WO2020067016A1

WO2020067016A1 - Sealing resin composition, electronic component device, and manufacturing method of electronic component device

Info

Publication number: WO2020067016A1
Application number: PCT/JP2019/037281
Authority: WO
Inventors: 実佳田中; 格山浦; 徹馬場; 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: 2019-09-24
Publication date: 2020-04-02
Also published as: TW202024168A; JPWO2020067016A1; JP7396290B2

Abstract

Provided is a sealing resin composition containing: an epoxy resin; a curing agent including an active ester compound; and an inorganic filler including alumina.

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.

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

On the other hand, the amount of transmission loss caused by the radio wave transmitted for communication being thermally converted in the 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.

(4) In the information and communication field, radio waves are becoming higher in frequency with the increase in the number of channels and the amount of information transmitted. At present, studies on the fifth generation mobile communication system are being promoted worldwide, and some of the candidates for the frequency band to be used are in the range of about 30 GHz to 70 GHz. In the future, since the mainstream of wireless communication will be communication in such a high frequency band, further improvement in dielectric properties is required for the material of communication members.

JP 2014-31460 A

(4) When alumina is used as the inorganic filler of the sealing resin composition, the heat conductivity is high and the heat dissipation is improved, but the relative dielectric constant is increased and the transmission loss may be increased.

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

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

According to the present disclosure, a sealing resin composition having an excellent balance between the heat dissipation properties and dielectric properties of a cured product, an electronic component device sealed using the same, and the production of an electronic component device sealed using the same A method 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 sealing resin composition of the present disclosure is a sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.

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

First, the sealing resin composition of the present disclosure contains alumina as an inorganic filler. Thereby, higher thermal conductivity is achieved as compared with the case where the sealing resin composition contains other inorganic filler such as silica.
Furthermore, the resin composition for sealing of the present disclosure contains an active ester compound as a curing agent. A phenol curing agent, an amine curing agent, and the like generally used as a curing agent for an epoxy resin generate a secondary hydroxyl group in a reaction with the epoxy resin. 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. As a result, even if the relative dielectric constant increases by using alumina as the inorganic filler, an increase in transmission loss can be suppressed.

(Epoxy resin)
The type of epoxy resin contained in the encapsulating resin composition of the present disclosure is not particularly limited.
Specific examples of the epoxy resin include 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. Novolak epoxy resin (phenol novolak type) obtained by epoxidizing a novolak resin obtained by condensing or co-condensing a phenolic compound of a type with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Epoxy resin, orthocresol novolak type epoxy resin, etc.); condensation of the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst or Is a triphenylmethane-type epoxy resin obtained by epoxidizing a triphenylmethane-type phenol resin obtained by co-condensation; a novolak obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst. Copolymer type epoxy resin obtained by epoxidation of resin; diphenylmethane type epoxy resin which is diglycidyl ether such as bisphenol A and bisphenol F; biphenyl type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene Stilbene type epoxy resin which is a diglycidyl ether of a phenolic compound; epoxy resin containing a sulfur atom which is a diglycidyl ether such as bisphenol S; butanediol, polyethylene glycol, polypropylene Epoxy resin which is a glycidyl ether of alcohols such as glycol; glycidyl ester type epoxy resin which is a glycidyl ester of a polycarboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; nitrogen such as aniline, diaminodiphenylmethane and isocyanuric acid A glycidylamine-type epoxy resin in which active hydrogen bonded to an atom is replaced by a glycidyl group; a dicyclopentadiene-type epoxy resin in which a cocondensation resin of dicyclopentadiene and a phenol compound is epoxidized; an olefin bond in a molecule Vinylcyclohexene diepoxide obtained by epoxidation of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5 An alicyclic epoxy resin such as spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin which is a glycidyl ether of a para-xylylene-modified phenol resin; a meta-xylylene-modified epoxy resin which is a glycidyl ether of a meta-xylylene-modified phenol resin; Terpene-modified epoxy resin which is a glycidyl ether of a terpene-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 an aromatic ring-modified phenolic resin; glycidyl ether of a naphthalene ring-containing phenolic resin Naphthalene-type epoxy resin, which is a polyester; halogenated phenol novolak-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; Aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol-aralkyl resins and naphthol-aralkyl resins; Further, an epoxidized product of an acrylic resin is also an example of the epoxy resin. These epoxy resins may be used alone or in combination of two or more.

(4) The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin 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 100 g / eq to 1000 g / eq, more preferably from 150 g / eq to 500 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.

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.

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 0.25%. 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, an esterified product of a heterocyclic hydroxy compound, and the like.

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 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.

エステル The ester 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 80% by mass or more, and more preferably 85% by mass, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. %, More preferably 90% by mass or more.

(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 Cyclic amidinium compounds such as tetraphenylborate salt of methyl-imidazole and tetraphenylborate salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Tertiary amine compounds such as tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexyl benzoate Ammonium salt compounds such as silammonium and tetrapropylammonium hydroxide; 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, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, Tertiary phosphines such as dialkylarylphosphines and alkyldiarylphosphines; complexes of the above tertiary phosphines with organic borons, etc. A phosphine compound; 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, Quinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone; and compounds having a π bond such as diazophenylmethane. A compound having an intramolecular polarization obtained by addition; 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 Phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6- After reacting a halogenated phenol compound such as di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4′-hydroxybiphenyl A compound having an intramolecular polarization obtained through the step of dehydrohalogenation; tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-substituted phosphonium and tetra-substituted without a phenyl group bonded to a boron atom such as tetra-p-tolyl borate Substituted borate; tetraphenylphosphonium and phenolic compound, tetraalkyl And salts with partial hydrolyzate of phosphonium and aromatic carboxylic acid anhydrides.

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 weight. 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 of the present disclosure contains alumina as an inorganic filler. By including alumina, an improvement in the thermal conductivity of the cured product can be expected. On the other hand, from the viewpoint of balance with other properties such as a coefficient of linear expansion and dielectric properties of the cured product, it is preferable to use alumina and an inorganic filler other than alumina in combination.

無機 Specific examples of the inorganic filler other than alumina include inorganic materials such as fused silica, crystalline silica, glass, talc, clay, and mica. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, 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 preferable from the viewpoint of reducing the coefficient of linear expansion. 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.

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

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 coupling agents such as silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. .

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 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 an element, and a cured product of the sealing resin composition of the present disclosure that seals the element.

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 proportions (parts by mass) shown in Table 1 to prepare sealing resin compositions of Examples and Comparative Examples.

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

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

Curing accelerator 1: p-benzoquinone adduct of triphenylphosphine

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

・ Release agent: montanic acid ester wax (Clariant Japan K.K., product name “HW-E”)
-Colorant: carbon black (Mitsubishi Chemical Corporation, product name "MA600")
・ Additive: Triphenylphosphine oxide (Hokuko Chemical Co., Ltd., product name “TP-50”)

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

<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).

(Gel time)
0.5 g of the resin composition for sealing is placed on a hot plate heated to 175 ° C., and the sample is placed at 2.0 to 2.5 cm at a rotation speed of 20 to 25 rotations / minute using a jig. Spread uniformly in a circle. After the sample was placed on the hot plate, the time required for the sample to lose its viscosity and to be in a gel state and come off from the hot plate was measured, and this was measured as a gel time (sec).

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

(Relative permittivity and dielectric loss tangent)
The encapsulating resin composition is charged into a transfer molding machine, molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and post-curing is performed at 175 ° C. for 6 hours to obtain a rod-shaped cured product ( 0.8 mm long, 0.6 mm wide, and 90 mm thick). Using this cured product as a test piece, using a cavity resonator (Kanto Electronics Application Development Co., Ltd., “CP561”) and a network analyzer (Keysight Technology, Inc., “PNA E8364B”), at a temperature of 25 ± 1 ° C. and 20 GHz Was measured for dielectric constant and dielectric loss tangent.

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

Claims

(4) A sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.
The sealing resin composition according to claim 1, wherein the proportion of alumina in the entire inorganic filler is 50% by mass or more.
A support member;
An element disposed on the support member,
A cured product of the encapsulating resin composition according to claim 1 or 2, which encapsulates 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 claim 1 or 2,
A method for manufacturing an electronic component device including: