Resin composition and method for producing resin composition

Abstract

A resin composition comprising resin components and inorganic particles, subjected to a shear rate of 10 s at 130°C. ‑1 Viscosity V measured below 10 Divide by the temperature at 130℃ and the shear rate at 1 second. ‑1 The value V is obtained by measuring the viscosity V1 at the time of measurement. 10 / V1 is 0.7 or higher.

Description

Technical Field

[0001] This disclosure relates to a resin composition and a method for manufacturing the resin composition. Background Technology

[0002] Electronic components, such as semiconductor chips, are made by sealing the area around an insulating material called a sealing material, or between the component and a substrate. These components are used in various electronic devices. Resin compositions containing thermosetting resins such as epoxy resins and inorganic particles such as silica are widely used as sealing materials.

[0003] One method for manufacturing semiconductor packages that uses resin compositions as sealing materials is the transfer molding method, which involves heating and melting a solid resin composition at room temperature, and then injecting the molten resin composition into a mold to harden it.

[0004] [Existing Technical Documents]

[0005] [Patent Literature]

[0006] Patent Document 1: Japanese Patent Application Publication No. 2023-082306 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] When manufacturing semiconductor packages using transfer molding, the shear rate applied to the resin composition can sometimes deviate due to the internal structure of the mold into which the resin composition is injected.

[0009] Resin compositions used as sealing materials typically exhibit a dependence on shear rate, and their viscosity tends to decrease as the shear rate increases. If a resin composition with a high viscosity dependence on shear rate is injected into a mold, the flow state of the resin composition is prone to deviation. This deviation in the flow state of the resin composition within the mold can potentially cause abnormal appearances (flow marks) in the hardened product obtained after the resin composition has hardened.

[0010] In view of the above situation, the object of this disclosure is to provide a resin composition with excellent flow characteristics when melted and a method for manufacturing the resin composition.

[0011] [Technical means to solve the problem]

[0012] The means to solve the aforementioned problem include the following implementation forms.

[0013] <1> A resin composition comprising resin components and inorganic particles, subjected to a shear rate of 10 s at 130°C. -1 Viscosity V measured below10 Divide by the temperature at 130℃ and the shear rate at 1 second. -1 The value V is obtained by measuring the viscosity V1 at the time of the test. 10 / V1 is 0.7 or higher.

[0014] <2> According to the resin composition described in <1>, the maximum particle size of the inorganic particles is less than 9.0 μm.

[0015] <3> The resin composition according to <1> or <2>, wherein the content of the inorganic particles is 70% or more by mass of the total resin composition.

[0016] <4> The resin composition according to any one of <1> to <3>, wherein the resin component comprises an epoxy resin.

[0017] <5> The resin composition according to any one of <1> to <4> is solid at room temperature and pressure.

[0018] <6> A method for manufacturing a resin composition, comprising the method of manufacturing a resin composition according to any one of <1> to <5>, wherein the method of manufacturing the resin composition includes...

[0019] Prepare a granule comprising at least a portion of the inorganic particles and at least a portion of the resin component.

[0020] [The effects of the invention]

[0021] This disclosure provides a resin composition with excellent flow characteristics upon melting and a method for manufacturing the resin composition. Attached Figure Description

[0022] [ Figure 1 [Image] is a graph showing the viscosity of the resin composition obtained in the examples at 130°C. Detailed Implementation

[0023] The following is a detailed description of the forms in which the present invention is carried out. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless specifically stated otherwise. Similarly, numerical values ​​and their ranges are not limited to the present invention.

[0024] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that, even if they cannot be clearly distinguished from other processes, are included as long as the purpose of the process is achieved.

[0025] In this disclosure, the numerical values ​​recorded before and after “~” in the numerical range represented by “~” are respectively the minimum value and the maximum value.

[0026] In the numerical ranges described in this disclosure, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of other numerical ranges described in different stages. Furthermore, the upper or lower limit of the numerical ranges described in this disclosure can also be replaced by the values ​​shown in the embodiments.

[0027] In this disclosure, each component may also comprise multiple equivalent substances. In the case where multiple substances equivalent to each component are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition.

[0028] In this disclosure, the particles corresponding to each component may also comprise multiple types. In the case where multiple particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component refers to a value relating to the mixture of the multiple particles present in the composition.

[0029] In this disclosure, the terms solid components, solids, liquids, and liquids, unless otherwise specified, refer to their properties at normal temperature and pressure (e.g., 25°C, atmospheric pressure).

