WO2020066856A1

WO2020066856A1 - Sealing resin composition, electronic component device, and method for manufacturing electronic component device

Info

Publication number: WO2020066856A1
Application number: PCT/JP2019/036837
Authority: WO
Inventors: 格山浦; 実佳田中; 徹馬場; 勇磨竹内; 児玉　俊輔; 貴大齋藤
Original assignee: 日立化成株式会社
Priority date: 2018-09-27
Filing date: 2019-09-19
Publication date: 2020-04-02
Also published as: CN112771094A; JPWO2020066856A1; JP2024026589A; TW202024166A

Abstract

This sealing resin composition contains: an epoxy resin including a polyfunctional epoxy resin and a bifunctional epoxy resin; and a curing agent containing an active ester compound.

Description

Sealing resin composition, electronic component device, and method of manufacturing electronic component device

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

伝送 The amount of transmission loss caused by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the frequency, the square root of the relative permittivity, and the dielectric loss tangent. In other words, a transmission signal is likely to change into heat in proportion to the frequency. Therefore, in order to suppress transmission loss, a material of a communication member is required to have a lower dielectric property in a higher frequency band.

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 a cured product can be suppressed.

JP 2012-246267 A JP 2014-114352 A

活性 The active ester compound as a curing agent for the epoxy resin is more advantageous than the phenol curing agent or the amine curing agent in that the cured product has a low dielectric constant. However, a sealing resin composition containing an active ester compound as a curing agent for an epoxy resin tends to be inferior in moldability.

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

The present disclosure relates to a sealing resin composition having both fluidity and curability at the time of molding and having a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a sealing device using the same. It is an object to provide a method for manufacturing an electronic component device.

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

[1] A sealing resin composition containing an epoxy resin containing a polyfunctional epoxy resin and a bifunctional epoxy resin, and a curing agent containing an active ester compound.
[2] The polyfunctional epoxy resin comprises a triphenylmethane type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthalene diol aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, and a dicyclopentadiene type epoxy resin. The sealing resin composition according to [1], comprising at least one member selected from the group.
[3] The bifunctional epoxy resin contains at least one selected from the group consisting of a bisphenol F epoxy resin, a bisphenol A epoxy resin, a biphenyl epoxy resin, a biphenylaralkyl epoxy resin, and a naphthalene epoxy resin. The sealing resin composition according to [1] or [2].
[4] Any one of [1] to [3], wherein the mass ratio of the polyfunctional epoxy resin to the total amount of the polyfunctional epoxy resin and the bifunctional epoxy resin is 50% by mass to 95% by mass. The resin composition for sealing according to the above.
[5] A support member, an element arranged on the support member, and the sealing resin composition according to any one of [1] to [4], which seals the element. Electronic component device to be equipped.
[6] An electronic component device comprising: a step of disposing an element on a support member; and a step of encapsulating the element with the encapsulating resin composition according to any one of [1] to [4]. Manufacturing method.

According to the present disclosure, a sealing resin composition that has both fluidity and curability at the time of molding and has a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and A method for manufacturing an electronic component device to be sealed is provided.

In the present disclosure, the term "step" includes, in addition to a step independent of other steps, even if the purpose of the step is achieved even if it cannot be clearly distinguished from the other steps, the step is also included. .
In the present disclosure, the numerical ranges indicated by using “to” include the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. . Further, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
In the present disclosure, each component may include a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content or content of each component is, unless otherwise specified, the total content or content of the plurality of substances present in the composition. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value of a mixture of the plurality of types of particles present in the composition unless otherwise specified.

<Sealing resin composition>
The resin composition for sealing of the present disclosure contains an epoxy resin containing a polyfunctional epoxy resin and a bifunctional epoxy resin, and a curing agent containing an active ester compound.

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

Conventionally, a phenol curing agent, an amine curing agent, and the like are generally used as a curing agent for an epoxy resin, but a secondary hydroxyl group is generated in a reaction between an epoxy resin and a phenol curing agent or an 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 a 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.

