JP2021116331A - Sealing resin composition, electronic component device, and method for producing electronic component device - Google Patents

Abstract

To provide a sealing resin composition that reduces a dielectric loss tangent of a cured product of it and reduces a defective appearances of the cured product.SOLUTION: A sealing resin composition contains epoxy resin, a curing agent containing an active ester compound, an inorganic filler, and polyether-modified silicone.SELECTED DRAWING: None

Description

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

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

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

Japanese Unexamined Patent Publication No. 2012-246367 Japanese Unexamined Patent Publication No. 2014-114352

In the information and communication field, the frequency of radio waves is increasing along with the increase in the number of channels and the amount of information to be transmitted. Currently, the 5th generation mobile communication system is being studied worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to have a lower dielectric loss tangent. In particular, a sealing resin composition used for sealing an element is required to have a low dielectric loss tangent when it becomes a cured product.
On the other hand, in the sealing resin composition containing the inorganic filler, the appearance of the cured product of the sealing resin composition formed by sealing the element may be poor due to the aggregation of the inorganic filler. Therefore, it is also required to suppress the appearance defect 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 suppresses an appearance defect 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
Inorganic filler and
With polyether-modified silicone,
A resin composition for sealing containing.
<2>
The sealing resin composition according to <1>, wherein the polyether-modified silicone has a viscosity at 25 ° C. of 1.00 Pa · s to 4.00 Pa · s.
<3>
The sealing resin composition according to <1> or <2>, wherein the content of the inorganic filler is 55% by volume to 80% by volume with respect to the entire sealing resin composition.
<4>
The sealing resin composition according to any one of <1> to <3> for a wafer level package.
<5>
The sealing resin composition according to any one of <1> to <4> for transfer molding.
<6>
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 <5>, which seals the element, and the cured product.
Electronic component device equipped with.
<7>
The process of arranging the element on the support member and
The step of sealing the element with the sealing resin composition according to any one of <1> to <5>, and
Manufacturing method of electronic component equipment including.
<8>
The process of arranging multiple elements on the wafer,
A step of collectively sealing the plurality of elements with the sealing resin composition according to any one of <1> to <5>, and a step of collectively sealing the plurality of elements.
The process of individualizing each sealed element and
Manufacturing method of electronic component equipment including.
<9>
The method for manufacturing an electronic component device according to <7> or <8>, wherein the sealing step is a step of sealing by transfer molding.

According to the present disclosure, a sealing resin composition that reduces the dielectric loss tangent of the cured product and suppresses the appearance defect of the cured product, an electronic component device sealed using the same, and the use thereof. A method of manufacturing an electronic component device to be sealed 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, modes for carrying out 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 one embodiment of the present disclosure contains an epoxy resin, a curing agent containing an active ester compound, an inorganic filler, and a polyether-modified silicone.

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. 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.

On the other hand, in the sealing resin composition containing the inorganic filler, the appearance of the cured product of the sealing resin composition formed by sealing the element may be poor due to the aggregation of the inorganic filler. There is. For example, when the element is sealed by transfer molding, the inorganic filler aggregates to reduce the fluidity of the sealing resin composition, and flow marks appear on the surface of the cured product, resulting in poor appearance. be. Further, when the element is sealed by compression molding, the inorganic filler agglomerates, which may cause appearance defects such as black spots in a region having a high resin ratio on the surface of the cured product.

On the other hand, in the sealing resin composition of the present embodiment, since it contains a polyether-modified silicone in addition to the epoxy resin, the curing agent containing the active ester compound, and the inorganic filler, the dielectric loss tangent of the cured product is formed. It is reduced and the appearance defect of the cured product is suppressed. Although the reason is not clear, the polyether-modified silicone contained in the sealing resin composition acts as a dispersant for the inorganic filler, thereby suppressing the aggregation of the inorganic filler and the sealing resin composition itself. It is presumed that the poor appearance of the cured product is suppressed by improving the fluidity 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 seed 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 epoxy resin obtained by epoxidizing the above; copolymerized epoxy obtained by co-condensing the above phenol compound, naphthol compound, and aldehyde compound under an acidic catalyst. 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 stilben-based phenol compound. Resin: Sulfur atom-containing epoxy resin that is a diglycidyl ether such as bisphenol S; Epoxy 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 which is an epoxidized cocondensate resin of a compound; vinylcyclohexene epoxide which is an epoxide of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylate, 2- (3,4-epoxy) cyclohexyl An alicyclic epoxy resin such as -5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is a glycidyl ether of a paraxylylene-modified phenol resin; metaxylylene which is a glycidyl ether of a metaxylylene-modified phenol resin. Modified epoxy resin; Terpen-modified epoxy resin, which is a glycidyl ether of a terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of a dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy, which is a glycidyl ether of a cyclopentadiene-modified phenol resin. 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; aralkyl which is an epoxidized aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. 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 the balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.
The epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.

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

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

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

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

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

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

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

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

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

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

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

As the active ester compound, a commercially available product may be used. Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene type diphenol structure; aromatics. "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Co., Ltd.) as active ester compounds containing a structure; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured); 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 characteristics such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is preferable. More preferred.
The ester equivalent of the active ester compound shall be a value measured by a method according to JIS K 0070: 1992.

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

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

Specifically, the phenol curing agent is a polyhydric phenol compound such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol. , 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; 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 (hydroxyl equivalents in the case of phenol curing agents) are not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
The functional group equivalents of other curing agents (hydroxyl equivalents in the case of phenol curing agents) shall be values measured by a method according to JIS K 0070: 1992.

The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..

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

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

The 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.

(Inorganic filler)
The sealing resin composition of the present embodiment contains an inorganic filler. The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mulite. , Titania, talc, clay, mica and other inorganic materials. 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 is preferably 0.2 μm to 100 μm, and more preferably 0.5 μm to 50 μm. When the average particle size 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 is 100 μm or less, the filling property 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 is 55% by volume to 80% by volume of the entire sealing resin composition from the viewpoint of controlling the dielectric adjacency of the cured product of the sealing resin composition. It is preferably 63% by volume to 78% by volume, more preferably 68% by volume to 75% 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.

(Polyether-modified silicone)
The polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group is introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond. As the polyether-modified silicone, one type may be used alone or two or more types may be used in combination.
The polyether-modified silicone may be a side chain-modified polyether-modified silicone or a terminal-modified polyether-modified silicone. Among these, the polyether-modified silicone is preferably a side chain-modified polyether-modified silicone from the viewpoint of suppressing poor appearance of the cured product.

An example of a polyether-modified silicone is an epoxy-polyether-modified silicone. The epoxy-polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group and an epoxy group are introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
The epoxy / polyether-modified silicone may be a side chain-modified epoxy / polyether-modified silicone, a terminal-modified epoxy / polyether-modified silicone, or a side-chain and terminal-modified epoxy / polyether-modified silicone. It may be silicone. Polydimethylsiloxane is preferred as the main skeleton of the epoxy-polyether-modified silicone. As the polyether group, a polyether group obtained by polymerizing one or both of ethylene oxide and propylene oxide is preferable.
The epoxy-polyether-modified silicone is a side chain in which a polyether group (preferably a polyether group in which one or both of ethylene oxide and propylene oxide are polymerized) and an epoxy group are present in the side chain of the silicone (preferably polydimethylsiloxane). It is preferably a modified epoxy / polyether modified silicone. Examples of commercially available products of the epoxy / polyether-modified silicone include "SIM768E" manufactured by Momentive Performance Materials.

The viscosity of the polyether-modified silicone at 25 ° C. is not particularly limited. The viscosity (25 ° C.) of the polyether-modified silicone is preferably 0.50 Pa · s to 40.00 Pa · s from the viewpoint of suppressing poor appearance of the cured product of the sealing resin composition and from the viewpoint of heat resistance, and is 0. .50 Pa · s to 20.00 Pa · s is more preferable, 1.00 Pa · s to 10.00 Pa · s is further preferable, and 1.00 Pa · s to 4.00 Pa · s is particularly preferable.
The viscosity of the polyether-modified silicone at 25 ° C. is a value measured by a method according to JIS Z 8803: 2011. Specifically, for example, a rheometer (TA instruments, product name "ARES-G2") is used as a measuring device, and measurement is performed under the conditions of a temperature of 25 ° C., a strain of 2%, and 1 Hz.

The glass transition temperature of the polyether-modified silicone is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and even more preferably 30 ° C. or lower, from the viewpoint of suppressing poor appearance of the cured product.
Here, the glass transition temperature of the polyether-modified silicone is a temperature obtained from the DSC curve obtained by differential scanning calorimetry (DSC), and is defined in JIS K7121: 1987, "Method for Measuring Transition Temperature of Plastics", "Glass". It is the "external glass transition start temperature" described in "How to determine the transition temperature".
Specifically, for example, TA instruments, product name "Q2000") is used as a measuring device, and measurement is performed under a nitrogen atmosphere at a heating rate of 5 ° C./min.

From the viewpoint of curability, the content of the polyether-modified silicone is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the epoxy resin. It is more preferably 8 parts by mass to 20 parts by mass.
Further, the content of the polyether-modified silicone is preferably 0.1 part by mass to 3 parts by mass with respect to 100 parts by mass of the inorganic filler, and is 0.4 mass by mass, from the viewpoint of suppressing poor appearance of the cured product. It is more preferably parts to 2.5 parts by mass, and further preferably 0.8 parts by mass to 2 parts by mass.
Further, the content of the polyether-modified silicone is preferably 0.07% by mass to 2.5% by mass, preferably 0.3% by mass to 2.5% by mass, based on the entire sealing resin composition, from the viewpoint of moldability. It is more preferably 1.8% by mass, and even more preferably 0.6% by mass to 1.2% by mass.

(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; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) ) Hosphin, Tris (alkyl / alkoxyphenyl) phosphin, Tris (dialkylphenyl) phosphin, Tris (trialkylphenyl) phosphin, Tris (tetraalkylphenyl) phosphin, Tris (dialkoxyphenyl) phosphin, Tris (trialkoxyphenyl) phosphine , Tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine and other tertiary phosphines; Phosphine compound; the tertiary phosphine or the phosphine compound, in which maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 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, diazophenylmethane and other compounds with π bonds Compound having intramolecular polarization formed by adding the above; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol. , 4-Io ratherated Phenol, 3-Iyoated Phenol, 2-Iodized Phenol, 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 A compound having intramolecular polarization obtained by reacting with a halogenated phenol compound such as -4'-hydroxybiphenyl and then undergoing a step of dehalogenating; a tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-p- Tetra-substituted phosphonium and tetra-substituted borate without a phenyl group bonded to a boron atom such as trillborate; salt of tetraphenylphosphonium and a phenol compound; salt of tetraalkylphosphonium and a partial hydrolyzate of aromatic carboxylic acid anhydride, 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 with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). More preferably, it is 1 part by mass to 15 parts by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

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

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

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

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

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

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

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

When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1 part by mass. More preferably, parts by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

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

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

(Colorant)
The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide.
The content of the colorant can be appropriately selected depending on 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, a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.

The sealing resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the sealing resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the sealing resin composition is in the 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.

(Use of sealing resin composition)
The sealing resin composition can be applied to, for example, an application for sealing an element in the manufacture of an electronic component device described later. The sealing resin composition is also suitably used in a mounting technique for sealing a relatively large area (for example, performing a sealing step before individualizing a package). Examples of such mounting technology include wafer level packages (hereinafter, also referred to as “WLP”) such as FO-WLP (Fan Out Wafer Level Package) and FI-WLP (Fan In Wafer Level Package). That is, the sealing resin composition of the present embodiment is also preferably used for wafer level packaging.
Examples of the method for sealing the semiconductor chip using the sealing resin composition include a compression molding method, a transfer molding method, an injection molding method, and the like, and any of these can be adopted. Among them, the sealing resin composition of the present embodiment is preferably used for transfer molding.

The material of the support when sealing with the sealing resin composition is not particularly limited. For example, semiconductors such as silicon, glass, ceramics and the like can be mentioned. The shape of the support is not particularly limited, and may be a disk shape (wafer) or another shape.
The material of the wafer used for WLP is usually a crystal of a semiconductor material, and a single crystal of silicon is generally used. The size of the wafer is not particularly limited, and is, for example, 6 inches to 12 inches, preferably 10 inches to 12 inches in diameter.

<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 (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors). , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition. Chip module, etc .; An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, a resin composition for sealing is provided. 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.

Further, the electronic component device according to the present embodiment may be manufactured by a wafer level package (WLP). That is, in the electronic component device of the present embodiment, after mounting a plurality of elements (active elements such as semiconductor chips, transistors, diodes, psyllistas, passive elements such as capacitors, resistors, coils, etc.) on a wafer, A plurality of elements may be collectively sealed with a sealing resin composition, and each sealed element may be individualized. The WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package.WLCSP) (also referred to as Wafer Level Chip Size Package).

<Manufacturing method of electronic component equipment>
The method for manufacturing an electronic component device according to an embodiment of the present disclosure includes a step of arranging an element on a support member and a step of sealing the element with the sealing resin composition of the present disclosure.
When the electronic component device is manufactured by WLP, the manufacturing method of the electronic component device includes a step of arranging a plurality of elements on a wafer and the plurality of elements in the sealing resin composition of the present disclosure. The manufacturing method may include a step of collectively sealing and a step of individualizing each sealed element (that is, including wafer level packaging).

The method of carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used. The types of wafers and elements used when manufacturing electronic component devices by WLP are not particularly limited, and wafers and devices generally used for manufacturing 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 transfer molding method such as a low-pressure transfer molding method, an injection molding method, and a compression molding method. Among these, the 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. Table 1 also shows the volume-based content of the entire inorganic filler with respect to the entire sealing resin composition.

-Epoxy resin 1: Biphenyl type epoxy resin, epoxy equivalent 186 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")
-Epoxy resin 2: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Co., Ltd., product name "1032H60")

-Curing agent 1: Active ester compound (DIC Corporation, product name "EXB-8")
-Curing agent 2: Phenol curing agent, biphenyl aralkyl resin, hydroxyl group equivalent 203 g / eq (Meiwa Kasei Co., Ltd., product name "MEHC7851SS")

-Curing accelerator 1: triphenylphosphine / 1,4-benzoquinone adduct-Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
-Coupling agent 3: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Release agent 1: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant 1: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

-Silicone 1: Side chain modified epoxy / polyether modified silicone, viscosity (25 ° C): 1.50 Pa · s (Momentive Performance Materials, product name "SIM768E")
-Silicone 2: Side chain modified epoxy / polyether modified silicone, viscosity (25 ° C): 2.40 Pa · s (Toray Dow Corning Co., Ltd., product name "BY16-876")
-Silicone 3: Side chain modified epoxy / polyether modified silicone, viscosity (25 ° C): 0.55 Pa · s (Toray Dow Corning Co., Ltd., product name "BY16-870")
-Silicone 4: Epoxy-modified silicone, viscosity (25 ° C): 6.00 Pa · s (Toray Dow Corning Co., Ltd., product name "BY16-839")
-Silicone 5: Epoxy-modified silicone, viscosity (25 ° C.): 17.00 Pa · s (Toray Dow Corning Co., Ltd., product name "SF-8413EG")
-Silicone 6: Side chain modified epoxy / polyether modified silicone, viscosity (25 ° C): 3.10 Pa · s (Toray Dow Corning Co., Ltd., product name "SF8421 EG")

-Inorganic filler 1: Fused silica (average particle size 4.5 μm)
-Inorganic filler 2: fused silica (average particle size 0.6 μm)

<Performance evaluation of sealing resin composition>
(Liquidity: Spiral flow)
Using a spiral flow measuring mold according to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. inch) was sought. The results are shown in Table 1.

(Melting viscosity)
The sealing resin composition was heated and melted, and the melt viscosity at 175 ° C. was measured using an enhanced flow tester. The results are shown in Table 1.

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

(Appearance evaluation)
The appearance was evaluated as follows.
A mold and a release film were prepared for molding a laminated body in which a cured resin product having a thickness of 300 μm was laminated on a silicon wafer having a diameter of 12 inches by transfer molding. Using this mold, mold release film, 12-inch silicon wafer, and sealing resin composition, the mold is sealed on the silicon wafer under the conditions of a mold temperature of 175 ° C., a clamping pressure of 0.7 MPa, and a curing time of 240 seconds. A laminate in which the cured product of the release resin composition was laminated was formed. The flow mark was evaluated by visually observing the cured product surface of this laminated body from the vertical direction. The evaluation criteria are as follows, and the results are shown in Table 1.

-Evaluation criteria-
A (○): Almost no flow mark was seen.
B (Δ): A flow mark was observed, but it was not remarkable.
C (x): Flow marks were prominently seen.

The sealing resin composition of the example reduced the dielectric loss tangent of the cured product and suppressed the appearance defect of the cured product as compared with the sealing resin composition of the comparative example.

Claims (9)

Epoxy resin and
A curing agent containing an active ester compound and
Inorganic filler and
With polyether-modified silicone,
A resin composition for sealing containing. The sealing resin composition according to claim 1, wherein the polyether-modified silicone has a viscosity at 25 ° C. of 1.00 Pa · s to 4.00 Pa · s. The sealing resin composition according to claim 1 or 2, wherein the content of the inorganic filler is 55% by volume to 80% by volume with respect to the entire sealing resin composition. The sealing resin composition according to any one of claims 1 to 3, which is for a wafer level package. The sealing resin composition according to any one of claims 1 to 4, which is for transfer molding. 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 5, which seals the element, and the cured product.
Electronic component device equipped with. The process of arranging the element on the support member and
The step of sealing the element with the sealing resin composition according to any one of claims 1 to 5.
Manufacturing method of electronic component equipment including. The process of arranging multiple elements on the wafer,
A step of collectively sealing the plurality of elements with the sealing resin composition according to any one of claims 1 to 5.
The process of individualizing each sealed element and
Manufacturing method of electronic component equipment including. The method for manufacturing an electronic component device according to claim 7 or 8, wherein the sealing step is a step of sealing by transfer molding.