[0030] <Resin Composition>

[0031] The resin composition disclosed herein comprises resin components and inorganic particles, and is subjected to a shear rate of 10 s at 130°C. -1 Viscosity V measured below 10 Divide by the temperature at 130℃ and the shear rate at 1 second. -1 The value V is obtained by measuring the viscosity V1 at the time of the test. 10 / V1 is 0.7 or higher.

[0032] V 10 / V1 represents the degree to which the viscosity change of the resin composition depends on the shear rate, V 10 The larger the / V1, the less the viscosity of the resin composition decreases as the shear rate increases (i.e., the viscosity change of the resin composition is less dependent on the shear rate).

[0033] V of the resin composition disclosed herein 10 The V1 ratio is 0.7 or higher. Therefore, the resin composition of this disclosure exhibits small deviations in flow state when injected into the mold, demonstrating excellent flow characteristics.

[0034] V of the resin composition 10 / V1 is preferably 0.75 or higher, more preferably 0.85 or higher, and even more preferably 0.90 or higher.

[0035] V of the resin composition 10There is no particular limit to the upper limit of / V1; for example, it can be below 1.1 or below 1.05.

[0036] The resin composition may be a composition that exhibits dilatancy (the phenomenon that viscosity increases as shear rate increases) or a composition that does not exhibit dilatancy.

[0037] Resin compositions typically exhibit a tendency for viscosity to decrease as shear rate increases, but the presence of swelling properties can sometimes help to suppress the decrease in viscosity with increasing shear rate.

[0038] When the resin composition exhibits swelling properties, it can be used at a shear rate of 10 s. -1 up to 100 S -1 It exhibits expansion within a certain range.

[0039] V of the resin composition at 130°C 10 There are no particular restrictions on the value of V1, and it can be selected according to the intended use of the resin composition.

[0040] For example, the V of the resin composition at 130°C 10 The values ​​of V1 can be independently below 2000 Pa·s, below 1500 Pa·s, or below 1000 Pa·s.

[0041] For example, the resin composition at 130°C V 10 The values ​​of V1 can be independently 10 Pa·s or more, 20 Pa·s or more, or 50 Pa·s or more.

[0042] In this disclosure, a rotational rheometer is used to determine the viscosity of the resin composition at 130°C.

[0043] The components contained in the resin composition disclosed herein will be described below.

[0044] There are no particular restrictions on the types of resin components contained in the resin composition; they can be selected according to the intended use of the resin composition.

[0045] For example, when the resin composition is used as a sealing material for electronic components, the resin composition may also contain a thermosetting resin and a hardener as resin components.

[0046] (Thermosetting resin)

[0047] There are no particular limitations on the types of thermosetting resins contained in the resin composition. Specifically, examples of thermosetting resins include: epoxy resins, phenolic resins, urea resins, melamine resins, urethane resins, silicone resins, and unsaturated polyester resins. In this disclosure, resins containing epoxy groups, such as acrylic resins, that exhibit both thermoplastic and thermosetting properties are included in the term "thermosetting resins." The thermosetting resin can be a solid or a liquid, but is preferably a solid. A single thermosetting resin can be used, or two or more can be used in combination.

[0048] The thermosetting resin preferably includes an epoxy resin. Specifically, examples of epoxy resins include: a phenolic varnish resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthol with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde under an acidic catalyst to obtain a phenolic varnish resin, and then epoxidizing the phenolic varnish resin to obtain a phenolic varnish-type epoxy resin (phenolic varnish-type epoxy resin, o-cresol varnish-type epoxy resin, etc.); and a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane-type epoxy resin obtained by epoxidation of alkyl phenolic resin; phenolic varnish resin obtained by co-condensation of the phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst, followed by epoxidation of the phenolic varnish resin; bisphenol-type epoxy resin as diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resin as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resin as diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing atom-type epoxy resin as diglycidyl ethers of bisphenol S, etc.; epoxy resin as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; and epoxy resin as phthalic acid or isophthalic acid. Glycidyl ester type epoxy resins of polycarboxylic acid compounds such as tetrahydrophthalic acid; glycidyl amine type epoxy resins obtained by replacing the active hydrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with glycidyl groups; dicyclopentadiene type epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and phenolic compounds; alicyclic epoxy resins such as diepoxidized vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclic (3,4-epoxy)cyclohexane-m-dioxane, obtained by epoxidizing the olefin bonds within the molecule; and glycidyl ethers as p-xylene-modified phenolic resins. p-Xylene-modified epoxy resin; p-Xylene-modified epoxy resin of glycidyl ether as a m-xylene-modified phenolic resin; terpene-modified epoxy resin of glycidyl ether as a terpene-modified phenolic resin; dicyclopentadiene-modified epoxy resin of glycidyl ether as a dicyclopentadiene-modified phenolic resin; cyclopentadiene-modified epoxy resin of glycidyl ether as a cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as a polycyclic aromatic ring-modified phenolic resin; naphthalene-type epoxy resin of glycidyl ether as a naphthalene-containing phenolic resin; halogenated phenolic varnish-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds using peracids such as peracetic acid.Aryl alkyl epoxy resins are obtained by epoxidation of aryl alkyl phenolic resins such as phenolic aryl alkyl resins and naphthol aryl alkyl resins. Epoxy resins can be used alone or in combination of two or more.

