TW202124503A - Resin composition of sealing, electronic component device, and method for manufacturing electronic component device - Google Patents

Abstract

A resin composition for sealing includes: an epoxy resin; a curing agent including an active ester compound; and a copolymer of an α-olefin having 5 to 30 carbon atoms and a maleic anhydride.

Description

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

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

The amount of transmission loss due to the thermal conversion of the radio waves transmitted for communication in the dielectric is expressed in the form of the product of frequency, the square root of the relative permittivity, and the dielectric tangent. That is, the transmission signal tends to become heat in proportion to the frequency. Therefore, in order to suppress transmission loss, the higher the frequency band, the lower the dielectric properties required for the material of the communication member.

For example, Patent Document 1 to Patent Document 2 disclose that thermosetting resin compositions containing an active ester resin as a curing agent for epoxy resins can suppress the dielectric tangent of the cured product to a low level. [Prior Art Literature] [Patent Literature]

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

[The problem to be solved by the invention] In the field of information communication, with the increase in the number of channels and the increase in the amount of information transmitted, the high frequency of radio waves is developing. Currently, research on the 5th generation mobile communication system is being carried out all over the world. As for the candidates for the frequency band to be used, several types in the range of approximately 30 GHz to 70 Ghz can be cited. In the future, the mainstream of wireless communication is communication in such a high frequency band. Therefore, materials of communication components are required to have a lower dielectric tangent.

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

The embodiments of the present disclosure are based on the above-mentioned circumstances. The subject of the present disclosure is to provide a resin composition for sealing that reduces the dielectric tangent of the cured product and is excellent in mold releasability of the cured product, an electronic component device sealed using the sealing resin composition, and an electronic device sealed using the electronic component device Manufacturing method of parts device. [Means to solve the problem]

Specific methods for solving the above-mentioned problems include the following aspects.

＜1＞ A resin composition for sealing, containing: Epoxy resin, Hardener containing active ester compound, and Copolymer of α-olefin with 5-30 carbon atoms and maleic anhydride. ＜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 resin composition for sealing as described in <1> or <2>, wherein the content of the copolymer is 0.01% by mass to 1.00% by mass relative to the entire resin composition for sealing. ＜4＞ The sealing resin composition according to any one of <1> to <3>, wherein the content of the copolymer is 0.25 to 5 parts by mass relative 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 5,000 to 100,000. ＜6＞ The resin composition for sealing as described in any one of <1> to <5> further contains at least one selected from the group consisting of polyolefin wax and ester wax. ＜7＞ The sealing resin composition according to <6>, wherein the content of the at least one selected from the group consisting of polyolefin waxes and ester waxes is 0.5 relative to 100 parts by mass of the epoxy resin Parts by mass ~ 10 parts by mass. ＜8＞ The resin composition for sealing as described in any one of <1> to <7> further contains an inorganic filler. ＜9＞ An electronic component device, including: Support components, The elements arranged on the supporting member, and The cured product of the sealing resin composition described in any one of <1> to <8> that seals the element. ＜10＞ A manufacturing method of an electronic component device includes: Arranging the components on the supporting member, and The element is sealed with the resin composition for sealing according to any one of <1> to <8>. [Effects of the invention]

According to the present disclosure, it is possible to provide a sealing resin composition that reduces the dielectric tangent of the cured product and is excellent in mold releasability of the cured product, an electronic component device sealed with the sealing resin composition, and an electronic device sealed using the electronic component device Manufacturing method of parts device.

In the present disclosure, in the term "step", in addition to a step independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved, the step is also included. In this disclosure, the numerical values described before and after the "～" included in the numerical range indicated by "~" are used as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in the present disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also include multiple equivalent substances. When there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple types of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may also be included. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component refers to a value with respect to a mixture of the multiple types of particles present in the composition.

Hereinafter, the mode for implementing the present disclosure will be described in detail. However, this disclosure is not limited to the following embodiments. In the following embodiments, the structural elements (including element steps, etc.) are not essential unless otherwise specified. The same is true for the numerical value and its range, which does not limit the present disclosure.

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

The active ester compound in the present disclosure refers to a compound that has one or more epoxy-reactive ester groups in one molecule and has a curing effect of epoxy resin.

Previously, phenol hardeners, amine hardeners, etc. are generally used as hardeners for epoxy resins. As a result, secondary hydroxyl groups are generated in the reaction of epoxy resin with phenol hardeners or amine hardeners. In contrast, 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 can be compared with a sealing resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent. The electric tangent is restrained low. In addition, the polar groups in the cured product increase the water absorption of the cured product. By using an active ester compound as the 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. Furthermore, by suppressing the water absorption of the cured product, that is, suppressing _{the content of H 2} O as a polar molecule, the dielectric tangent of the cured product can be suppressed to be lower.

However, with regard to the sealing resin composition containing an active ester compound as a curing agent for epoxy resins, although the dielectric tangent of the cured product is reduced, the cured product may have poor mold releasability. The reason for this 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 mold releasability. On the other hand, in the sealing resin composition of the present embodiment, in addition to the epoxy resin and the active ester compound, a specific copolymer is further contained, thereby achieving both the reduction of the dielectric tangent of the cured product and the releasability of the cured product . The reason is not clear, but it is estimated as follows. The specific copolymer has a long-chain alkyl group. On the other hand, the structure derived from maleic anhydride in the specific copolymer has affinity with the active ester compound, thereby improving the dispersibility of the active ester compound. Therefore, it is considered that the improvement of the reaction efficiency of the active ester compound prevents the unreacted active ester compound from remaining in the cured product, and suppresses the decrease in the releasability caused by the unreacted active ester compound. Based on the above speculation, the sealing resin composition of the present embodiment reduces the dielectric tangent of the cured product, and has excellent mold releasability of the cured product. Hereinafter, each component contained in the resin composition for sealing of this embodiment is demonstrated.

(Epoxy resin) If the epoxy resin has an epoxy group in the molecule, its kind is not particularly limited.

Specific examples of epoxy resins include phenolic compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and α-naphthol and β-naphthalene. At least one phenolic compound in the group consisting of naphthol compounds such as phenol and dihydroxy naphthalene is condensed or co-condensed with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolac resin and The novolak type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) obtained by epoxidizing the novolak resin; combining the phenolic compound with benzaldehyde and salicylaldehyde And other aromatic aldehyde compounds are condensed or co-condensed under an acid catalyst to obtain a triphenylmethane type phenol resin and the triphenylmethane type phenol resin is epoxidized to obtain a triphenylmethane type epoxy resin; The phenol compound and the naphthol compound and the aldehyde compound are co-condensed under an acid catalyst to obtain a novolak resin and the novolak resin is epoxidized to obtain a copolymer type epoxy resin; as bisphenol A, bisphenol F, etc. Diphenylmethane type epoxy resin of diglycidyl ether; Biphenyl type epoxy resin of diglycidyl ether of alkyl-substituted or unsubstituted biphenol; Diglycidyl ether of stilbene-based phenol compound Stilbene type epoxy resin; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol Resins; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; Glycidylamine type epoxy resin obtained by substituting the active hydrogen bonded to the nitrogen atom such as polycyanic acid with a glycidyl group; a bicyclic ring obtained by epoxidizing a co-condensed resin of dicyclopentadiene and a phenol compound Pentadiene type epoxy resin; diepoxy vinylcyclohexene obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy Acid ester, 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclo(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; as a pair Para-xylene-modified epoxy resin of glycidyl ether of xylene-modified phenol resin; meta-xylene-modified epoxy resin of glycidyl ether of meta-xylene-modified phenol resin; and terpene-modified phenol resin Terpene-modified epoxy resin of glycidyl ether; dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; glycidol as phenolic resin of cyclopentadiene-modified Cyclopentadiene-modified epoxy resin of ether; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as polycyclic aromatic ring-modified phenol resin; naphthalene type of glycidyl ether as phenol resin containing naphthalene ring Epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic ring obtained by oxidizing olefin bonds with peracetic acid and other peracids Oxygen resin; aralkyl type ring obtained by epoxidizing aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin Oxygen resin and so on. Furthermore, epoxide of acrylic resin etc. can also be mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.

The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq. Let the epoxy equivalent of an epoxy resin be the value measured by the method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.

When the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoints of formability and reflow resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C, and from the viewpoint of workability during the preparation of the sealing resin composition, it is more preferable 50℃～130℃. Let the softening point or melting point of an epoxy resin be the value measured by the method (ring and ball method) based on differential scanning calorimetry (Differential scanning calorimetry, DSC) or JIS K 7234:1986.

From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the mass ratio of the epoxy resin in the total amount of the sealing resin composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass %～30% by mass.

(hardener) The resin composition for sealing of this embodiment contains at least an active ester compound as a curing agent. The resin composition for sealing 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 tangent of the cured product can be suppressed to be low.

As long as the active ester compound is a compound having one or more ester groups that react with an epoxy group in the molecule, its kind is not particularly limited. Examples of the active ester compound include ester compounds of phenol ester compounds, thiophenol ester compounds, N-hydroxy amine ester compounds, and heterocyclic hydroxy compounds.

Examples of the active ester compound include at least one selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids and at least one selected from the group consisting of aliphatic hydroxy compounds and aromatic hydroxy compounds The obtained ester compound. An ester compound containing an aliphatic compound as a polycondensation component tends to have an aliphatic chain and therefore has excellent compatibility with epoxy resins. An ester compound containing an aromatic compound as a polycondensation component tends to be excellent in heat resistance by having an aromatic ring.

As a specific example of an active ester compound, the aromatic ester obtained by the condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group is mentioned. Among them, the active ester compound is preferably obtained by substituting 2 to 4 hydrogen atoms of aromatic rings such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid with carboxyl groups. A mixture of the aromatic carboxylic acid component, a monohydric phenol in which one hydrogen atom of the aromatic ring is substituted by a hydroxyl group, and a mixture of a polyhydric phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted by a hydroxyl group as The raw material is an aromatic ester obtained by the condensation reaction of an aromatic carboxylic acid 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 phenol resins having a molecular structure in which a phenol compound is nodded through an aliphatic cyclic hydrocarbon group described in Japanese Patent Laid-Open No. 2012-246367, and having an aromatic dicarboxylic acid Or an active ester resin of a structure obtained by reacting its halide and an aromatic monohydroxy compound. The active ester resin is preferably a compound represented by the following structural formula (1).

[化1]

In the structural formula (1), R ¹ is an alkyl group having 1 to 4 carbons, and X is a benzene ring, a naphthalene ring, a benzene ring substituted by an alkyl group having 1 to 4 carbons, or a naphthalene ring, 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 and is 0.25 to 1.5.

As specific examples of the compound represented by the structural formula (1), for example, the following exemplified compounds (1-1) to (1-10) can be cited. The t-Bu in the structural formula is the tertiary butyl group.

[化2]

[化3]

As other specific examples 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 2014-114352 A can be cited.

[化4]

In the structural formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, and Z is selected from the group consisting of benzyl and naphthyl An acyl group, a benzyl group or naphthyl group substituted by an alkyl group having 1 to 4 carbons, and an ester in the group consisting of an acyl group having 2 to 6 carbons form a structural site (z1) or At least one of the hydrogen atom (z2) and Z is an ester formation structure 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 carbons, or an alkoxy group having 1 to 4 carbons, and Z is selected from the group consisting of benzyl and naphthyl An acyl group, a benzyl group or naphthyl group substituted by an alkyl group having 1 to 4 carbons, and an ester in the group consisting of an acyl group having 2 to 6 carbons form a structural site (z1) or At least one of the hydrogen atom (z2) and Z is an ester formation structure site (z1).

As specific examples of the compound represented by the structural formula (2), for example, the following exemplified compounds (2-1) to (2-6) can be cited.

[化5]

As specific examples of the compound represented by the structural formula (3), for example, the following exemplified compounds (3-1) to (3-6) can be cited.

[化6]

As the active ester compound, commercially available products can also be used. As commercially available active ester compounds, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Co., Ltd.) ); Active ester compounds containing aromatic structures include "EXB9416-70BK", "EXB-8", and "EXB-9425" (manufactured by DIC Co., Ltd.); active ester compounds containing phenol novolac acetate can be Examples include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); active ester compounds containing phenol novolac-based benzyl compounds include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).

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

The ester equivalent of the active ester compound is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, 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, more preferably 200 g/eq to 250 g/eq. Let the ester equivalent of an active ester compound be the value measured by the method based on JISK 0070:1992.

From the viewpoint of suppressing the dielectric tangent of the cured product to a low level, the equivalent ratio of the epoxy resin to the active ester compound, that is, the number of ester groups/the number of epoxy groups is preferably 0.9 or more, more preferably 0.95 or more, and still more preferably It is 0.97 or more. From the viewpoint of reducing the amount of unreacted components of the active ester compound, the equivalent ratio of the epoxy resin and the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, and still more preferably 1.03 or less.

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

Specific examples of the phenol hardener include polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; selected from the group consisting of phenol, cresol, and two Cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds Novolac-type phenol resin obtained by condensation or co-condensation of at least one phenolic compound in the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicaldehyde and other aldehyde compounds under an acidic catalyst; Phenol aralkyl resins, naphthol aralkyl resins and other aralkyl phenol resins synthesized by synthetic compounds with dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; p-xylene modified phenol Resin, meta-xylene-modified phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; dicyclopentadiene-type phenol resin synthesized by copolymerization of the phenolic compound and dicyclopentadiene, and Dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; combining the phenolic compound with aromatics such as benzaldehyde and salicylaldehyde A triphenylmethane type phenol resin obtained by condensation or co-condensation of an aldehyde compound under an acidic catalyst; a phenol resin obtained by copolymerizing two or more of these. These phenol hardeners may be used alone or in combination of two or more kinds.

The functional group equivalents of other hardeners are not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, the functional group equivalent of other hardeners is preferably 70 g/eq to 1000 g/eq, more preferably 80 g/eq to 500 g/eq. Furthermore, when the other hardener is a phenol hardener, the functional group equivalent of the other hardener refers to the hydroxyl equivalent. The functional group equivalents of the other curing agents are set to values measured by a method based on JIS K 0070:1992.

The softening point or melting point of the hardener is not particularly limited. From the viewpoints of formability and reflow resistance, the softening point or melting point of the curing agent is preferably 40°C to 180°C. From the viewpoint of workability during the manufacture of the sealing resin composition, the softening of the curing agent The point or melting point is more preferably 50°C to 130°C.

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 epoxy resin to all hardeners, that is, the ratio of the number of functional groups in the hardener to the number of functional groups in the epoxy resin, that is, the value of the number of functional groups in the hardener/the number of functional groups in the epoxy resin is not special limit. From the viewpoint of reducing the respective unreacted components, 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, more preferably 0.6 to 1.3 Range. From the viewpoint of formability and reflow resistance, it is more preferable to set it to the range of 0.8 to 1.2. Furthermore, when the hardener includes other hardeners, all the hardeners include both the active ester compound and the other hardeners.

From the viewpoint of suppressing the dielectric tangent of the cured product to a low level, the mass ratio of the active ester compound in the total amount of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass Above, more preferably 90% by mass or more.

From the viewpoint of suppressing the dielectric tangent of the cured product to a low level, 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 mass. % Or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more.

(Specific copolymer) The specific copolymer is not particularly limited as long as it is a copolymer of α-olefin having 5 to 30 carbon atoms and maleic anhydride. By being contained in the resin composition for sealing, the specific copolymer functions as a dispersant of, for example, an epoxy resin and a specific release agent described later. From the viewpoint of expressing the function as an epoxy resin and a dispersant of a specific release agent, the carbon number of the α-olefin is 5-30, preferably 10-25, and more preferably 15-25. The α-olefin may be linear or branched. A specific copolymer may be used individually by 1 type, and may be used in combination of 2 or more types.

Specific examples of α-olefins are not particularly limited, and include: 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene Carboxene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene Ene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentadecene, 1- Straight-chain α-olefins such as hexadecene and 1-heptadecene; 3-methyl-1-butene, 3,4-dimethyl-pentene, 3-methyl-1-nonane Ene, 3,4-dimethyl-octene, 3-ethyl-1-dodecene, 4-methyl-5-ethyl-1-octadecene, 3,4,5-triethyl Branched α-olefins such as group-1-1-eicosene, etc. As the α-olefin, these may be used alone or in combination of two or more kinds. As the α-olefin, among these, α-olefins having 10 to 25 carbon atoms are preferred, and α-olefins having 15 to 25 carbon atoms are more preferred.

It does not specifically limit as a specific example of a specific copolymer, The compound represented by the following general formula (VI), the compound represented by the following general formula (VII), etc. are mentioned. As a commercial product of a specific copolymer, Nissan Electol WPB-1 (Nippon Oil Co., Ltd., trade name), etc.

[化7]

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

From the viewpoint of both the expression of the function as a dispersant and the affinity for the active ester compound, the copolymerized molar ratio of the α-olefin and the maleic anhydride in the specific copolymer, that is, the α-olefin is X When the mol and maleic anhydride are Y mol, X:Y is preferably 20:1 to 1:2, more preferably 15:1 to 1:1.5, and still more preferably 10:1 to 1:1.

From the viewpoints of mold contamination suppression and moldability, the weight average molecular weight of the specific copolymer is preferably 5,000 to 100,000, more preferably 10,000 to 70,000, and still more preferably 15,000 to 50,000. When the weight average molecular weight of the specific copolymer is 5000 or more, it is easy to obtain the effect of suppressing mold contamination. When the weight average molecular weight of the specific copolymer is 100,000 or less, it is possible to suppress the decrease in kneading property caused by the increase in the softening point of the specific copolymer. Here, the weight average molecular weight refers to a value measured by Gel Permeation Chromatography (GPC). In the measurement of the weight average molecular weight by GPC, for example, Tosoh Corporation’s G2000HXL and 3000HXL are used for analytical GPC columns, and tetrahydrofuran is used for the mobile phase. The sample concentration is 0.2% by mass and the flow rate is 1.0 mL/ min for measurement. A calibration curve was prepared using polystyrene standard samples, and the weight average molecular weight was calculated based on the polystyrene conversion value.

From the viewpoint of improving the releasability of the cured product, the content of the specific copolymer relative to the entire sealing resin composition is preferably 0.01% by mass to 1.00% by mass, more preferably 0.02% by mass to 0.50% by mass, More preferably, it is 0.05 mass%-0.10 mass %. In addition, from the viewpoint of improving the releasability of the cured product, the content of the specific copolymer 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 relative to 100 parts by mass of the epoxy resin. .

There are no particular limitations on the method for producing the specific copolymer, and general copolymerization methods such as reacting raw materials can be used. In the reaction, an organic solvent that can dissolve α-olefin and maleic anhydride can also be used. The organic solvent is not particularly limited. Among them, toluene is preferred, and alcohol-based solvents, ether-based solvents, amine-based solvents, and the like can also be used. The reaction temperature varies depending on the type of organic solvent used, but from the viewpoint of reactivity and productivity, it is preferably 50°C to 200°C, more preferably 80°C to 120°C. The reaction time is not particularly limited as long as the copolymer can be obtained. From the viewpoint of productivity, it is preferably from 1 hour to 30 hours, more preferably from 2 hours to 15 hours, and even more preferably from 4 hours to 4 hours. 10 hours. After the reaction is completed, unreacted components, solvents, etc. may be removed under heating and reduced pressure as needed. The removal conditions of unreacted components, solvents, etc. are preferably set at 100°C to 220°C, more preferably at 120°C to 180°C, pressure at 13.3×10 ³ Pa or less, and more preferably at 8× 10 ³ Pa or less, and the time is 0.5 hour to 10 hours. In addition, reaction catalysts such as amine catalysts and acid catalysts can also be added during the reaction as needed. The pH of the reaction system is preferably set to about 1-10.

(Specific release agent) The resin composition for sealing may further contain at least one selected from the group consisting of polyolefin-based wax and ester-based wax (hereinafter also referred to as "specific release agent"). That is, the resin composition for sealing may contain an epoxy resin, an active ester compound, a specific copolymer, and a specific mold release agent. It is believed that the long-chain alkyl group of the specific copolymer has affinity with the specific release agent, and the structure of maleic anhydride derived from the specific copolymer has affinity with the active ester compound, thereby improving the dispersion of both the specific release agent and the active ester compound. sex. Therefore, it is estimated that the sealing resin composition contains an epoxy resin, an active ester compound, a specific copolymer, and a specific mold release agent, so that both the reduction of the dielectric tangent of the cured product and the mold release property of the cured product can be achieved.

The specific 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 wax may be an oxidized polyolefin wax or a non-oxidized polyolefin wax. Examples of polyolefin waxes include oxidized polyethylene, non-oxidized polyethylene, oxidized polypropylene, non-oxidized polypropylene, oxidized polybutene, and non-oxidized polybutene. Examples of ester waxes include montanic acid esters, saponified montanic acid esters, glycerides, carnauba wax, and rice wax (Rice wax). Among these, the specific release agent preferably contains polyolefin wax, and more preferably contains oxidized polyethylene. The oxidized polyethylene can be linear oxidized polyethylene or branched oxidized polyethylene. In addition, the specific mold release agent may be used individually by 1 type of these, and may combine 2 or more types.

From the standpoint of releasability, the weight average molecular weight of the polyolefin wax is preferably 2000 or more, and from the standpoint of adhesion and mold contamination suppression, it is preferably 30,000 or less, more preferably 5,000 to 20,000, and more preferably It is 7000～15000. Here, the weight average molecular weight refers to a value measured by GPC at a high temperature.

The acid value of the polyolefin-based wax is not particularly limited, but from the viewpoint of mold releasability and adhesion, it is preferably 0 mg/KOH to 100 mg/KOH, and more preferably 10 mg/KOH to 60 mg/KOH. In addition, the acid value is the number of moles of potassium hydroxide required to neutralize 1 g of the measurement object, and can be determined by a measurement method based on JIS K0070:1992.

The saponification value of the ester wax is not particularly limited, but from the viewpoint of release properties and adhesion, it is preferably 1 mg/KOH to 200 mg/KOH, and more preferably 30 mg/KOH to 100 mg/KOH. In addition, the saponification value is the number of moles of potassium hydroxide required to saponify 1 g of the measuring object, and can be obtained by a measurement method based on JIS K0070: 1992.

The melting point of the specific mold release agent is not particularly limited, but from the viewpoint of kneading properties and moldability, it is preferably 40°C to 180°C, more preferably 60°C to 140°C. In addition, the said melting point shall be the value measured similarly to the melting point of an epoxy resin.

The content of the specific mold release agent is not particularly limited. From the viewpoint of the mold release properties of the cured product and the suppression of mold contamination, it is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the epoxy resin, and more preferably 1 part by mass to 5 parts by mass.

(Hardening accelerator) The resin composition for sealing may optionally contain a hardening accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin or curing agent, the required characteristics of the sealing resin composition, and the like.

Examples of hardening accelerators include: 1,5-Diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN), 1,8-diazabicyclo[4.3.0]nonene-5, DBN Diazabicycloalkenes such as bicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU), 2-methylimidazole, 2-phenylimidazole, 2- Cyclic amidine compounds such as phenyl-4-methylimidazole and 2-heptadecylimidazole; derivatives of said cyclic amidine compounds; phenol novolak salts of said cyclic amidine compounds or derivatives thereof; and Add maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, and 2,6-dimethylbenzoquinone to these compounds , 2,3-Dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds , Diazophenylmethane and other compounds with π bond forming compounds with intramolecular polarization; DBU tetraphenylboron salt, DBN tetraphenylboron salt, 2-ethyl-4-methylimidazole Cyclic amidinium compounds such as tetraphenyl boron salt and tetraphenyl boron salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amine compounds such as ethyl alcohol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethyl acetate Ammonium salt compounds such as ammonium, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide; primary phosphines such as ethyl phosphine and phenyl phosphine, secondary phosphines such as dimethyl phosphine and diphenyl phosphine, and triphenyl phosphine , Diphenyl(p-toluene)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(tetraalkoxy) Organic phosphines such as tertiary phosphines such as phenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphine, etc.; the organic phosphine and organic boron Phosphine compounds such as complex compounds; add maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3- Dimethyl benzoquinone, 2,6-dimethyl benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4- Compounds with intramolecular polarization formed by quinone compounds such as benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, and compounds with π bonds such as diazophenylmethane; to make the organic phosphine or the Phosphine compounds and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4- Bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2, 6 -Di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and other halogenated phenol compounds After the reaction, a compound with intramolecular polarization obtained through the step of dehydrohalogenation; tetra-substituted phosphonium such as tetraphenyl phosphonium, tetra-substituted phosphonium such as tetraphenyl phosphonium tetra-p-toluene borate, tetraphenyl borate of tetra-substituted phosphonium, tetrakis Tetra-substituted phosphonium compounds such as salts of substituted phosphonium and phenolic compounds; salts of partial hydrolysates of tetraalkyl phosphonium and aromatic carboxylic anhydrides; Phosphobetaine compounds; adducts of phosphonium compounds and silane compounds, etc. One kind of hardening accelerator may be used alone, or two or more kinds may be used in combination. Among these, as particularly preferable hardening accelerators, triphenylphosphine, adducts of triphenylphosphine and quinone compounds, adducts of tributylphosphine and quinone compounds, tri-p-tolylphosphine and quinone Compound adducts, etc.

When the sealing resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass relative to 100 parts by mass of the resin component. If the amount of the hardening accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency to harden well in a short time. If the amount of the hardening accelerator relative to 100 parts by mass of the resin component is 30 parts by mass or less, there is a tendency that a good molded product with a hardening rate not too fast can be obtained. In addition, in this specification, the resin component means epoxy resin and hardener. In addition, in this specification, the term "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 resin composition for sealing may optionally contain an inorganic filler. The type of inorganic filler is not particularly limited. As the inorganic filler, specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, oxide Beryllium, zirconia, zircon, forsterite, talc, spinel, mullite, titanium dioxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate.

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

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

From the viewpoint of controlling the elastic coefficient of the cured product of the sealing resin composition, the content of the inorganic filler contained in the sealing resin composition of the present disclosure is preferably 70% to 90% by volume of the entire sealing resin composition % By volume, more preferably 78% by volume to 88% by volume, and still more preferably 80% by volume to 85% by volume.

The volume ratio of the inorganic filler in the resin composition for sealing can be determined by the following method. A scanning electron microscope (Scanning Electron Microscope, SEM) photographed a thin sample of the cured product of the sealing resin composition. 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 defined as the volume ratio of the inorganic filler in the sealing resin composition. The area S is set to a sufficiently large area with respect to the size of the inorganic filler. For example, it is assumed that the size includes 100 or more inorganic fillers. The area S may be the total of a plurality of cut surfaces. The inorganic filler may have a deviation in the ratio of the sealing resin composition in the direction of gravity at the time of curing. In this case, when imaging with SEM, the entire gravity direction of the hardened object is imaged, and the area S including the entire gravity direction of the hardened object is specified.

[Various additives] In addition to the above-mentioned components, the sealing resin composition may also contain various coupling agents, ion exchangers, dispersants other than specific copolymers, mold release agents other than specific mold release agents, flame retardants, colorants, etc., as exemplified below. additive. In addition to the additives exemplified below, the sealing resin composition may optionally contain various additives known in the technical field.

(Coupling agent) The resin composition for sealing may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include epoxy silanes, mercapto silanes, amino silanes, alkyl silanes, urea silanes, vinyl silanes, disilazanes and other silane-based compounds, titanium-based compounds, aluminum chelate compounds, Well-known coupling agents such as aluminum/zirconium compounds.

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

(Ion Exchanger) The resin composition for sealing may contain an ion exchanger. From the viewpoint of improving the humidity resistance and high-temperature storage characteristics of an electronic component device including a sealed element, the resin composition for sealing preferably contains an ion exchanger. The ion exchanger is not particularly limited, and previously known ones can be used. Specific examples of the ion exchanger include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. One kind of ion exchanger may be used alone, or two or more kinds may be used in combination. Among them, the hydrotalcite represented by the following general formula (A) is preferred.

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 resin composition for sealing includes an ion exchanger, the content is not particularly limited as long as the content is a sufficient amount for capturing halogen ion plasma. For example, with respect to 100 parts by mass of the resin component, the content of the ion exchanger is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 10 parts by mass.

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

As the esterified product of the specific copolymer, for example, a compound obtained by esterifying the specific copolymer with a monohydric alcohol can be cited. The monoalcohol obtained by esterifying the specific copolymer is not particularly limited, and examples thereof include pentanol, isoamyl alcohol, hexanol, heptanol, octyl alcohol, capryl alcohol, and nonyl alcohol. Alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecanol, eicosanol and other linear or branched types Aliphatic saturated alcohols; hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol and other linear or branched Aliphatic unsaturated alcohols; alicyclic alcohols such as cyclopentanol and cyclohexanol; aromatic alcohols such as benzyl alcohol and cinnamyl alcohol; heterocyclic alcohols such as furfuryl alcohol; these can 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 straight chain alcohol having 10 to 20 carbon atoms, and still more preferably a straight chain aliphatic saturated alcohol having 15 to 20 carbon atoms.

The method for esterifying a specific copolymer with a monohydric alcohol is not particularly limited, and general methods such as an addition reaction of a monohydric alcohol and a 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. Organic solvents and the like can also be used in the reaction. The organic solvent is not particularly limited, and toluene, alcohol-based solvents, ether-based solvents, amine-based solvents, and the like can be mentioned. The reaction temperature varies depending on the type of organic solvent used, but from the viewpoint of reactivity and productivity, it is preferably 50°C to 200°C, more preferably 80°C to 120°C. From the viewpoint of productivity, the reaction time is preferably 1 hour to 30 hours, more preferably 2 hours to 15 hours, and still more preferably 4 hours to 10 hours. After the reaction is completed, unreacted components, solvents, etc. may be removed under heating and reduced pressure as needed. In addition, reaction catalysts such as amine catalysts and acid catalysts can also be added during the reaction as needed. The pH of the reaction system is preferably set to about 1-10.

From the viewpoints of mold contamination suppression and moldability, the weight average molecular weight of the esterified product of the specific copolymer is preferably 3,000 to 100,000, more preferably 10,000 to 70,000, and still more preferably 15,000 to 50,000. 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 preferably 0.01% by mass relative to the entire sealing resin composition -1.00% by mass, more preferably 0.02% by mass to 0.50% by mass, and still more preferably 0.05% by mass to 0.10% by mass. In addition, when the sealing resin composition contains an esterified product of a specific copolymer and a specific copolymer, the total content of the esterified product of the specific copolymer and the specific copolymer is preferably 0.25 mass parts with respect to 100 parts by mass of the epoxy resin. Parts to 5 parts by mass, more preferably 0.5 parts by mass to 2 parts by mass.

(Release agents other than specific release agents) The resin composition for sealing may optionally contain a mold release agent other than a specific mold release agent. There are no particular restrictions on the release agent other than the specific release agent, and those previously known can be used. Specifically, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, and the like can be cited. A mold release agent other than a specific mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types.

When the resin composition for sealing includes 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 to 10 parts by mass, more preferably, relative to 100 parts by mass of the resin component 0.1 parts by mass to 5 parts by mass. If the total content of the release agent with respect to 100 parts by mass of the resin component is 0.01 parts by mass or more, there is a tendency that sufficient release properties can be obtained. If the total content of the release agent is 10 parts by mass or less, there is a tendency that better adhesiveness can be obtained.

(Flame retardant) The resin composition for sealing may contain a flame retardant. The flame retardant is not particularly limited, and previously known ones can be used. As the flame retardant, specifically, an organic compound 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 cited. One kind of flame retardant may be used alone, or two or more kinds may be used in combination.

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

(Colorant) The resin composition for sealing may contain a coloring agent. As the coloring agent, well-known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, plumbum, and iron oxide can be cited. The content of the coloring agent can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.

(Preparation method of resin composition for sealing) The preparation method of the resin composition for sealing is not specifically limited. As a general method for preparing a resin composition for sealing, the following method can be cited: after fully mixing the components in a predetermined amount by a mixer or the like, then melting and kneading by a grinding roll, an extruder, etc., and cooling And crush it. As a method of preparing the resin composition for sealing, more specifically, for example, a method of uniformly stirring and mixing a predetermined amount of the components, using a kneader, roller, and extruder heated to 70°C to 140°C in advance. The press etc. are mixed, cooled and pulverized. In addition, when mixing the components of a predetermined blending amount, part or all of the epoxy resin may be pre-mixed with the specific copolymer. Moreover, when the resin composition for sealing contains a specific mold release agent, you may premix a part or all of an epoxy resin, a specific copolymer, and a specific mold release agent.

The resin composition for sealing is preferably solid at normal temperature and normal pressure (for example, 25° C., atmospheric pressure). The shape of the resin composition for sealing when it is solid is not particularly limited, and examples include powder, granules, and flakes. From the viewpoint of operability, the size and quality when the sealing resin composition is in the form of a sheet are preferably the size and quality in accordance with the molding conditions of the package.

＜Electronic component device＞ An electronic component device as an 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.

Examples of electronic component devices include those obtained by sealing the following component parts with a resin composition for sealing, the component parts being lead frames, wired conveyor tapes, wiring boards, glass, silicon wafers, organic substrates, etc. It is obtained by mounting components (such as active components such as semiconductor wafers, transistors, diodes, and thyristors, passive components such as capacitors, resistors, coils, etc.) on the supporting member. More specifically, it can include: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), small outline package (Small Outline Package, SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have components that are fixed on a lead frame and connect the terminals and lead portions of the components such as bonding pads by wire bonding, bumps, etc., and then use a sealing resin composition and use Transfer molding and other sealing structure; tape carrier package (Tape Carrier Package, TCP), which has a structure in which the components connected to the carrier tape by bumps are sealed with a resin composition for sealing; chip on board (Chip On Board) , COB) modules, hybrid ICs, polycrystalline modules, etc., which have a sealing resin composition to seal the components connected to the wiring formed on the support member by wire bonding, flip-chip bonding, solder, etc. Structure; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (Multi Chip Package, MCP), etc., which have the surface of a supporting member forming wiring board connection terminals on the back A structure in which the component is mounted on the top, and the component is connected to the wiring formed on the support member by bumps or wire bonding, and then the component is sealed with a sealing resin composition. In addition, a resin composition for sealing can also be preferably used in a printed wiring board.

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

The method of implementing the arrangement and sealing is not particularly limited, and can be performed by a general method. In addition, the types of support members and components used in the manufacture of electronic component devices are not particularly limited, and support members and components generally used in the manufacture of electronic component devices can be used.

As a method of sealing an element using the resin composition for sealing of the present disclosure, a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like can be cited. Among these, the low-pressure transfer molding method is generally used. [Example]

Hereinafter, the embodiments are described in detail with examples, but the scope of the embodiments is not limited to these examples.

＜Preparation of resin composition for sealing＞ The components shown below were mixed at the blending ratio (parts by mass) shown in Table 1 to prepare the sealing resin compositions of Examples and Comparative Examples. The resin composition for sealing is solid at normal temperature and pressure. In addition, the content of the inorganic filler with respect to the entire obtained sealing resin composition was 83.1% by volume in any of the examples and the 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 Co., Ltd., product name "EXB-8" ·Phenol hardener 1: Phenol aralkyl resin, hydroxyl equivalent 202 g/eq (Minghe Chemical Co., Ltd., product name "MEH7851SS")

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

·Oxidized polyethylene 1: Oxidized polyethylene, weight average molecular weight 2600, acid value 17 mg/KOH, melting point 100°C (Mitsui Chemicals Co., Ltd., product name "Hi-Wax 4202E") ·Oxidized polyethylene 2: Oxidized polyethylene, weight average molecular weight 8800, acid value 24.5 mg/KOH, melting point 140°C (Clariant Japan Co., Ltd., product name "Licowax PED153") ·Oxidized polyethylene 3: Oxidized polyethylene, weight average molecular weight 3000, acid value 1 mg/KOH, melting point 114°C (Mitsui Chemicals Co., Ltd., product name "Hi-Wax 310MP") ·Ester wax 1: montan ester wax (Clariant Japan Co., Ltd., product name "HW-E") ·Oxidized polyethylene 4: Oxidized polyethylene, weight average molecular weight 3100, acid value 25 mg/KOH, melting point 101°C (Clariant Japan Co., Ltd., product name "Licowax PED522") ·Oxidized polyethylene 5: Oxidized polyethylene, melting point 138°C (Dainichi Chemical Industry 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-aminopropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573") ·Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803") ·Coloring agent: carbon black (Mitsubishi Chemical Corporation, product name "MA600")

＜Performance evaluation of resin composition for sealing＞ (Relative dielectric constant and dielectric tangent) The sealing resin composition was put into a vacuum manual press, and molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds. After curing at 180°C for 6 hours, a plate-shaped cured product was obtained. (12.5 mm in length, 25 mm in width, 0.2 mm in thickness). The plate-shaped hardened material was used as a test piece, and a dielectric constant measurement device (Agilent Technologies, product name "Network Analyzer N5227A") was used to measure the temperature at 25±3°C and 60 GHz. Relative permittivity and dielectric tangent. The results are shown in Table 1.

(Releasability) Using a mold consisting of four upper and lower molds (outer diameter 100 mm × total thickness 63 mm), the sealing resin composition was molded under the conditions of 180°C, 6.9 MPa, and 180 seconds to fill the upper diameter 10.2 mm × lower diameter 12.5 mm × Immediately after the molded product in the cavity with a thickness of 20 mm, use a push-pull gauge (manufactured by IMADA Co., Ltd.) to push the molded product from above to measure when the molded product comes out The load (exit load: N). Molding was performed four times (shot) without using the release recovery material, and the fourth-shot molded product was evaluated based on the measurement result (release load: N). The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Epoxy resin Epoxy 1 75 75 75 75 75 75 75 75 75 Epoxy 2 25 25 25 25 25 25 25 25 25 hardener Active ester compound 1 120 120 120 120 120 120 120 120 0 Phenol hardener 1 0 0 0 0 0 0 0 0 100 Specific copolymer Specific copolymer 1 0.5 0.3 0.6 1.2 0.4 1.0 0.3 0 1.0 Specific release agent Oxidized polyethylene 1 2.0 2.0 0 0 0 2.0 0 2.4 2.0 Oxidized polyethylene 2 0 0 2.4 2.4 0 0 0 0 0 Oxidized polyethylene 3 0 0 0 0 1.6 0 0 0 0 Oxidized polyethylene 4 0 0 0 0 0 0 1.9 0 0 Oxidized polyethylene 5 0 0 0 0 0 0 0.6 0 0 Ester wax 1 1 1 1 1 1 1 1 1 1 Hardening accelerator Hardening accelerator 1 5 5 5 5 5 5 5 5 5 Inorganic filler Inorganic filler 1 (fused silica) 918 918 918 918 918 918 913 918 918 Inorganic filler 2 (fused silica) 230 230 230 230 230 230 230 230 230 Inorganic filler content (vol%) 83.1 83.1 83.1 83.1 83.1 83.1 83.1 83.1 83.1 Coupling agent Coupling agent 1 3 3 3 3 3 3 3 3 3 Coupling agent 2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Colorant Carbon black 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 Relative permittivity 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.5 Dielectric Tangent 0.0045 0.0043 0.0043 0.0044 0.0045 0.0046 0.0045 0.0043 0.0091 Evaluation of mold release, release load (N) 0 0 0 70 60 50 0 150 30

Compared with the resin composition for sealing of the comparative example, the resin composition for sealing of an Example has a reduced dielectric tangent of a hardened|cured material, and the mold release property of a hardened|cured material is excellent.

The entire content of the disclosure of Japanese Patent Application No. 2019-221333 for which an application was filed on December 6, 2019 is incorporated into this specification by reference. All the documents, patent applications, and technical specifications described in this specification are incorporated into this specification to the same extent as when it is specifically and separately described that each document, patent application, and technical specifications are incorporated by reference.

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Claims (10)

A resin composition for sealing, containing: Epoxy resin, Hardener containing active ester compound, and Copolymer of α-olefin with 5-30 carbon atoms and maleic anhydride. 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 resin composition for sealing according to claim 1 or 2, wherein the content of the copolymer is 0.01% by mass to 1.00% by mass relative to the entire resin composition for sealing. 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 relative to 100 parts by mass of the epoxy resin. The sealing resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the copolymer is 5,000 to 100,000. The sealing resin composition according to any one of claims 1 to 5 further contains at least one selected from the group consisting of polyolefin waxes and ester waxes. The sealing resin composition according to claim 6, wherein the content of the at least one selected from the group consisting of polyolefin waxes and ester waxes is 0.5 relative to 100 parts by mass of the epoxy resin Parts by mass ~ 10 parts by mass. The resin composition for sealing according to any one of claims 1 to 7 further contains an inorganic filler. An electronic component device, including: Support components, The elements arranged on the supporting member, and A cured product of the sealing resin composition according to any one of claims 1 to 8 that seals the element. A manufacturing method of an electronic component device includes: Arranging the components on the supporting member, and The element is sealed with the resin composition for sealing according to any one of claims 1 to 8.