content is 1 / g or less.

[0033] The specific surface area of ​​the inorganic particles measured by the BET method can be measured from the nitrogen adsorption capacity of the inorganic particles in accordance with JIS Z 8830:2013.

[0034] The specific surface area of ​​the inorganic particles as measured by image analysis is not particularly limited. From the viewpoint of suppressing a decrease in viscosity at high shear rates, the specific surface area of ​​the inorganic particles as measured by image analysis is preferably 0.1 m ２ / g or more, and 0.5m ２ / g or more, and more preferably 1.0m ２ From the viewpoint of suppressing aggregation of inorganic particles, it is more preferable that the specific surface area of ​​inorganic particles measured by image analysis method is 50 m ２ / g or less, and ２ / g or less is more preferable, and 20m ２ It is more preferable that the SiO2 content is 1 / g or less.

[0035] The specific surface area of ​​inorganic particles by image analysis can be calculated by obtaining an image of the inorganic particles using an electron microscope or the like and assuming that the particles in the obtained image are spherical.

[0036] The shape of the inorganic particles is not particularly limited, but from the viewpoints of packing properties and suppression of mold wear, spherical shapes are preferred.

[0037] The content of inorganic particles is not particularly limited. From the viewpoint of further improving the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured resin composition, the content of inorganic particles is preferably 30% by volume or more of the entire resin composition, more preferably 40% by volume or more, even more preferably 50% by volume or more, particularly preferably 60% by volume or more, and extremely preferably 65% ​​by volume or more. From the viewpoint of improving the fluidity and reducing the viscosity of the resin composition, the content of inorganic particles is preferably 95% by volume or less of the entire resin composition, preferably 90% by volume or less, and more preferably 85% by volume or less.

[0038] The content of inorganic particles in a cured product of a resin composition can be measured as follows: First, the total mass of the cured product is measured, and the cured product is baked at 400°C for 2 hours and then at 700°C for 3 hours to evaporate the resin components, etc., and the mass of the remaining inorganic particles is measured. The volumes are calculated from the obtained masses and their specific gravities, and the ratio of the volume of the inorganic particles to the total volume of the cured product is determined as the content of inorganic particles.

[0039] (Curing Accelerator) The resin composition may contain a curing accelerator. Specific 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, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; these compounds plus maleic anhydride, quinone compounds such as 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 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(alkylalkoxyphenyl)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 complexes of the organic phosphines or the phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, compounds having intramolecular polarization obtained by adding a compound having a π bond, such as 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, or diazophenylmethane; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as bromo-1-naphthol, 3-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-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, 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 phenol compounds; 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.

[0040] When an epoxy resin is used as the thermosetting resin, examples of a particularly suitable curing accelerator include triphenylphosphine and an adduct of triphenylphosphine and a quinone compound.

[0041] The content of the curing accelerator 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 resin component. When the amount of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the resin component, good curing tends to occur 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 resin component, the curing speed is not too fast, and good molded products tend to be obtained.

[0042] (Additives) In addition to the above-mentioned components, the resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, a stress relaxation agent, etc. In addition to the additives exemplified below, the resin composition may also contain various additives commonly used in the technical field as needed.

[0043] (Coupling Agent) The resin composition may contain a coupling agent to enhance adhesion between the resin component and the inorganic particles. Examples of the coupling agent include known coupling agents such as silane compounds, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0044] Examples of silane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0045] Examples of titanium compounds include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0046] When the resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the inorganic particles.

[0047] (Ion Exchanger) The resin composition may contain an ion exchanger. In particular, when the resin composition is used as an encapsulating molding material, it is preferable to contain an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be encapsulated. 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.

[0048] Mg （１－Ｘ） Al Ｘ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O ……(A) (0<X≦0.5, m is a positive number)

[0049] When the resin 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 is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the resin component.

[0050] (Mold Release Agent) The resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability 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.

[0051] When the resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 part by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When the amount is 10 parts by mass or less, better adhesion and curability tend to be obtained.

[0052] (Flame retardant) The resin composition may contain a flame retardant. There are no particular limitations on the flame retardant, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0053] When the resin 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 is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component.

[0054] (Colorant) The resin composition 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. The colorant may be used alone or in combination of two or more.

[0055] (Stress Relaxant) The resin composition may contain a stress relaxation agent. By containing a stress relaxation agent, warpage of the package and the occurrence of package cracks can be reduced when the resin composition is used as an encapsulant. 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; 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. One type of stress relaxation agent may be used alone, or two or more types may be used in combination.

[0056] The resin composition may be solid or liquid at room temperature and normal pressure (for example, 25°C and atmospheric pressure), and is preferably solid. When the resin composition is solid, its shape is not particularly limited, and examples include powder, granules, tablets, etc.

[0057] <Applications of Resin Composition> The resin composition produced by the method of the present disclosure can be used for various applications. Suitable applications of the resin composition include as a sealant for electronic component devices.

[0058] Examples of electronic component devices 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, an element (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils) mounted on the support member, and a sealing material that seals the periphery of the element.