[0049] When the thermosetting resin is epoxy resin, there is no particular limitation on the epoxy equivalent (molecular weight / number of epoxy groups). From the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability, 100 g / eq to 1000 g / eq is preferred, and 150 g / eq to 500 g / eq is more preferred. The epoxy equivalent of the epoxy resin is set as a value obtained by measuring according to the method of Japanese Industrial Standards (JIS) K 7236:2009.

[0050] When the thermosetting resin is solid at 25°C, there are no particular limitations on its melting point or softening point. From the viewpoint of resistance to caking, the melting point or softening point of the thermosetting resin is preferably 40°C or higher, more preferably 50°C or higher. From the viewpoint of suppressing thickening of the resin composition caused by mixing, 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.

[0051] From the viewpoints of strength, flowability, heat resistance, and formability, the content of thermosetting resin is preferably 0.5% to 50% by mass relative to the total mass of the resin composition, more preferably 2% to 30% by mass, and even more preferably 2% to 20% by mass.

[0052] (hardener)

[0053] The resin composition may contain a curing agent used in conjunction with a thermosetting resin. Examples of curing agents used in conjunction with epoxy resins include: phenolic curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, block isocyanate curing agents, etc. A single curing agent may be used alone, or two or more may be used in combination. From the viewpoint of improving heat resistance, a phenolic curing agent (a curing agent containing phenolic hydroxyl groups as functional groups that react with epoxy groups) is preferred. The curing agent may be solid or liquid at room temperature and pressure (e.g., 25°C, atmospheric pressure), but is preferably solid.

[0054] Specifically, examples of phenolic curing agents include: resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol, and other polyphenolic compounds; phenolic varnish-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthol with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; and phenolic varnish-type phenolic resins obtained by condensing or co-condensing the aforementioned phenolic compounds with dimethoxy-p-xylene, bis(methoxy)-xylene, etc. Aryl alkyl phenol resins such as phenol and naphthol aryl alkyl resins synthesized from methyl biphenyl, etc.; p-xylene and / or m-xylene modified phenol resins; melamine modified phenol resins; terpene modified phenol resins; dicyclopentadiene-type phenol resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the aforementioned phenolic compounds with dicyclopentadiene; cyclopentadiene modified phenol resins; polycyclic aromatic ring modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the aforementioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenol resins obtained by copolymerizing two or more of these. Phenolic curing agents can be used alone or in combination of two or more.

[0055] There are no particular limitations on the functional group equivalent of the hardener (hydroxyl equivalent in the case of phenolic hardeners, and active hydrogen equivalent in the case of amine hardeners). From the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability, the functional group equivalent of the hardener is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 500 g / eq.

[0056] In the case of phenolic curing agents, the hydroxyl equivalent refers to the value calculated based on the hydroxyl value determined according to JIS K0070:1992. In the case of amine curing agents, the active hydrogen equivalent refers to the value calculated based on the amine value determined according to JIS K7237:1995.

[0057] When the hardener is a solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance when the resin composition is used, for example, in a sealing material application, the softening point or melting point of the hardener is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of workability during the manufacture of the resin composition.

[0058] The melting point or softening point of the hardener is set to a value obtained by measuring the same way as the melting point or softening point of the epoxy resin.

[0059] The equivalent ratio of thermosetting resin to 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 (functional groups in the curing agent / functional groups in the thermosetting resin), is not particularly limited. In terms of minimizing unreacted components, the equivalent ratio of thermosetting resin to curing agent is preferably set in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoint of formability, the equivalent ratio of thermosetting resin to curing agent is further preferably set in the range of 0.8 to 1.2.

