WO2021112142A1

WO2021112142A1 - Resin composition for sealing, electronic device, and method for producing electronic device

Info

Publication number: WO2021112142A1
Application number: PCT/JP2020/044931
Authority: WO
Inventors: 圭一春日; 格山浦; 貴大齋藤; 俊輔児玉; 智博池田
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2019-12-06
Filing date: 2020-12-02
Publication date: 2021-06-10
Also published as: TW202124503A; JPWO2021112142A1

Abstract

Provided is a resin composition for sealing which contains: an epoxy resin; a curing agent containing an active ester compound; and a copolymer of a C5-30 α-olefin and maleic anhydride.

Description

Resin composition for sealing, electronic component equipment, and manufacturing method of electronic component equipment

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

The amount of transmission loss generated by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the square root of frequency and relative permittivity and the dielectric loss tangent. That is, since the transmission signal is easily converted into heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties in the high frequency band in order to suppress the transmission loss.

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

Patent Document 1: Japanese Patent Application Laid-Open No. 2012-246367 Patent Document 2: Japanese Patent Application Laid-Open No. 2014-114352

In the information and communication field, the frequency of radio waves is increasing as the number of channels increases and the amount of information transmitted increases. Currently, studies on 5th generation mobile communication systems are underway worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to have a lower dielectric loss tangent.

An active ester compound as a curing agent for an epoxy resin is advantageous in that the dielectric property of a cured product is suppressed to be lower than that of a phenol curing agent or an amine curing agent. However, the sealing resin composition containing an active ester compound as a curing agent for the epoxy resin tends to be inferior in the releasability of the cured product.

The embodiments of the present disclosure have been made under the above circumstances.
In the present disclosure, a sealing resin composition that reduces the dielectric loss tangent of a cured product and has excellent releasability of the cured product, an electronic component device sealed using the same, and sealing using the same. An object of the present invention is to provide a method for manufacturing an electronic component device.

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

<1>
Epoxy resin and
A curing agent containing an active ester compound and
A copolymer of α-olefin having 5 to 30 carbon atoms and maleic anhydride,
A resin composition for sealing containing.
<2>
The sealing resin composition according to <1>, wherein the copolymerization molar ratio of the α-olefin and the maleic anhydride in the copolymer is 20: 1 to 1: 2.
<3>
The sealing resin composition according to <1> or <2>, wherein the content of the copolymer is 0.01% by mass to 1.00% by mass with respect to the entire sealing resin composition.
<4>
The sealing resin composition according to any one of <1> to <3>, wherein the content of the copolymer is 0.25 parts by mass to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
<5>
The sealing resin composition according to any one of <1> to <4>, wherein the weight average molecular weight of the copolymer is 5000 to 100,000.
<6>
The sealing resin composition according to any one of <1> to <5>, which further contains at least one selected from the group consisting of polyolefin waxes and ester waxes.
<7>
The sealing content according to <6>, wherein the content of at least one selected from the group consisting of the polyolefin-based wax and the ester-based wax is 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Resin composition.
<8>
The sealing resin composition according to any one of <1> to <7>, which further contains an inorganic filler.
<9>
Support members and
The element arranged on the support member and
The cured product of the sealing resin composition according to any one of <1> to <8>, which seals the element, and the cured product.
Electronic component device equipped with.
<10>
Placing the element on the support member and
Sealing the element with the sealing resin composition according to any one of <1> to <8>.
Manufacturing method of electronic component equipment including.

According to the present disclosure, a sealing resin composition that reduces the dielectric loss tangent of the cured product and has excellent releasability of the cured product, an electronic component device sealed using the same, and sealing using the same. A method of manufacturing an electronic component device to be stopped is provided.

In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.

Hereinafter, the mode for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit this disclosure.

<Resin composition for sealing>
The sealing resin composition according to the embodiment of the present disclosure is a copolymer of an epoxy resin, a curing agent containing an active ester compound, an α-olefin having 5 to 30 carbon atoms, and maleic anhydride (hereinafter, "" Also referred to as "specific copolymer").