[0059] Examples of methods for encapsulating electronic component devices using a resin composition include low-pressure transfer molding, injection molding, and compression molding.

[0060] <Method for producing resin composition> The method for producing a resin composition of the present disclosure is the method for producing a resin composition of the present disclosure described above, and includes preparing a granulated product containing at least a portion of the inorganic particles and at least a portion of the resin component.

[0061] In the present disclosure, the term "granulated material containing inorganic particles and a resin component" refers to a material that contains at least inorganic particles and a resin component and is granulated. １０ / V １ It is possible to effectively produce a resin composition having a value of 0.7 or more. The reason for this is thought to be that, for example, by forming the inorganic particles into a granulated product together with the resin component, aggregation due to interactions between the inorganic particles is suppressed.

[0062] The method of the present disclosure is particularly suitable when the particle size of the inorganic particles used in the production of the resin composition is small (for example, the maximum particle size is 9.0 μm or less). As shown in the examples described later, when the particle size of the inorganic particles contained in the resin composition is small, the resin composition can be easily sintered at a low shear rate (for example, 10 s －１ The resin composition produced by the method of the present disclosure maintains a low viscosity at low shear rates even when the particle size of the inorganic particles is small.

[0063] In the method of the present disclosure, the resin component used to prepare the granules may be all or part of the resin component contained in the resin composition. For example, when the resin composition contains a thermosetting resin and a curing agent as resin components, a granule containing inorganic particles and a thermosetting resin and a granule containing inorganic particles and a curing agent may be prepared separately, or only one of a granule containing inorganic particles and a thermosetting resin and a granule containing inorganic particles and a curing agent may be prepared as a granule containing inorganic particles and a resin component.

[0064] In the method of the present disclosure, the inorganic particles used to prepare the granules may be all or part of the inorganic particles contained in the resin composition. From the viewpoint of suppressing aggregation of the inorganic particles, it is preferable that the resin component used to prepare the granules has an opposite charge to that of the inorganic particles. For example, if the surfaces of the inorganic particles are positively charged, it is preferable to use a resin component having an anionic functional group such as a phenolic hydroxyl group, and if the surfaces of the inorganic particles are negatively charged, it is preferable to use a resin component having a cationic functional group such as an amino group.

[0065] The particle size of the granulated product is not particularly limited and can be selected taking into consideration workability when mixing with other materials, etc. The particle size of the granulated product can be selected, for example, from the range of 10 μm to 10,000 μm, preferably from 100 μm to 5,000 μm, and more preferably from 500 μm to 3,000 μm. The particle shape of the granulated product is not particularly limited and may be spherical, columnar, scaly, needle-like, etc.

[0066] The method for preparing a granulated material containing inorganic particles and a resin component is not particularly limited and can be carried out by a known method. For example, a mixture containing at least inorganic particles and a resin component can be granulated using a grinder, extruder, or the like to obtain a granulated material. If necessary, a solvent may be used when preparing the mixture. The granulated material used in the production of the resin composition may be prepared by hand or may be obtained as a ready-made product. The granulated material containing inorganic particles and a resin component may contain components other than the inorganic particles and the resin component.

[0067] In the method of the present disclosure, a granulated material containing inorganic particles and a resin component may be mixed with other raw materials to produce a resin composition. The method for mixing the granulated material with other raw materials is not particularly limited and can be carried out by a known method.

[0068] The method of the present disclosure is particularly suitable for producing a resin composition using a kneading extruder when the particle size of the inorganic particles used in producing the resin composition is small. That is, when inorganic particles not in a granulated state are fed from the feeder of the kneading extruder, if the particle size of the inorganic particles is too small, it is likely to cause a decrease in the efficiency of the kneading operation, poor kneading, etc. In the method of the present disclosure, the inorganic particles are first made into a granulated state and then fed into the kneading extruder. Therefore, even when the particle size of the inorganic particles is small (for example, the maximum particle size is 9.0 μm or less), a uniform resin composition can be efficiently produced using the kneading extruder.

[0069] The above-described embodiment will be specifically described below using examples, but the present disclosure is not limited to these examples.

[0070] (1) Preparation of Resin Composition The materials (parts by mass) shown in Table 1 were charged into an extrusion kneader to obtain a kneaded mixture. The obtained kneaded mixture was pulverized to obtain a resin composition having a particle diameter of 1000 μm. The epoxy resin 2, curing agent 1, inorganic particles 4, and inorganic particles 5 used in Example 1 were in the form of granules obtained by the following method.

[0071] (Preparation of Granules) The raw materials for the granules were placed in a 3 L separable flask, a stirring blade was inserted, and the mixture was stirred at 200 rpm (revolutions per minute) for 2 hours to obtain a varnish-like mixture. The mixture was then vacuum dried at 140°C for 2 hours to remove the solvent until the residual solvent content of the mixture was less than 1% by mass, obtaining a solid. The obtained solid was pulverized to produce granules with an average particle size of 1000 μm.

