JP2023100761A - Resin composition for encapsulation, electronic component device and method for manufacturing electronic component device - Google Patents

Abstract

To provide a resin composition for encapsulation, a cured product of which has a low dielectric loss tangent, an electronic component device encapsulated thereby, and a method for manufacturing an electronic component device encapsulated thereby.SOLUTION: Provided is a resin composition for encapsulation, the composition containing an epoxy resin, a hardening agent and an inorganic filler material. The hardening agent contains an activate ester compound, and the average particle diameter of the inorganic filler material is 5 μm-100 μm.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a sealing resin composition, an electronic component device, and a method for manufacturing an electronic component device.

The amount of transmission loss that occurs when radio waves transmitted for communication are thermally converted in a dielectric is expressed as the product of the frequency, the square root of the dielectric constant, and the dielectric loss tangent. In other words, since the transmission signal is likely to be converted into heat in proportion to the frequency, the higher the frequency band, the lower the dielectric property of the material of the communication member is required in order to suppress the transmission loss.

For example, Patent Documents 1 and 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for epoxy resins, and it is said that the dielectric loss tangent of the cured product can be kept low.

JP 2012-246367 A JP 2014-114352 A

2. Description of the Related Art In the field of information communication, radio waves are becoming higher in frequency with an increase in the number of channels and an increase in the amount of information to be transmitted. Fifth generation mobile communication systems are currently being studied worldwide, and some frequency bands in the range of about 30 GHz to 70 GHz are listed as candidates for the frequency band to be used. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so the material of communication members is required to have a lower dielectric loss tangent.

The embodiments of the present disclosure have been made under the above circumstances.

An object of the present disclosure is to provide a sealing resin composition having a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a method for manufacturing an electronic component device sealed using the same. and

Specific means for solving the above problems include the following aspects.

[1] A sealing resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the inorganic filler has an average particle size of 5 μm to 100 μm.
[2] An electronic component device comprising a supporting member, an element arranged on the supporting member, and a cured product of the encapsulating resin composition according to [1] sealing the element.
[3] A method of manufacturing an electronic component device, comprising the steps of: placing an element on a support member; and sealing the element with the sealing resin composition according to [1].

According to the present disclosure, a sealing resin composition having a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a method for manufacturing an electronic component device sealed using the same are provided. .

In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
Particles corresponding to each component in the present disclosure may include a plurality of types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

<Resin composition for encapsulation>
The encapsulating resin composition of the present disclosure contains an epoxy resin, a curing agent and an inorganic filler, the curing agent contains an active ester compound, and the inorganic filler has an average particle size of 5 μm to 100 μm.

The active ester compound in the present disclosure refers to a compound that has one or more ester groups that react with epoxy groups in one molecule and that has the effect of curing the epoxy resin.

Conventionally, phenol curing agents, amine curing agents, and the like are generally used as curing agents for epoxy resins, and secondary hydroxyl groups are generated in the reaction between epoxy resins and phenol curing agents or amine curing agents. In contrast, the reaction between the epoxy resin and the active ester compound produces ester groups instead of secondary hydroxyl groups. Since the ester group has a lower polarity than the secondary hydroxyl group, the encapsulating resin composition of the present disclosure contains only a curing agent that generates a secondary hydroxyl group as a curing agent, The dielectric loss tangent of the cured product can be kept low.

In the encapsulating resin composition of the present disclosure, the dielectric loss tangent of the cured product can be suppressed to a lower level by including the inorganic filler having an average particle diameter of 5 μm or more. The smaller the particle size of the inorganic filler, the larger the specific surface area and the more the amount of surface hydroxyl groups per unit amount. Therefore, the amount of hydroxyl groups contained in the cured product of the encapsulating resin composition can be reduced, and as a result, the dielectric loss tangent of the cured product can be kept lower.
On the other hand, from the viewpoint of ensuring the filling properties of the encapsulating resin composition, the average particle size of the inorganic filler contained in the encapsulating resin composition of the present disclosure is 100 μm or less.

(Epoxy resin)
The type of epoxy resin is not particularly limited as long as it has an epoxy group in its molecule.

Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolak type epoxy resins, ortho-cresol novolac-type epoxy resins, etc.); triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of acidic catalysts as epoxy resins. a triphenylmethane-type epoxy resin obtained by epoxidizing a triphenylmethane-type epoxy resin; a copolymer-type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, diphenylmethane-type epoxy resins that are diglycidyl ethers such as bisphenol F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers such as S; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxy resin which is a glycidyl ester of; aniline, diaminodiphenylmethane, glycidyl amine type epoxy resin in which the active hydrogen bonded to the nitrogen atom of isocyanuric acid is substituted with a glycidyl group; dicyclopentadiene type epoxy resins obtained by epoxidizing condensation resins; vinylcyclohexene diepoxides obtained by epoxidizing intramolecular olefin bonds, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, Alicyclic epoxy resins such as 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; paraxylylene-modified epoxy resins that are glycidyl ethers of paraxylylene-modified phenol resins; Metaxylylene-modified epoxy resin that is a glycidyl ether of meta-xylylene-modified phenolic resin; Terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenolic resin; Dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenolic resin; Cyclopentadiene-modified phenol Cyclopentadiene-modified epoxy resin that is a glycidyl ether of a resin; Polycyclic aromatic ring-modified epoxy resin that is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; Naphthalene-type epoxy resin that is a glycidyl ether of a naphthalene ring-containing phenol resin; Halogenated phenol Novolak type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; aralkyl type such as phenol aralkyl resin and naphthol aralkyl resin aralkyl type epoxy resins obtained by epoxidizing phenolic resins; and the like. Further examples of epoxy resins include epoxidized acrylic resins and the like. These epoxy resins may be used singly or in combination of two or more.

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, more preferably 150 g/eq to 500 g/eq.

Let the epoxy equivalent of an epoxy resin be the value measured by the method according to JISK7236:2009.

If the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability in preparation of the encapsulating resin composition, it is more preferably 50° C. to 130° C.

The melting point or softening point of the epoxy resin is a value measured by differential scanning calorimetry (DSC) or a method (ring and ball method) according to JIS K 7234:1986.

The content of the epoxy resin in the resin composition for sealing is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc. % is more preferred.

(curing agent)
The encapsulating resin composition of the present disclosure contains at least an active ester compound as a curing agent. The encapsulating resin composition of the present disclosure may contain a curing agent other than the active ester compound.

As described above, the encapsulating resin composition of the present disclosure can reduce the dielectric loss tangent of the cured product by using an active ester compound as a curing agent.
In addition, since the polar groups in the cured product increase the water absorption of the cured product, the concentration of polar groups in the cured product can be suppressed by using an active ester compound as a curing agent, and the water absorption of the cured product can be suppressed. can. By suppressing the water absorption of the cured product, that is, by suppressing the content of H ₂ O, which is a polar molecule, the dielectric loss tangent of the cured product can be further reduced. The water absorption rate of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, even more preferably 0% to 0.25%. Here, the water absorption rate of the cured product is the mass increase rate determined by the pressure cooker test (121° C., 2.1 atm, 24 hours).

The type of active ester compound is not particularly limited as long as it is a compound having at least one ester group in the molecule that reacts with an epoxy group.

Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esters of heterocyclic hydroxy compounds.

Examples of active ester compounds include ester compounds obtained from at least one of aliphatic carboxylic acids and aromatic carboxylic acids and at least one of aliphatic hydroxy compounds and aromatic hydroxy compounds. Ester compounds containing an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to having an aliphatic chain. Ester compounds containing an aromatic compound as a polycondensation component tend to have excellent heat resistance due to having an aromatic ring.

A specific example of the active ester compound is an aromatic ester obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group, and the hydrogen atom of the aromatic ring described above. A mixture of a monohydric phenol in which one of is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 of the hydrogen atoms on the aromatic ring are substituted with a hydroxyl group is used as a raw material, and a mixture of an aromatic carboxylic acid and a phenolic hydroxyl group is used. Aromatic esters obtained by condensation reactions are preferred. That is, aromatic esters having structural units derived from the aromatic carboxylic acid component, structural units derived from the monohydric phenol, and structural units derived from the polyhydric phenol are preferred.

Specific examples of the active ester compound include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group, described in JP-A-2012-246367, and an aromatic dicarboxylic acid or Examples thereof include active ester resins having a structure obtained by reacting the halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferable.

In structural formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms, and X is a benzene ring, a naphthalene ring, a benzene or naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group. where Y is a benzene ring, a naphthalene ring, or a benzene or naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average number of repetitions of 0.0. 25 to 1.5.

Specific examples of the compound represented by Structural Formula (1) include the following exemplary compounds (1-1) to (1-10). t-Bu in the structural formula is a tert-butyl group.

Another specific example of the active ester compound is a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3), which are described in JP-A-2014-114352. mentioned.