[0060] (Inorganic particles)

[0061] There are no particular limitations on the materials of the inorganic particles contained in the resin composition. Specifically, examples of inorganic particle materials include: fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllium oxide, zircon, zircon, forsterite, steatite, spinel, aluminum-rich andalusite, titanium dioxide, talc, clay, mica, and other inorganic materials. Inorganic particles with flame-retardant properties may also be used. Examples of inorganic particles with flame-retardant properties include: aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc hydroxides, zinc borate, etc. From the viewpoint of reducing the coefficient of linear expansion, fused silica and other silica are preferred; from the viewpoint of high thermal conductivity, alumina is preferred.

[0062] The inorganic particles contained in the resin composition may be only one type or two or more types.

[0063] The maximum particle size of the inorganic particles contained in the resin composition is preferably 9.0 μm or less.

[0064] If the maximum particle size of the inorganic particles is below 9.0 μm, the viscosity will be higher at high shear rates (e.g., 10 s⁻¹). -1 The decrease below (above) is suppressed, V 10 The value of / V1 tends to increase.

[0065] If the maximum particle size of the inorganic particles is below 9.0 μm, there are no special restrictions. For example, it can be below 8.0 μm, below 7.0 μm, below 6.0 μm, below 5.0 μm, less than 5.0 μm, below 4.5 μm, below 4.0 μm, or below 3.5 μm.

[0066] There are no particular restrictions on the volume average particle size of inorganic particles.

[0067] From the viewpoint of suppressing the decrease in viscosity at high shear rates, the volume average particle size 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.

[0068] From the viewpoint of suppressing the aggregation of inorganic particles, the volume average particle size 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.

[0069] The volume average particle size of inorganic particles can be determined as the particle size (D50) at which the cumulative particle size distribution from the small diameter side is 50% in the volume reference particle size distribution obtained by laser scattering diffraction particle size distribution measuring device.

[0070] There are no particular limitations on the specific surface area obtained by the Brunauer-Emmett-Teller (BET) method for inorganic particles.

[0071] From the perspective of suppressing the decrease in viscosity at high shear rates, the specific surface area obtained by the BET method for inorganic particles is preferably 0.1 m². 2 / g or more, more preferably 0.5 m 2 / g or more, and preferably 1.0 m 2 / g or more.

[0072] From the perspective of suppressing the aggregation of inorganic particles, the preferred specific surface area of ​​inorganic particles obtained by the BET method is 50 m². 2 / g or less, preferably 30 m 2 / g or less, and preferably 20 m 2 / g or less.

[0073] The specific surface area of ​​inorganic particles obtained by the BET method can be determined according to JIS Z 8830:2013 and based on the nitrogen adsorption capacity of the inorganic particles.

[0074] There are no particular limitations on the specific surface area obtained by image analysis of inorganic particles.

[0075] From the perspective of suppressing the decrease in viscosity at high shear rates, the specific surface area of ​​inorganic particles obtained by image analysis is preferably 0.1 m². 2 / g or more, more preferably 0.5 m 2 / g or more, and preferably 1.0 m 2 / g or more.

[0076] From the perspective of suppressing the aggregation of inorganic particles, the preferred specific surface area of ​​inorganic particles obtained by image analysis is 50 m². 2 / g or less, preferably 30 m2 / g or less, and preferably 20 m 2 / g or less.

[0077] The specific surface area of ​​inorganic particles can be obtained by using image analysis methods. This can be achieved by using an electron microscope or similar tool to obtain images of inorganic particles and assuming that the particles in the obtained images are spherical.

[0078] There are no particular restrictions on the shape of the inorganic particles, but spherical shapes are preferred in terms of filling properties and mold wear suppression.

[0079] There is no particular limitation on the content of inorganic particles. From the viewpoint of further improving the properties of the cured resin composition, such as the coefficient of thermal expansion, coefficient of thermal conductivity, and coefficient of elasticity, the content of inorganic particles is preferably 30% or more by volume of the total resin composition, more preferably 40% or more by volume, more preferably 50% or more by volume, particularly preferably 60% or more by volume, and most preferably 65% ​​or more by volume.

[0080] From the viewpoint of improving the fluidity of the resin composition and reducing its viscosity, the content of inorganic particles is preferably 95% or less of the total volume of the resin composition, preferably 90% or less, and more preferably 85% or less.