However, a sealing resin composition containing an active ester compound as a curing agent for an epoxy resin tends to be inferior in moldability. The reason for this is that the reactivity between the active ester compound and the epoxy resin is lower than the reactivity between the phenol curing agent or the amine curing agent and the epoxy resin, so that the crosslinking density and the glass transition temperature after heat curing are relatively low. This is presumed to be due to poor curing properties during molding. Further, a sealing resin composition containing an active ester compound as a curing agent for an epoxy resin tends to be inferior in fluidity to a sealing resin composition containing another curing agent (for example, a phenol curing agent). It is presumed that there are also some effects.
On the other hand, the sealing resin composition of the present disclosure can improve the crosslink density and glass transition temperature after thermosetting by including the polyfunctional epoxy resin while using the active ester compound as a curing agent. It is presumed that it is excellent in curability at the time of molding. The sealing resin composition of the present disclosure ensures fluidity during molding by using a bifunctional epoxy resin in combination with a polyfunctional epoxy resin.
Therefore, the sealing resin composition of the present disclosure can achieve both fluidity and curability during molding, and as a result, is excellent in moldability.
Here, the curability at the time of molding of the encapsulating resin composition of the present disclosure is a performance evaluated by the hardness at the time of molding immediately after molding.

(Epoxy resin)
The type of the epoxy resin is not particularly limited as long as the resin has an epoxy group in a molecule. The type of the polyfunctional epoxy resin is not particularly limited as long as the resin has three or more epoxy groups in the molecule. The type of the bifunctional epoxy resin is not particularly limited as long as the resin has two epoxy groups in a molecule.

は The number of epoxy groups in the polyfunctional epoxy resin is preferably 3 to 8, more preferably 3 to 5.

Examples of the polyfunctional epoxy resin include, for example, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, phenol novolak epoxy resin, dihydroxybenzene novolak epoxy resin, cresol novolak epoxy resin, glycidylamine epoxy resin, and naphthalene skeleton Type epoxy resin, naphthalene diol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin and the like, and derivatives thereof. These polyfunctional epoxy resins may be used alone or in combination of two or more.

As polyfunctional epoxy resins, from the viewpoint of crosslinking density, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene diol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and dicyclopentadiene type epoxy resin It is preferable to include at least one selected from the group consisting of resins.

The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material, and an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin is preferable.

Examples of the bifunctional epoxy resin include bisphenol F epoxy resin, bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol A novolak epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, and naphthalene epoxy resin. And their derivatives. These bifunctional epoxy resins may be used alone or in combination of two or more.

As the bifunctional epoxy resin, from the viewpoint of fluidity, at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin and naphthalene type epoxy resin It is preferred to include. Among them, biphenyl type epoxy resin is more preferable from the viewpoint of fluidity.

単 A monofunctional epoxy resin may be used together with the polyfunctional epoxy resin and the bifunctional epoxy resin. The monofunctional epoxy resin may be used alone or in combination of two or more.

The polyfunctional epoxy resin preferably accounts for 50% by mass to 95% by mass, and preferably accounts for 60% by mass to 93% by mass of the total mass of the epoxy resin from the viewpoint of achieving both fluidity and curability during molding. Is more preferable, and further preferably accounts for 70% by mass to 90% by mass.

The mass ratio of the polyfunctional epoxy resin to the total amount of the polyfunctional epoxy resin and the bifunctional epoxy resin is preferably 50% by mass to 95% by mass from the viewpoint of achieving both fluidity and curability during molding. , 60% by mass to 93% by mass, more preferably 70% by mass to 90% by mass.

(4) The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably from 80 g / eq to 500 g / eq, more preferably from 90 g / eq to 200 g / eq.

(4) The epoxy equivalent of the epoxy resin is a value measured by a method according to JIS K7236: 2009.

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

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

The content of the epoxy resin in the encapsulating resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass in view of strength, fluidity, heat resistance, moldability and the like. % Is more preferable.