In structural formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon an ester-forming structural moiety (z1) selected from the group consisting of a benzoyl group or naphthoyl group substituted with an alkyl group of number 1 to 4, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); at least one of which is an ester-forming structural site (z1).

In structural formula (3), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon an ester-forming structural moiety (z1) selected from the group consisting of a benzoyl group or naphthoyl group substituted with an alkyl group of number 1 to 4, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); at least one of which is an ester-forming structural site (z1).

Specific examples of the compound represented by Structural Formula (2) include the following exemplary compounds (2-1) to (2-6).

Specific examples of the compound represented by Structural Formula (3) include the following exemplary compounds (3-1) to (3-6).

A commercially available product may be used as the active ester compound. Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene type diphenol structure; "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Corporation) as active ester compounds containing structures; "DC808" (Mitsubishi Chemical Corporation (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolak include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

An active ester compound may be used individually by 1 type, or may be used in combination of 2 or more type.

The ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of balance of various properties such as formability, reflow resistance, and electrical reliability, it is preferably 150 g/eq to 400 g/eq, more preferably 170 g/eq to 300 g/eq, and 200 g/eq to 250 g/eq. More preferred.

The ester group equivalent of the active ester compound is a value measured by a method according to JIS K 0070:1992.

The equivalent ratio (ester group/epoxy group) between the epoxy resin and the active ester compound is preferably 0.9 or more, more preferably 0.95 or more, and 0.97 or more from the viewpoint of keeping the dielectric loss tangent of the cured product low. is more preferred.
The equivalent ratio (ester group/epoxy group) between the epoxy resin and the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted amount of the active ester compound. 03 or less is more preferable.

The curing agent may contain curing agents other than the active ester compound. In this case, the type of other curing agent is not particularly limited, and can be selected according to the desired properties of the encapsulating resin composition. Other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like.

Specific examples of phenol curing agents include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol , at least one phenolic compound selected from the group consisting of phenolic compounds such as aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and an aldehyde compound such as formaldehyde, acetaldehyde and propionaldehyde with an acidic catalyst. Novolac type phenolic resins obtained by condensation or cocondensation under the following conditions; aralkyl type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. ; para-xylylene-modified phenolic resin, meta-xylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; Resin; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; and triphenylmethane type phenol resins obtained by copolymerizing two or more of these phenol resins. These phenol curing agents may be used singly or in combination of two or more.

The functional group equivalent weight (hydroxyl group equivalent weight in the case of a phenol curing agent) of other curing agents is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g/eq to 1000 g/eq, more preferably 80 g/eq to 500 g/eq.

The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of phenol curing agents) is a value measured by a method according to JIS K 0070:1992.

If the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the encapsulating resin composition, it is more preferably 50° C. to 130° C. .

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

The equivalent ratio of the epoxy resin to all curing agents (active ester compounds and other curing agents), that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / number of functional groups) is not particularly limited. From the viewpoint of suppressing the unreacted amount of each, it 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 and reflow resistance, it is more preferable to set the ratio in the range of 0.8 to 1.2.

The content of the active ester compound with respect to the total mass of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is preferably 90% by mass or more, and more preferably 90% by mass or more.

From the viewpoint of keeping the dielectric loss tangent of the cured product low, the total content of the epoxy resin and the active ester compound relative to the total mass of the epoxy resin, the active ester compound, and other curing agents is preferably 70% by mass or more, and preferably 80% by mass. % or more, more preferably 85 mass % or more.

(Curing accelerator)
The encapsulating resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin or curing agent, the desired properties of the encapsulating resin composition, and the like.

Curing accelerators 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 derivatives thereof; 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 other quinone compounds, and diazophenylmethane and other compounds having π bonds, which have intramolecular polarization. Compound; cyclic amidinium compound such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholine tetraphenylborate salt, and isocyanate Compound: isocyanate adduct of DBU, isocyanate adduct of DBN, isocyanate adduct of 2-ethyl-4-methylimidazole, isocyanate adduct of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanol Tertiary amine compounds such as amines, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, benzoin Ammonium salt compounds such as tetra-n-hexylammonium acid and tetrapropylammonium hydroxide; Phenyl)phosphine, Tris(dialkylphenyl)phosphine, Tris(trialkylphenyl)phosphine, Tris(tetraalkylphenyl)phosphine, Tris(dialkoxyphenyl)phosphine, Tris(trialkoxyphenyl)phosphine, Tris(tetraalkoxyphenyl)phosphine , trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; phosphine compounds such as complexes of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine compound and maleic anhydride; -benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy A compound having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds such as -1,4-benzoquinone and phenyl-1,4-benzoquinone, and diazophenylmethane; the tertiary phosphine or the phosphine compound; and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodinated phenol, 2-iodinated phenol, 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, 4-bromo-4′-hydroxybiphenyl and other halogenated phenol compounds are reacted, followed by dehalogenation. compounds with intramolecular polarization, obtained via a hydrogenation process; tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetrasubstituted phosphoniums and tetrasubstituted borates without a phenyl group bonded to the boron atom such as tetra-p-tolylborate; A salt of tetraphenylphosphonium and a phenol compound; a salt of a tetraalkylphosphonium and a partial hydrolyzate of an aromatic carboxylic acid anhydride;