[0072] (2) Evaluation of Physical Properties of Resin Composition (Melt Viscosity) The resin composition was heated to melt it, and the melt viscosity (ηFT) at 175° C. was measured using a Koka flow tester. The results are shown in Table 1.

[0073] (Gel Time) A 0.5 g sample of the resin composition was placed on a hot plate heated to 175°C, and the sample was spread into a circle of 2.0 cm to 2.5 cm using a jig at a rotation speed of 20 to 25 revolutions per minute. The gel time (GT) was measured as the time (seconds) from when the sample was placed on the hot plate until the sample lost its viscosity, became gelled, and could be peeled off from the hot plate. The gel time of the resin composition at 175°C is preferably 30 to 90 seconds, and more preferably 40 to 60 seconds.

[0074] (Viscosity) The viscosity of the resin composition at 130°C was measured using a rotational rheometer manufactured by NETZSCH while changing the shear rate. －１ Viscosity V measured at １０ , shear rate 1S －１ Viscosity V measured at １ , and V calculated from these １０ / V １ The values ​​are shown in Table 1. In addition, a graph of the viscosity measurement results at 130°C of the resin compositions obtained in Example 1 and Comparative Example 2 is shown in Figure 1.

[0075] Details of the materials listed in Table 1 are as follows: Epoxy resin 1: YX-4000 (trade name, Mitsubishi Chemical Corporation, biphenyl-type epoxy resin with an epoxy equivalent of 180 g / eq to 192 g / eq and a melting point of 105°C) Epoxy resin 2: NC-3000 (trade name, Nippon Kayaku Co., Ltd., aralkyl-type epoxy resin with an epoxy equivalent of 265 g / eq to 285 g / eq and a softening point of 53°C to 63°C) Curing agent 1: MEHC-7851SS (trade name, Meiwa Kasei Co., Ltd., biphenylene aralkyl-type phenol resin with a hydroxyl group equivalent of 205 g / eq and a softening point of 60°C to 70°C) Curing agent 2: HP-850N (trade name, Resonac Co., Ltd., phenol novolac resin with a hydroxyl group equivalent of 108)

[0076] Curing accelerator: phosphorus-based curing accelerator Coupling agent 1: KBM-573 (trade name, Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) Coupling agent 2: KBM-503 (trade name, Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane) Mold release agent: montanic acid ester Colorant: carbon black

[0077] Inorganic particle 1: Spherical silica particles with a maximum particle size of 20.0 μm or less and a volume average particle size of 11 μm. Inorganic particle 2: Spherical silica particles with a maximum particle size of 10.0 μm or less and a volume average particle size of 4 μm. Inorganic particle 3: Spherical silica particles with a maximum particle size of 9.0 μm or less and a volume average particle size of 2.3 μm. Inorganic particle 4: Spherical silica particles with a maximum particle size of 5.0 μm or less and a volume average particle size of 1.5 μm. Inorganic particle 5: Spherical silica particles with a maximum particle size of 5.0 μm or less and a volume average particle size of 0.3 μm. Inorganic particle 6: Spherical silica particles with a maximum particle size of 5.0 μm or less and a volume average particle size of 0.6 μm.

[0078]

[0079] As shown in Table 1, the resin compositions obtained in Examples 1 to 4 were heated at 130°C and a shear rate of 10 s －１ Viscosity V when measured １０ at 130°C and a shear rate of 1 S －１ Viscosity V when measured １ The value V obtained by dividing １０ / V １ The V of the resin compositions obtained in Examples 1 to 4 was 0.7 or more, indicating excellent flow properties. １０ / V １ The value shown is the V of the resin compositions obtained in Comparative Examples 1 and 2. １０ / V １ The reason why the maximum particle diameters of the inorganic particles contained in the resin compositions of Examples 1 to 4 are larger than the value shown by (1) above is thought to be that the maximum particle diameters of the inorganic particles contained in the resin compositions of Comparative Examples 1 and 2 were smaller than the maximum particle diameters of the inorganic particles contained in the resin compositions of Examples 1 to 4, which contributed to suppressing the decrease in viscosity at high shear rates.

[0080] The disclosure of Japanese Patent Application No. 2023-216233 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated by reference into this specification 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. Contains resin components and inorganic particles, 130°C, shear rate 10S －１ Viscosity V measured at １０ at 130°C and a shear rate of 1S －１ Viscosity V measured at １ The value V obtained by dividing １０ / V １ The resin composition, 2. The resin composition according to claim 1, wherein the maximum particle size of the inorganic particles is 9.0 μm or less.

3. The resin composition according to claim 1, wherein the content of the inorganic particles is 70 mass % or more of the total resin composition.

4. The resin composition according to claim 1, wherein the resin component comprises an epoxy resin.

5. The resin composition according to claim 1, which is solid at room temperature and pressure.

6. A method for producing a resin composition according to any one of claims 1 to 5, comprising preparing a granulated product containing at least a portion of the inorganic particles and at least a portion of the resin component.

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