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

Conventionally, a phenol curing agent, an amine curing agent, or the like is generally used as a curing agent for an epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, the sealing resin composition of the present disclosure is compared with the sealing resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent. The dielectric positive contact of the cured product can be kept low.
Further, the polar groups in the cured product enhance the water absorption of the cured product, and by using an active ester compound as the curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. it can. Then, suppressing the water absorption of the cured product, that is, by suppressing the H _{2 O} content is a polar molecule, it is possible to suppress even lower dielectric loss tangent of a cured product.

However, a sealing resin composition containing an active ester compound as a curing agent for an epoxy resin may be inferior in releasability of the cured product, although the dielectric loss tangent of the cured product is reduced. The reason is not clear, but it is presumed that the unreacted active ester compound contained in the cured product is the cause of the decrease in releasability.
On the other hand, in the sealing resin composition of the present embodiment, by further containing a specific copolymer in addition to the epoxy resin and the active ester compound, the dielectric loss tangent of the cured product can be reduced and the releasability of the cured product can be improved. Are compatible. The reason is not clear, but it is presumed as follows.
While the specific copolymer has a long-chain alkyl group, the structure derived from maleic anhydride in the specific copolymer is compatible with the active ester compound, so that the dispersibility of the active ester compound is improved. Therefore, it is considered that the reaction efficiency of the active ester compound is improved and the unreacted active ester compound is less likely to remain in the cured product, thereby suppressing the decrease in releasability due to the unreacted active ester compound.
From the above, it is presumed that the sealing resin composition of the present embodiment reduces the dielectric loss tangent of the cured product and is excellent in the releasability of the cured product.
Hereinafter, each component contained in the sealing resin composition according to the present embodiment will be described.

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

Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolak) which is an epoxidized novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Type epoxy resin, orthocresol novolac type epoxy resin, etc.); Triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxide resin obtained by epoxidizing the above; a copolymerized epoxy obtained by co-condensing the above phenol compound, naphthol compound and aldehyde compound under an acidic catalyst and epoxidizing a novolak resin. Resin: Diphenylmethane type epoxy resin which is a diglycidyl ether such as bisphenol A and bisphenol F; Biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; Stilben-type epoxy which is a diglycidyl ether of a stelvene-based phenol compound. Resin: Sulfur atom-containing epoxy resin that is a diglycidyl ether such as bisphenol S; Epoxide resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; Glysidyl ester type epoxy resin which is a glycidyl ester of a carboxylic acid compound; Glysidylamine type epoxy resin which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group; dicyclopentadiene and phenol. Dicyclopentadiene-type epoxy resin obtained by epoxidizing a cocondensation resin of a compound; vinylcyclohexene epoxide obtained by epoxidizing an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylate, 2- (3,4-epoxide) cyclohexy An alicyclic epoxy resin such as Lu-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin which is a glycidyl ether of a paraxylylene-modified phenol resin; a glycidyl ether of a metaxylylene-modified phenol resin. Metaxylylene-modified epoxy resin; Terpen-modified epoxy resin, which is a glycidyl ether of terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified, which is a glycidyl ether of cyclopentadiene-modified phenol resin. Epoxy resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; Naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; Halogenated phenol novolac type epoxy resin; Hydroquinone type epoxy resin Trimethylol propane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Epoxy aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. Aralkill type epoxy resin; etc. Further, an epoxy resin such as an acrylic resin is also mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.

The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and is 150 g / eq to 500 g / eq. Is more preferable.
The epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.

When the epoxy resin is a solid, the softening point or melting point of the epoxy resin is not particularly limited. The softening point or melting point of the epoxy resin is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and 50 ° C. to 180 ° C. from the viewpoint of handleability when preparing the sealing resin composition. More preferably, it is 130 ° C.
The softening point or melting point of the epoxy resin shall be a value measured by differential scanning calorimetry (DSC) or a method according to JIS K 7234: 1986 (ring ball method).

The mass ratio of the epoxy resin to the total amount of the sealing resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and is preferably 2% by mass to 50% by mass. It is more preferably 30% by mass.

(Hardener)
The sealing resin composition of the present embodiment contains at least an active ester compound as a curing agent. The sealing resin composition may contain a curing agent other than the active ester compound.
As described above, by using the active ester compound as the curing agent, the dielectric loss tangent of the cured product can be suppressed to a low level.

The type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with the epoxy group. Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.

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

Specific examples of the active ester compound include aromatic esters obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, the active ester compound is 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. Aromatic carboxylic acid using a mixture of a monovalent phenol in which one hydrogen atom of the aromatic ring is substituted with a hydroxyl group and a polyvalent phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material. It is preferably an aromatic ester obtained by a condensation reaction between and a phenolic hydroxyl group. That is, the active ester compound is preferably 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.

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

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

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

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

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

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

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

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

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

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

The ester equivalent of the active ester compound is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the ester equivalent of the active ester compound is preferably 150 g / eq to 400 g / eq, more preferably 170 g / eq to 300 g / eq, and 200 g. / Eq to 250 g / eq is more preferable.
The ester equivalent of the active ester compound shall be a value measured by a method according to JIS K 0070: 1992.

The equivalent ratio of the epoxy resin to the active ester compound, that is, the value of the number of ester groups / the number of epoxy groups is preferably 0.9 or more, more preferably 0.95 or more, and 0, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. .97 or more is more preferable.
The equivalent ratio of the epoxy resin to the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, still more preferably 1.03 or less, from the viewpoint of suppressing the unreacted content of the active ester compound to be small.

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

Specifically, the phenol curing agent is a polyhydric phenol compound such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenol compounds such as aminophenols and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. A novolac-type phenolic resin obtained by condensing or co-condensing a compound with an acidic catalyst; a phenol-aralkyl resin, naphthol-aralkyl, which is synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. Aralkyl-type phenolic resin such as resin; paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type synthesized from the above phenolic compound and dicyclopentadiene by copolymerization. Phenol resin and dicyclopentadiene type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; the above phenolic compound and aromatic aldehyde compound such as benzaldehyde and salicylaldehyde are acid catalysts. Examples thereof include a triphenylmethane-type phenol resin obtained by condensing or co-condensing below; a phenol resin obtained by copolymerizing two or more of these. These phenol curing agents may be used alone or in combination of two or more.

The functional group equivalents of other curing agents are not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of other curing agents is preferably 70 g / eq to 1000 g / eq, and is preferably 80 g / eq to 500 g / eq. Is more preferable. When the other curing agent is a phenol curing agent, the functional group equivalent of the other curing agent means the hydroxyl group equivalent.
The functional group equivalent of the other curing agent shall be a value measured by a method according to JIS K 0070: 1992.

The softening point or melting point of the curing agent is not particularly limited. The softening point or melting point of the curing agent is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and 50 ° C. from the viewpoint of handleability during production of the sealing resin composition. More preferably, it is at ~ 130 ° C.

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

The equivalent ratio of the epoxy resin to all the 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, that is, the value of the number of functional groups in the curing agent / the number of functional groups in the epoxy resin is particularly limited. Not done. From the viewpoint of suppressing each unreacted component to a small value, the value of the number of functional groups in the curing agent / the number of functional groups in the epoxy resin is preferably set in the range of 0.5 to 2.0, and is preferably 0.6 to 2.0. It is more preferable to set it in the range of 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the range from 0.8 to 1.2. When the curing agent contains other curing agents, all the above-mentioned curing agents include both an active ester compound and other curing agents.

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

The total mass ratio of the epoxy resin and the active ester compound to the total amount of the epoxy resin, the active ester compound and other curing agents is preferably 80% by mass or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. It is more preferably mass% or more, and further preferably 90 mass% or more.

(Specific copolymer)
The specific copolymer is not particularly limited as long as it is a copolymer of an α-olefin having 5 to 30 carbon atoms and maleic anhydride. When the specific copolymer is contained in the sealing resin composition, it functions as, for example, an epoxy resin and a dispersant for a specific mold release agent described later.
The carbon number of the α-olefin is 5 to 30, preferably 10 to 25, and more preferably 15 to 25, from the viewpoint of exhibiting the function of the epoxy resin and the specific release agent as a dispersant.
The α-olefin may be a linear type or a branched type.
As the specific copolymer, one type may be used alone or two or more types may be used in combination.

