JP2021127404A - Sealing resin composition, electronic component device and method for producing electronic component device - Google Patents

Abstract

To provide a sealing resin composition that has excellent fluidity during molding and can prevent the occurrence of mold warpage.SOLUTION: A sealing resin composition contains an epoxy resin, a curing agent, a curing accelerator and an inorganic filler, the curing accelerator containing an isocyanate masked imidazole compound.SELECTED DRAWING: None

Description

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

For example, Patent Document 1 discloses a thermosetting resin composition containing an isocyanate masked imidazole compound, and discloses that it is used for prepreg applications.

Japanese Unexamined Patent Publication No. 2013-064136

For example, a relatively large area such as a wafer level package (WLP) may be sealed with a sealing resin composition. In this case, in order to spread the sealing resin composition to every corner of the mold, there is a demand for a sealing resin composition having excellent fluidity during molding. Further, the larger the area to be sealed with the sealing resin composition, the more remarkable the molding warp tends to be. Therefore, there is a demand for a sealing resin composition capable of suppressing the occurrence of the molding warp.

The embodiments of the present disclosure have been made under the above circumstances.
The present disclosure describes a sealing resin composition having excellent fluidity during molding and capable of suppressing the occurrence of molding warpage, an electronic component device sealed using the resin composition, and an electronic component device sealed using the same. An object is to provide a manufacturing method.

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

<1> A sealing resin composition containing an epoxy resin, a curing agent, a curing accelerator, and an inorganic filler, and the curing accelerator containing an isocyanate masked imidazole compound.
<2> The sealing resin composition according to <1>, wherein the epoxy resin contains a polyfunctional epoxy resin.
<3> The polyfunctional epoxy resin comprises a triphenylmethane type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalenediol aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, and a dicyclopentadiene type epoxy resin. The sealing resin composition according to <2>, which comprises at least one selected from the group.
<4> The sealing resin composition according to any one of <1> to <3>, wherein the curing agent contains a phenol curing agent.
<5> The sealing resin composition according to any one of <1> to <4> for use in a wafer level package.
<6> The cured product of the sealing resin composition according to any one of <1> to <5>, which seals the support member, the element arranged on the support member, and the element. And equipped with electronic component devices.
<7> An electronic component device including a step of arranging an element on a support member and a step of sealing the element with the sealing resin composition according to any one of <1> to <5>. Manufacturing method.

According to the present disclosure, a sealing resin composition having excellent fluidity during molding and capable of suppressing the occurrence of molding warpage, an electronic component device sealed using the resin composition, and an electronic component sealed using the resin composition. A method of manufacturing the device 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 contains an epoxy resin, a curing agent, a curing accelerator, and an inorganic filler, and the curing accelerator contains an isocyanate masked imidazole compound.
The isocyanate masked imidazole compound is desorbed from the isocyanate mask by applying heat to become an imidazole compound. The imidazole compound produced from the isocyanate masked imidazole compound acts as a curing accelerator on the epoxy resin.
The sealing resin composition of the present disclosure can be made fluid at the time of molding by ensuring fluidity until the isocyanate mask is desorbed from the isocyanate masked imidazole compound which is a curing accelerator when heat is applied. Excellent.
Since the imidazole compound has a high curing promoting activity on the epoxy resin, the sealing resin composition can be cured at a relatively low temperature (for example, 130 ° C. to 150 ° C.). The molding warpage of the cured product increases as the curing temperature rises. However, since the sealing resin composition of the present disclosure can be cured at a relatively low temperature, the occurrence of molding warpage can be suppressed.

In recent years, with the sophistication of SiP (System in Package), relatively heat-sensitive members such as sensors and MEMS (Micro Electro Mechanical Systems) may be mounted, which is relatively heat-sensitive. In order to reduce damage to weak members, it is required to lower the curing temperature of the sealing resin composition. However, the sealing resin composition of the present disclosure can be cured at a relatively low temperature. Therefore, it is suitable for mounting a member that is relatively sensitive to heat.

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

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 that is a diglycidyl ether such as A and bisphenol F; biphenyl-type epoxy resin that is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben-type epoxy resin that 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 a terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of a dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of a 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 such as an acrylic resin is also mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.

The epoxy resin preferably contains a polyfunctional epoxy resin from the viewpoint of lowering the curing temperature and suppressing the occurrence of molding warpage. The type of the polyfunctional epoxy resin is not particularly limited as long as it is a resin having three or more epoxy groups in the molecule. The number of epoxy groups in the polyfunctional epoxy resin is preferably 3 to 8, and more preferably 3 to 5. The polyfunctional epoxy resin may be used alone or in combination of two or more.

Examples of the polyfunctional epoxy resin include triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, phenol novolac type epoxy resin, dihydroxybenzene novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, and naphthalene skeleton. Examples thereof include type epoxy resins, naphthalenediol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins and the like, and derivatives thereof.

The polyfunctional epoxy resin includes triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalenediol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and dicyclopentadiene type epoxy from the viewpoint of cross-linking density. It preferably contains at least one selected from the group consisting of resins.

The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton, and an epoxy resin obtained by converting a triphenylmethane type phenol resin into a glycidyl ether is preferable.

The epoxy resin may contain a bifunctional epoxy resin. As the epoxy resin, a bifunctional epoxy resin may be used together with the polyfunctional epoxy resin. The type of bifunctional epoxy resin is not particularly limited as long as it is a resin having two epoxy groups in the molecule. The polyfunctional epoxy resin may be used alone or in combination of two or more.

Examples of the bifunctional epoxy resin include bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin and the like. , And derivatives of these.

The bifunctional epoxy resin is at least selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin and naphthalene type epoxy resin from the viewpoint of fluidity during molding. It is preferable to include one type. Of these, a biphenyl type epoxy resin is more preferable from the viewpoint of fluidity during molding.

The epoxy resin may contain a monofunctional epoxy resin. As the epoxy resin, a monofunctional epoxy resin may be used together with one or both of the polyfunctional epoxy resin and the bifunctional epoxy resin. The monofunctional epoxy resin may be used alone or in combination of two or more.

The polyfunctional epoxy resin preferably occupies 30% by mass to 95% by mass, and occupies 40% by mass to 80% by mass, based on the total mass of the epoxy resin, from the viewpoint of achieving both fluidity and curability during molding. Is more preferable, and it is further preferable to occupy 50% by mass to 70% by mass.

When the polyfunctional epoxy resin and the bifunctional epoxy resin are used in combination, the mass ratio of the polyfunctional epoxy resin to the total amount of the polyfunctional epoxy resin and the bifunctional epoxy resin achieves both fluidity and curability during molding. From the viewpoint of the above, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 93% by mass, and further preferably 70% by mass to 90% by mass.

The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balancing 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, the softening point or melting point of the epoxy resin 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 mass ratio of the epoxy resin to the total amount of the sealing resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and is preferably 2% by mass to 50% by mass. It is more preferably 30% by mass.

(Hardener)
The sealing resin composition of the present disclosure contains a curing agent. The type of the 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 the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, and an ester curing agent.

As the curing agent, a phenol curing agent is preferable from the viewpoint of lowering the curing temperature and suppressing the occurrence of molding warpage.
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 mass ratio of the phenol curing agent to the total amount of the curing agent is preferably 80% by mass or more, more preferably 85% by mass or more, from the viewpoint of lowering the curing temperature and suppressing the occurrence of molding warpage. It is more preferably 90% by mass or more.

The functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) is 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 equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) is a value 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.

The equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent / the number of functional groups in the epoxy resin) 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.

(Curing accelerator)
The sealing resin composition of the present disclosure contains at least an isocyanate masked imidazole compound as a curing accelerator. The isocyanate masked imidazole compound may be used alone or in combination of two or more.

Examples of the isocyanate masked imidazole compound include compounds represented by the following general formula (1).

In the general formula (1), R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen atoms, aliphatic hydrocarbon groups or phenyl groups having 1 to 20 carbon atoms, and A is an alkylene group or an aromatic group. It is a hydrocarbon group.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms. It is more preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms. The aliphatic hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) may be a saturated aliphatic hydrocarbon group (that is, an alkyl group), or an unsaturated aliphatic hydrocarbon group (for example, an alkenyl group or an alkynyl group). But it may be.
Linear alkyl groups having 20 or less carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group. The group etc. can be mentioned.
Examples of the branched alkyl group having 20 or less carbon atoms include an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, a 2-ethylhexyl group, a tertiary butyl group, a tertiary pentyl group, and an isopentadecyl group.
Examples of the cyclic alkyl group having 20 or less carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a norbornyl group, and an adamantyl group.
Examples of the alkenyl group having 20 or less carbon atoms include a vinyl group (ethenyl group), a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 1-butenyl group, a 1-hexenyl group, a 2-dodecenyl group and the like. ..
Examples of the alkynyl group having 20 or less carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 3-hexynyl group, a 2-dodecynyl group and the like.

The alkylene group represented by A in the general formula (1) is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms. It is an alkylene group of.
Examples of the linear alkylene group having 20 or less carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group and n. -Nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, tridecylene group, n-tetradecylene group, n-pentadecylene group, n-heptadecylene group, n-octadecylene group, n-nonadecilene group, n-icosilene The group etc. can be mentioned.
Examples of the branched alkylene group having 20 or less carbon atoms include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentylene group, a neopentylene group, a tert-pentylene group, an isohexylene group, a sec-hexylene group and a tert-. Hexylene group, isoheptylene group, sec-heptylene group, tert-heptylene group, isooctylene group, sec-octylene group, tert-octylene group, isononylene group, sec-nonylene group, tert-nonylene group, isodecylene group, sec-decylene group, Examples thereof include a tert-decylene group, an isododecylene group, a sec-dodecylene group, a tert-dodecylene group, a tert-tetradecylene group, a tert-pentadecylene group and the like.
Examples of the cyclic alkylene group having 20 or less carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group and the like.

Examples of the aromatic hydrocarbon group represented by A in the general formula (1) include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthracenylene group, a phenanthrylene group and the like. The aromatic hydrocarbon group in the general formula (1) may be substituted with an aliphatic hydrocarbon group, and examples of the aliphatic hydrocarbon group include the above-mentioned aliphatic hydrocarbon group having 1 to 20 carbon atoms. Be done.

Examples of the compound represented by the general formula (1) include Dai-ichi Kogyo Seiyaku Co., Ltd. “G8009L”. G8009L is a compound in which R ³ and R ⁵ are CH ₃ , R ⁴ and R ⁶ are C ₂ H ₅ , and A is C ₄ H ₈ in the general formula (1).

In addition to the compound represented by the general formula (1), examples of the isocyanate masked imidazole compound include an isocyanate adduct of 2-ethyl-4-methylimidazole.

The sealing resin composition of the present disclosure may contain other curing accelerators other than the isocyanate masked imidazole compound. The type of other curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin or curing agent, 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). Cyclic amidin compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole; derivatives of the cyclic amidin compound; said cyclic amidin compound. Or a phenol novolac salt of a derivative thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 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 Compounds with added intramolecular polarization; such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, etc. Cyclic amidinium compound and compound with isocyanate added; DBU isocyanate adduct, DBN isocyanate adduct, N-methylmorpholin isocyanate adduct; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamino Tertiary amine compounds such as ethanol and tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n benzoate -Ammonium salt compounds such as hexylammonium and tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, Tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetra) Alkoxyphenyl) Tertiary phosphine such as phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; phosphine compound such as a complex of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine compound and 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, and diazophenylmethane and other compounds with an intramolecular polarization formed by adding a compound having a π bond; Alternatively, the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodinated phenol, 2-iodide Phenol compound, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6 A halogenated phenol compound such as −di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl was reacted. Compounds with intramolecular polarization, which are later obtained through the process of dehalogenation; tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra-substituted phosphoniums without phenyl groups attached to boron atoms such as tetra-p-tolylbolate, and Tetra-substituted borates; salts of tetraphenylphosphoniums and phenolic compounds; salts of tetraalkylphosphoniums and partial hydrolysates of aromatic carboxylic acid anhydrides and the like.

The mass ratio of the isocyanate masked imidazole compound to the total amount of the curing accelerator is preferably 80% by mass to 100% by mass, more preferably 85% by mass to 100% by mass, and 90% by mass to 100% by mass. Is more preferable.

The amount of the curing accelerator contained in the sealing resin composition 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 the epoxy resin and the curing agent). It is more preferably parts 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 an inorganic filler. The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mulite. , Titania, talc, clay, mica and other inorganic materials. 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, and alumina is preferable from the viewpoint of high thermal conductivity. 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 content of the inorganic filler contained in the sealing resin composition is not particularly limited. From the viewpoint of fluidity during molding, 90% by volume or less of the entire sealing resin composition is preferable, 85% by volume or less is more preferable, and 80% by volume or less is further preferable. From the viewpoint of the strength and thermal conductivity of the cured product, 40% by volume or more is preferable, 45% by volume or more is more preferable, 50% by volume or more is further preferable, and 55% by volume or more is further preferable. preferable.
The content of the inorganic filler contained in the sealing resin composition is preferably 90% by mass or less, more preferably 85% by mass or less of the entire sealing resin composition from the viewpoint of fluidity during molding. More preferably, it is 80% by mass or less. From the viewpoint of the strength and thermal conductivity of the cured product, 40% by mass or more is preferable, 45% by mass or more is more preferable, 50% by mass or more is further preferable, and 55% by mass or more is further preferable. preferable.

[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, a colorant, and a stress relaxation agent 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, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.

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.

(Stress relaxation agent)
The sealing resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles. By including the stress relaxation agent, it is possible to further reduce the warping deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic. Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples include rubber particles having a structure. As the stress relaxation agent, 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>
The electronic component device according to the embodiment of the present disclosure includes a support member, an element arranged on the support member, and a cured product of the sealing resin composition of the present disclosure that seals the element. To be equipped.

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.

<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 sealing resin composition of the present disclosure is suitable for a wafer level package (WLP) because it has excellent fluidity during molding and can suppress the occurrence of molding warpage. The WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package. WLCSP (Wafer level Chip Size Package)).

When wafer level packaging is performed using the sealing resin composition of the present disclosure, a step of arranging a plurality of elements on the wafer and the plurality of elements are collectively combined with the sealing resin composition of the present disclosure. This includes a step of sealing the device and a step of separating each sealed element into individual pieces.

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.

The material of the wafer used for WLP is usually a crystal of a semiconductor material, and a single crystal of silicon is generally used. The size of the wafer is not particularly limited, and is, for example, 6 inches to 12 inches in diameter, preferably 10 inches to 12 inches in diameter.

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 at the blending ratios (parts by mass) shown in Table 1 to prepare resin compositions for encapsulation of Examples and Comparative Examples. This sealing resin composition was a solid under normal temperature and pressure.

-Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 2: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
-Epoxy resin 3: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

-Phenol curing agent 1: Phenol aralkyl resin, hydroxyl group equivalent 175 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7800SS")
-Phenol curing agent 2: Biphenyl aralkyl resin, hydroxyl group equivalent 275 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7851SS")

-Curing accelerator 1: Isocyanate masked imidazole compound (Daiichi Kogyo Seiyaku Co., Ltd., product name "G8009L")
-Curing accelerator 2: Imidazole compound (Shikoku Kasei Kogyo Co., Ltd., product name "Curesol 2PZ")
-Curing accelerator 3: Triphenylphosphine / 1,4-benzoquinone adduct

-Inorganic filler: fused silica (DENKA, product name "FB9454FC", volume average particle size 10 μm)
-Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Stress relaxation agent: Polymer 1: Polycaprolactone-modified dimethyl silicone, amorphous polymer, Tg55 ° C (Gerest, product name "DBL-C32")
-Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

<Performance evaluation of sealing resin composition>
(Liquidity: Spiral flow)
Using a spiral flow measuring mold according to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 150 ° C., a molding pressure of 6.9 MPa, and a curing time of 180 seconds. cm) was calculated.

(Hardness at heat)
The sealing resin composition was charged into a transfer molding machine and molded under the conditions of a mold temperature of 150 ° C., a molding pressure of 7 MPa, and a curing time of 120 seconds to obtain a disk-shaped molded product (diameter 40 mm, thickness 5 mm). .. Using this molded product as a test piece, the shore D hardness within 10 seconds after the mold was released was measured using a shore D hardness tester.

(Molding warp)
A mold was prepared for molding a laminated body in which a cured resin product having a thickness of 200 μm was laminated on a silicon wafer having a diameter of 300 mm by transfer molding. Using this mold, a silicon wafer with a diameter of 300 mm, and a sealing resin composition, a sealing resin is placed on a silicon wafer under the conditions of a mold temperature of 150 ° C. or 175 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds. A laminate in which the cured product of the composition was laminated was formed.
This laminate was placed on a horizontal table with the silicon wafer facing down, and the height (mm) of the highest point of the outer edge of the laminate was measured, and this height was used as an index of molding warpage. ..

The sealing resin composition of the example was curable even at a relatively low temperature. The sealing resin composition of the example was superior in fluidity during molding and suppressed the occurrence of molding warpage as compared with the sealing resin composition of the comparative example.

Claims (7)

Contains epoxy resin, curing agent, curing accelerator, and inorganic filler,
The curing accelerator contains an isocyanate masked imidazole compound.
Resin composition for sealing. The sealing resin composition according to claim 1, wherein the epoxy resin contains a polyfunctional epoxy resin. The polyfunctional epoxy resin is selected from the group consisting of triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalenediol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and dicyclopentadiene type epoxy resin. The sealing resin composition according to claim 2, which comprises at least one of the following types. The sealing resin composition according to any one of claims 1 to 3, wherein the curing agent contains a phenol curing agent. The sealing resin composition according to any one of claims 1 to 4, for use in a wafer level package. Support members and
The element arranged on the support member and
The cured product of the sealing resin composition according to any one of claims 1 to 5, 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 any one of claims 1 to 5.
Manufacturing method of electronic component equipment including.