JPWO2020065873A1 - Manufacturing method of sealing resin composition, electronic component device and electronic component device - Google Patents

Abstract

A sealing resin composition for use in narrow-pass filling, which contains an epoxy resin, a curing agent, and an inorganic filler, the curing agent contains an active ester compound, and the average particle size of the inorganic filler is less than 10 μm. thing.

Description

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

The amount of 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 is easily converted into heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties in the high frequency band in order to suppress the transmission loss.

For example, Patent Documents 1 and 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for an epoxy resin, 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, radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases. Currently, studies on 5th generation mobile communication systems are underway worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to have a lower dielectric loss tangent.

In addition, as semiconductor devices become smaller, thinner, or more sophisticated, the bump pitch or the spacing between elements is becoming narrower, and there is a demand for a sealing resin composition having excellent narrow path filling properties. ..

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

The present disclosure discloses a sealing resin composition having excellent narrow path filling property and low dielectric loss tangent of a cured product, an electronic component device sealed using the resin composition, and an electronic component device sealed using the resin composition. The challenge is to provide a method.

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

[1] Sealing for use in narrow road filling, which contains an epoxy resin, a curing agent, and an inorganic filler, the curing agent contains an active ester compound, and the average particle size of the inorganic filler is less than 10 μm. Resin composition for.
[2] The sealing resin composition according to [1], wherein the maximum particle size of the inorganic filler is less than 20 μm.
[3] The sealing resin composition according to [1] or [2], which is used for mold underfilling.
[4] The sealing resin composition according to any one of [1] to [3], which fills a support member, an element arranged on the support member, and a narrow path around the element. An electronic component device including a cured product of an object.
[5] A step of arranging the element on the support member and a step of filling the narrow path around the element with the sealing resin composition according to any one of [1] to [3]. Manufacturing method of electronic component equipment including.

According to the present disclosure, a sealing resin composition having excellent narrow path filling property and low dielectric loss tangent of a cured product, an electronic component device sealed using the resin composition, and an electronic component device sealed using the resin composition. Manufacturing method is provided.

It is a top view (partial perspective view) explaining the test chip used in an Example. It is sectional drawing explaining the test chip used in an Example.

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.
When the embodiment is described in the present disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this.

<Resin composition for sealing>
The sealing resin composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, the curing agent contains an active ester compound, and the average particle size of the inorganic filler is less than 10 μm. It is a sealing resin composition for road filling.

The narrow path in which the sealing resin composition of the present disclosure is used refers to a gap in which at least one of the height and the width is 100 μm or less. Examples of the narrow path include a gap between the support member and the element, a gap between the elements adjacent to each other, and the like.

The sealing resin composition of the present disclosure is used for filling a narrow path of an electronic component device, and is also used for sealing a part of a space other than the narrow path in the electronic component device or the entire electronic component device. It may be a resin composition for use.
As an example of the above embodiment, a sealing resin composition for mold underfill (MUF) that seals an element arranged on a support member and fills a gap between the support member and the element; SiP. Examples thereof include a sealing resin composition for (system in a package).

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

Conventionally, a phenol curing agent, an amine curing agent, or the like is generally used as a curing agent for an 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, the sealing resin composition of the present disclosure is compared with the sealing resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent. The dielectric loss tangent of the cured product can be kept low.

The sealing resin composition of the present disclosure is excellent in narrow road filling property because the average particle size of the contained inorganic filler is less than 10 μm. It is presumed that the reason for this is that when the melt of the sealing resin composition flows through the narrow path, the inorganic filler does not easily block the narrow path.
In the sealing resin composition of the present disclosure, the lower limit of the average particle size of the inorganic filler is not particularly limited. For example, from the viewpoint of suppressing aggregation of the inorganic fillers, it is preferably 3 μm or more.

(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 equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, reflow resistance and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

The epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.

When the epoxy resin is a solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C.

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

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

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

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

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

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

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

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

Specific examples of the active ester compound include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group described in JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Equivalent ratio of epoxy resin to all curing agents (active ester compounds and other curing agents), that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the range from 0.8 to 1.2.

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

The total content of the epoxy resin and the active ester compound with respect to the total mass of the epoxy resin, the active ester compound and the other curing agent is preferably 70% by mass or more, preferably 80% by mass, from the viewpoint of keeping the dielectric equirect contact of the cured product low. It is more preferably% or more, and further preferably 85% by mass or more.

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

Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidin compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidin compound; phenol novolac salts of the cyclic amidin compound or derivatives thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, and diazophenylmethane and other quinone compounds with π-bonded compounds added. Compounds: Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, and isocyanates 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-hexyl ammonium acid, tetrapropyl ammonium hydroxide, etc .; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxy Phenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phos Tertiary phosphines such as fins, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; phosphine compounds such as complexes 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, and a compound having an intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane. The tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodinated Phenol, 2-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Halogenated 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 dehalogenation after reacting the compound; a phenyl group bonded to a boron atom such as tetra-substituted phosphonium such as tetraphenylphosphonium or tetra-p-tolylborate. Examples thereof include tetra-substituted phosphoniums and tetra-substituted borates; salts of tetraphenylphosphoniums and phenolic compounds; salts of tetraalkylphosphoniums and partial hydrolysates of aromatic carboxylic acid anhydrides.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). More preferably, it is 1 part by mass to 15 parts by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

(Inorganic filler)
In the sealing resin composition of the present disclosure, the average particle size of the contained inorganic filler is less than 10 μm. The average particle size of the inorganic filler is less than 10 μm and preferably less than 9 μm from the viewpoint of improving the narrow road filling property. The average particle size of the inorganic filler is preferably 3 μm or more, and more preferably 5 μm or more, from the viewpoint of suppressing aggregation of the inorganic fillers.

From the viewpoint of further improving the narrow road filling property, the sealing resin composition of the present disclosure preferably contains an inorganic filler having a maximum particle size of less than 30 μm, more preferably less than 25 μm, and more preferably 20 μm. It is more preferably less than.

The average particle size of the inorganic filler was determined by measuring the major axis of 100 randomly selected inorganic fillers in an image obtained by imaging a flaky sample of the sealing resin composition or a cured product thereof with a scanning electron microscope. It is the value obtained by arithmetically averaging it. The maximum particle size of the inorganic filler is the maximum value among the above 100 major axes.

The type of inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as molten 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, 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.

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

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

(Coupling agent)
The sealing resin composition may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, 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.

(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 is a sealing resin composition of the present disclosure that fills a support member, an element arranged on the support member, and a narrow path around the element. It is provided with a cured product.

The electronic component device according to the embodiment of the present disclosure has a narrow path filled with the sealing resin composition of the present disclosure. Examples of the narrow path include a gap between the support member and the element, a gap between the elements adjacent to each other, and the like. The electronic component device according to the embodiment of the present disclosure may be partially or wholly sealed with the sealing resin composition of the present disclosure except for the narrow road.

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 .; An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, a resin composition for sealing is provided. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package) having a structure in which elements are sealed with an object; SiP (system in a package) in which a plurality of elements are sealed in one package. And so on.

<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 filling a narrow path around the element with the sealing resin composition of the present disclosure.

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

In the step of filling the narrow path around the element with the sealing resin composition of the present disclosure, at the same time as filling the narrow path around the element, a part of the space other than the narrow path in the electronic component apparatus or an electronic component It may be a step of sealing the entire device.

Examples of the method of filling the narrow path around 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 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 shown in Table 1 to prepare resin compositions for sealing in Examples and Comparative Examples. This sealing resin composition was a solid under normal temperature and pressure.

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

-Active ester compound 1: DIC Corporation, product name "EXB-8"
-Active ester compound 2: DIC Corporation, product name "EXB-9425"
-Phenol curing agent 1: Phenol aralkyl resin, hydroxyl group equivalent 175 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7800SS")

-Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct-Curing accelerator 2: Imidazole compound (Shikoku Kasei Kogyo Co., Ltd., product name "Curesol 2E4MZ")

-Filler 1: Fused silica (DENKA, product name "FB-310MDC")
-Filler 2: Fused silica (Micron, product name "ST7010-2")
-Filler 3: Fused silica (Admatex, product name "SO-25R")
-Filler 4: Fused silica (DENKA, product name "FB-9454FC")
-Filler 5: Fused silica (Micron, product name "ST7010-3")

-Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803")
-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>
(Average particle size and maximum particle size of inorganic filler)
The major axis (μm) of 100 randomly selected inorganic fillers was measured in an image of a flaky sample of the encapsulating resin composition taken with a scanning electron microscope, and the major axis (μm) was arithmetically averaged to obtain the average particle size. .. Further, the maximum value among the 100 major axes (μm) was defined as the maximum particle size.

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

(Narrow road filling property)
The test chips of the forms shown in FIGS. 1 and 2 were prepared. That is, a die 3 (length 10 mm ×) obtained by dicing a silicon wafer on a substrate 1 (length 50 mm × width 250 mm × thickness 0.2 mm) via a die attach tape 6 (width 1.0 mm, thickness 40 μm). Three sheets (10 mm wide × 250 μm thick) were arranged and pressure-bonded at 200 ° C. for 10 seconds.
Next, 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 150 seconds, and post-curing was performed at 180 ° C. for 5 hours. The molding dimensions were 50 mm in length × 250 mm in width × 0.5 mm in thickness on the substrate 1.
^{The area of voids of 1 mm 2} or more visible between the die 3 and the substrate 1 was measured from the surface opposite to the element mounting surface, and the total area was obtained.

(Relative permittivity and dielectric loss tangent)
The sealing resin composition is charged into a vacuum hand press machine, molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and post-curing is performed at 180 ° C. for 6 hours to cure the plate. An article (length 12.5 mm, width 25 mm, thickness 0.2 mm) was obtained. Using this plate-shaped cured product as a test piece, a permittivity measuring device (Agilent Technologies, Inc., product name "Network Analyzer N5227A") was used to determine the relative permittivity and dielectric loss tangent at about 60 GHz at a temperature of 25 ± 3 ° C. It was measured.

(Water absorption rate)
The plate-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.

All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

1: Substrate 3: Die 6: Diatach tape

Claims (5)

Contains epoxy resin, hardener and inorganic filler,
The curing agent contains an active ester compound and contains
The average particle size of the inorganic filler is less than 10 μm.
A sealing resin composition for use in narrow road filling. The sealing resin composition according to claim 1, wherein the maximum particle size of the inorganic filler is less than 20 μm. The sealing resin composition according to claim 1 or 2, which is for mold underfilling. 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 3, which fills the narrow path around the element.
Electronic component device equipped with. The process of arranging the element on the support member and
The step of filling the narrow path around the element with the sealing resin composition according to any one of claims 1 to 3.
Manufacturing method of electronic component equipment including.

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