JP2023183768A - Sealing resin composition - Google Patents

Abstract

To provide a sealant whose cured product has both a low linear expansion coefficient and a low elastic modulus, resulting in a superior appearance.SOLUTION: A sealing resin composition includes (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a low stress material. The component (D) includes at least one first low stress material where the distance of the Hansen solubility parameter with the component (A) is 8.5 MPa1/2 or more and 9.9 MPa1/2 or less.SELECTED DRAWING: None

Description

The present invention relates to a sealing resin composition.

As a technique related to a sealing resin composition, there is a technique described in Patent Document 1 (Japanese Patent Laid-Open No. 2002-146163). The same document describes a sealing product containing an epoxy resin, a phenol resin, a polyglycerin fatty acid ester, and an inorganic filler as essential components, and each containing the polyglycerin fatty acid ester and the inorganic filler in specific proportions to the resin composition. (Claim 1) and specifically describes decaglyceryl pentaoleate as the polyglycerin fatty acid ester (Paragraph 0013, Examples 1 to 3). The same document also states that the resin composition for encapsulation in the same document has excellent moldability and electrical properties, and has good fillability and workability, so this resin composition is used for encapsulating electronic components. It is stated that by doing so, it is possible to improve both the workability and performance of the semiconductor sealing device (paragraph 0034).

Japanese Patent Application Publication No. 2002-146163

As a result of the inventors' study of the technology described in the above patent document, it is clear that there is room for improvement in terms of achieving both a low coefficient of linear expansion and a low modulus of elasticity of the cured product, as well as providing a desirable appearance. Became.

According to the present invention, the following sealing resin composition, cured product, wafer level package, panel level package, and electronic device are provided.
[1] (A) Epoxy resin,
(B) a curing agent;
(C) an inorganic filler, and (D) a low stress material,
A sealing resin in which the component (D) contains one or more first low stress materials whose Hansen solubility parameter distance with the component (A) is 8.5 MPa ^1/2 or more and 9.9 MPa ^{1/2 or} less. Composition.
[2] The sealing resin composition according to [1], wherein the first low stress material contains triglyceride.
[3] The sealing resin composition according to [2], wherein all three fatty acid residues in the triglyceride are the same.
[4] The content of the component (D) in the encapsulating resin composition is 0.1% by mass or more and 2.5% by mass or less based on the entire encapsulating resin composition, [1 ] to [3] The sealing resin composition according to any one of [3].
[5] The sealing according to any one of [1] to [4], wherein the component (A) contains at least one selected from the group consisting of biphenylaralkyl epoxy resin and triphenylmethane epoxy resin. Resin composition for use.
[6] The sealing resin composition according to any one of [1] to [5], which is used for sealing a wafer level package (WLP) or a panel level package (PLP).
[7] The sealing resin composition according to any one of [1] to [6], which is in the form of granules.
[8] A cured product that is a cured product of the sealing resin composition according to any one of [1] to [7].
[9] A wafer level package in which a plurality of electronic components are collectively sealed with the sealing resin composition according to any one of [1] to [7].
[10] A panel level package in which a plurality of electronic components are collectively sealed with the sealing resin composition according to any one of [1] to [7].
[11] An electronic device in which the wafer level package according to [9] is diced.
[12] An electronic device in which the panel level package according to [10] is separated into pieces.

According to the present invention, it is possible to obtain a sealing material in which a cured product has both a low coefficient of linear expansion and a low modulus of elasticity, and has a desirable appearance.

1 is a cross-sectional view schematically showing an example of a method for manufacturing an electronic device according to an embodiment. 1 is a cross-sectional view schematically showing an example of a method for manufacturing an electronic device according to an embodiment.

In this embodiment, the composition may contain each component alone or in combination of two or more.
In this specification, "~" indicating a numerical range represents the above or below, and includes both ends of the numerical value.

(Sealing resin composition)
In this embodiment, the sealing resin composition (hereinafter also simply referred to as "resin composition") contains the following components (A) to (D).
(A) epoxy resin,
(B) a curing agent;
(C) an inorganic filler, and (D) a low stress material, and component (D) has a Hansen solubility parameter distance from component (A) of 8.5 MPa ^1/2 or more and 9.9 MPa ^1/2 or less. Contains one or more types of first low stress materials.

The present inventor investigated reducing both the linear expansion coefficient and elastic modulus of the cured product. As a result, the resin composition contained a combination of components (A) to (D), and the distance of Hansen solubility parameter (hereinafter also referred to as "ΔHSP") between component (D) and component (A) was determined. By configuring the composition to include one or more types of first low stress materials within the range of , it is possible to suitably lower both the linear expansion coefficient and elastic modulus of the cured product, which are properties that are originally in a trade-off relationship. I discovered something new.
Although it is not necessarily clear why the coefficient of linear expansion and the modulus of elasticity decrease by making the resin composition have the above structure, the degree of dispersion of the first low stress material in the resin composition becomes preferable, and the degree of dispersion of the first low stress material in the resin composition becomes favorable. It is conceivable that domains derived from the first low stress material are generated in a preferable size.
That is, the present inventor newly focused on the ΔHSP between the component (A) and the first low stress material as an index for lowering the coefficient of linear expansion and the modulus of elasticity. By using the first low stress material having a ΔHSP in a specific range in combination and using these in combination with components (B) and (C), the linear expansion coefficient and elastic modulus of the cured product are preferably reduced. It has been found that a resin composition can be obtained.