[0081] The content of inorganic particles in the cured resin composition can be determined as follows: First, the total mass of the cured composition is measured. The cured composition is then calcined at 400°C for 2 hours, followed by calcination at 700°C for 3 hours to evaporate the resin components. The mass of the remaining inorganic particles is then measured. Based on the obtained masses and their specific gravities, the volume is calculated. The ratio of the volume of inorganic particles to the total volume of the cured composition is used as the content of inorganic particles.

[0082] (hardening accelerator)

[0083] The resin composition may also contain a curing accelerator. Specifically, examples of curing accelerators include: 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBN).[0]undecene-7, DBU) and other diazabicyclic alkenes, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other cyclic amidine compounds; derivatives of said cyclic amidine compounds; phenolic varnish salts of said cyclic amidine compounds or their derivatives; compounds with intramolecular polarization formed by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, diazonylphenylmethane and other compounds with π bonds to these compounds; Cyclic amidine compounds such as tetraphenylboron salts of DBU, DBN, 2-ethyl-4-methylimidazolium, and N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the aforementioned tertiary amine compounds; ammonium salts such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide; primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, and tri(alkylalkoxyphenyl)phosphine. Organophosphorus compounds such as tri(dialkylphenyl)phosphorus, tri(trialkylphenyl)phosphorus, tri(tetraalkylphenyl)phosphorus, tri(dialkoxyphenyl)phosphorus, tri(trialkoxyphenyl)phosphorus, tri(tetraalkoxyphenyl)phosphorus, trialkylphosphorus, dialkylarylphosphorus, alkyldiarylphosphorus, trinaphthylphosphorus, tri(benzyl)phosphorus, etc.; phosphorus compounds such as complexes of the organophosphorus with organoborons; phosphorus compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, etc., heavy... Compounds with intramolecular polarization formed by the addition of π-bonded compounds such as phenylmethane; compounds with intramolecular polarization obtained by reacting the organophosphorus or the phosphorus compound with halogenated phenol compounds such as 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 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-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation process.

[0084] Tetraphenylphosphonium and other tetrasubstituted phosphonium compounds; tetraphenylborates of tetraphenylphosphonium tetra-p-tolueneborate and other tetrasubstituted phosphonium compounds; tetrasubstituted phosphonium compounds such as salts of tetrasubstituted phosphonium and phenolic compounds; phosphate betaine compounds; adducts of phosphonium compounds and silane compounds, etc. Curing accelerators can be used alone or in combination of two or more.

[0085] When using epoxy resin as a thermosetting resin, triphenylphosphine, adducts of triphenylphosphine and quinone compounds are particularly preferred curing accelerators.

[0086] The content of the curing accelerator is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the resin component. If the amount of the curing accelerator is 0.1 parts by weight or more relative to 100 parts by weight of the resin component, there is a tendency for good curing in a short time. If the amount of the curing accelerator is 30 parts by weight or less relative to 100 parts by weight of the resin component, there is a tendency to obtain a molded article with a good curing speed that is not too fast.

[0087] (additive)

[0088] In addition to the components described above, the resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, and stress relievers. Besides the additives exemplified below, the resin composition may also contain various additives commonly used in the art, as needed.

[0089] (Coupling agent)

[0090] To improve the adhesion between the resin components and inorganic particles, the resin composition may also contain a coupling agent. Examples of known coupling agents include silane compounds, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0091] Examples of silane compounds include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 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 methacryloyloxyoctyltrimethoxysilane, etc.

[0092] Examples of titanium-based compounds include: isopropyl triisostearoyl titanate, isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(di-tetrazyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tetrazyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)vinyl titanate, isopropyl trioctyl oxytane titanate, isopropyl dimethacrylate isostearoyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylate titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis(dioctyl phosphate) titanate, etc.

[0093] When the resin composition contains a coupling agent, the amount of coupling agent is preferably 0.05 to 30 parts by mass relative to 100 parts by mass of inorganic particles, more preferably 0.1 to 20 parts by mass.

[0094] (Ion exchanger)

[0095] The resin composition may also contain an ion exchanger. Particularly when using the resin composition as a sealing molding material, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of electronic components including sealed elements, the presence of an ion exchanger is preferred. There are no particular limitations on the ion exchanger, and existing known alternatives may be used. Specifically, examples include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. One ion exchanger may be used alone, or two or more may be used in combination. Hydrotalcite represented by the following general formula (A) is preferred.

[0096] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ······(A)

[0097] (0 < X ​​≦ 0.5, m is a positive number)

[0098] When the resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture halogen ions, etc. For example, it is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the resin component, and more preferably 1 to 10 parts by mass.