When the encapsulating resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). , more preferably 1 to 15 parts by mass. When the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for satisfactory curing in a short period of 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 speed is not too fast and a good molded article tends to be obtained.

(Inorganic filler)
The encapsulating resin composition of the present disclosure contains an inorganic filler with an average particle size of 5 μm to 100 μm. The average particle diameter of the inorganic filler is 5 μm or more, preferably 8 μm or more, and preferably 10 μm or more, from the viewpoint of reducing the amount of surface hydroxyl groups per unit amount and, as a result, keeping the dielectric loss tangent of the cured product low. It is more preferable to have The average particle size of the inorganic filler is 100 µm or less, preferably 50 µm or less, more preferably 20 µm or less, from the viewpoint of improving the filling properties of the encapsulating resin composition.

The average particle size of the inorganic filler is obtained by measuring the major diameter of 100 randomly selected inorganic fillers in an image obtained by imaging a thin piece sample of the encapsulating resin composition or its cured product with a scanning electron microscope, It is the value obtained by arithmetically averaging them.

The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay, and mica. Inorganic fillers having a flame retardant effect may also be used. Inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types. Examples of the form of the inorganic filler include powder, beads obtained by spheroidizing powder, and fiber.

The content of the inorganic filler contained in the encapsulating resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% to 90% by volume, more preferably 35% to 80% by volume, and 40% to 70% by volume of the entire sealing resin composition. % is more preferred. When the content of the inorganic filler is 30% by volume or more of the entire encapsulating resin composition, the properties of the cured product, such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire encapsulating resin composition, an increase in viscosity of the encapsulating resin composition is suppressed, fluidity is further improved, and moldability is further improved. tend to become

[Various additives]
In addition to the components described above, the encapsulating resin composition may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, and colorants exemplified below. The encapsulating resin composition may contain various additives known in the art as necessary, in addition to the additives exemplified below.

(coupling agent)
The encapsulating resin composition may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Coupling agents include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium compounds, aluminum chelate compounds, and aluminum/zirconium compounds. mentioned.

When the encapsulating resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler, and 0.1 part by mass. More preferably, it is up to 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The encapsulating resin composition may contain an ion exchanger. The encapsulating resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. The ion exchangers may be used singly or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _X/2 ·mH ₂ O (A)
(0<X≤0.5, m is a positive number)

When the encapsulating resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to trap ions such as halogen ions. For example, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

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

When the encapsulating resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent), and 0.1 More preferably 5 parts by mass to 5 parts by mass. When the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained. When the amount is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The encapsulating resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, and metal hydroxides. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type.

When the encapsulating resin composition contains a flame retardant, its amount is not particularly limited as long as it is sufficient to obtain the 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 (total amount of epoxy resin and curing agent).

(coloring agent)
The encapsulating resin composition may contain a coloring agent. Examples of coloring agents include known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the coloring agent can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, or may be used in combination of 2 or more type.

(Method for preparing encapsulating resin composition)
A method for preparing the encapsulating resin composition is not particularly limited. As a general method, there can be mentioned a method of thoroughly mixing components in predetermined amounts with a mixer or the like, melt-kneading the mixture with a mixing roll, an extruder or the like, cooling, and pulverizing. More specifically, for example, predetermined amounts of the components described above are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.

The encapsulating resin composition is preferably solid at room temperature and normal pressure (eg, 25° C., atmospheric pressure). When the encapsulating resin composition is solid, the shape is not particularly limited, and examples thereof include powder, granules, tablets, and the like. When the encapsulating resin composition is in the form of a tablet, it is preferable from the standpoint of handleability that the dimensions and mass are such that they meet the molding conditions of the package.

<Electronic parts equipment>
An electronic component device that is an embodiment of the present disclosure includes a support member, an element arranged on the support member, a cured product of the sealing resin composition of the present disclosure that seals the element, Prepare.

As an electronic component device, elements (active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, etc.) , passive elements such as coils, etc.) are sealed with a sealing resin composition.
More specifically, the element is fixed on a lead frame, and the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps, or the like, and then transfer molding or the like is performed using a sealing resin composition. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead packa ge), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package) and other general resin-sealed ICs; TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with bumps is sealed with a sealing resin composition ; COB (Chip On Board) modules, hybrid ICs, multi Chip module, etc.: After mounting an element on the surface of a support member on which terminals for wiring board connection are formed on the back surface, and connecting the element and the wiring formed on the support member by bumps or wire bonding, resin composition for sealing BGAs (Ball Grid Arrays), CSPs (Chip Size Packages), MCPs (Multi Chip Packages), etc., which have a structure in which an element is sealed with a substance, can be mentioned. Moreover, the resin composition for sealing can be used suitably also in a printed wiring board.

<Method for manufacturing electronic component device>
A method of manufacturing an electronic component device of the present disclosure includes a step of placing an element on a support member and a step of encapsulating the element with the encapsulating resin composition of the present disclosure.

The method for implementing each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of supporting members and elements used for manufacturing electronic component devices are not particularly limited, and supporting members and elements generally used for manufacturing electronic component devices can be used.

Examples of methods for encapsulating an element using the encapsulating resin composition of the present disclosure include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like. Among these, the low pressure transfer molding method is common.

EXAMPLES Hereinafter, the above-described embodiments will be specifically described with reference to examples, but the scope of the above-described embodiments is not limited to these examples.

<Preparation of encapsulating resin composition>
The components shown below were mixed in the proportions shown in Table 1 to prepare encapsulating resin compositions of Examples and Comparative Examples. This encapsulating resin composition was solid at normal temperature and normal pressure.

・ Epoxy resin 1: biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name “NC-3000”)
・ Epoxy resin 2: dicyclopentadiene type epoxy resin, epoxy equivalent 258 g / eq (DIC Corporation, product name “HP-7200”)
・ Epoxy resin 3: triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
・ Epoxy resin 4: biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

- Active ester compound 1: DIC Corporation, product name "EXB-8"
- Phenol curing agent 1: phenol aralkyl resin, hydroxyl equivalent 175 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7800SS")

・Curing accelerator 1: triphenylphosphine/1,4-benzoquinone adduct

・ Filler 1: fused silica (DENKA, product name “FB-870FD”)
・ Filler 2: Fused silica (Takimori Co., Ltd., product name “EUF-46V”)
・ Filler 3: Fused silica (Takimori Co., Ltd., product name “MUF-2BV”)
・ Filler 4: Fused silica (Admatechs, product name “SO-25R”)

Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-573”)
・ Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-803”)
・Mold release agent: Montan acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
・ Coloring agent: carbon black (Mitsubishi Chemical Corporation, product name “MA600”)

<Performance evaluation of encapsulating resin composition>
(Average particle size of inorganic filler)
In an image obtained by imaging a thin piece sample of the resin composition for sealing with a scanning electron microscope, the major diameters (μm) of 100 randomly selected inorganic fillers were measured and arithmetically averaged.

(spiral flow)
Using a spiral flow measurement mold according to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance ( cm) was obtained.

(relative permittivity and dielectric loss tangent)
The encapsulating resin composition is charged into a vacuum hand press, molded under the conditions of a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds. A product (length 12.5 mm, width 25 mm, thickness 0.2 mm) was obtained. Using this plate-shaped cured product as a test piece, using a dielectric constant measurement device (Agilent Technologies, product name "Network Analyzer N5227A"), the relative dielectric constant and dielectric loss tangent at about 60 GHz at a temperature of 25 ± 3 ° C. It was measured.

(water absorption rate)
The plate-like cured product immediately after production was charged into a pressure cooker test apparatus at 121° C./2.1 atm, taken out after 24 hours, and the rate of increase (%) from the mass immediately before charging was determined.

All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

Claims (3)

containing an epoxy resin, a curing agent and an inorganic filler,
the curing agent comprises an active ester compound,
The encapsulating resin composition, wherein the inorganic filler has an average particle size of 5 μm to 100 μm. a support member;
an element disposed on the support member; and
A cured product of the sealing resin composition according to claim 1, which seals the element;
An electronic component device comprising: placing the element on a support member;
A step of encapsulating the element with the encapsulating resin composition according to claim 1;
A method of manufacturing an electronic component device comprising: