JP2022011184A - Encapsulating resin composition and electronic component equipment - Google Patents

Abstract

To provide a sealing resin composition which enables production of a cured product that can reduce a relative dielectric constant while suppressing an increase in a dielectric loss tangent, and an electronic component device sealed using the same.SOLUTION: A sealing resin composition contains an epoxy resin, a curing agent and a filler containing an organic filler containing a fluorine atom and an inorganic filler, in which a porosity of the filler is 30 vol.% or less.SELECTED DRAWING: None

Description

The present invention relates to a sealing resin composition and an electronic component device.

The amount of transmission loss caused by the thermal 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 tends to change to heat in proportion to the frequency, the material of the communication member is required to have low dielectric characteristics in the high frequency band in order to suppress the transmission loss.

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

Japanese Unexamined Patent Publication No. 2012-246367 Japanese Unexamined Patent Publication No. 2014-114352

In the information and communication field, the frequency of radio waves is increasing with the increase in the number of channels and the amount of information transmitted. 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. Since the mainstream of wireless communication will be communication in such a high frequency band in the future, it is required to reduce the relative permittivity and the dielectric loss tangent in order to reduce the energy loss in the material of the communication member. However, for example, if the amount of the filler in the thermosetting resin composition is reduced, the relative dielectric constant is lowered, while the dielectric loss tangent is increased, and the dielectric loss tangent and the relative permittivity are in a trade-off relationship. Therefore, a sealing resin composition or the like capable of producing a cured product capable of reducing the relative permittivity while suppressing an increase in dielectric loss tangent is desirable.

The present disclosure provides a sealing resin composition capable of producing a cured product capable of reducing the relative permittivity while suppressing an increase in dielectric loss tangent, and an electronic component device sealed using the same. Make it an issue.

Specific means for solving the above-mentioned problems include the following aspects.
<1> For encapsulation, which contains an epoxy resin, a curing agent, and a filler containing an organic filler containing a fluorine atom and an inorganic filler, and the void ratio of the filler is 30% by volume or less. Resin composition.
<2> For encapsulation, which contains an epoxy resin, a curing agent, and a filler containing an organic filler containing a fluorine atom and an inorganic filler, and the average particle size of the inorganic filler is 10 μm or less. Resin composition.
<3> The sealing resin composition according to <1> or <2>, wherein the average particle size of the organic filler containing a fluorine atom is 10 μm or less.
<4> The sealing according to any one of <1> to <3>, wherein the content of the organic filler containing a fluorine atom is 5% by mass to 30% by mass with respect to the entire filler. Resin composition for.
<5> The sealing resin composition according to any one of <1> to <4>, wherein the curing agent contains at least one selected from the group consisting of a phenol curing agent and an active ester compound.
<6> The sealing resin composition according to any one of <1> to <5> for underfilling.
<7> The sealing resin composition according to any one of <1> to <6>, which has a relative permittivity of 3.3 or less at 10 GHz when it is a cured product.
<8> An electronic component device comprising an element and a cured product of the sealing resin composition according to any one of <1> to <7> that seals the element.

According to the present disclosure, there is provided a sealing resin composition capable of producing a cured product capable of reducing the relative permittivity while suppressing an increase in dielectric loss tangent, and an electronic component device sealed using the same. be able to.

In the present disclosure, the term "process" includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
In the present disclosure, the numerical range indicated by using "-" 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 the numerical range described in another stepwise description. .. 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.

[First Embodiment]
<Plastic composition for encapsulation>
The sealing resin composition of the first embodiment of the present disclosure contains an epoxy resin, a curing agent, and a filler containing an organic filler containing a fluorine atom and an inorganic filler, and the filler of the filler. The void ratio is 30% by volume or less.

The sealing resin composition of the first embodiment contains an organic filler containing a fluorine atom and a filler containing an inorganic filler, and is a part of the inorganic filler in a normal sealing resin composition. Has a form in which is replaced with an organic filler. This makes it possible to produce a cured product capable of reducing the relative permittivity while suppressing an increase in the dielectric loss tangent.

Further, in the sealing resin composition of the first embodiment, the porosity of the filler is 30% by volume or less. The void ratio of the filler is a value representing the ratio of voids to the bulk volume of the filler ((volume of voids / bulk volume of filler) × 100 (%)). When fillers of the same material are used, if the weights of the fillers are the same, the bulk volume of the filler decreases as the porosity decreases. When the bulk volume of the filler contained in the sealing resin composition becomes small, even if the content of the filler contained in the sealing resin composition is the same, the filling material is taken from the volume of the sealing resin composition. The value obtained by subtracting the bulk volume of is large. Hereinafter, this value may be referred to as "amount of surplus resin".
As the amount of the surplus resin increases (that is, the porosity of the filler decreases), the curability, fluidity, moldability, and thermal conductivity of the cured resin composition improve. Tend.

It is not clear why the curability, fluidity, moldability and thermal conductivity of the cured resin composition improve as the amount of surplus resin increases, but the amount of surplus resin increases. Therefore, it is considered that the viscosity of the sealing resin composition is reduced and the fluidity is improved. Further, by increasing the amount of the surplus resin, the dispersibility of the sealing resin composition at the time of kneading is improved, which contributes to the improvement of curability, moldability and thermal conductivity of the cured product. It is presumed.
The porosity of the filler means the porosity of the filler which is a mixture of the inorganic filler and the organic filler.

Hereinafter, each component constituting the sealing resin composition will be described. The sealing resin composition of the present embodiment contains an epoxy resin, a curing agent, and a filler containing an organic filler containing a fluorine atom and an inorganic filler, and if necessary, contains other components. You may.

(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. A novolak type epoxy resin (phenol novolak type) which is an epoxidation of a novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. Epoxide resin, orthocresol novolak 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 epoxide resin; a copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol. 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 stilben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin that is a diglycidyl ether such as S; epoxy resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; and a polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid. Glysidyl ester type epoxy resin, which is a glycidyl ester; glycidylamine type epoxy resin, which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group; Dicyclopentadiene-type epoxy resin, which is an epoxide of a condensed resin; vinylcyclohexene epoxide, which is an epoxide of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxide) cyclohexyl-5,5 An alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin that is a glycidyl ether of a paraxylylene-modified phenol formaldehyde; a metaxylylene-modified epoxy resin that is a glycidyl ether of a metaxylylene-modified phenol resin. A terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol form; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of a ring-fragrant ring-modified phenol resin; naphthalene-type epoxy resin, which is a glycidyl ether of a naphthalene ring-containing phenol resin; Type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl type epoxy resin obtained by epoxidizing 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 can also 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. % Is more preferable.

(Hardener)
The sealing resin composition 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 other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polypeptide curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, active ester compounds and the like. These curing agents may be used alone or in combination of two or more.

Above all, from the viewpoint of suppressing the dielectric loss tangent of the cured product to a low level and from the viewpoint of moldability, the curing agent preferably contains at least one selected from the group consisting of a phenol curing agent and an active ester compound.

Specific examples of the phenol curing agent include polyvalent phenol compounds such as resorsin, catecol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, and 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 are acid catalysts. Novorac-type phenolic resin obtained by condensation or co-condensification under the following; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., naphthol-aralkyl resin, etc. Paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; Melamine-modified phenolic resin; Terpen-modified phenolic resin; Resin; Cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; The above phenolic compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde are condensed or co-condensed under an acidic catalyst. The triphenylmethane type phenol resin to be used; examples thereof include a phenol resin obtained by copolymerizing two or more of these types. These phenol curing agents may be used alone or in combination of two or more.

Among the phenol curing agents, an alkyl-modified phenol resin is preferable, and a low-polarity alkyl-modified phenol resin is particularly preferable, from the viewpoint of suppressing the dielectric loss tangent and the relative permittivity of the cured product to be lower.