In this embodiment, the ΔHSP between component (A) and the first low stress material is 8.5 MPa 1/2 or more, preferably 8.7 MPa ^1/2 or more, more preferably 8.7 MPa ^1/2 or more, from the viewpoint of decreasing the linear expansion coefficient. is 8.9 MPa ^1/2 or more.
Further, from the viewpoint of making the appearance of the cured product preferable, the ΔHSP between component (A) and the first low stress material is 9.9 MPa ^1/2 or less, preferably 9.6 MPa ^1/2 or less, and Preferably it is 9.3 MPa ^1/2 or less.

Here, Hansen's solubility parameter (HSP) is an index representing the solubility of a certain substance in another substance. In HSP, solubility is expressed as a three-dimensional vector. This three-dimensional vector can typically be expressed by a dispersion term (δd), a polarity term (δp), and a hydrogen bond term (δh). It can be determined that substances with similar vectors have high solubility. It is possible to judge the similarity of vectors by ΔHSP.

The computer software HSPiP, developed by Hansen and Abbott, includes the ability to calculate ΔHSP and a database containing Hansen parameters for various resins and solvents or non-solvents. The HSP value used in this specification can be calculated using software called HSPiP (Hansen Solbility Parameters in Practice). For example, the values listed in the Solvent list and Polymer list included in HSPiP 3rd version may be corrected to 25° C. and referred to. Here, resins and solvents or nonsolvents that are not listed in the solvent list can be calculated by an estimation method using a neural network method called Y-MB. By inputting the molecular structure into the Y-MB calculation software included with HSPiP, it is automatically decomposed into atomic groups and the HSP value and molecular volume are calculated.

ΔHSP is specifically represented by R ² shown in the following formula (1).
In this embodiment, ΔHSP is calculated by the following formula (1), for example, when the HSP of component (A) is (d1, p1, h1) and the HSP of the first low stress material is (d2, p2, h2). ) can be calculated.

In the present embodiment, the resin composition includes a combination of components (A) to (D), and component (D) includes one or more types of first low stress materials whose ΔHSP with component (A) is within a specific range. Therefore, the coefficient of linear expansion and modulus of elasticity of the cured product, which are originally in a trade-off relationship, can both be suitably reduced. Therefore, even when sealing a large area such as WLP or PLP, warping of the base material can be effectively suppressed.
Hereinafter, the components contained in the resin composition will be explained in more detail.

(Component (A))
Component (A) is an epoxy resin.
Epoxy resins include, for example, biphenyl-type epoxy resins such as biphenylaralkyl-type epoxy resins; bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and tetramethylbisphenol F-type epoxy resins; stilbene-type epoxy resins; Novolak-type epoxy resins such as novolak-type epoxy resins and cresol novolac-type epoxy resins; polyfunctional epoxy resins such as triphenylmethane-type epoxy resins exemplified by triphenolmethane-type epoxy resins, alkyl-modified triphenolmethane-type epoxy resins, etc.; Phenol aralkyl epoxy resins such as phenol aralkyl epoxy resins having a phenylene skeleton, naphthol aralkyl epoxy resins having a phenylene skeleton, phenol aralkyl epoxy resins having a biphenylene skeleton, naphthol aralkyl epoxy resins having a biphenylene skeleton; dihydroxynaphthalene type epoxy resins; Epoxy resin, naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer; triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate; and dicyclopentadiene-modified phenol One or more selected from the group consisting of bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as type epoxy resins.

From the viewpoint of suppressing warping of the cured product of the resin composition and improving the balance of various properties such as fillability, heat resistance, and moisture resistance, component (A) is preferably a biphenylaralkyl type epoxy resin and a triphenylmethane type epoxy resin. It contains at least one selected from the group consisting of resins.

In component (A), the polarity term (P), hydrogen term (H), and dispersion term (D) of HSP can be set to values such that ΔHSP with the first low stress material falls within the above range. can.
The polar term (P) of the HSP of component (A) is preferably 3.0 MPa ^1/2 or more, more preferably 4.0 MPa ^1/2 or more, still more preferably 5.0 MPa ^1/2 or more.
Moreover, the polar term (P) of the HSP of component (A) is 7.5 MPa ^1/2 or less, more preferably 6.5 MPa ^1/2 or less, and still more preferably 5.5 MPa ^1/2 or less.

The hydrogen term (H) of the HSP of component (A) is preferably 2.0 MPa ^1/2 or more, more preferably 3.0 MPa ^1/2 or more, still more preferably 4.0 MPa ^1/2 or more.
Further, the hydrogen term (H) of the HSP of component (A) is 6.5 MPa ^1/2 or less, more preferably 5.5 MPa ^1/2 or less, still more preferably 4.5 MPa ^1/2 or less.

The HSP dispersion term (D) of component (A) is preferably 18.0 MPa ^1/2 or more, more preferably 19.0 MPa ^1/2 or more, and still more preferably 20.3 MPa ^{1/2 or} more.
Further, the dispersion term (D) of the HSP of component (A) is 22.5 MPa ^1/2 or less, more preferably 21.5 MPa ^1/2 or less, still more preferably 20.5 MPa ^1/2 or less.
This makes it possible to achieve both a low coefficient of linear expansion and a low modulus of elasticity.