Specific examples of the α-olefin are not particularly limited, and 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-Tetradecene, 1-Pentadecene, 1-Hexadecene, 1-Heptadecene, 1-Ocdecene, 1-Nonedecene, 1-Eikosen, 1-Dodecene, 1-Tricosene, 1-Tetracosen, 1-Pentacosene, 1-Hexacosene, 1- Linear α-olefins such as heptacosene; 3-methyl-1-butene, 3,4-dimethyl-pentene, 3-methyl-1-nonene, 3,4-dimethyl-octene, 3-ethyl-1-dodecene, Examples thereof include branched α-olefins such as 4-methyl-5-ethyl-1-octadecene and 3,4,5-triethyl-1-1-eicosene. As the α-olefin, these may be used alone, or two or more kinds may be used in combination. Among these, the α-olefin is preferably an α-olefin having 10 to 25 carbon atoms, and more preferably an α-olefin having 15 to 25 carbon atoms.

Specific examples of the specific copolymer are not particularly limited, and examples thereof include a compound represented by the following general formula (VI), a compound represented by the following general formula (VII), and the like. As commercially available products of the specific copolymer, Nissan Electol WPB-1 (NOF CORPORATION, trade name) and the like using 1-eicosene, 1-dococene, and 1-trichothecene as raw materials are available.

In the above general formulas (VI) and (VII), R represents a monovalent aliphatic hydrocarbon group having 3 to 28 carbon atoms, n represents an integer of 1 or more, and m is 1/2 to 10 on a molar basis. Indicates / 1.

The copolymerization molar ratio of the α-olefin and the maleic anhydride in the specific copolymer, that is, X: Y when the α-olefin is X mol and the maleic anhydride is Y mol, functions as a dispersant. From the viewpoint of achieving both the expression of the above and the affinity for the active ester compound, the ratio is preferably 20: 1 to 1: 2, more preferably 15: 1 to 1: 1.5, and 10: 1 to 1. It is more preferably 1: 1.

The weight average molecular weight of the specific copolymer is preferably 5,000 to 100,000, more preferably 10,000 to 70,000, and even more preferably 15,000 to 50,000, from the viewpoint of mold stain suppression and moldability.
When the weight average molecular weight of the specific copolymer is 5000 or more, the mold stain suppressing effect can be easily obtained. When the weight average molecular weight of the specific copolymer is 100,000 or less, the decrease in kneadability due to the increase in the softening point of the specific copolymer is suppressed.
Here, the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC). For the measurement of the weight average molecular weight by GPC, for example, G2000HXL, 3000HXL of Tosoh Corporation is used for the GPC column for analysis, tetrahydrofuran etc. is used for the mobile phase, the sample concentration is 0.2% by mass, and the flow velocity is 1. Measure at 0.0 mL / min. A calibration curve is prepared using a polystyrene standard sample, and the weight average molecular weight is calculated using polystyrene-equivalent values.

The content of the specific copolymer is preferably 0.01% by mass to 1.00% by mass, preferably 0.02, based on the entire sealing resin composition, from the viewpoint of improving the releasability of the cured product. It is more preferably from mass% to 0.50 mass%, and even more preferably from 0.05 mass% to 0.10 mass%.
The content of the specific copolymer is preferably 0.25 parts by mass to 5 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the epoxy resin, from the viewpoint of improving the releasability of the cured product. It is more preferably about 2 parts by mass.

The method for producing the specific copolymer is not particularly limited, and a general copolymer method such as reacting raw materials can be used. An organic solvent or the like capable of dissolving α-olefin and maleic anhydride may be used for the reaction. The organic solvent is not particularly limited, and among them, toluene is preferable, and alcohol solvents, ether solvents, amine solvents and the like can also be used. The reaction temperature varies depending on the type of organic solvent used, but is preferably 50 to 200 ° C., more preferably 80 to 120 ° C. from the viewpoint of reactivity and productivity. The reaction time is not particularly limited as long as the copolymer can be obtained, but is preferably 1 to 30 hours, more preferably 2 to 15 hours, still more preferably 4 to 10 hours from the viewpoint of productivity.
After completion of the reaction, unreacted components, solvents and the like can be removed, if necessary, under heating and reduced pressure. The conditions for removing unreacted components, solvents, etc. are as follows: temperature is 100 to 220 ° C., more preferably 120 to 180 ° C., pressure is 13.3 × 10 ³ Pa or less, more preferably 8 × 10 ³ Pa or less, time. It is preferably 0.5 to 10 hours.
Further, a reaction catalyst such as an amine catalyst or an acid catalyst may be added to the reaction, if necessary. The pH of the reaction system is preferably about 1 to 10.

(Specific mold release agent)
The sealing resin composition may further contain at least one selected from the group consisting of polyolefin-based waxes and ester-based waxes (hereinafter, also referred to as "specific mold release agent"). That is, the sealing resin composition may contain an epoxy resin, an active ester compound, a specific copolymer, and a specific mold release agent. The long-chain alkyl group of the specific copolymer is compatible with the specific mold release agent, and the structure derived from maleic anhydride of the specific copolymer is compatible with the active ester compound, so that the specific mold release agent and the active ester compound are compatible. It is considered that the dispersibility in both of these is improved. Therefore, by containing the epoxy resin, the active ester compound, the specific copolymer, and the specific mold release agent in the sealing resin composition, both the reduction of the dielectric loss tangent of the cured product and the releasability of the cured product are achieved. It is presumed that.

The specific mold release agent is not particularly limited as long as it contains at least one selected from the group consisting of polyolefin waxes and ester waxes.
The polyolefin-based wax may be an oxidized polyolefin-based wax or a non-oxidized polyolefin-based wax. Examples of the polyolefin-based wax include polyethylene oxide, non-oxidized polyethylene, polypropylene oxide, non-oxidized polypropylene, polybutene oxide, and non-oxidized polybutene.
Examples of the ester wax include montanic acid ester, saponified montanic acid ester, glycerin ester, carbana wax, rice wax and the like.
Among these, the specific mold release agent preferably contains a polyolefin wax, and more preferably contains polyethylene oxide. The polyethylene oxide may be a linear polyethylene oxide or a branched polyethylene oxide.
As the specific release agent, one of these may be used alone, or two or more thereof may be combined.

The weight average molecular weight of the polyolefin wax is preferably 2000 or more from the viewpoint of mold releasability, preferably 30,000 or less from the viewpoint of adhesiveness and mold stain suppression, more preferably 5000 to 20000, and 7000. ~ 15000 is more preferable. Here, the weight average molecular weight refers to a value measured by high-temperature GPC.

The acid value of the polyolefin wax is not particularly limited, and is preferably 0 mg / KOH to 100 mg / KOH, more preferably 10 mg / KOH to 60 mg / KOH, from the viewpoint of releasability and adhesiveness.
The acid value is the number of moles of potassium hydroxide required to neutralize 1 g of the measurement target, and is determined by the measurement method according to JIS K0070: 1992.

The saponification value of the ester wax is not particularly limited, and is preferably 1 mg / KOH to 200 mg / KOH, and more preferably 30 mg / KOH to 100 mg / KOH from the viewpoint of releasability and adhesiveness. ..
The saponification value is the number of moles of potassium hydroxide required to saponify 1 g of the measurement target, and is determined by the measurement method according to JIS K0070: 1992.

The melting point of the specific mold release agent is not particularly limited, and is preferably 40 ° C. to 180 ° C., more preferably 60 ° C. to 140 ° C. from the viewpoint of kneadability and moldability.
The melting point is a value measured in the same manner as the melting point of the epoxy resin.

The content of the specific mold release agent is not particularly limited, and may be 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of mold releasability of the cured product and suppression of mold stains. It is preferably 1 part by mass to 5 parts by mass, more preferably.

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

Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidin compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidin compound; phenol novolac salt of the cyclic amidin compound or a derivative thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, and diazophenylmethane and other quinone compounds with π-bonded compounds added. Compounds; Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt; pyridine, triethylamine, tri Tertiary amine compounds such as ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, tetra-n-phosphate Ammonium salt compounds such as butylammonium, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; first phosphine such as ethylphosphine and phenylphosphine, second phosphine such as dimethylphosphine and diphenylphosphine, tri Phenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (Tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dial Organic phosphine such as tertiary phosphine such as killarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris (benzyl) phosphine; phosphine compound such as a complex of the organic phosphine and organic borons; the organic phosphine or the phosphine compound. In addition, maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, Intramolecular polarization by adding a quinone compound such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, or a compound having a π bond such as diazophenylmethane. Compounds; The organic phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodide phenol, 3-iow Compound, 2-iodide, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4 Halogenization of -bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc. A compound having intramolecular polarization obtained through a step of hydrogen dehalogenation after reacting with a phenol compound; tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylbolate. Tetra-substituted phosphonium compounds, such as tetraphenylborate salts, salts of tetra-substituted phosphoniums and phenolic compounds; salts of tetraalkylphosphoniums and partial hydrolysates of aromatic carboxylic acid anhydrides; phosphobetaine compounds; phosphonium compounds and silanes. Additives with compounds; etc.
The curing accelerator may be used alone or in combination of two or more.
Among these, particularly suitable curing accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound. Things etc. can be mentioned.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass to 30 parts by mass, and 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component. Is more preferable. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained. In addition, in this specification, a resin component means an epoxy resin and a curing agent. Further, in the present specification, 100 parts by mass of the resin component means that the total amount of the epoxy resin and the curing agent is 100 parts by mass.

(Inorganic filler)
The sealing resin composition may contain an inorganic filler, if necessary. The type of inorganic filler is not particularly limited. Specific examples of the inorganic filler include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, and steer. Examples include inorganic materials such as tight, spinel, mulite, titania, talc, clay and mica. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.

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

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

The content of the inorganic filler contained in the sealing resin composition of the present disclosure is 70% by volume or more of the entire sealing resin composition from the viewpoint of controlling the elasticity of the cured product of the sealing resin composition. It is preferably 90% by volume, more preferably 78% by volume to 88% by volume, and even more preferably 80% by volume to 85% by volume.

The volume ratio of the inorganic filler in the sealing resin composition can be determined by the following method.
A flaky sample of the cured resin composition for encapsulation is imaged with a scanning electron microscope (SEM). An arbitrary area S is specified in the SEM image, and the total area A of the inorganic filler contained in the area S is obtained. The value obtained by dividing the total area A of the inorganic filler by the area S is converted into a percentage (%), and this value is taken as the volume ratio of the inorganic filler in the sealing resin composition.
The area S is a sufficiently large area with respect to the size of the inorganic filler. For example, the size may include 100 or more inorganic fillers. The area S may be the sum of a plurality of cut surfaces.
The presence ratio of the inorganic filler may be biased in the direction of gravity during curing of the sealing resin composition. In that case, when the image is taken by the SEM, the entire gravity direction of the cured product is imaged, and the area S including the entire gravity direction of the cured product is specified.

[Various additives]
In addition to the above-mentioned components, the sealing resin composition includes a coupling agent, an ion exchanger, a dispersant other than the specific copolymer, a release agent other than the specific release agent, a flame retardant, and a coloring agent, in addition to the above-mentioned components. Various additives such as agents may be contained. The sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

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

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The sealing resin composition may contain an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples of the ion exchanger include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.

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

When the sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. The content of the ion exchanger is, for example, preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component.

(Dispersants other than specific copolymers)
The sealing resin composition may further contain a dispersant other than the specific copolymer. Examples of the dispersant other than the specific copolymer include esterified products of the specific copolymer.

Examples of the esterified product of the specific copolymer include a compound obtained by esterifying the above-mentioned specific copolymer with a monohydric alcohol. The monohydric alcohol that esterifies the specific copolymer is not particularly limited, and for example, amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, and un. Linear or branched aliphatic saturated alcohols such as decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecil alcohol, eikosyl alcohol; hexenol, Linear or branched aliphatic unsaturated alcohols such as 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol; cyclopentanol, cyclohexanol, etc. Alicyclic alcohols; aromatic alcohols such as benzyl alcohol and cinnamyl alcohol; heterocyclic alcohols such as furfuryl alcohol; and the like can be mentioned, and these may be used alone or in combination of two or more.
The monohydric alcohol is preferably a monohydric alcohol having 5 to 25 carbon atoms, more preferably a linear alcohol having 10 to 20 carbon atoms, and a linear fat having 15 to 20 carbon atoms. It is more preferably a group saturated alcohol.

The method for esterifying the specific copolymer with a monohydric alcohol is not particularly limited, and general methods such as addition reaction of a monohydric alcohol to the specific copolymer can be mentioned. The reaction molar ratio of the specific copolymer and the monohydric alcohol is not particularly limited and can be set arbitrarily. An organic solvent or the like may be used for the reaction. The organic solvent is not particularly limited, and examples thereof include toluene, alcohol-based solvent, ether-based solvent, and amine-based solvent. The reaction temperature varies depending on the type of organic solvent used, but is preferably 50 to 200 ° C., more preferably 80 to 120 ° C. from the viewpoint of reactivity and productivity. The reaction time is preferably 1 to 30 hours, more preferably 2 to 15 hours, still more preferably 4 to 10 hours from the viewpoint of productivity. After completion of the reaction, unreacted components, solvents and the like can be removed, if necessary, under heating and reduced pressure. Further, a reaction catalyst such as an amine catalyst or an acid catalyst may be added to the reaction, if necessary. The pH of the reaction system is preferably about 1 to 10.

The weight average molecular weight of the esterified product of the specific copolymer is preferably 3000 to 100,000, more preferably 10,000 to 70,000, still more preferably 15,000 to 50,000, from the viewpoint of mold stain suppression and moldability.
When the sealing resin composition contains a specific copolymer and an esterified product of the specific copolymer, the total content of the specific copolymer and the esterified product of the specific copolymer is determined by the sealing resin composition. It is preferably 0.01% by mass to 1.00% by mass, more preferably 0.02% by mass to 0.50% by mass, and 0.05% by mass to 0.10% by mass with respect to the whole. It is more preferable to have.
When the sealing resin composition contains the specific copolymer and the esterified product of the specific copolymer, the total content of the specific copolymer and the esterified product of the specific copolymer is 100 mass of epoxy resin. It is preferably 0.25 parts by mass to 5 parts by mass, and more preferably 0.5 parts by mass to 2 parts by mass.

(Release agents other than specific release agents)
The sealing resin composition may contain a release agent other than the specific release agent, if necessary. The release agent other than the specific release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as montanic acid and stearic acid, and higher fatty acid metal salts. As the release agent other than the specific release agent, one type may be used alone or two or more types may be used in combination.

When the sealing resin composition contains a specific mold release agent and a mold release agent other than the specific mold release agent, the total content thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component. , 0.1 part by mass to 5 parts by mass is more preferable. When the total content of the release agent is 0.01 part by mass or more with respect to 100 parts by mass of the resin component, the releasability tends to be sufficiently obtained. When the total content of the release agent is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples of the flame retardant include an organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

When the sealing resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. The amount of the flame retardant is, for example, preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component.

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

(Method for preparing resin composition for sealing)
The method for preparing the sealing resin composition is not particularly limited. As a general method for preparing a resin composition for sealing, a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized. Can be mentioned. More specifically, as a method for preparing the sealing resin composition, for example, a kneader, a roll, or an extruder in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed and preheated to 70 ° C. to 140 ° C. Examples thereof include a method of kneading with, cooling, and crushing.
When mixing the components in a predetermined blending amount, a part or all of the epoxy resin and the specific copolymer may be premixed. When the sealing resin composition contains a specific release agent, a part or all of the epoxy resin, the specific copolymer, and the specific release agent may be premixed.

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

<Electronic component equipment>
The electronic component device according to the embodiment of the present disclosure includes a support member, an element arranged on the support member, and a cured product of the sealing resin composition of the present disclosure that seals the element. To be equipped.

Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (for example, semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, etc.). Examples thereof include those in which an element portion obtained by mounting a resistor, a passive element such as a coil, etc.) is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition. Chip module, etc .; An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, a resin composition for sealing is provided. Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the sealing resin composition can also be preferably used in the printed wiring board.

<Manufacturing method of electronic component equipment>
A method for manufacturing an electronic component device according to an embodiment of the present disclosure includes arranging an element on a support member and sealing the element with the sealing resin composition of the present disclosure.

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

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

Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the scope of the above-mentioned Embodiment is not limited to these Examples.

<Preparation of resin composition for sealing>
The components shown below were mixed at the blending ratios (parts by mass) shown in Table 1 to prepare resin compositions for encapsulation of Examples and Comparative Examples. This sealing resin composition was a solid under normal temperature and pressure. The content of the inorganic filler in the obtained sealing resin composition as a whole was 83.1% by volume in both Examples and Comparative Examples.

-Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 2: 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"
-Phenol curing agent 1: Phenol aralkyl resin, hydroxyl group equivalent 202 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7851SS")

-Specific copolymer 1: Copolymer of α-olefin having 20 carbon atoms and maleic anhydride, copolymerization molar ratio (X: Y) 1: 1, weight average molecular weight 20,800

-Polyethylene oxide 1: Polyethylene oxide, weight average molecular weight 2600, acid value 17 mg / KOH, melting point 100 ° C. (Mitsui Chemicals Co., Ltd., product name "High Wax 4202E")
-Polyethylene oxide 2: Polyethylene oxide, weight average molecular weight 8800, acid value 24.5 mg / KOH, melting point 140 ° C. (Clariant Japan Co., Ltd., product name "Ricowax PED153")
-Polyethylene oxide 3: Polyethylene oxide, weight average molecular weight 3000, acid value 1 mg / KOH, melting point 114 ° C. (Mitsui Chemicals Co., Ltd., product name "High Wax 310MP")
-Ester wax 1: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Polyethylene oxide 4: Polyethylene oxide, weight average molecular weight 3100, acid value 25 mg / KOH, melting point 101 ° C. (Clariant Japan Co., Ltd., product name "Ricowax PED522")
-Polyethylene oxide 5: Polyethylene oxide, melting point 138 ° C, Dainichi Kagaku Kogyo Co., Ltd., product name "PE-A")

-Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct-Inorganic filler 1: Fused silica 1 (volume average particle size 4.5 μm)
-Inorganic filler 2: Fused silica 2 (volume average particle size 0.6 μm)
-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")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

<Performance evaluation of sealing resin composition>
(Relative permittivity and dielectric loss tangent)
The sealing resin composition is charged into a vacuum hand press machine, molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and post-curing is performed at 180 ° C. for 6 hours to cure the plate. An article (length 12.5 mm, width 25 mm, thickness 0.2 mm) was obtained. Using this plate-shaped cured product as a test piece, measure the relative permittivity and dielectric loss tangent at 60 GHz at a temperature of 25 ± 3 ° C. using a dielectric constant measuring device (Agilent Technologies, Inc., product name “Network Analyzer N5227A”). did. The results are shown in Table 1.

(Releasability)
Using a four-piece set of upper and lower molds (outer diameter 100 mm x total thickness 63 mm), the sealing resin composition was applied under the conditions of 180 ° C., 6.9 MPa, and 180 seconds, with an upper diameter of 10.2 mm and a lower diameter of 12. Immediately after molding into a molded product filled in a cavity with a size of 5 mm x 20 mm in thickness, a push-pull gauge (manufactured by Imada Co., Ltd.) is used to poke the molded product from above, and the load when the molded product comes off. (Pulling load: N) was measured. Four shots were molded without using a mold release recovery material, and the results of measurement (pulling load: N) of the molded product on the fourth shot were evaluated. The results are shown in Table 1.

The sealing resin composition of the example has a reduced dielectric loss tangent of the cured product and is excellent in releasability of the cured product as compared with the sealing resin composition of the comparative example.

The disclosure of Japanese Patent Application No. 2019-221333, filed December 6, 2019, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein.

Claims

Epoxy resin and
A curing agent containing an active ester compound and
A copolymer of α-olefin having 5 to 30 carbon atoms and maleic anhydride,
A resin composition for sealing containing.
The sealing resin composition according to claim 1, wherein the copolymerization molar ratio of the α-olefin and the maleic anhydride in the copolymer is 20: 1 to 1: 2.
The sealing resin composition according to claim 1 or 2, wherein the content of the copolymer is 0.01% by mass to 1.00% by mass with respect to the entire sealing resin composition.
The sealing resin composition according to any one of claims 1 to 3, wherein the content of the copolymer is 0.25 parts by mass to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
The sealing resin composition according to any one of claims 1 to 4, wherein the copolymer has a weight average molecular weight of 5000 to 100,000.
The sealing resin composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of polyolefin waxes and ester waxes.
The sealing material according to claim 6, wherein the content of at least one selected from the group consisting of the polyolefin-based wax and the ester-based wax is 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Resin composition.
The sealing resin composition according to any one of claims 1 to 7, further comprising an inorganic filler.
Support members and
The element arranged on the support member and
The cured product of the sealing resin composition according to any one of claims 1 to 8, which seals the element, and the cured product.
Electronic component device equipped with.
Placing the element on the support member and
The element is sealed with the sealing resin composition according to any one of claims 1 to 8.
Manufacturing method of electronic component equipment including.