[0099] (Mold release agent)

[0100] From the viewpoint of achieving good release properties from the mold during molding, the resin composition may also contain a release agent. There are no particular limitations on the release agent; existing known agents can be used. Specifically, examples include: palm wax, higher fatty acids such as lignite acid and stearic acid, metal salts of higher fatty acids, ester waxes such as lignite esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. A single release agent may be used, or two or more may be used in combination.

[0101] When the resin composition contains a release agent, its amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the resin component. If the amount of release agent is 0.01 parts by weight or more relative to 100 parts by weight of the resin component, there is a tendency to obtain sufficient release properties. If it is 10 parts by weight or less, there is a tendency to obtain better adhesion and curing properties.

[0102] (Flame retardant)

[0103] The resin composition may also contain flame retardants. There are no particular limitations on the flame retardant; existing known flame retardants may be used. Specifically, examples include organic or inorganic compounds, metal hydroxides, etc., containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms. A single flame retardant may be used, or two or more may be used in combination.

[0104] When the resin composition contains a flame retardant, there is no particular limitation as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 30 parts by weight relative to 100 parts by weight of the resin component, and more preferably 2 to 20 parts by weight.

[0105] (Coloring agent)

[0106] The resin composition may also contain a colorant. Examples of known colorants include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and iron oxide. The content of the colorant can be appropriately selected according to the intended purpose. A single colorant may be used, or two or more may be used in combination.

[0107] (Stress reliever)

[0108] Resin compositions may also contain stress relievers. By including stress relievers, warpage and cracking of the encapsulation can be reduced when the resin composition is used in sealing applications. Commonly used and known stress relievers (flexible agents) 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 natural rubber (NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, and silicone powder; and rubber particles with a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. Stress relievers can be used alone or in combination of two or more.

[0109] The resin composition can be solid or liquid at room temperature and pressure (e.g., 25°C, atmospheric pressure), but is preferably solid. When the resin composition is solid, there are no particular limitations on its shape; examples include powder, granules, and flakes.

[0110] <Uses of Resin Compositions>

[0111] The resin compositions manufactured using the methods of this disclosure can be used for a variety of applications. Preferred applications of the resin compositions include sealing materials for electronic component devices.

[0112] As electronic component devices, examples include lead frames, wiring conveyor tapes, wiring boards, glass, silicon wafers, organic substrates and other support components, components mounted on the support components (active components such as semiconductor chips, transistors, diodes, thyristors, etc., passive components such as capacitors, resistors, coils, etc.), and devices for sealing materials that seal around the components.

[0113] Methods for sealing electronic components using resin compositions include low-pressure transfer molding, injection molding, and compression molding.

[0114] <Method for manufacturing resin composition>

[0115] The method of manufacturing the resin composition disclosed herein includes preparing a granule comprising at least a portion of the inorganic particles and at least a portion of the resin components.

[0116] In this disclosure, "granules containing inorganic particles and resin components" refers to a substance formed by granulating a material containing at least inorganic particles and resin components.

[0117] The method disclosed herein can be used to effectively manufacture V. 10 Resin compositions with a V1 value of 0.7 or higher.

[0118] The rationale is that, for example, by making the inorganic particles and resin components into granules, the agglomeration caused by the interaction of the inorganic particles with each other can be suppressed.

[0119] The method disclosed herein is particularly preferred when the inorganic particles used in the manufacture of the resin composition have a small particle size (e.g., a maximum particle size of 9.0 μm or less).

[0120] As shown in the examples described later, if the particle size of the inorganic particles contained in the resin composition is reduced, then at low shear rates (e.g., 10 s), -1 The viscosity tends to increase when measured under the following conditions. In the resin composition produced by the method of this disclosure, even if the particle size of the inorganic particles is small, the viscosity remains low at low shear rates.

[0121] In the method disclosed herein, the resin component used in the preparation of the granules may be the entirety or a portion of the resin component contained in the resin composition.

[0122] For example, when the resin composition includes a thermosetting resin and a curing agent as resin components, granules containing inorganic particles and thermosetting resin, and granules containing inorganic particles and curing agent can be prepared separately. Alternatively, granules containing only inorganic particles and thermosetting resin, and granules containing inorganic particles and curing agent can be prepared as granules containing inorganic particles and resin components.

[0123] In the method disclosed herein, the inorganic particles used in the preparation of the granules may be the entirety or a portion of the inorganic particles contained in the resin composition.

[0124] From the viewpoint of suppressing the aggregation of inorganic particles, the resin component used in the preparation of the granules is preferably one with a charge opposite to that of the inorganic particles. For example, when the surface of the inorganic particles is positively charged, it is preferable to use a resin component with anionic functional groups such as phenolic hydroxyl groups; when the surface of the inorganic particles is negatively charged, it is preferable to use a resin component with cationic functional groups such as amino groups.

[0125] There are no particular restrictions on the particle size of the granules; selection can be made by considering factors such as workability when mixed with other materials.

[0126] The particle size of the granules can be selected from, for example, the range of 10 μm to 10000 μm, preferably the range of 100 μm to 5000 μm, and more preferably the range of 500 μm to 3000 μm.

[0127] There are no particular restrictions on the shape of the granules; they can be spherical, columnar, scaly, needle-like, etc.

[0128] There are no particular limitations on the method for preparing granules containing inorganic particles and resin components, and it can be carried out by known methods. For example, a granulator, extruder, or similar device can be used to granulate a mixture containing at least inorganic particles and resin components to obtain granules. Solvents may be used in the preparation of the mixture if necessary.

[0129] The granules used in the manufacture of the resin composition can be produced in-house or obtained as finished products.

[0130] Granulated materials containing inorganic particles and resin components may contain components other than inorganic particles and resin components.

[0131] In the method disclosed herein, granules containing inorganic particles and resin components can be mixed with other raw materials to manufacture a resin composition.

[0132] There are no particular restrictions on the method of mixing granules with other raw materials, and it can be carried out by known methods.

[0133] The method disclosed herein is particularly preferred when the resin composition is manufactured using a compounding extruder and when the inorganic particles used in the manufacture of the resin composition have a small particle size.

[0134] In other words, when inorganic particles that are not yet granulated are fed into the feeder of a mixing extruder, if the particle size of the inorganic particles is too small, it can easily lead to decreased efficiency and poor mixing in the mixing process. In the method disclosed herein, the inorganic particles are pre-granulated before being fed into the mixing extruder. Therefore, even when the particle size of the inorganic particles is small (e.g., the maximum particle size is 9.0 μm or less), a homogeneous resin composition can be efficiently manufactured using a mixing extruder.

[0135] [Example]

[0136] The following embodiments illustrate the implementation methods in detail, but this disclosure is not limited to these embodiments.

[0137] (1) Preparation of resin composition

[0138] The materials (parts by mass) shown in Table 1 were fed into an extrusion mixer to obtain a compound. The obtained compound was then pulverized to obtain a resin composition with a particle size of 1000 μm.

[0139] The epoxy resin 2, hardener 1, inorganic particles 4 and inorganic particles 5 used in Example 1 are in the state of granules obtained by the following method.

[0140] (Preparation of granules)

[0141] The raw material for granulation was added to a 3 L separable flask, a stirrer was inserted, and the mixture was stirred at 200 rpm for 2 hours to obtain a varnish-like mixture. Subsequently, the mixture was vacuum dried at 140°C for 2 hours to remove the solvent until the residual solvent content was less than 1% by mass, obtaining a solid substance. The obtained solid substance was pulverized to produce granules with an average particle size of 1000 μm.

[0142] (2) Evaluation of the physical properties of the resin composition

[0143] (Melt viscosity)

[0144] The resin composition was heated and melted, and the melt viscosity (ηFT) at 175°C was measured using a Koka Flow Tester. The results are shown in Table 1.

[0145] (Gel time)

[0146] A 0.5 g sample of the resin composition was placed on a hot plate heated to 175°C. Using a clamp, the sample was spread into a circle of 2.0 cm to 2.5 cm using a rotation speed of 20 to 25 rpm. The time (in seconds) from when the sample was placed on the hot plate until the tackiness of the sample disappeared and it became a gel and was peeled off from the hot plate was measured as the gel time (GT).

[0147] The gelation time of the resin composition at 175°C is preferably 30 to 90 seconds, more preferably 40 to 60 seconds.

[0148] (Viscosity)

[0149] The viscosity of the resin composition at 130°C was determined using a rotational rheometer manufactured by NETZSCH while varying the shear rate. The shear rate was 10 s⁻¹. -1 Viscosity V during measurement 10 At a shearing speed of 1 second -1 The viscosity V1 measured during the test, and the V calculated from it. 10 The value of / V1 is shown in Table 1.