Here, the HSP of component (A) is calculated by the method described above.
Further, when component (A) contains two or more types of epoxy resins, each term of HSP of component (A) can be determined as the sum of the products of the HSP value and mass fraction of each component.

From the viewpoint of improving moldability, the content of component (A) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass based on the entire resin composition. % or more, even more preferably 5% by mass or more.
In addition, from the viewpoint of suppressing shrinkage during molding, the content of component (A) in the resin composition is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 10% by mass or less based on the entire resin composition. Preferably it is 8% by mass or less.

(Component (B))
Component (B) is a curing agent.
Examples of the curing agent include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4' - Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis(4-aminophenyl)phenylmethane, 1 , 5-diaminonaphthalene, metaxylene diamine, paraxylene diamine, 1,1-bis(4-aminophenyl)cyclohexane, dicyanodiamide, and other amines;
Resol-type phenolic resins such as aniline-modified resol resins and dimethyl ether resol resins;
Novolac type phenolic resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin;
Multifunctional phenolic resin such as trihydroxyphenylmethane phenolic resin;
Phenol aralkyl resins such as phenylene skeleton-containing phenol aralkyl resins and biphenylene skeleton-containing phenol aralkyl resins;
A phenolic resin having a fused polycyclic structure such as a naphthalene skeleton or anthracene skeleton;
Phenolic resins other than those listed above;
Polyoxystyrene such as polyparaoxystyrene;
Alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenonetetracarboxylic acid (BTDA), etc. Acid anhydrides, etc., including aromatic acid anhydrides;
Examples include one or more selected from the group consisting of polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.
In addition, component (B) preferably contains at least one selected from the group consisting of a phenol novolac resin, a trisphenylmethane mixed phenolic resin, and a biphenylaralkyl phenolic resin, and more preferably a trisphenylmethane mixed phenolic resin and Contains biphenylaralkyl phenolic resin.

From the viewpoint of improving curing properties, the content of component (B) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and Preferably it is 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more.
In addition, from the viewpoint of improving fluidity and filling properties during molding, the content of component (B) in the resin composition is preferably 10.0% by mass or less, more preferably 10.0% by mass or less, based on the entire resin composition. is 7.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less.

(Component (C))
Component (C) is an inorganic filler. Examples of component (C) include silica such as fused silica and crystalline silica; alumina; talc; titanium oxide; silicon nitride; and aluminum nitride.
From the viewpoint of excellent versatility, component (C) preferably contains silica, and more preferably silica.
Examples of the shape of silica include spherical silica such as fused spherical silica, and crushed silica.

The average particle diameter d ₅₀ of component (C) is preferably 0.5 μm or more, more preferably 1.0 μm or more from the viewpoint of suppressing shrinkage during molding.
Furthermore, from the viewpoint of improving filling properties during molding, the average particle diameter _d50 of component (C) is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and even more preferably 5 μm or less. It is.

Here, the average particle size d ₅₀ of component (C) is the average particle size measured with a commercially available laser particle size distribution analyzer (for example, SALD-7000 manufactured by Shimadzu Corporation).

From the viewpoint of suppressing warpage, the content of component (C) in the resin composition is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass, based on the entire resin composition. That's all.
In addition, from the viewpoint of improving fluidity and filling properties during molding, the content of component (C) in the resin composition is preferably 98% by mass or less, more preferably 95% by mass or less, based on the entire resin composition. % or less, more preferably 90% by mass or less, even more preferably 88% by mass or less.

(Component (D))
Component (D) is a low stress material. As mentioned above, component (D) contains one or more of the above-mentioned first low stress materials. Moreover, component (D) may further contain other low stress materials.

In the first low stress material, the polar term (P), hydrogen term (H), and dispersion term (D) of HSP can be set to values such that ΔHSP with component (A) falls within the above range. can.
The polar term (P) of the HSP of the first low stress material is, for example, 0.5 MPa ^1/2 or more, preferably 1.0 MPa ^1/2 or more, and, for example, 3.5 MPa ^1/2 or less. , preferably 2.0 MPa ^1/2 or less.
The hydrogen term (H) of the HSP of the first low stress material is, for example, 0.05 MPa ^1/2 or more, preferably 1.2 MPa ^1/2 or more, and, for example, 3.6 MPa ^1/2 or less. , preferably 2.0 MPa ^1/2 or less.
Further, the HSP dispersion term (D) of the first low stress material is, for example, 12.0 MPa ^1/2 or more, preferably 15.0 MPa ^1/2 or more, and, for example, 20.0 MPa ^1/2 or less. and preferably 18.0 MPa ^1/2 or less.

When component (D) includes two or more types of first low stress materials, each term of HSP of the first low stress material can be determined as the product of the HPS value and mass fraction of each component.

The first low stress material preferably contains triglyceride, more preferably triglyceride, from the viewpoint of reducing the coefficient of linear expansion and reducing the modulus of elasticity.
The three fatty acid residues in one molecule of triglyceride may be the same type or different types, and from the viewpoint of decreasing the coefficient of linear expansion and decreasing the elastic modulus, preferably all three fatty acid residues are the same.

The three fatty acid residues in the triglyceride are independently saturated or unsaturated fatty acid residues. Triglycerides may contain three saturated fatty acid residues, one unsaturated fatty acid residue and two saturated fatty acid residues, or two unsaturated fatty acid residues. It may contain a group and one saturated fatty acid residue, or it may contain three unsaturated fatty acid residues.

The number of carbon atoms in the fatty acid residue in the triglyceride is, for example, 8 or more, preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, even more preferably 16 or more, and, for example, 24 or less. and is preferably 22 or less, more preferably 20 or less.
Specific examples of fatty acids in fatty acid residues include palmitic acid (number of carbons: number of double bonds = C16:0), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), Linolenic acid (C18:3) is mentioned.
Further, the fatty acid may have a substituent, and examples of such fatty acid residues include 12-hydroxystearic acid and 2-ethylhexanoic acid.

From the viewpoint of improving dispersibility in the resin composition, triglyceride is liquid at 25°C, that is, has fluidity at 25°C.
From the same viewpoint, the iodine value of the triglyceride is preferably 100 or more, more preferably 105 or more, and still more preferably 110 or more.
Further, from the viewpoint of improving heat resistance, the iodine value of the triglyceride is preferably 250 or less, preferably 230 or less, more preferably 210 or less, and still more preferably 180 or less.

The first low stress material may include a mixture of two or more triglycerides.
Moreover, it is also preferable that the first low stress material is a vegetable oil from the viewpoint of improving dispersibility in the resin composition.
Specific examples of vegetable oils include one or two selected from the group consisting of soybean oil, linseed oil, rapeseed oil, sunflower oil, corn oil, olive oil, safflower oil, rice oil, palm oil, coconut oil, sesame oil, and perilla oil. The above can be mentioned. From the viewpoint of improving dispersibility in the composition, the first low stress material is preferably one or more selected from the group consisting of soybean oil, linseed oil, rapeseed oil, and sunflower oil.

From the viewpoint of suppressing warpage, the content of the first low stress material in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and Preferably it is 1.0% by mass or more, even more preferably 1.5% by mass or more.
Further, from the viewpoint of improving mechanical strength, the content of the first low stress material in the resin composition is preferably 3.0% by mass or less, more preferably 2.5% by mass, based on the entire resin composition. The content is preferably 2.3% by mass or less.

Among components (D) other than the first low stress material, for example, silicone oil may be mentioned.
Specific examples of the silicone oil include organopolysiloxane. Here, the organopolysiloxane has functional groups such as epoxy, amino, methoxy, phenyl, carboxy, hydroxy, alkyl, vinyl, mercapto, and polyether groups introduced into its structure. You may also use The functional group introduced into the structure of the organopolysiloxane is preferably at least one selected from the group consisting of a carboxy group, an epoxy group, and a polyether group. Commercially available products containing silicone oil include, for example, FZ-3730 and BY-750 manufactured by Dow Toray Industries.

The total content of component (D) containing the first low stress material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more based on the entire resin composition, from the viewpoint of suppressing warpage. , more preferably 1.0% by mass or more.
Further, from the viewpoint of improving mechanical strength, the total content of component (D) including the first low stress material is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, and even more preferably It is 2.3% by mass or less.

The resin composition may further contain components other than components (A) to (D). For example, the resin composition may further include one or more selected from the group consisting of a curing accelerator, a coupling agent, a mold release agent, an ion catcher, a colorant, and other additives.

(hardening accelerator)
As the curing accelerator, for example, one that accelerates the crosslinking reaction between the epoxy resin of component (A) and the curing agent of component (B) can be used. Examples of curing accelerators include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, and other phosphorus atom-containing compounds; 1,8-diazabicyclo [5.4.0] One or more nitrogen atom-containing compounds selected from amidines, tertiary amines, quaternary salts of the above-mentioned amidines and amines, exemplified by undecene-7, benzyldimethylamine, 2-methylimidazole, etc. Two or more types can be included.

From the viewpoint of improving curability, the content of the curing accelerator in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the entire resin composition. be.
In addition, from the viewpoint of increasing the production stability of the cured product, the content of the curing accelerator in the resin composition is preferably 1% by mass or less, more preferably 0.5% by mass, based on the entire resin composition. % or less, more preferably 0.3% by mass or less.

(coupling agent)
Coupling agents include various epoxysilanes such as γ-glycidoxypropylmethyldimethoxysilane, mercaptosilanes, aminosilanes such as phenylaminopropyltrimethoxysilane and phenylaminosilane, alkylsilanes, ureidosilanes, vinylsilanes, and methacrylsilanes. One or more types selected from known coupling agents such as silane compounds; titanium compounds; aluminum chelates; and aluminum/zirconium compounds can be included.
From the viewpoint of improving the strength and toughness of the cured product in a well-balanced manner, the coupling agent is preferably a silane coupling agent, and more preferably at least one of aminosilane and epoxysilane.

From the viewpoint of improving curability, the content of the coupling agent in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the entire resin composition. More preferably, it is 0.3% by mass or more.
In addition, from the viewpoint of increasing the production stability of the cured product, the content of the coupling agent in the resin composition is preferably 2% by mass or less, more preferably 1% by mass or less, based on the entire resin composition. , more preferably 0.7% by mass or less.

