Resin composition and method for producing resin composition

Abstract

To provide a resin composition having superior flow characteristics during melting, and a method for producing the resin composition.SOLUTION: A 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 a viscosity V10 measured at 130°C and a shear rate of 10S-1 by a viscosity V1 measured at 130°C and a shear rate of 1S-1.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] An electronic component device formed by encapsulating the periphery of an element such as a semiconductor chip or the space between the element and the substrate with an insulating material called an encapsulant is used in various electronic devices. As the encapsulant, a resin composition containing a thermosetting resin such as an epoxy resin and inorganic particles such as silica is widely used. As one of the methods for manufacturing a semiconductor package using a resin composition as an encapsulant, there is a method (transfer molding method) in which a resin composition that is solid at room temperature is heated and melted, and the melted resin composition is injected into a mold and cured.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When manufacturing a semiconductor package by the transfer molding method, variations may occur in the shear rate applied to the resin composition due to the structure inside the mold into which the resin composition is injected. The resin composition used as an encapsulant generally exhibits dependence on the shear rate, and the viscosity tends to decrease as the shear rate increases. When a resin composition with a large dependence of viscosity change on the shear rate is injected into the mold, variations are likely to occur in the flow state of the resin composition. Variations in the flow state of the resin composition inside the mold may cause appearance abnormalities (flow marks) in the cured product obtained by curing the resin composition. In view of such a situation, an object of the present disclosure is to provide a resin composition having excellent flow characteristics during melting and a method for producing the resin composition.

Means for Solving the Problems

[0005] The means for solving the above problems include the following embodiments. <1>A resin composition containing a resin component and inorganic particles, wherein a value V obtained by dividing the viscosity V measured at 130 °C and a shear rate of 10 S -1 by the viscosity V1 measured at 130 °C and a shear rate of 1 S 10 is 0.7 or more. -1 10 / V1 is 0.7 or more. <2>The resin composition according to <1>, wherein the maximum particle diameter of the inorganic particles is 9.0 μm or less. <3>The resin composition according to <1> or <2>, wherein the content of the inorganic particles is 70% by mass or more of the entire resin composition. <4>The resin composition according to any one of <1> to <3>, wherein the resin component contains an epoxy resin. <5>The resin composition according to any one of <1> to <4>, which is solid at normal temperature and normal pressure. <6>A method for producing the resin composition according to any one of <1> to <5>, including preparing a granulated product containing at least a part of the inorganic particles and at least a part of the resin component.

Advantages of the Invention

[0006] According to the present disclosure, a resin composition having excellent flow characteristics during melting and a method for producing the resin composition are provided.

Brief Description of the Drawings

[0007]

Figure 1

Embodiments for Carrying Out the Invention

[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, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present invention.

[0009] In the present disclosure, the term "step" includes, in addition to steps independent of other steps, the step even if it cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the numerical range indicated by "~" in the present disclosure, the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stepwise descriptions. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may include a plurality of types. When there are a plurality of types of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of types of particles present in the composition, unless otherwise specified. In the present disclosure, solid, solid state, liquid state, and liquid mean the properties under normal temperature and normal pressure (for example, 25 °C, under atmospheric pressure), unless otherwise specified.

[0010] <Resin composition> The resin composition of the present disclosure contains a resin component and inorganic particles, and the viscosity V measured at 130 °C and a shear rate of 10 S -1 when measured 10 is divided by the viscosity V1 measured at 130 °C and a shear rate of 1 S -1 when measured to obtain a value V 10 / V1 is 0.7 or more.

[0011] V 10 / V1 indicates the degree of dependence of the viscosity change of the resin composition on the shear rate, and V 10 The larger the / V1, the smaller the degree of decrease in the viscosity of the resin composition with an increase in the shear rate (that is, the smaller the dependence of the viscosity change of the resin composition on the shear rate). The resin composition of the present disclosure has V 10 / V1 is 0.7 or more. Therefore, the resin composition of the present disclosure has little variation in the flow state when injected into the mold and exhibits excellent flow characteristics.

[0012] The V 10 / V1 of the resin composition is preferably 0.75 or more, more preferably 0.85 or more, and still more preferably 0.90 or more. The V 10 The upper limit value of / V1 of the resin composition is not particularly limited, and may be, for example, 1.1 or less, or 1.05 or less.