[0150] The viscosity measurements of the resin compositions obtained in Example 1 and Comparative Example 2 at 130°C are also plotted in the figure. Figure 1 .

[0151] The details of the materials recorded in Table 1 are as follows.

[0152] • Epoxy Resin 1: YX-4000 (trade name, Mitsubishi Chemical Corporation, biphenyl type epoxy resin with epoxy equivalent of 180 g / eq to 192 g / eq and melting point of 105℃)

[0153] • Epoxy Resin 2: NC-3000 (trade name, Nippon Kayaku Co., Ltd., aralkyl type epoxy resin with epoxy equivalent of 265 g / eq to 285 g / eq and softening point of 53℃ to 63℃)

[0154] • Hardener 1: MEHC-7851SS (trade name, Meiwa Kasei Corporation, biphenyl aralkyl phenolic resin with a hydroxyl equivalent of 205 g / eq, softening point 60℃~70℃)

[0155] • Hardener 2: HP-850N (trade name, Resonac Inc., phenolic varnish resin with hydroxyl equivalent of 108)

[0156] • Hardening accelerators: Phosphorus-based hardening accelerators

[0157] Coupling agent 1: KBM-573 (trade name, Shin-Etsu Chemical Industry Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane)

[0158] Coupling agent 2: KBM-503 (trade name, Shin-Etsu Chemical Industry Co., Ltd., 3-methacryloyloxypropyltrimethoxysilane)

[0159] Release agent: lignite ester

[0160] • Colorant: Carbon black

[0161] • Inorganic particles 1: Spherical silica particles with a maximum particle size of less than 20.0 μm and a volume average particle size of 11 μm.

[0162] • Inorganic particles 2: Spherical silica particles with a maximum particle size of less than 10.0 μm and a volume average particle size of 4 μm.

[0163] • Inorganic particles 3: Spherical silica particles with a maximum particle size of less than 9.0 μm and a volume average particle size of 2.3 μm.

[0164] • Inorganic particles 4: Spherical silica particles with a maximum particle size of less than 5.0 μm and a volume average particle size of 1.5 μm.

[0165] • Inorganic particles 5: Spherical silica particles with a maximum particle size of less than 5.0 μm and a volume average particle size of 0.3 μm.

[0166] • Inorganic particles 6: Spherical silica particles with a maximum particle size of less than 5.0 μm and a volume average particle size of 0.6 μm.

[0167] [Table 1]

[0168]

[0169] As shown in Table 1, in the resin compositions obtained in Examples 1 to 4, the temperature was 130°C and the shear rate was 10 s. -1 Viscosity V measured below 10 Divide by the temperature at 130℃ and the shear rate at 1 second. -1 The value V is obtained by measuring the viscosity V1 at the time of the test. 10 With a V1 value of 0.7 or higher, it exhibits excellent flow characteristics.

[0170] V, as the resin composition obtained in Examples 1 to 4 10 The value shown as / V1 is greater than the V of the resin compositions obtained in Comparative Examples 1 and 2. 10 The reason for the value shown in / V1 is that, for example, the fact that the maximum particle size of the inorganic particles contained in the resin compositions of Examples 1 to 4 is smaller than the maximum particle size of the inorganic particles contained in the resin compositions of Comparative Example 1 and Comparative Example 2 helps to suppress the decrease in viscosity at high shear rates.

[0171] The entire contents of the disclosure of Japanese Patent Application No. 2023-216233 are incorporated herein by reference.

[0172] All documents, patent applications and technical specifications set forth in this specification are incorporated herein by reference to the same extent as those specifically and separately described and incorporated herein by reference.

Claims

1. A resin composition comprising a resin component and inorganic particles, subjected to a shear rate of 10 s at 130°C. -1 Viscosity V measured below 10 Divide by the temperature at 130℃ and the shear rate at 1 second. -1 The value V is obtained by measuring the viscosity V1 at the time of measurement. 10 / V1 is 0.7 or higher.

2. The resin composition according to claim 1, wherein, The maximum particle size of the inorganic particles is less than 9.0 μm.

3. The resin composition according to claim 1, wherein, The inorganic particles comprise more than 70% by mass of the total resin composition.

4. The resin composition according to claim 1, wherein, The resin component includes epoxy resin.

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

6. A method for manufacturing a resin composition, comprising the method of manufacturing a resin composition according to any one of claims 1 to 5, wherein the method of manufacturing the resin composition includes... Prepare a granule comprising at least a portion of the inorganic particles and at least a portion of the resin component.

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