Examples of mold release agents include natural waxes such as carnauba wax; oxidized polyethylene waxes, montanic acid ester waxes, and reaction products of polycondensates of 1-alkenes (C>10)/maleic anhydride and stearyl alcohol. It can contain one or more selected from synthetic wax; higher fatty acids such as zinc stearate and metal salts thereof; and paraffin.
The content of the mold release agent in the resin composition is preferably 0.05% by mass or more, more preferably The content is 0.1% by mass or more, preferably 2% by mass or less, and more preferably 1% by mass or less.

The ion catcher includes, for example, hydroxytalsite.
The content of the ion catcher in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more based on the entire resin composition, from the viewpoint of improving the reliability of the cured product. The content is preferably 1% by mass or less, more preferably 0.5% by mass or less.

The coloring agent includes, for example, one or more types selected from the group consisting of carbon black, black titanium oxide, red iron oxide, organic pigments, and the like.
The content of the colorant in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass, based on the entire resin composition, from the viewpoint of making the appearance of the cured product more preferable. It is at least 1% by mass, preferably at most 1% by mass, and more preferably at most 0.5% by mass.

Further, other additives include, for example, flame retardants or antioxidants other than components (A) to (D).

Next, the properties, physical properties, etc. of the resin composition will be explained.
The properties of the resin composition are, for example, liquid or solid, and from the viewpoint of ensuring favorable manufacturing stability during molding even when forming a sealing material on a large area base material, it is preferably solid. granular form, more preferably granular form. The granular resin composition may be, for example, an aggregate obtained by hardening resin composition powders (powder-like kneaded material) together, or a granulated product obtained by a known granulation method.

When the resin composition is in the form of granules, the average particle diameter is preferably 0.03 mm or more, more preferably 0.05 mm or more, and even more preferably 0.1 mm, from the viewpoint of improving the handleability of the resin composition. That's all.
Further, from the viewpoint of improving filling properties, the average particle size of the resin composition is preferably 3.0 mm or less, more preferably 2.5 mm or less, and still more preferably 2.0 mm or less.

Here, the particle size distribution of the resin composition can be determined by measuring the particle size distribution of particles on a volume basis using a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000, manufactured by Shimadzu Corporation).

(linear expansion coefficient)
The linear expansion coefficient CTE1 of the resin composition at a temperature below the glass transition temperature is preferably 9.0 ppm/°C or less, more preferably 8.5 ppm/°C or less, and even more preferably 8.0 ppm from the viewpoint of warpage suppression. /℃ or less.
Although the lower limit of CTE1 is not limited, it is preferably equal to or higher than the linear expansion coefficient of the silicon wafer used, and may be, for example, 3.5 ppm/° C. or higher.
Here, the linear expansion coefficient is specifically measured by the following method.

(Method of measuring linear expansion coefficient)
The resin composition is injection molded using a transfer molding machine at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds to obtain a test piece with a long side of 15 mm x a short side of 4.5 mm x a thickness of 3 mm. . After post-curing the test piece at 175°C for 4 hours, it was measured in compression mode using a thermomechanical analyzer (manufactured by Hitachi High-Tech Science, TMA7100), at a temperature range of -60°C to 400°C, at a heating rate of 5°C/ Measurements are carried out under conditions of 30 minutes. From the measurement results, the average coefficient of linear expansion from 50°C to 70°C is calculated and defined as CTE1.

(bending modulus)
The flexural modulus of the cured product of the resin composition at 25°C is preferably 10 GPa or more, more preferably 15 GPa or more, still more preferably 20 GPa or more, from the viewpoint of improving handling properties.
Further, from the viewpoint of suppressing warpage, the flexural modulus of the cured resin composition at 25° C. is preferably 35 GPa or less, more preferably 30 GPa or less, and still more preferably 25 GPa or less.
The flexural modulus of the cured product is measured by the method described below.

(bending strength)
The bending strength at 25° C. of the cured product of the resin composition may be, for example, 100 MPa or more, preferably 130 MPa or more, and more preferably 140 MPa or more, from the viewpoint of improving mechanical strength.
Further, from the viewpoint of preventing brittle fracture due to the cured product being too hard, the bending strength at 25°C of the cured product of the resin composition is preferably 250 MPa or less, more preferably 220 MPa or less, and still more preferably 180 MPa or less. .
The flexural modulus and flexural strength of the cured product are measured by the following method.

(Method for measuring bending modulus and bending strength)
The resin composition is injection molded using a transfer molding device at a mold temperature of 175° C., an injection pressure of 9.8 MPa, and a curing time of 180 seconds to obtain a molded article with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm. The obtained molded article is post-cured at 175° C. for 4 hours to obtain a test piece. The flexural modulus and flexural strength of the obtained test piece at 25° C. are measured according to JIS K 6911.

The resin composition is preferably used for sealing a wafer level package (WLP) or a panel level package (PLP).
Typically, WLP is a process in which everything from rewiring, electrode formation, resin sealing, and dicing is performed in the wafer process, and the size of the semiconductor chip that is finally cut from the wafer becomes the size of the package. say.
Further, PLP is specifically a technology for batch manufacturing electronic devices using a panel-shaped substrate that is larger than a normal wafer (for example, a 12-inch wafer) used for WLP.
Both WLP and PLP involve bulk encapsulation of a large area of a substrate, rather than encapsulation of relatively small semiconductor chips one by one.

Next, a method for producing the resin composition will be explained. In this embodiment, the resin composition can be obtained, for example, by mixing the above-mentioned components by a known method, melt-kneading the mixture with a kneader such as a roll, kneader, or extruder, cooling it, and then pulverizing it. Can be done. Further, if necessary, after the pulverization in the above method, the product may be compressed into a tablet shape. Further, the degree of dispersion, fluidity, etc. of the obtained resin composition may be adjusted as appropriate.

(hardened body)
The main cured product is a cured product of the resin composition in this embodiment. The cured product is suitably used, for example, as a sealing material.
Specifically, the cured product includes a part composed of component (C) and a part composed of other organic components. Among these, the portion composed of the organic component preferably has a domain containing the first low stress material and a domain containing the component (A) from the viewpoint of decreasing the coefficient of linear expansion and the modulus of elasticity. The size of the domain containing the first low stress material may be, for example, about several μm to several tens of μm.

(WLP, PLP)
In WLP and PLP, a plurality of electronic components are collectively sealed with the resin composition in this embodiment.
Moreover, the electronic device is one in which the above-mentioned WLP or PLP is separated into pieces.

An example of a method for manufacturing an electronic device will be described below with reference to the drawings.
FIGS. 1(a) to 1(f) show that a WLP or PLP in which a plurality of electronic components are collectively sealed with the resin composition of this embodiment is obtained, and the electronic device 50 (see FIG. 1(f)) is schematically shown.

As shown in FIG. 1A, first, as an arrangement step, a plurality of electronic components (not shown) are arranged on a base material 10. This forms the circuit surface 21.
As the base material 10, various base materials known in the field of electronic devices can be used. Note that, typically, SiN or the like is exposed on the circuit surface 21.
In the case of WLP, the size and shape of the base material 10 is, for example, circular with a diameter of 12 inches, and in the case of PLP, it is approximately rectangular with a length of 300 to 800 mm and a width of 300 to 800 mm, for example.

Next, bumps 22 such as metal posts are formed on the circuit surface 21 in order to electrically connect solder balls 96 (FIG. 1(e)) to be described later and electronic components (FIG. 1(b)). ).
Next, as a sealing step, a sealing material layer 30 is formed using the resin composition of this embodiment so as to cover the circuit surface 21 (FIG. 1(c)).
Then, by scraping the encapsulant layer 30, the bumps 22 are exposed from the encapsulant layer 30 (FIG. 1(d)). Note that when forming the encapsulant layer 30, if the encapsulant layer 30 is formed so that the bumps 22 are exposed as shown in FIG. 1(d), the encapsulant layer 30 does not need to be scraped. .
Next, as a wiring step, solder balls 96 are connected to the bumps 22 (FIG. 1(e)).
Then, as a singulation step, the sealing material layer 30 and the base material 10 are cut to obtain the electronic device 50 (FIG. 1(f)). A dicing blade, laser, or the like can be used for cutting. Note that the number of bumps 22 and solder balls 96 connected to the electronic device 50 to be diced is not limited, and can be set depending on the type of the electronic device 50.

2(a) to 2(g) schematically show steps for obtaining an electronic device 52 (FIG. 2(g)) different from the electronic device 50 shown in FIG. 1(f). This process is preferably applied to the manufacture of electronic devices in so-called FaN-Out type packages.

First, a sacrificial material 70 having a release layer 71 provided on the base material 10 is prepared. Then, as a placement step, a plurality of electronic components 20 are placed on the release layer 71 of the sacrificial material 70 so as to be spaced apart from each other (FIG. 2(a)).
As the release layer 71, for example, an adhesive with low adhesive strength, a resin containing a foaming agent, or the like can be used. Thereby, the peeling layer 71, the electronic component 20, and the sealing material layer 30 can be easily peeled off in a peeling process described later.

Next, as a sealing step, the resin composition of this embodiment is used to fill in the gaps between adjacent electronic components, and further to cover the release layer 71 and the surfaces of all the electronic components 20. Sealing electronic components. This forms the sealing material layer 30 (FIG. 2(b)).

Subsequently, in a peeling step, the peeling layer 71 is peeled off from the sealing material layer 30 (FIG. 2(c)).
The peeling can be performed by foaming the peeling layer 71 made of a thermally foamable adhesive by, for example, heat treatment, electron beam irradiation, ultraviolet ray irradiation, or the like. Further, when the peeling layer 71 is made of an adhesive with low adhesive strength, the peeling process can be performed without foaming or the like.

Next, as a wiring step, an insulating resin layer 80 for rewiring is formed on the surface of the sealing material layer 30 on the electronic component 20 side (FIG. 2(d)).
The rewiring insulating resin layer 80 is formed by, for example, forming a pattern by photolithography using a photosensitive resin composition and performing a curing process. As the photosensitive resin composition, one containing polyimide resin, polybenzoxide resin, benzocyclobutene resin, etc. can be used. Note that via holes 82 may be formed in the insulating resin layer 80 for rewiring.

Furthermore, as a wiring process, for example, as shown in FIG. 2E, a power supply layer is formed on the entire surface of the rewiring insulating resin layer 80 by a method such as sputtering, and then a resist layer is formed on the power supply layer. After exposing and developing a predetermined pattern, vias 92 and rewiring circuits 94 can be formed by electrolytic copper plating. Then, the resist layer can be peeled off and the power supply layer can be etched.
Next, as shown in FIG. 2F, for example, as a wiring step, solder balls 96 can be mounted on the rewiring circuit 94. Next, a solder resist layer 98 can be formed to cover part of the rewiring circuit 94 and the solder balls 96.

Next, as a singulation process, the sealing material layer 30, the rewiring insulating resin layer 80, and the solder resist layer 98 are cut to obtain singulated electronic devices. (Figure 2(g)).
The number of electronic components 20 included in the electronic device 52 is not limited and can be set depending on the type of the electronic device 52.

Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above may also be adopted.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited to these Examples.

(Examples 1 to 4 and Comparative Examples 1 to 3)
For each example, each component shown in Table 1 was mixed using a mixer. Next, the obtained mixture was kneaded with a roll, and then the kneaded product was cooled and pulverized to obtain a granular resin composition.

The coefficient of linear expansion (CTE1), flexural modulus at 25° C., and flexural strength of the resin compositions or cured products thereof obtained in each example were measured, and the appearance of the cured products was evaluated.
The measurement results are also shown in Table 1.

Details of each component in Table 1 are as follows.
(Inorganic filler)
(C) Inorganic filler 1: Silica, MUF-4, manufactured by Ryumorisha, average particle size 3.8 μm
(C) Inorganic filler 2: Silica, SC-2500-SQ, manufactured by Admatex, average particle size 0.5 μm
(C) Inorganic filler 3: Silica, SC-5500-SQ, manufactured by Admatex, average particle size 1.5 μm
(coupling agent)
Coupling agent 1: Phenylaminopropyltrimethoxysilane, CF-4083, manufactured by Dow-Toray Co., Ltd. Coupling agent 2: Hydrolyzate of γ-glycidoxypropylmethyldimethoxysilane, KE-6137, manufactured by Kyushu Sumitomo Bakelite Co., Ltd. ( Epoxy resin)
(A) Epoxy resin 1: Biphenylaralkyl epoxy resin represented by the following general formula, NC3000, manufactured by Nippon Kayaku Co., Ltd.

(In the above general formula, n=1 to 10.)

(A) Epoxy resin 2: Mixture of trisphenylmethane type epoxy resin and biphenyl type epoxy resin, YL6677, manufactured by Mitsubishi Chemical Corporation (B) Curing agent 1: Trisphenylmethane mixed type phenolic resin, HE910-20, Air Water Co., Ltd. (B) Curing agent 2: Biphenylaralkyl phenolic resin, MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd. (curing accelerator)
Curing accelerator 1: Tetraphenylphosphonium 4,4'-sulfonyl diphenolate, manufactured by Sumitomo Bakelite Co., Ltd. Curing accelerator 2: Tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, manufactured by Sumitomo Bakelite Co., Ltd. colorant)
Colorant 1: Carbon black, manufactured by Mitsubishi Chemical Corporation, carbon #5
(ion catcher)
Ion catcher 1: Hydrotalcite, DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd. (low stress agent)
(D) Triglyceride 1: Caprylic acid triglyceride, manufactured by Kao Corporation (D) Triglyceride 2: 2-ethylhexanoic acid triglyceride, manufactured by Kao Corporation (D) Triglyceride 3: Oleic acid triglyceride, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 4:12 - Hydroxystearic acid triglyceride, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 5: Stearic acid triglyceride, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 6: Soybean oil, manufactured by Nisshin Oilio Group Co., Ltd.

(How to calculate ΔHSP)
For each structural unit of component (A) or the low stress agent, the structural formula for HSP calculation was converted into SMILES notation using editor software (Chem Draw). When the SMILES formula was input into the Y-MB calculation software attached to HSPiP, the HSP (δd, δp, δh) of each constituent unit was calculated. ΔHSP is represented by R ² shown in the above formula (1). Table 2 shows the SMILES formula and HSP of each component.

Here, HSP of triglyceride 6 (soybean oil) was determined by the following procedure.
1. We listed the combinations of the five main types of fatty acids contained in soybean oil and calculated their existence probabilities. Then, the subsequent calculations were performed for the triglycerides with the highest probability of existence up to the top 75.8%.
2. Each of the listed triglycerides was expressed using the SMILES formula, and HSP (δd, δp, δh) was calculated using HSPiP software.
3. Each HSP component of the listed triglycerides was multiplied by the existence probability, and each component was summed to form the HSP.
Each procedure will be explained in more detail below.