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. A phenol curing agent, an amine curing agent, or the like is generally used as the curing agent for the epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent. 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, there is a tendency that the dielectric loss tangent of the cured product can be reduced by using the active ester compound as the curing agent.

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

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 due to having 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 a carboxy group, and the hydrogen atom of the above-mentioned aromatic ring. Aromatic carboxylic acid and a phenolic hydroxyl group are prepared from a mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyvalent phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group. 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 exemplary 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. It is an ester-forming structural site (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of the number 1 to 4 and an acyl group having the number of carbon atoms 2 to 6, and is 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. It is an ester-forming structural site (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of the number 1 to 4 and an acyl group having the number of carbon atoms 2 to 6, and is 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 exemplary compounds (2-1) to (2-6).

Specific examples of the compound represented by the structural formula (3) include the following exemplary 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. ); Examples of the active ester compound containing a benzoyl compound of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).

The functional group equivalent of the curing agent other than the active ester compound (for example, the hydroxyl group equivalent in the case of the phenol curing agent) is not particularly limited. From the viewpoint of 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 ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of balance of 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 functional group equivalent of the curing agent other than the active ester compound (for example, the hydroxyl group equivalent in the case of the phenol curing agent) and the ester group equivalent of the active ester compound 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.

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 amount, 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 it in the range of 0.8 to 1.2.

When the curing agent contains an active ester compound, the content of the active ester compound with respect to the total mass of the curing agent is preferably 80% by mass or more, preferably 85% by mass or more, from the viewpoint of keeping the dielectric adjacency of the cured product low. It is more preferably present, 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 characteristics 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 amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds 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, and diazophenylmethane and other compounds with π bonds are added to form an intramolecular polarization. Compounds; Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt and isocyanate are added. Compounds; DBU isocyanate adduct, DBN isocyanate adduct, 2-ethyl-4-methylimidazole isocyanate adduct, N-methylmorpholin isocyanate adduct; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanol Tertiary amine compounds such as amine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, benzo Ammonium salt compounds such as tetra-n-hexylammonium acid acid, tetrapropylammonium hydroxide, etc .; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxy). Phenyl) phosphin, tris (dialkylphenyl) phosphin, tris (trialkylphenyl) phosphin, tris (tetraalkylphenyl) phosphin, tris (dialkoxyphenyl) phosphin, tris (trialkoxyphenyl) phos Tertiary phosphin such as fin, tris (tetraalkoxyphenyl) phosphine, trialkylphosphin, dialkylarylphosphin, alkyldiarylphosphine; phosphin compound such as a complex of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine. Compounds and maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, A quinone compound such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having an intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane. The tertiary phosphine or the phosphenyl compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodylated phenol, 3-iodylated Phenyl, 2-iodide phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Halogenized phenols such as bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl A compound having intramolecular polarization obtained through a step of dehalogenating after reacting the compound; a tetra-substituted phosphonium such as tetraphenylphosphonium, or a phenyl group bonded to a boron atom such as tetra-p-tolylbolate. Not tetra-substituted phosphonium and tetra-substituted borate; salts of tetraphenylphosphonium and phenol compounds; salts of tetraalkylphosphonium and partial hydrolyzates of aromatic carboxylic acid anhydrides 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 the epoxy resin and the curing agent). It is more preferably 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 cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

(Filler)
The sealing resin composition contains an organic filler containing a fluorine atom and a filler containing an inorganic filler. Further, the porosity of the filler contained in the sealing resin composition is 30% by volume or less.

The type of the inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as fused silica, crystalline silica, glass, alumina, 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, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic 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.

The type of the organic filler containing a fluorine atom is not particularly limited. Specifically, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene- Fluororesin particles such as ethylene copolymer (ETFE) can be mentioned.

Among the organic fillers containing fluorine atoms, polytetrafluoroethylene (PTFE) is preferable from the viewpoint of heat resistance. As the organic filler containing a fluorine atom, one type may be used alone or two or more types may be used in combination.

The porosity of the filler is 30% by volume or less, preferably 28% by volume or less, and more preferably 25% by volume or less. The porosity of the filler may be 7% by volume or more.

The porosity of the filler is a value measured by the following method.
The particle size distribution of the inorganic filler and the particle size distribution of the organic filler containing fluorine atoms were obtained using a laser diffraction / scattering particle size distribution measuring device (for example, Horiba Seisakusho Co., Ltd., LA920), and the respective particle sizes were obtained. From the distribution, the void ratio ε is calculated using the formula of Ouchiyama below. For details on Ouchiyama's formula, see the following documents.
N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam. , 19, 338 (1980)
N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam. , 20, 66 (1981)
N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam. , 23, 490 (1984)

The average particle size of the inorganic filler is preferably 10 μm or less from the viewpoint of filling property of the sealing resin composition, preferably 1 μm to 8 μm, and preferably 2 μm to 6 μm from the viewpoint of filling property. Is more preferable.

The maximum particle size of the inorganic filler is preferably 50 μm or less, and more preferably 30 μm or less, from the viewpoint of the filling property of the sealing resin composition. The maximum particle size of the inorganic filler is not particularly limited.

The average particle size of the organic filler containing a fluorine atom is preferably 10 μm or less from the viewpoint of filling property of the sealing resin composition, and preferably 1 μm to 8 μm from the viewpoint of filling property. It is more preferably 2 μm to 6 μm.

The maximum particle size of the organic filler containing a fluorine atom is preferably 50 μm or less, and more preferably 30 μm or less, from the viewpoint of the filling property of the sealing resin composition.

The average particle size of the inorganic filler can be measured as follows. The sealing resin composition is placed in a crucible and left at 800 ° C. for 4 hours to incinerate. The particle size distribution of ash obtained by using a laser diffraction / scattering type particle size distribution measuring device (for example, Horiba Seisakusho Co., Ltd., LA920) was obtained, and the average particle size of the inorganic filler was used as the volume average particle size (D50) from the particle size distribution. The particle size can be determined.
The average particle size of the organic filler containing a fluorine atom was determined by 100 randomly selected inorganic fillers in an image obtained by imaging a flaky sample of a sealing resin composition or a cured product thereof with a scanning electron microscope. It is a value obtained by measuring the major axis and arithmetically averaging it.

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

The total content of the inorganic filler contained in the filler and the organic filler containing a fluorine atom may be 50% by mass to 100% by mass, or 70% by mass to 100% by mass with respect to the entire filler. It may be 90% by mass to 100% by mass.

The content of the organic filler containing fluorine atoms contained in the sealing resin composition is preferably 5% by mass to 30% by mass, and 6% by mass to 25% by mass with respect to the entire filler. It is more preferably present, and further preferably 8% by mass to 22% by mass. When the content of the organic filler containing fluorine atoms is 5% by mass or more, the relative permittivity of the cured product tends to be further reduced, and the content of the organic filler containing fluorine atoms is 30% by mass. By the following, the moldability of the sealing resin composition tends to be excellent.

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, 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 part by mass to 5 parts by mass, and 0.1 part by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 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 release property 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. The release agent may be used alone or in combination of two or more.

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. More preferably, it is by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 part 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 (total amount of epoxy resin and curing agent) of the resin component.

(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 encapsulation)
The method for preparing the sealing resin composition is not particularly limited. As a general method, a method of sufficiently mixing a predetermined amount of components with a mixer or the like, melt-kneading with a mixing roll, an extruder or the like, cooling and pulverizing 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 shape of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.

The sealing resin composition is preferably for underfill, and more preferably for mold underfill.
For example, the sealing resin composition is bump-connected by an electronic component device in which a semiconductor element is directly bump-connected onto a wiring substrate having a ceramic, a glass epoxy resin, a glassimide resin, a polyimide film, or the like as a substrate. It can be used as an underfill material for filling the gap between the semiconductor element and the wiring substrate.
Further, the sealing resin composition is an electronic component device that is directly bump-connected on the wiring board described above, and has an underfill that fills a gap between the bump-connected semiconductor element and the wiring board, and a semiconductor. It can also be used as a mold underfill material for collectively molding the element.

From the viewpoint of suppressing the transmission loss of the cured product, the sealing resin composition preferably has a relative permittivity of 3.3 or less at 10 GHz when it is made into a cured product, and is preferably 3.25 or less. More preferably, it is more preferably 3.2 or less. The above-mentioned relative permittivity may be 3.0 or more.
The method for measuring the relative permittivity described above is as described in Examples described later.

[Second Embodiment]
<Plastic composition for encapsulation>
The sealing resin composition of the second embodiment of the present disclosure contains an epoxy resin, a curing agent, and a filler containing an organic filler containing a fluorine atom and an inorganic filler, and the inorganic filler. The average particle size of is 10 μm or less.

The sealing resin composition of the second embodiment contains an organic filler containing a fluorine atom and a filler containing an inorganic filler, and is a part of the inorganic filler in a normal sealing resin composition. Has a form in which is replaced with an organic filler. This makes it possible to produce a cured product capable of reducing the relative permittivity while suppressing an increase in the dielectric loss tangent.

Further, in the sealing resin composition of the second embodiment, the average particle size of the inorganic filler is 10 μm or less. As a result, the sealing resin composition has excellent filling property, and can be used, for example, for underfilling, preferably for mold underfilling.

The preferred embodiment of the sealing resin composition of the second embodiment is the same as the sealing resin composition of the first embodiment described above.

<Electronic component equipment>
The electronic component apparatus of the present disclosure includes an element and a cured product of the above-mentioned 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, support members such as organic substrates, active elements such as semiconductor chips, transistors, diodes, and thyristers, capacitors, and resistors. , 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 Readed Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) TS- 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, a hybrid IC, or a multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like to a wiring formed on a support member is sealed with a sealing resin composition. Chip module, etc .; After mounting the element on the surface of the support member having terminals for connecting the wiring board on the back surface and connecting the element and the wiring formed on the support member by bump or wire bonding, the resin composition for sealing 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.

Examples of the method for sealing the device 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 present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Preparation of resin composition for encapsulation>
The components shown below were mixed at the blending ratios (unit: 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.
The porosity of the filler in the sealing resin composition was measured by the above method.

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

-Curing agent 1: Active ester compound containing aromatic structure-Curing agent 2: Aralkyl type phenol resin, hydroxyl group equivalent 201 g / eq-205 g / eq (trade name: MEHC7851-SS, Meiwa Kasei Co., Ltd., softening point 64 ° C- 69 ° C)
-Curing agent 3: Alkyl-modified phenolic resin, hydroxyl group equivalent 238 g / eq

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

-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")
-Coupling agent 3: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")

-Inorganic filler 1: Fused silica (average particle size 0.7 μm, maximum particle size 45 μm)
-Inorganic filler 2: fused silica (average particle size 6.5 μm, maximum particle size 20 μm)
-Inorganic filler 3: fused silica (average particle size 4.7 μm, maximum particle size 10 μm)

-Organic filler 1: PTFE filler (average particle size 3 μm, maximum particle size 45 μm)
-Organic filler 2: PTFE filler (average particle size 0.7 μm, maximum particle size 45 μm)

(Spiral flow)
Using a mold for measuring spiral flow 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.
The results are shown in Table 2.

(PKG molding evaluation)
PKG molding evaluation was performed as follows for Example 3 in which the content of the organic filler containing a fluorine atom was higher than that in Examples 1 and 2, and Comparative Example 3 which was a comparison target of Example 3. ..
First, a sealing resin composition was molded on a Cu substrate using a transfer mold device (Apic Yamada Corporation, G-LINE PRESS T / F 3MAP) at a mold temperature of 175 ° C. and a curing time of 120 seconds. The appearance of the obtained molded product was confirmed, and when there were no voids or chips on the surface, the moldability was evaluated as good.

(Evaluation of extract)
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 perform a test for measuring impurities. Pieces were made. The prepared test piece for measuring impurities was finely pulverized, 5 g of a sample was put into an Acom Uniseal (extraction jig) together with 50 ml of distilled water, and the sample was extracted in a constant temperature bath at 121 ° C. for 20 hours. The extract was filtered to obtain a test solution. Ionic impurities (F- and ^Cl- ), electrical conductivity ^and pH were measured using the test solution. The measuring equipment used is shown below.
<Measurement target and measuring equipment>
Electric conductivity: Electric conductivity meter, model CM-115, Kyoto Electronics Co., Ltd. pH: pH meter, model F ^- 8L, HORIBA, Ltd. F- ^and Cl -... ion chromatograph, model AA- 6200, Metrohm Japan Limited The results are shown in Table 2.

(Water absorption rate)
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 cure the disk. (Diameter 50 mm, thickness 3 mm) was obtained. The disk-shaped cured product immediately after production was charged into a pressure cooker test apparatus at 121 ° C./2.1 atm, taken out 24 hours later, and the rate of increase (%) from the mass immediately before charging was determined.
The results are shown in Table 2.

(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). 90 mm in length, 0.6 mm in width, 0.8 mm in thickness) were obtained. Using this cured product as a test piece, using a cavity resonator (Kanto Electronics Applied Development Co., Ltd.) and a network analyzer (Keysight Technology Co., Ltd., product name "PNA E8364B") at a temperature of 25 ± 3 ° C., 1 GHz, 5 GHz and The relative permittivity and the dielectric loss tangent at 10 GHz were measured.
The model of the cavity resonator used at each measurement frequency is as follows.
1GHz ・ ・ ・ CP431
5GHz ・ ・ ・ CP511
10GHz ・ ・ ・ CP531
The results are shown in Table 2.

The sealing resin composition is molded with a hand press machine under the conditions of a mold temperature of 175 ° C., a molding pressure of 2.5 MPa, and a curing time of 600 seconds, and post-curing is performed at 175 ° C. for 6 hours to obtain a plate-shaped cured product (a plate-shaped cured product). 12.5 mm in length, 25 mm in width, and about 0.2 mm in thickness) were obtained. Using a plate-shaped cured product as a test piece, the relative permittivity and dielectric loss tangent at 36 GHz were measured at a temperature of 25 ± 3 ° C. using a dielectric constant measuring device (Agilent, product name “Network Analyzer N5227A”). ..
The results are shown in Table 2.

In each item listed in Table 2, "-" means that it has not been evaluated.

Comparing Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3 having the same composition other than the filler, the increase in dielectric loss tangent (Df) in each example. It was possible to produce a cured product capable of reducing the relative permittivity (Dk) while suppressing the above.

Claims (8)

Epoxy resin and
Hardener and
Organic fillers containing fluorine atoms and fillers containing inorganic fillers,
Contains,
A sealing resin composition having a porosity of 30% by volume or less of the filler. Epoxy resin and
Hardener and
Organic fillers containing fluorine atoms and fillers containing inorganic fillers,
Contains,
A sealing resin composition having an average particle size of 10 μm or less of the inorganic filler. The sealing resin composition according to claim 1 or 2, wherein the average particle size of the organic filler containing a fluorine atom is 10 μm or less. The sealing resin composition according to any one of claims 1 to 3, wherein the content of the organic filler containing a fluorine atom is 5% by mass to 30% by mass with respect to the entire filler. thing. The sealing resin composition according to any one of claims 1 to 4, wherein the curing agent contains at least one selected from the group consisting of a phenol curing agent and an active ester compound. The sealing resin composition according to any one of claims 1 to 5, which is for underfilling. The sealing resin composition according to any one of claims 1 to 6, wherein the cured product has a relative permittivity of 3.3 or less at 10 GHz. An electronic component device comprising an element and a cured product of the sealing resin composition according to any one of claims 1 to 7, which seals the element.