(Curing agent)
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 include a curing agent other than the active ester compound.

As described above, the sealing resin composition of the present disclosure can reduce the dielectric loss tangent of a cured product by using an active ester compound as a curing agent.
In addition, the polar group in the cured product enhances the water absorption of the cured product.However, by using an active ester compound as a curing agent, the concentration of the polar group in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. it can. By suppressing the water absorption of the cured product, that is, by suppressing the content of H ₂ O, which is a polar molecule, the dielectric loss tangent of the cured product can be further reduced. The water absorption of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and still more preferably 0% to 0.28%. Here, the water absorption of the cured product is a mass increase rate determined by a pressure cooker test (121 ° C., 2.1 atm, 24 hours).

(4) The type of the active ester compound is not particularly limited as long as it has at least one ester group in the molecule that reacts 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 an ester compound obtained from at least one kind of aliphatic carboxylic acid and aromatic carboxylic acid and at least one kind of aliphatic hydroxy compound and aromatic hydroxy compound. An ester compound containing an aliphatic compound as a component of polycondensation tends to have excellent compatibility with an epoxy resin due to having an aliphatic chain. An ester compound containing an aromatic compound as a component of polycondensation tends to have excellent heat resistance due to having an aromatic ring.

Specific examples of the active ester compound include an aromatic ester obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group; A mixture of an aromatic carboxylic acid and a phenolic hydroxyl group is obtained by using a mixture of a monohydric phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 of the hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material. Aromatic esters obtained by a 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 monohydric 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 JP-A-2012-246467, and an aromatic dicarboxylic acid or An active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound is exemplified. 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 is an average of the number of repetitions. 25 to 1.5.

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

Other specific examples of the active ester compound include a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3) described in JP-A-2014-114352. No.

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

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

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

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

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

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

エステル The ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of the 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 ester group equivalent of the active ester compound is a value measured by a method according to JIS K 0070: 1992.

The equivalent ratio of the epoxy resin to the active ester compound (ester group / epoxy group) is preferably 0.9 or more, more preferably 0.95 or more, and 0.97 or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low. Is more preferred.
The equivalent ratio (ester group / epoxy group) between the epoxy resin and the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted component 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 the other curing agent is not particularly limited, and can be selected according to the desired characteristics of the sealing resin composition. Other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.

Specific examples of the phenol curing agent include polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and phenylphenol. Phenolic compounds such as aminophenols, aminophenols and the like and at least one phenolic compound selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde Novolak-type phenolic resin obtained by condensation or co-condensation under the following conditions: the above-mentioned phenolic compound, dimethoxyparaxylene, bis (methoxymethyl) biffe Phenol aralkyl resins such as phenol aralkyl resins, naphthol aralkyl resins, etc .; para-xylylene-modified phenol resins, meta-xylylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; A dicyclopentadiene-type phenol resin and a dicyclopentadiene-type naphthol resin synthesized by copolymerization with: a cyclopentadiene-modified phenolic resin; a polycyclic aromatic ring-modified phenolic resin; a biphenyl-type phenolic resin; the phenolic compound, benzaldehyde, and salicyl Triphenylmethane-type phenolic resin obtained by condensing or co-condensing an aromatic aldehyde compound such as an aldehyde in the presence of an acidic catalyst; Phenol resins obtained by. These phenol curing agents may be used alone or in combination of two or more.

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

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

場合 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 from 40 ° C. to 180 ° C., and from the viewpoint of handleability during the production of the sealing resin composition, it is more preferably from 50 ° C. to 130 ° C. .

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

The equivalent ratio of the epoxy resin to all the curing agents (active ester compound 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 (the number of functional groups in the curing agent / the number of functional groups in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of minimizing the amount of each unreacted component, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the ratio in the range of 0.8 to 1.2.