Above step 1. The "5 main types of fatty acids" in the above are the 5 main types of fatty acids that make up soybean oil, specifically palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid. The composition ratio of each fatty acid in soybean oil was 11.0% palmitic acid, 4.7% stearic acid, 23.7% oleic acid, 53.5% linoleic acid, and 7.1% linolenic acid. In soybean oil, any three molecules of the above-mentioned fatty acids are bound to one molecule of glycerin, so all combinations of five types of fatty acids are listed. A method for calculating the existence probability of the listed triglycerides is shown below based on a specific example.
(Example) In the case of triglyceride with 3 molecules of linoleic acid bonded, 0.53 x 0.53 x 0.53 = 0.149
Similarly, the existence probabilities of other triglycerides were calculated. These were arranged in descending order of existence probability, and calculations were then performed for the top 75.8% of triglycerides.
2. Each of the listed triglycerides was expressed using the SMILES formula and calculated using HSPiP software.
(Example) For triglyceride with three molecules of linoleic acid bound together, SMILES formula: CCCCC/C=C/C/C=C/CCCCCCCC(OCC(COC(CCCCCC/C=C/C/C=C/CCCCC)=O )OC(CCCCCCC/C=C/C/C=C/CCCCC)=O)=O
HSP (δd, δp, δh) = (16.6, 1.7, 4.1)
HSP was calculated for other triglycerides in a similar manner.

3. Step 2 above. Each HSP component of the triglycerides listed above was multiplied by the probability of existence, and each component was summed to form the HSP.
(Example) In the case of triglyceride with three molecules of linoleic acid bound together (δd, δp, δh) = (16.6 x 0.149, 1.7 x 0.149, 4.1 x 0.149) = (2. 47, 0.253, 0.611)

Step 3 above. The HSP components calculated in the above were added together to obtain the HSP of soybean oil.
HSP (δd, δp, δh) = (15.77, 1.61, 3.45)

(Measurement method and evaluation method)
(linear expansion coefficient)
The resin composition obtained in each example was injection molded using a transfer molding machine at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds, and the length was 15 mm on the long side x 4.5 mm on the short side x thickness. A test piece with a diameter of 3 mm was obtained.
After post-curing the obtained test piece at 175°C for 4 hours, using a thermomechanical analyzer (manufactured by Hitachi High-Tech Science, TMA7100), it was measured in the compression mode at a temperature range of -60°C to 400°C and at a heating rate. Measurements were carried out at a rate of 5° C./min.
From the measurement results, the average coefficient of linear expansion from 50°C to 70°C was calculated and set as CTE1.
Those with a CTE1 of less than 9.3 ppm/°C were considered to be passed.

(Bending modulus and bending strength)
The resin composition obtained in each example was injection molded using a transfer molding device at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds to form a mold of 10 mm width x 4 mm thickness x 80 mm length. I got the item. The obtained molded article was post-cured at 175° C. for 4 hours to obtain a test piece.
The flexural modulus and flexural strength of the obtained test piece at 25°C were measured in accordance with JIS K 6911.
Those with a flexural modulus of less than 22.5 GPa were considered to be acceptable.

(exterior)
The resin composition obtained in each example was injection molded using a transfer molding device at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds to form a disc-shaped molded product with a diameter of 90 mm and a thickness of 5 mm. Obtained. The obtained molded article was post-cured at 175° C. for 4 hours to obtain a test piece.
The appearance of the obtained test piece was visually observed and evaluated according to the following criteria.
A: No surface contamination or slight surface contamination B: Surface contamination throughout the test piece

From Table 1, in each Example, the ΔHSP between the epoxy resin and the low stress material was within a suitable range, and the effects of reducing CTE1 and reducing the elastic modulus were well balanced. Furthermore, in each Example, deterioration in appearance was also suitably suppressed.

10 Base material 20 Electronic component 21 Circuit surface 22 Bump 30 Sealing material layer 50 Electronic device 52 Electronic device 70 Sacrificial material 71 Peeling layer 80 Insulating resin layer for rewiring 82 Via hole 92 Via 94 Rewiring circuit 96 Solder ball 98 Solder resist layer

Claims (12)

(A) epoxy resin,
(B) a curing agent;
(C) an inorganic filler, and (D) a low stress material,
A sealing resin in which the component (D) contains one or more first low stress materials whose Hansen solubility parameter distance with the component (A) is 8.5 MPa ^1/2 or more and 9.9 MPa ^{1/2 or} less. Composition. The sealing resin composition according to claim 1, wherein the first low stress material contains triglyceride. The sealing resin composition according to claim 2, wherein all three fatty acid residues in the triglyceride are the same. Claims 1 to 3, wherein the content of the component (D) in the encapsulating resin composition is 0.1% by mass or more and 2.5% by mass or less based on the entire encapsulating resin composition. The sealing resin composition according to any one of the items. The sealing resin composition according to any one of claims 1 to 3, wherein the component (A) contains at least one selected from the group consisting of a biphenylaralkyl epoxy resin and a triphenylmethane epoxy resin. The sealing resin composition according to any one of claims 1 to 3, which is used for sealing a wafer level package (WLP) or a panel level package (PLP). The sealing resin composition according to any one of claims 1 to 3, which is in the form of granules. A cured product that is a cured product of the sealing resin composition according to any one of claims 1 to 3. A wafer level package in which a plurality of electronic components are collectively sealed with the sealing resin composition according to any one of claims 1 to 3. A panel level package in which a plurality of electronic components are collectively sealed with the sealing resin composition according to any one of claims 1 to 3. An electronic device in which the wafer level package according to claim 9 is diced. An electronic device in which the panel level package according to claim 10 is singulated.

Images