JPWO2020067016A1 - Manufacturing method of sealing resin composition, electronic component device and electronic component device - Google Patents

Abstract

A sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.

Description

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

The amount of heat generated by semiconductor devices tends to increase as the density and output of electronic communication devices increase. Therefore, improvement of thermal conductivity has been studied in order to improve the heat dissipation of the material used for sealing the semiconductor device. For example, Patent Document 1 describes an epoxy resin composition for encapsulation in which 60% by volume or more of an inorganic filler is alumina in order to enhance thermal conductivity.

On the other hand, the amount of transmission loss generated by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the square root of frequency and relative permittivity and the dielectric loss tangent. That is, since the transmission signal is easily converted into heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties in the high frequency band in order to suppress the transmission loss.

In the information and communication field, radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases. Currently, studies on 5th generation mobile communication systems are underway worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to further improve the dielectric characteristics.

Japanese Unexamined Patent Publication No. 2014-31460

When alumina is used as the inorganic filler of the sealing resin composition, the thermal conductivity is high and the heat dissipation is improved, but the relative permittivity may increase and the transmission loss may increase.

In view of the above circumstances, the present disclosure describes a sealing resin composition having an excellent balance between heat dissipation and dielectric properties of a cured product, an electronic component device sealed using the resin composition, and an electronic component device sealed using the resin composition. It is an object to provide a manufacturing method of the above.

Specific means for solving the above problems include the following aspects.
<1> A sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.
<2> The sealing resin composition according to <1>, wherein the proportion of alumina in the entire inorganic filler is 50% by mass or more.
<3> An electron comprising a support member, an element arranged on the support member, and a cured product of the sealing resin composition according to <1> or <2> that seals the element. Parts equipment.
<4> A method for manufacturing an electronic component device, comprising a step of arranging the element on a support member and a step of sealing the element with the sealing resin composition according to <1> or <2>.

According to the present disclosure, a resin composition for sealing having an excellent balance between heat dissipation and dielectric properties of a cured product, an electronic component device sealed using the resin composition, and an electronic component device sealed using the resin composition are manufactured. A method is provided.

In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "~" in the present disclosure includes the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range 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 another numerical range described stepwise. .. Further, in the numerical range 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 applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality 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 plurality of particles present in the composition unless otherwise specified.

<Resin composition for sealing>
The sealing resin composition of the present disclosure is a sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.

As a result of the studies by the present inventors, the cured product obtained by curing the sealing resin composition having the above structure is compared with the cured product of the sealing resin composition using the conventional epoxy resin and the curing agent. It was found that the cured product has an excellent balance between heat dissipation and dielectric properties. The reason is not always clear, but it can be considered as follows.

First, the sealing resin composition of the present disclosure contains alumina as an inorganic filler. As a result, a higher thermal conductivity is achieved as compared with the case where the sealing resin composition contains other inorganic fillers such as silica.
Further, the sealing resin composition of the present disclosure contains an active ester compound as a curing agent. Phenol curing agents, amine curing agents, etc., which are generally used as curing agents for epoxy resins, generate secondary hydroxyl groups in the reaction with epoxy resins. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, the sealing resin composition of the present disclosure is compared with the sealing resin composition containing 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. As a result, by using alumina as the inorganic filler, it is possible to suppress an increase in transmission loss even if the relative permittivity increases.

(Epoxy resin)
The type of epoxy resin contained in the sealing resin composition of the present disclosure is not particularly limited.
Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolac type epoxy resin (phenol novolac type) which is obtained by epoxidizing a novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde under an acidic catalyst. Epoxy resin, orthocresol novolac type epoxy resin, etc.); A triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxy resin; a copolymerized epoxy resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; Diphenylmethane-type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl-type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben-type epoxy resin which is a diglycidyl ether of a stelvene-based phenol compound; bisphenol Sulfur atom-containing epoxy resin such as diglycidyl ether such as S; epoxy resin which is glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; polyhydric carboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxy resin, which is a glycidyl ester of Dicyclopentadiene-type epoxy resin obtained by epoxidizing a condensed resin; vinylcyclohexene diepoxide, which is an epoxidized olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5 Alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin which is glycidyl ether of metaxylylene-modified phenol resin Terpen-modified epoxy resin, which is a glycidyl ether of terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a ring aromatic ring-modified phenol resin; naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylol propane 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 epoxyizing an aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. ; And so on. Further, an epoxy resin of an acrylic resin or the like can be mentioned as an epoxy resin. These epoxy resins may be used alone 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 balance of various characteristics 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 a value measured by a method according to JIS K 7236: 2009.

When the epoxy resin is a 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 when preparing the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C.

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

The content of the epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. More preferably.

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

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

As described above, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to be low by using the active ester compound as the curing agent.
Further, the polar groups in the cured product enhance the water absorption of the cured product, and by using an active ester compound as the curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. can. Then, suppressing the water absorption of the cured product, that is, by suppressing the H _{2 O} content is a polar molecule, it is possible to suppress even lower dielectric loss tangent of a cured product. The water absorption rate of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and even more preferably 0% to 0.25%. Here, the water absorption rate of the cured product is the mass increase rate obtained by the pressure cooker test (121 ° C., 2.1 atm, 24 hours).

The type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with the epoxy group.

Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.

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

Specific examples of the active ester compound include aromatic esters 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 carboxy groups, and the hydrogen atom of the aromatic ring described above. A mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material, and an aromatic carboxylic acid and a phenolic hydroxyl group are used as raw materials. Aromatic esters obtained by the condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monovalent phenol, and a structural unit derived from the polyhydric phenol is preferable.

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 JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin 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 the 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 ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group. Y is a benzene ring, a naphthalene ring, or a benzene ring or a 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. It is 25 to 1.5.

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

As another specific example of the active ester compound, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP-A-2014-114352 can be used. Can be mentioned.

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

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

Specific examples of the compound represented by the structural formula (2) include the following exemplified compounds (2-1) to (2-6).

Specific examples of the compound represented by the structural formula (3) include the following exemplified compounds (3-1) to (3-6).

As the active ester compound, a commercially available product may be used. Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene type diphenol structure; aromatics. "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Co., Ltd.) as active ester compounds containing a structure; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured by); Examples of the active ester compound containing a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).

The active ester compound may be used alone or in combination of two or more.

The ester equivalent of the active ester compound is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is preferable. More preferred.

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

The equivalent ratio (ester group / epoxy group) of the epoxy resin to 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 suppressing the dielectric loss tangent of the cured product to be low. Is even more preferable.
The equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted content of the active ester compound. 03 or less is more preferable.

The curing agent may contain other 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 sealing resin composition and the like. Examples of 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.

Specifically, the phenol curing agent is a polyhydric phenol compound such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol. , Aminophenol and other phenolic compounds and at least one phenolic compound selected from the group consisting of α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde as acidic catalysts. Novorac-type phenolic resin obtained by condensing or co-condensing below; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound with dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc. Paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound with dicyclopentadiene. Resin; Cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Obtained by condensing or co-condensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst. The triphenylmethane type phenol resin to be used; a phenol resin obtained by copolymerizing two or more of these types can be mentioned. These phenol curing agents may be used alone or in combination of two or more.

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

The functional group equivalents of other curing agents (hydroxyl equivalents in the case of phenol curing agents) shall be values measured by a method according to JIS K 0070: 1992.

When the curing agent is a 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 sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C. ..

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.

Equivalent ratio of 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 / in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small extent, 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 range from 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 suppressing the dielectric adjacency of the cured product to be low. It is preferably 90% by mass or more, and more preferably 90% by mass or more.

The total content of the epoxy resin and the active ester compound with respect to the total mass of the epoxy resin, the active ester compound and the other curing agent is preferably 80% by mass or more, preferably 85% by mass, from the viewpoint of keeping the dielectric equirect contact of the cured product low. It is more preferably% or more, and further preferably 90% by mass or more.

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

Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] Nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] Undecene-7 (DBU). Cycrine amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compound; phenol novolac salts of the cyclic amidine compound or derivatives thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 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, diazophenylmethane and other quinone compounds with a π bond added to have intramolecular polarization. Compounds; cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholine tetraphenylborate salt; pyridine, triethylamine, tri Teruaryamine compounds such as ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, tetra-n-phosphate. Triphenylphosphine, diphenyl (p-tryl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) ) Hosphine, tris (alkyl / alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine , Triphenylphosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc .; Phosphine compound; said tertiary phosphine or said phosphin compound and maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, Kinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane. Addition of a compound having intramolecular polarization; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-Ioated 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- A compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4'-hydroxybiphenyl and then undergoing a step of dehalogenating; tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-p-tolylbolate. Tetra-substituted phosphonium and tetra-substituted borate without a phenyl group bonded to a boron atom, such as salts of tetraphenylphosphonium and a phenolic compound, tetraalkylphosphonium and a partial hydrolyzate of an aromatic carboxylic acid anhydride, and the like.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass 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, it is 1 part by mass to 15 parts by mass. 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 be cured 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.

(Inorganic filler)
The sealing resin composition of the present disclosure contains alumina as an inorganic filler. By containing alumina, improvement in thermal conductivity of the cured product can be expected. On the other hand, from the viewpoint of the balance with other properties such as the coefficient of linear expansion and the dielectric property of the cured product, it is preferable to use alumina and an inorganic filler other than alumina in combination.

Specific examples of the inorganic filler other than alumina include inorganic materials such as fused silica, crystalline silica, glass, talc, clay, and mica. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, and zinc borate.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion. The inorganic filler may be used alone or in combination of two or more. Examples of the form of the inorganic filler include powder, beads obtained by spheroidizing the powder, fibers and the like.

When the inorganic filler is in the form of particles, its average particle size is not particularly limited. For example, the average particle size is preferably 0.2 μm to 100 μm, and more preferably 0.5 μm to 50 μm. When the average particle size is 0.2 μm or more, the increase in viscosity of the sealing resin composition tends to be further suppressed. When the average particle size is 100 μm or less, the filling property tends to be further improved. The average particle size of the inorganic filler is determined as the volume average particle size (D50) by a laser scattering diffraction method particle size distribution measuring device.

The proportion of alumina in the inorganic filler contained in the sealing resin composition is not particularly limited. From the viewpoint of improving the thermal conductivity of the cured product, for example, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. From the viewpoint of balance with other properties of the cured product, it is preferably 90% by mass or less, for example.

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

[Various additives]
In addition to the above-mentioned components, the sealing resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below. The sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
The sealing 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. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. ..

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. More preferably, it is ~ 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 adhesiveness with 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 sealing resin composition may contain an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing 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 thereof include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, 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 sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

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

When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1 part by mass. More preferably, parts by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more.

When the sealing resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

(Colorant)
The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.

(Preparation method of resin composition for sealing)
The method for preparing the sealing resin composition is not particularly limited. As a general method, a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is 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 sealing resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the sealing resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the sealing resin composition is in the form of a tablet, it is preferable that the dimensions and mass match the molding conditions of the package from the viewpoint of handleability.

<Electronic component equipment>
An electronic component device according to an embodiment of the present disclosure includes an element and a cured product of the sealing resin composition of the present disclosure that seals the element.

Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, etc.). , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition. Chip module, etc .; After mounting the element on the front surface of the support member having terminals for connecting the wiring plate on the back surface and connecting the element and the wiring formed on the support member by bump or wire bonding, the sealing resin composition. Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the sealing resin composition can also be preferably used in the printed wiring board.

<Manufacturing method of electronic component equipment>
The method for manufacturing an electronic component device of the present disclosure includes a step of arranging an element on a support member and a step of sealing the element with the sealing resin composition of the present disclosure.

The method of carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used.

Examples of the method for sealing the element using the sealing 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.

Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the scope of the above-mentioned Embodiment is not limited to these Examples.

<Preparation of resin composition for sealing>
The components shown below were mixed in the formulations (parts by mass) shown in Table 1 to prepare resin compositions for encapsulation of Examples and Comparative Examples.

-Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 275 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
-Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

-Curing agent 1: Biphenyl aralkyl type phenol resin, hydroxyl group equivalent 199 g / eq (Air Water Inc., product name "HE200C-10")
-Curing agent 2: Active ester compound (DIC Corporation)

-Curing accelerator 1: p-benzoquinone adduct of triphenylphosphine

-Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
-Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803")

-Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
-Additive: Triphenylphosphine oxide (Hokuko Chemical Industry Co., Ltd., product name "TP-50")

-Inorganic filler 1: Silica filler (Denka Co., Ltd., product name "FB-9454FC", average particle size 18 μm)
-Inorganic filler 2: Silica filler (Denka Co., Ltd., product name "FB-9454", average particle size 19 μm)
-Inorganic filler 3: A mixture of alumina / silica = 9/1 (Denka Co., Ltd., product name "DAB-10FC", average particle size 10 μm)

<Performance evaluation of sealing resin composition>
(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. cm) was calculated.

(Gel time)
Place 0.5 g of the sealing resin composition on a hot plate heated to 175 ° C., and use a jig to rotate the sample at a rotation speed of 20 rpm to 25 rpm and 2.0 cm to 2.5 cm. Spread evenly in a circle. The time from when the sample was placed on the hot plate until the sample became less viscous and became a gel state and peeled off from the hot plate was measured, and this was measured as the gel time (sec).

(Thermal conductivity)
A test piece for thermal conductivity evaluation (length 10 mm x width 10 mm x) using the sealing composition with a vacuum hand press molding machine under the conditions of a mold temperature of 175 ° C to 180 ° C, a molding pressure of 250 kPa, and a curing time of 600 seconds. Thickness 0.8 mm) was produced. Next, the thermal diffusivity in the thickness direction of the molded test piece was measured. The thermal diffusivity was measured by a laser flash method (apparatus: LFA467 nanoflash, manufactured by NETZSCH). The pulsed light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247 V. The measurement was performed at an atmospheric temperature of 25 ° C. ± 1 ° C. The density of the test piece was measured using an electronic hydrometer (AUX220, Shimadzu Corporation). For the specific heat, the theoretical specific heat of the sealing composition was calculated from the literature value of the specific heat of each material and the compounding ratio.
Then, the value of thermal conductivity was obtained by multiplying the specific heat and density by the thermal diffusivity using the equation (1).
λ = α × Cp × ρ ・ ・ ・ Equation (1)
(In equation (1), λ is the thermal conductivity (W / (m · K)), α is the thermal diffusivity (m ² / s), Cp is the specific heat (J / (kg · K)), and ρ is the density. (D: kg / m ³ ) are shown respectively.)

(Relative permittivity and dielectric loss tangent)
The sealing resin composition was charged into a transfer molding machine, 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 post-cured at 175 ° C. for 6 hours to obtain a rod-shaped cured product (a rod-shaped cured product). A length of 0.8 mm, a width of 0.6 mm, and a thickness of 90 mm) were obtained. Using this cured product as a test piece, a cavity resonator (Kanto Denshi Applied Development Co., Ltd., "CP561") and a network analyzer (Keysight Technology Co., Ltd., "PNA E8364B") are used at a temperature of 25 ± 1 ° C. and 20 GHz. The relative permittivity and the dielectric loss tangent were measured at.

As shown in Table 1, the sealing resin compositions of Examples 1 and 3 in which alumina was used as the inorganic filler were cured as compared with Comparative Examples 1 and 2 in which alumina was not used as the inorganic filler. The thermal conductivity of the object was high. On the other hand, the relative permittivity of Examples 1 and 3 was higher than that of Comparative Examples 1 and 2. However, Example 1 in which the active ester compound is used as the curing agent has a lower dielectric loss tangent than Comparative Example 3 in which the phenol resin is used as the curing agent, so that the increase in transmission loss is suppressed, and as a result, heat dissipation and dielectric are suppressed. The balance of characteristics was excellent.
Further, in Examples 1 and 2, by using an active ester having a lower viscosity than the phenol resin as the curing agent, the fluidity is improved as compared with Comparative Examples 1 and 3 in which the phenol resin is used as the curing agent. However, Example 1 in which alumina is used as the inorganic filler is more effective in improving the fluidity than Comparative Example 3 in which alumina is not used as the inorganic filler.
Further, in Example 1, the gel time is shorter than that in Comparative Examples 1 to 3. Alumina generally causes a delay in the curing reaction, but it is considered that the curability is improved because the reactivity of the active ester compound and the epoxy resin is higher than the reactivity of the phenol resin and the epoxy resin.

Claims (4)

A sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina. The sealing resin composition according to claim 1, wherein the proportion of alumina in the entire inorganic filler is 50% by mass or more. Support members and
The element arranged on the support member and
The cured product of the sealing resin composition according to claim 1 or 2, which seals the element, and the cured product.
Electronic component device equipped with. The process of arranging the element on the support member and
The step of sealing the element with the sealing resin composition according to claim 1 or 2.
Manufacturing method of electronic component equipment including.