[0013] The resin composition may exhibit dilatancy (a phenomenon in which the viscosity increases as the shear rate increases) or may not exhibit dilatancy. The resin composition generally shows a tendency for the viscosity to decrease as the shear rate increases, but the occurrence of dilatancy may contribute to the suppression of the decrease in viscosity accompanying the increase in the shear rate. When the resin composition exhibits dilatancy, dilatancy may be exhibited within the range of shear rate from 10S -1 to 100S -1 The values of V

[0014] and V1 of the resin composition at 130 °C are not particularly limited and can be selected according to the use of the resin composition and the like. 10 For example, the values of V and V1 of the resin composition at 130 °C may each independently be 2000 Pa·s or less, 1500 Pa·s or less, or 1000 Pa·s or less. 10 ​For example, the values of V and V1 of the resin composition at 130°C may each independently be 10 Pa·s or more, 20 Pa·s or more, or 50 Pa·s or more. 10

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

[0016] Hereinafter, each component included in the resin composition of the present disclosure will be described. The type of the resin component included in the resin composition is not particularly limited and can be selected according to the use of the resin composition and the like. For example, when the resin composition is used as a sealing material for an electronic component device, the resin composition may contain a thermosetting resin and a curing agent as resin components.

[0017] (Thermosetting resin) The type of the thermosetting resin included in the resin composition is not particularly limited. Specific examples of the thermosetting resin include epoxy resins, phenolic resins, urea resins, melamine resins, urethane resins, silicone resins, unsaturated polyester resins, and the like. In the present disclosure, those exhibiting both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups, are included in the "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.

[0018] The thermosetting resin preferably contains an epoxy resin. Specifically, as the epoxy resin, a novolac epoxy resin obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst (phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc.); a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by condensing or co-condensing the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst; a copolymer type epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensing the above phenolic compound and naphthol compound and an aldehyde compound under an acidic catalyst; a diphenylmethane type epoxy resin which is a diglycidyl ether such as bisphenol A, bisphenol F; a biphenyl type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a stilbene type epoxy resin which is a diglycidyl ether of a stilbene-based phenolic compound; a sulfur atom-containing type epoxy resin which is a diglycidyl ether such as bisphenol S; an epoxy resin which is a glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol; a glycidyl ester type epoxy resin which is a glycidyl ester of a polycarboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; a glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid is substituted with a glycidyl group; a dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenolic compound;Vinylcyclohexene diepoxide, which is obtained by epoxidizing the olefin bond within the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; Paraxylylene-modified epoxy resin, which is the glycidyl ether of paraxylylene-modified phenol resin; Metaxylylene-modified epoxy resin, which is the glycidyl ether of metaxylylene-modified phenol resin; Terpene-modified epoxy resin, which is the glycidyl ether of terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is the glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is the glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin, which is the glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene-type epoxy resin, which is the glycidyl ether of naphthalene ring-containing phenol resin; Halogenated phenol novolac-type epoxy resin; Hydroquinone-type epoxy resin; Trimethylolpropane-type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin; and the like. The epoxy resin 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 the 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 shall be the value measured by the method according to 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 perspective of blocking resistance, the melting point or softening point of the thermosetting resin is preferably 40°C or higher, more preferably 50°C or higher. From the perspective of suppressing the thickening of the resin composition by 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 perspectives 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 based on the total mass of the resin composition.

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

[0023] Specific examples of phenolic curing agents include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and at least one phenolic compound selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, which are condensed or co-condensed under an acidic catalyst to obtain a novolak-type phenolic resin; aralkyl-type phenolic resins such as phenolic resins and naphthol aralkyl resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.; p-xylylene and / or m-xylylene modified phenolic resins; melamine modified phenolic resins; terpene modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization from the above phenolic compounds and dicyclopentadiene; cyclopentadiene modified phenolic resins; polycyclic aromatic ring modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenolic resins obtained by copolymerizing two or more of these, and the like. The phenolic curing agent may be used alone or in combination of two or more kinds.

[0024] The functional group equivalent of the curing agent (the hydroxyl group equivalent in the case of a phenolic curing agent and the 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 in the case of a phenolic curing agent refers to a value calculated based on the hydroxyl value measured in accordance with JIS K0070:1992. Further, the active hydrogen equivalent in the case of an amine curing agent refers to 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. From the viewpoints of moldability and reflow resistance when the resin composition is used as a sealing material, the softening point or melting point of the curing agent is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of handleability during the production of the resin composition.

[0027] The melting point or softening point of the curing agent shall be 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, that is, 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. From the related aspect of suppressing each unreacted component as little as possible, 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 set in the range of 0.6 to 1.3. From the viewpoint of moldability, the equivalent ratio of the thermosetting resin to the curing agent is more preferably 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 silica such as fused silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, mica and other inorganic materials. Inorganic particles having a flame retardant effect may be used. Examples of the inorganic particles having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc, and zinc borate. Among the inorganic particles, silica such as fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic particles contained in the resin composition may be only one kind or two or more kinds.

[0030] The maximum particle diameter of the inorganic particles contained in the resin composition is preferably 9.0 μm or less. When the maximum particle diameter of the inorganic particles is 9.0 μm or less, the decrease in viscosity at a high shear rate (for example, 10 s -1 or more) is suppressed, and the value of V 10 / V1 tends to increase. The maximum particle diameter 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 the decrease in viscosity at a high shear rate, 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 the 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 value from the smaller diameter side becomes 50% in the volume-based particle size distribution measured by a laser scattering diffraction method particle size distribution measuring device.

[0032] The specific surface area of the inorganic particles by the BET method is not particularly limited. From the viewpoint of suppressing the decrease in viscosity at high shear rates, the specific surface area of the inorganic particles by the BET method is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, and even more preferably 1.0 m 2 / g or more. From the viewpoint of suppressing the aggregation of the inorganic particles, the specific surface area of the inorganic particles by the BET method is preferably 50 m 2 / g or less, more preferably 30 m 2 / g or less, and even more preferably 20 m 2 / g or less.

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

[0034] The specific surface area of the inorganic particles by the image analysis method is not particularly limited. From the viewpoint of suppressing the decrease in viscosity at high shear rates, the specific surface area of the inorganic particles by the image analysis method is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, and even more preferably 1.0 m 2 / g or more. From the viewpoint of suppressing the aggregation of the inorganic particles, the specific surface area of the inorganic particles by the image analysis method is preferably 50 m 2 / g or less, more preferably 30 m 2 / g or less, and even more preferably 20 m 2 / g or less.

[0035] The specific surface area of inorganic particles by the image analysis method 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, and spherical shape is preferable from the viewpoints of filling property and suppression of mold wear.

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

[0038] The content of the inorganic particles in the cured product of the resin composition can be measured as follows. First, measure the total mass of the cured product, bake the cured product at 400 °C for 2 hours and then at 700 °C for 3 hours to evaporate the resin component etc., and measure the mass of the remaining inorganic particles. Calculate the volume from each obtained mass and respective specific gravity, obtain the ratio of the volume of the inorganic particles to the total volume of the cured product, and take it as the content of the 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 novolak salts of the cyclic amidine compounds or their derivatives; compounds having intramolecular polarization formed by adding a compound having a π bond, such as maleic anhydride, 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, phenyl-1,4-benzoquinone, and diazophenylmethane, to these compounds; 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 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 like ethylphosphine and phenylphosphine, secondary phosphines like dimethylphosphine and diphenylphosphine, and tertiary phosphines like 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, tris(benzyl)phosphine, etc.; phosphine compounds such as complexes of the above organic phosphines and organic borons; compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, 1,4-benzoquinone, 2,5-xylenequinone, 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. to the above organic phosphine or the above phosphine compound; compounds having intramolecular polarization obtained by reacting the above organic phosphine or the above phosphine compound with a halogenated phenol compound 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-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and then undergoing a dehydrohalogenation step.Tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetra-substituted phosphonium tetraphenylborate salts such as tetraphenylphosphonium tetra-p-tolylborate, salts of tetra-substituted phosphonium and phenolic compounds, etc.; phosphobetaine compounds; adducts of phosphonium compounds and silane compounds, etc. are exemplified. The curing accelerator may be used alone or in combination of two or more kinds.

[0040] When an epoxy resin is used as the thermosetting resin, particularly preferred curing accelerators include triphenylphosphine, adducts of triphenylphosphine and quinone compounds, etc.

[0041] The content of the curing accelerator is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

[0042] (Additive) In addition to the above components, the resin composition may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, stress relaxants, etc. The resin composition may contain various additives generally used in the technical field as needed in addition to the additives exemplified below.

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

[0044] Examples of the 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, methacryloxyoctyltrimethoxysilane, and the like.

[0045] Examples of the titanium compounds include isopropyltriisostearoyl titanate, isopropyltris(dioctyl pyrophosphate) titanate, isopropyltri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearyldiacryl titanate, isopropyltri(dioctyl phosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis(dioctyl phosphite) titanate, and the like.

[0046] When the resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 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 a molding material for sealing, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed, it is preferable to contain an ion exchanger. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, hydrotalcite compounds, and hydrated oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth can be mentioned. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0048] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0049] When the resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component.

[0050] (Release agent) The resin composition may contain a release agent from the viewpoint of obtaining good mold release property with the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, carnauba wax, higher fatty acids such as montanic acid and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene can be mentioned. The release agent may be used alone or in combination of two or more.

[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, the releasability tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness and curability tend to be obtained.

[0052] (Flame retardant) The resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specifically, organic or inorganic compounds containing a halogen atom, antimony atom, nitrogen atom or phosphorus atom, metal hydroxides, etc. can be mentioned. The flame retardant 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 a desired flame retardant effect. For example, it is preferably 1 to 30 parts by mass, 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 according to the purpose and the like. The colorant may be used alone or in combination of two or more.

[0055] (Stress reliever) The resin composition may contain a stress reliever. By containing a stress reliever, it is possible to reduce warping deformation of the package and the occurrence of package cracks when the resin composition is used as a sealing material. Examples of the stress reliever include known stress relievers (plasticizers) generally used. Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress reliever may be used alone or in combination of two or more kinds.

[0056] The resin composition may be solid or liquid at normal temperature and pressure (for example, 25 ° C, atmospheric pressure), and it is preferably solid. The shape of the resin composition when it is solid is not particularly limited, and examples include powder form, granular form, and tablet form.

[0057] <Uses of the 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 a sealing material for electronic component devices.

[0058] Examples of the electronic component device include a support member such as a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, and an organic substrate, an element (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) mounted on the support member, and a sealing material for sealing the periphery of the element.

[0059] Examples of the method for sealing an electronic component device using the resin composition include a low-pressure transfer molding method, an injection molding method, and a compression molding method.

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

[0061] In the present disclosure, the "granulated product containing inorganic particles and a resin component" refers to a granulated material containing at least inorganic particles and a resin component. According to the method of the present disclosure, V 10 A resin composition having a V / V1 value of 0.7 or more can be effectively produced. For example, it is considered that aggregations due to the interaction between inorganic particles are suppressed by forming the inorganic particles into a granulated product together with the resin component.

[0062] The method of the present disclosure is particularly suitable when the particle diameter of the inorganic particles used in the production of the resin composition is small (for example, the maximum particle diameter is 9.0 μm or less). As shown in the examples described below, when the particle diameter of the inorganic particles contained in the resin composition is reduced, the viscosity measured at a low shear rate (for example, 10 S -1 or less) tends to increase. The resin composition produced by the method of the present disclosure maintains a low viscosity at a low shear rate even when the particle diameter of the inorganic particles is small.

[0063] In the method of the present disclosure, the resin component used for preparing the granulated product may be the whole or a 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 granulated product containing inorganic particles and the thermosetting resin and a granulated product containing inorganic particles and the curing agent may be prepared respectively, or only one of the granulated product containing inorganic particles and the thermosetting resin and the granulated product containing inorganic particles and the curing agent may be prepared as the granulated product containing inorganic particles and a resin component.

[0064] In the method of the present disclosure, the inorganic particles used for preparing the granulated product may be all or part of the inorganic particles contained in the resin composition. From the viewpoint of suppressing aggregation of inorganic particles, it is preferable that the resin component used for preparing the granulated product has an opposite charge property to the inorganic particles. For example, when the surface of the inorganic particles is positively charged, it is preferable to use a resin component having an anionic functional group such as a phenolic hydroxyl group. When the surface of the inorganic particles is 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 in consideration of workability when mixing with other materials. The particle size of the granulated product can be selected, for example, from the range of 10 μm to 10,000 μm, preferably in the range of 100 μm to 5,000 μm, and more preferably in the range of 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 the granulated product containing inorganic particles and a resin component is not particularly limited and can be carried out by known methods. For example, a mixture containing at least inorganic particles and a resin component can be granulated using a pulverizer, an extruder, etc. to obtain a granulated product. If necessary, a solvent may be used when preparing the mixture. The granulated product used for manufacturing the resin composition may be produced by itself or obtained as a ready-made product. The granulated product containing inorganic particles and a resin component may contain components other than inorganic particles and the resin component.

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

[0068] The method of the present disclosure is particularly suitable for producing a resin composition using a kneading extruder, especially when the particle size of the inorganic particles used in the production of the resin composition is small. That is, when inorganic particles that are not in the form of pellets 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 and poor kneading. In the method of the present disclosure, the inorganic particles are made into pellets in advance 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 a kneading extruder.

Examples

[0069] Hereinafter, the above-described embodiments will be specifically described by way of 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 put into an extrusion kneader to obtain a kneaded product. The obtained kneaded product was pulverized to obtain a resin composition having a particle size of 1000 μm. The epoxy resin 2, curing agent 1, inorganic particles 4, and inorganic particles 5 used in Example 1 are in the form of pellets obtained by the following method.

[0071] (Preparation of pellets) The raw materials for the pellets were put into 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. Next, vacuum drying was performed at 140 °C for 2 hours to remove the solvent until the residual solvent rate of the mixture was less than 1% by mass to obtain a solid. The obtained solid was pulverized to produce pellets having an average particle size of 1000 μm.

[0072] (2) Physical property evaluation of resin composition (Melt viscosity) The resin composition was heated and melted, and the melt viscosity (ηFT) at 175 °C was measured using a Koka-type flow tester. The results are shown in Table 1.

[0073] (Gel time) 0.5 g of the resin composition sample was placed on a hot plate heated to 175°C, and using a jig, the sample was spread into a circular shape with a diameter of 2.0 cm to 2.5 cm at a rotational speed of 20 to 25 revolutions per minute. The time (seconds) from when the sample was placed on the hot plate until the sample lost its viscosity and became gel-like and peeled off from the hot plate was measured as the gel time (GT). The gel time of the resin composition at 175°C is preferably 30 seconds to 90 seconds, and more preferably 40 seconds 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. The viscosity V measured at a shear rate of 10 S -1 The viscosity V1 measured at a shear rate of 1 S 10 and the value of V -1 calculated from these and V1 are shown in Table 1. 10 / V1 are shown in Table 1. In addition, a graph of the viscosity measurement results of the resin compositions obtained in Example 1 and Comparative Example 2 at 130°C is shown in FIG. 1.

[0075] The details of the materials described 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) ·Hardener 1: MEHC-7851SS (trade name, Meiwafosis Co., Ltd., biphenylene aralkyl-type phenol resin with a hydroxyl equivalent of 205 g / eq, softening point 60°C to 70°C) ·Hardener 2: HP-850N (trade name, Resonac Co., Ltd., phenol novolak resin with a hydroxyl 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) · Release agent: montanic acid ester · Colorant: carbon black

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

[0078]

Table 1

[0079] As shown in Table 1, the resin compositions obtained in Examples 1 to 4 had a viscosity V -1 measured at 130°C and a shear rate of 10 S 10 divided by the viscosity V1 measured at 130°C and a shear rate of 1 S -1 gave a V 10 / V1 of 0.7 or more, indicating excellent flow characteristics. The V 10 / V1 of the resin compositions obtained in Examples 1 to 4 was higher than the V 10As a reason for being larger than / V1, for example, it is considered that the fact that the maximum particle diameter of the inorganic particles contained in the resin compositions of Examples 1 to 4 is smaller than the maximum particle diameter of the inorganic particles contained in the resin compositions of Comparative Examples 1 and 2 contributed to the suppression of the decrease in viscosity at a high shear rate.

Claims

1. A resin composition containing a resin component and inorganic particles, having a viscosity V measured at 130°C and a shear rate of 10 S －１ and a viscosity V measured at 130°C and a shear rate of 1 S １０ wherein a value V －１ obtained by dividing the former by the latter, i.e., V １ / V １０ is 0.7 or more １ is provided.

2. The resin composition according to claim 1, wherein the maximum particle diameter 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% by mass or more of the entire resin composition.

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

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

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

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