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

(Curing accelerator)
The sealing resin composition may include 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] nonene-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU); Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof; To maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1 Quinone compounds such as 4-benzoquinone, and compounds having an intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane; tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, 2-ethyl-4 Compounds obtained by adding a cyclic amidinium compound and an isocyanate such as tetraphenylborate salt of methyl-imidazole and tetraphenylborate salt of N-methylmorpholine; isocyanate adduct of DBU, isocyanate adduct of DBN, 2-ethyl-4- Isocyanate adduct of methylimidazole, isocyanate adduct of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamido Tertiary amine compounds such as nomethyl) phenol; derivatives of the above tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and hydroxide Ammonium salt compounds such as tetrapropylammonium; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine , Tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine Tertiary phosphines such as fin, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; phosphine compounds such as complexes of the tertiary phosphine with organic borons; the tertiary phosphine or the phosphine Compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, Quinone compounds such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds 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-iodophenol, 3-iodophenol, 2-iodophenol , 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di After reacting a halogenated phenol compound such as -tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, Compound having intramolecular polarization obtained through the step of dehydrohalogenation; tetraphenylphosphonium Tetra-substituted phosphonium and tetra-substituted borate having no phenyl group bonded to a boron atom such as tetra-substituted phosphonium and tetra-p-tolyl borate; salts of tetraphenyl phosphonium and phenolic compounds; tetraalkyl phosphonium and aromatic carboxylic anhydride And a salt with a partial hydrolyzate of the product.

When the sealing resin composition contains a curing accelerator, the amount is preferably from 0.1 to 30 parts by mass based on 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent). And more preferably 1 to 15 parts by mass. When the amount of the curing accelerator is 0.1 parts by mass or more based on 100 parts by mass of the resin component, the curing tends to be performed well in a short time. If the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, the curing rate tends to be too high and a good molded product tends to be obtained.

(Inorganic filler)
The sealing resin composition may include an inorganic filler. The type of the inorganic filler is not particularly limited. Specifically, inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay, and mica are exemplified. 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.

シリカ Among the inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One inorganic filler may be used alone, or two or more inorganic fillers may be used in combination. Examples of the form of the inorganic filler include powder, beads obtained by making the powder spherical, fibers, and the like.

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

含有 The content of the inorganic filler contained in the sealing resin composition is not particularly limited. From the viewpoints of fluidity and strength, the content is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, and more preferably 40% by volume to 70% by volume of the entire sealing resin composition. % Is more preferable. When the content of the inorganic filler is 30% by volume or more of the entire sealing resin composition, properties such as a thermal expansion coefficient, a thermal conductivity, and an 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 flowability is further improved, and the moldability is more improved. Tend to be.

[Various additives]
The sealing resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, and a coloring agent exemplified below, in addition to the above components. The sealing resin composition may contain various additives known in the art as needed, in addition to the additives exemplified below.

(Coupling agent)
The sealing resin composition may include a coupling agent. From the viewpoint of increasing 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 silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and disilazane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. No.

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 part by mass, based on 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 based on 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 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 include an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and a conventionally known ion exchanger can be used. Specific examples include a hydrotalcite compound and a hydrated oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types may be used in combination. Among them, hydrotalcite represented by the following general formula (A) is preferable.

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

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

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

When the encapsulating resin composition contains a release agent, the amount is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the resin component (total amount of the epoxy resin and the curing agent). More preferred is from 5 parts by mass to 5 parts by mass. When the amount of the release agent is 0.01 part by mass or more based on 100 parts by mass of the resin component, there is a tendency that sufficient releasability is obtained. When the amount 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 a conventionally known one can be used. Specifically, an organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, a metal hydroxide and the like can be mentioned. The flame retardants may be used alone or in combination of two or more.

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

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

(Preparation method of sealing resin composition)
The method for preparing the sealing resin composition is not particularly limited. As a general method, there can be mentioned a method in which components of a predetermined compounding amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder, or the like, cooled, and pulverized. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-described components, kneading with a kneader, roll, extruder or the like which has been heated to 70 ° C. to 140 ° C., cooling, and pulverizing. Can be mentioned.

(4) The sealing resin composition is preferably solid at normal temperature and normal pressure (for example, 25 ° C. and atmospheric pressure). The shape when the sealing resin composition is a solid is not particularly limited, and examples thereof include powder, granules, and tablets. When the resin composition for sealing is in the form of a tablet, it is preferable from the viewpoint of handleability that the dimensions and the mass be such as to match the molding conditions of the package.

<Electronic component device>
An electronic component device according to an embodiment of the present disclosure includes a support member, an element disposed on the support member, and a cured product of the sealing resin composition of the present disclosure sealing the element. Is provided.

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

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

方法 The method of performing each of the above steps is not particularly limited, and can be performed by a general method. Further, the types of the support members and the elements used for manufacturing the electronic component device are not particularly limited, and the support members and the elements generally used for manufacturing the electronic component device can be used.

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

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

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

Epoxy resin 1 (polyfunctional): triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
Epoxy resin 2 (polyfunctional): Cresol novolak type epoxy resin, epoxy equivalent 264 g / eq (DIC Corporation, product name "HP-5600")
Epoxy resin 3 (polyfunctional): naphthalene diol aralkyl type epoxy resin, epoxy equivalent 170 g / eq (Nippon Steel & Sumikin Chemical Co., Ltd., product name "ESN-375")
Epoxy resin 4 (bifunctional): 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 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 Chemicals Co., Ltd., product name “Curesol 2MA-OK”)

-Filler 1: Fused silica (DENKA, product name "FB9454FC", volume average particle size 10 m)
・ 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 K.K., product name “HW-E”)
-Colorant: carbon black (Mitsubishi Chemical Corporation, product name "MA600")

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

(Heat hardness)
The encapsulating resin composition is charged into a transfer molding machine and 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. Obtained. Using this molded product as a test piece, the Shore D hardness within 10 seconds after releasing the mold was measured using a Shore D hardness meter.

(Glass-transition temperature)
The sealing resin composition is charged into a transfer molding machine and 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 to obtain a bar-shaped molded product (5 mm × 5 mm × 20 mm). Was. Using this molded product as a test piece, TMA (Thermomechanical Analysis, thermomechanical analysis) was performed using a thermomechanical analyzer (NETZSCH Japan, product name “TMA4000SE”) at a temperature-raising rate of 5 ° C./min. The intersection of the tangents before and after the inflection point of the chart thus obtained was defined as the glass transition temperature.

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

(Water absorption)
The plate-shaped cured product immediately after the production was put into a 121 ° C./2.1 atm pressure cooker tester, taken out 24 hours later, and the rate of increase (%) from the mass just before the addition was determined.

All documents, patent applications, and technical standards mentioned herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
The disclosure of Japanese Patent Application No. 2018-182710 filed on September 27, 2018 is incorporated herein by reference in its entirety.

Claims

An epoxy resin including a polyfunctional epoxy resin and a bifunctional epoxy resin,
A curing agent containing an active ester compound,
A sealing resin composition containing:
The polyfunctional epoxy resin is selected from the group consisting of triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene diol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and dicyclopentadiene type epoxy resin. The sealing resin composition according to claim 1, comprising at least one of the following.
The bifunctional epoxy resin comprises at least one selected from the group consisting of a bisphenol F epoxy resin, a bisphenol A epoxy resin, a biphenyl epoxy resin, a biphenyl aralkyl epoxy resin and a naphthalene epoxy resin. The sealing resin composition according to claim 2.
4. The method according to claim 1, wherein a mass ratio of the polyfunctional epoxy resin to the total amount of the polyfunctional epoxy resin and the bifunctional epoxy resin is 50% by mass to 95% by mass. A sealing resin composition.
A support member;
An element disposed on the support member,
The sealing resin composition according to any one of claims 1 to 4, which seals the element,
Electronic component device comprising:
Arranging the element on a support member;
A step of sealing the element with the sealing resin composition according to any one of claims 1 to 4,
A method for manufacturing an electronic component device including: