Sealing resin composition

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

[Technical Field]

[0001] This invention relates to a resin composition for sealing. [Background technology]

[0002] Regarding technology related to encapsulating resin compositions, there is a document described in Patent Document 1 (Japanese Patent Application Publication No. 2002-146163). This document describes an encapsulating resin composition in which epoxy resin, phenolic resin, polyglycerin fatty acid ester, and inorganic filler are essential components, and the polyglycerin fatty acid ester and inorganic filler are contained in specific proportions relative to the resin composition (Claim 1). Specifically, decaglyceryl pentaoleate is described as the polyglycerin fatty acid ester (Paragraph 0013, Examples 1-3). Furthermore, the document states that the encapsulating resin composition in this document has excellent moldability and electrical properties, as well as good filling and workability, and that by using this resin composition to encapsulate electronic components, improvements can be made in both the workability and performance of semiconductor encapsulation equipment (Paragraph 0034). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2002-146163 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] When the present inventors examined the technology described in the above-mentioned patent document, it became clear that there is room for improvement in achieving both a low coefficient of thermal expansion and a low modulus of elasticity in the cured product, while also providing a desirable appearance. [Means for solving the problem]

[0005] According to the present invention, there are provided the following resin compositions for encapsulation, cured products, wafer-level packages, panel-level packages, and electronic devices. [1] (A) An epoxy resin, (B) A curing agent, (C) An inorganic filler, and (D) A low stress material which contains, where the distance of the Hansen solubility parameter between the component (D) and the component (A) is 8.5 MPa 1 / 2 or more and 9.9 MPa 1 / 2 or less, and includes one or more first low stress materials, a resin composition for encapsulation. [2] The resin composition for encapsulation according to [1], wherein the first low stress material contains triglyceride. [3] The resin composition for encapsulation according to [2], wherein all three fatty acid residues in the triglyceride are the same. [4] The resin composition for encapsulation according to any one of [l] to [3], wherein the content of the component (D) in the resin composition for encapsulation is 0.1% by mass or more and 2.5% by mass or less with respect to the entire resin composition for encapsulation. [5] The resin composition for encapsulation according to any one of [1] to [4], wherein the component (A) contains at least one selected from the group consisting of biphenyl aralkyl type epoxy resins and triphenylmethane type epoxy resins. [6] The resin composition for encapsulation according to any one of [1] to [5], which is used for encapsulation of a wafer-level package (WLP) or a panel-level package (PLP). [7] The resin composition for encapsulation according to any one of [1] to [6], which is granular. [8] A cured product which is a cured product of the resin composition for encapsulation according to any one of [1] to [7]. [9] A wafer-level package in which a plurality of electronic components are collectively encapsulated with the resin composition for encapsulation according to any one of [1] to [7].

[10] A panel-level package in which a plurality of electronic components are collectively encapsulated with the resin composition for encapsulation according to any one of [1] to [7]. The electronic device in which the wafer level package described in

[11] [9] is separated into individual pieces. The electronic device in which the panel level package described in

[12]

[10] is separated into individual pieces.

Advantages of the Invention

[0006] According to the present invention, it is possible to obtain a sealing material in which a cured product has both a low linear expansion coefficient and a low elastic modulus and has a preferable appearance.

Brief Description of the Drawings

[0007] [Figure 1] It is a cross-sectional view schematically showing an example of a method for manufacturing an electronic device in an embodiment. [Figure 2] It is a cross-sectional view schematically showing an example of a method for manufacturing an electronic device in an embodiment.

Mode for Carrying Out the Invention

[0008] In the present embodiment, the composition can contain each component alone or in combination of two or more. In this specification, "~" indicating a numerical range represents "above" and "below", and includes both numerical values at both ends.

[0009] (Resin composition for sealing) In the present embodiment, the resin composition for sealing (hereinafter, also simply referred to as "resin composition") contains the following components (A) to (D). (A) Epoxy resin, (B) Curing agent, (C) Inorganic filler, and (D) Low stress material And the component (D) contains one or more first low stress materials in which the distance of the Hansen solubility parameter from the component (A) is 8.5 MPa 1 / 2 or more and 9.9 MPa 1 / 2 or less.

[0010] The present inventors have studied reducing both the linear expansion coefficient and the elastic modulus of the cured product. As a result, the resin composition contains components (A) to (D) in combination, and component (D) contains one or more first low-stress materials having a distance of Hansen solubility parameter (hereinafter also referred to as "ΔHSP") from component (A) within a specific range. By adopting such a configuration, it has been newly found that the properties of the cured product, namely the linear expansion coefficient and the elastic modulus, which are originally in a trade-off relationship, can both be suitably reduced. By configuring the resin composition as described above, the reason why the linear expansion coefficient and the elastic modulus are reduced is not necessarily clear, but it is considered that the degree of dispersion of the first low-stress material in the resin composition becomes favorable, and domains derived from the first low-stress material are formed in the resin composition with a favorable size. That is, the present inventors newly focused on the ΔHSP between component (A) and the first low-stress material as an index for reducing the linear expansion coefficient and the elastic modulus. And by using in combination a first low-stress material having a ΔHSP within a specific range and combining these with components (B) and (C), it has been found that a resin composition in which the linear expansion coefficient and the elastic modulus of the cured product are preferably reduced can be obtained.

[0011] In the present 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 8.9 MPa 1 / 2 or more from the viewpoint of reducing the linear expansion coefficient. Also, from the viewpoint of making the appearance of the cured product favorable, 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, more preferably 9.3 MPa 1 / 2 or less.

[0012] Here, Hansen's solubility parameter (HSP) is an index that represents the solubility of one substance, indicating how much of it dissolves in another substance. In HSP, solubility is represented by a three-dimensional vector. This three-dimensional vector can typically be represented by a dispersion term (δd), a polarity term (δp), and a hydrogen bonding term (δh). Substances with similar vectors are judged to have high solubility. The similarity of vectors can be judged using ΔHSP.

[0013] The computer software HSPiP, developed by Hansen and Abbott, includes a function to calculate ΔHSP and a database listing Hansen parameters for various resins and solvents or non-solvents. The HSP values ​​used in this specification can be calculated using the HSPiP (Hansen Solubility Parameters in Practice) software. For example, values ​​listed in the Solvent list and Polymer list included in HSPiP 3rd version, adjusted for 25°C, may be referenced. For resins and solvents or non-solvents not listed in the Solvent list, the values ​​can be calculated 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.

[0014] Specifically, ΔHSP is R shown in equation (1) below. 2 It is represented as follows. In this embodiment, ΔHSP can be calculated, for example, by the following formula (1), where the HSP of component (A) is (d1, p1, h1) and the HSP of the first low-stress material is (d2, p2, h2).

[0015]

number

[0016] In this embodiment, the resin composition contains a combination of components (A) to (D), and component (D) contains one or more first low-stress materials whose ΔHSP with component (A) is within a specific range. As a result, the coefficient of linear expansion and the modulus of elasticity of the cured product, which are inherently in a trade-off relationship, can both be suitably reduced. Therefore, even when large-area sealing such as WLP and PLP is involved, the warping of the substrate can be effectively suppressed. The components included in the resin composition will be explained in more detail below.

[0017] (Component (A)) Component (A) is 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; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; polyfunctional epoxy resins such as triphenylmethane-type epoxy resins and triphenylmethane-type epoxy resins exemplified by alkyl-modified triphenolmethane-type epoxy resins; phenol aralkyl-type epoxy resins having a phenylene skeleton, and naphth having a phenylene skeleton. One or more selected from the group consisting of phenol aralkyl epoxy resins such as phenol aralkyl epoxy resins, phenol aralkyl epoxy resins having a biphenylene skeleton, and naphthol aralkyl epoxy resins having a biphenylene skeleton; naphthol epoxy resins such as dihydroxynaphthalene epoxy resins and epoxy resins obtained by glycidyl etherification of a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol epoxy resins such as dicyclopentadiene-modified phenol epoxy resins.

[0018] From the viewpoint of suppressing warping of the cured resin composition and improving the balance of various properties such as filling ability, heat resistance, and moisture resistance, component (A) preferably includes at least one selected from the group consisting of biphenylaralkyl type epoxy resins and triphenylmethane type epoxy resins.

[0019] In component (A), the polarity term (P), hydrogen term (H), and dispersion term (D) of HSP can be set to values ​​such that the ΔHSP with respect to the first low-stress material falls within the range described above. The polarity term (P) of the HSP of component (A) is preferably 3.0 MPa. 1 / 2 The above is more preferable, and 4.0 MPa 1 / 2 More preferably, 5.0 MPa 1 / 2 That's all. Furthermore, the polarity term (P) of the HSP in component (A) is 7.5 MPa. 1 / 2 The following, more preferably 6.5 MPa 1 / 2 More preferably, 5.5 MPa 1 / 2 The following applies:

[0020] The hydrogen atom (H) of the HSP of component (A) is preferably 2.0 MPa. 1 / 2 The above is preferable to 3.0 MPa. 1 / 2 More preferably, 4.0 MPa 1 / 2 That's all. Furthermore, the hydrogen atom (H) of the HSP in component (A) is 6.5 MPa. 1 / 2 The following, and more preferably 5.5 MPa 1 / 2 More preferably, 4.5 MPa 1 / 2 The following applies:

[0021] The dispersion term (D) of the HSP of component (A) is preferably 18.0 MPa. 1 / 2 The above is preferable, and more preferably 19.0 MPa 1 / 2 More preferably, 20.3 MPa 1 / 2 That's all. Furthermore, the dispersion term (D) of the HSP in component (A) is 22.5 MPa. 1 / 2 The following, and more preferably 21.5 MPa 1 / 2More preferably, 20.5 MPa 1 / 2 The following applies: This makes it possible to achieve both a low coefficient of thermal expansion and a low modulus of elasticity.

[0022] Here, the HSP of component (A) is calculated using the method described above. Furthermore, when component (A) contains two or more epoxy resins, each term of HSP in component (A) can be determined as the sum of the products of the HSP values ​​and mass fractions of each component.

[0023] 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, even more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total resin composition. Furthermore, 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 even more preferably 8% by mass or less, relative to the total resin composition.

[0024] (Component (B)) Component (B) is a hardening agent. Examples of curing agents include linear aliphatic diamines with 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine; amines such as 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, metaxylenediamine, paraxylenediamine, 1,1-bis(4-aminophenyl)cyclohexane, and dicyanodiamide; Resol-type phenolic resins such as aniline-modified resol resins and dimethyl ether resol resins; Novolac-type phenolic resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, and nonylphenol novolac resins; Polyfunctional phenolic resins such as trihydroxyphenylmethane-type phenolic resins; Phenolic aralkyl resins such as phenol aralkyl resins containing a phenylene skeleton and phenol aralkyl resins containing a biphenylene skeleton; Phenolic resins having condensed polycyclic structures such as naphthalene skeletons or anthracene skeletons; Phenolic resins other than those mentioned above; Polyoxystyrene such as polyparaoxystyrene; Acid anhydrides, including alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA); Polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and One or more selected from the group consisting of organic acids such as carboxylic acid-containing polyester resins. Furthermore, component (B) preferably comprises at least one selected from the group consisting of phenol novolac resin, trisphenylmethane mixed phenol resin, and biphenyl aralkyl type phenol resin, and more preferably comprises trisphenylmethane mixed phenol resin and biphenyl aralkyl type phenol resin.

[0025] 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, even more preferably 1% by mass or more, even more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, relative to the total resin composition. Furthermore, 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 7.0% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less, relative to the total resin composition.

[0026] (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. Component (C) preferably contains silica, and more preferably silica, from the viewpoint of excellent versatility. Examples of silica shapes include spherical silica such as molten spherical silica and crushed silica.

[0027] Average particle size d of component (C) 50 From the viewpoint of suppressing shrinkage during molding, the thickness is preferably 0.5 μm or more, and more preferably 1.0 μm or more. Furthermore, from the viewpoint of improving filling performance during molding, the average particle size d of component (C) 50 The particle size 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.

[0028] Here, the average particle size d of component (C) 50 This represents the average particle size measured using a commercially available laser particle size analyzer (for example, the SALD-7000 manufactured by Shimadzu Corporation).

[0029] From the viewpoint of suppressing warping, 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 or more, relative to the entire resin composition. Furthermore, from the viewpoint of improving fluidity and fillability 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, even more preferably 90% by mass or less, and even more preferably 88% by mass or less, relative to the entire resin composition.

[0030] (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. Furthermore, component (D) may also contain other low-stress materials.

[0031] In the first low-stress material, the polarity term (P), hydrogen term (H), and dispersion term (D) of HSP can be set to values ​​such that the ΔHSP with respect to component (A) falls within the range described above. The polarity term (P) of the HSP for the first low-stress material is, for example, 0.5 MPa. 1 / 2 The above is preferable, and preferably 1.0 MPa 1 / 2 That's all, and also, for example, 3.5 MPa 1 / 2 The following, preferably 2.0 MPa 1 / 2 The following applies: The hydrogen term (H) of the HSP of the first low-stress material is, for example, 0.05 MPa. 1 / 2 The above is preferable, and preferably 1.2 MPa 1 / 2 That's all, and also, for example, 3.6 MPa 1 / 2 The following, preferably 2.0 MPa 1 / 2 The following applies: Furthermore, the dispersion term (D) of the HSP for the first low-stress material is, for example, 12.0 MPa. 1 / 2 The above is preferable, and preferably 15.0 MPa 1 / 2 That's all, and also, for example, 20.0 MPa 1 / 2 The following, preferably 18.0 MPa 1 / 2 The following applies:

[0032] When component (D) contains two or more types of first low-stress materials, each term of the HSP of the first low-stress material can be determined as the product of the HPS value and mass fraction of each component.

[0033] The first low-stress material preferably contains triglycerides, and more preferably triglycerides, from the viewpoint of reducing the coefficient of linear expansion and the modulus of elasticity. The three fatty acid residues in a single triglyceride molecule may be of the same type or different types, but from the viewpoint of reducing the coefficient of linear expansion and the elastic modulus, it is preferable that all three fatty acid residues are the same.

[0034] The three fatty acid residues in a triglyceride are independently either saturated or unsaturated fatty acid residues. A triglyceride may contain three saturated fatty acid residues, one unsaturated fatty acid residue and two saturated fatty acid residues, two unsaturated fatty acid residues and one saturated fatty acid residue, or three unsaturated fatty acid residues.

[0035] The number of carbon atoms in the fatty acid residues in the triglyceride is, for example, 8 or more, preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, even more preferably 16 or more, and also, for example, 24 or less, preferably 22 or less, even more preferably 20 or less. Specific examples of fatty acids in fatty acid residues include palmitic acid (number of carbon atoms: number of double bonds = C16:0), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), and linolenic acid (C18:3). Furthermore, fatty acids may have substituents, and examples of such fatty acid residues include 12-hydroxystearic acid and 2-ethylhexanoic acid.

[0036] From the viewpoint of improving dispersibility in resin compositions, triglycerides are liquid at 25°C, i.e., fluid at 25°C. From a similar viewpoint, the iodine value of the triglyceride is preferably 100 or more, more preferably 105 or more, and even more preferably 110 or more. Furthermore, 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 even more preferably 180 or less.

[0037] The first low-stress material may contain a mixture of two or more triglycerides. Furthermore, the first low-stress material is preferably a vegetable oil from the viewpoint of improving dispersibility in the resin composition. Specific examples of vegetable oils include one or more 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. 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.

[0038] From the viewpoint of suppressing warping, 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, even more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more, relative to the total resin composition. Furthermore, 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 or less, and even more preferably 2.3% by mass or less, relative to the total resin composition.

[0039] Among the components (D), silicone oil is an example of a component other than the first low-stress material. Specifically, examples of silicone oils include organopolysiloxanes. Here, organopolysiloxanes may be those in which functional groups such as epoxy groups, amino groups, methoxy groups, phenyl groups, carboxyl groups, hydroxyl groups, alkyl groups, vinyl groups, mercapto groups, and polyether groups have been introduced into their structure. As for the functional groups introduced into the structure of organopolysiloxanes, at least one selected from the group consisting of carboxyl groups, epoxy groups, and polyether groups is preferred. Examples of commercially available products containing silicone oil include Dow-Toray's FZ-3730 and BY-750.

[0040] 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, and even more preferably 1.0% by mass or more, relative to the entire resin composition, from the viewpoint of suppressing warping. Furthermore, 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 2.3% by mass or less.

[0041] The resin composition may further contain components other than components (A) to (D). For example, the resin composition may further contain one or more selected from the group consisting of curing accelerators, coupling agents, mold release agents, ion catchers, colorants, and other additives.

[0042] (Curing accelerator) As a curing accelerator, for example, one that promotes 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 phosphorus atom-containing compounds such as organophosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; and nitrogen atom-containing compounds such as amidines and tertiary amines, and quaternary salts of the above amidines and amines, exemplified by 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, and 2-methylimidazole. One or more of these may be selected from these.

[0043] From the viewpoint of improving curability, the content of the curing accelerator in the resin composition is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, relative to the total resin composition. Furthermore, from the viewpoint of improving the manufacturing 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 or less, and even more preferably 0.3% by mass or less, relative to the total resin composition.

[0044] (Coupling agent) The coupling agent may include one or more known coupling agents selected from, for example, epoxysilanes such as γ-glycidoxypropylmethyldimethoxysilane, mercaptosilanes, aminosilanes such as phenylaminopropyltrimethoxysilane and phenylaminosilane, alkylsilanes, ureidosilanes, vinylsilanes, methacrylicsilanes, and other silane compounds; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. From the viewpoint of improving the strength and toughness of the cured product in a balanced manner, the coupling agent is preferably a silane coupling agent, and more preferably at least one of aminosilane and epoxysilane.

[0045] 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, and even more preferably 0.3% by mass or more, relative to the total resin composition. Furthermore, from the viewpoint of improving the manufacturing 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, and even more preferably 0.7% by mass or less, relative to the total resin composition.

[0046] The release agent may include, for example, one or more selected from natural waxes such as carnauba wax; synthetic waxes such as polyethylene oxide wax, montanic acid ester wax, and reaction products of polycondensates of 1-alkene (C>10) maleic anhydride and stearyl alcohol; higher fatty acids such as zinc stearate and their metal salts; and paraffin. From the viewpoint of obtaining more favorable release properties and curing characteristics, the content of the mold release agent in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 2% by mass or less, and more preferably 1% by mass or less, relative to the total resin composition.

[0047] Ion catchers include, for example, hydroxytalsites. From the viewpoint of improving the reliability of the cured product, the ion catcher content in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1% by mass or less, and more preferably 0.5% by mass or less, relative to the total resin composition.

[0048] The coloring agent includes, for example, one or more selected from the group consisting of carbon black, black titanium dioxide, red iron oxide, and organic dyes. From the viewpoint of obtaining a more favorable appearance of the cured product, the content of the colorant in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 1% by mass or less, and more preferably 0.5% by mass or less, relative to the total resin composition.

[0049] Other additives include, for example, flame retardants or antioxidants other than components (A) to (D).

[0050] Next, the properties and physical characteristics of the resin composition will be explained. The properties of the resin composition may be, for example, liquid or solid. From the viewpoint of ensuring manufacturing stability during molding, especially when forming a sealant on a large surface area substrate, the resin composition is preferably solid, and more preferably granular. The granular resin composition may be, for example, an aggregate formed by solidifying powders (powdered kneaded material) of the resin composition, or granules obtained by a known granulation method.

[0051] When the resin composition is in granular form, its average particle size is preferably 0.03 mm or larger, more preferably 0.05 mm or larger, and even more preferably 0.1 mm or larger, from the viewpoint of improving the handling properties of the resin composition. Furthermore, 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 even more preferably 2.0 mm or less.

[0052] Here, the particle size distribution of the resin composition can be measured on a volume basis using a commercially available laser diffraction particle size distribution analyzer (for example, the SALD-7000 manufactured by Shimadzu Corporation).

[0053] (Coefficient of linear expansion) From the viewpoint of suppressing warping, the coefficient of linear expansion CTE1 of the resin composition at temperatures 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 / °C or less. The lower limit of CTE1 is not limited, but it is preferably greater than or equal to the coefficient of thermal expansion of the silicon wafer used, and may be, for example, 3.5 ppm / °C or higher. Here, the coefficient of linear expansion is measured specifically by the following method.

[0054] (Method for measuring the coefficient of linear expansion) Using a transfer molding machine, the resin composition was injected and molded 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 specimen measuring 15 mm (long side) x 4.5 mm (short side) x 3 mm (thickness). After post-curing the test specimen at 175°C for 4 hours, measurements were performed using a thermomechanical analyzer (Hitachi High-Tech Science, TMA7100) in compression mode, under conditions of a measurement temperature range of -60°C to 400°C and a heating rate of 5°C / min. From the measurement results, the average linear expansion coefficient from 50°C to 70°C was calculated and defined as CTE1.

[0055] (Flexural modulus) From the viewpoint of improving handling properties, the flexural modulus of the cured resin composition at 25°C is preferably 10 GPa or higher, more preferably 15 GPa or higher, and even more preferably 20 GPa or higher. Furthermore, from the viewpoint of suppressing warping, the flexural modulus of the cured resin composition at 25°C is preferably 35 GPa or less, more preferably 30 GPa or less, and even more preferably 25 GPa or less. The flexural modulus of the cured material is measured by the method described later.

[0056] (Bending strength) The flexural strength of the cured resin composition at 25°C 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. Furthermore, from the viewpoint of preventing brittle fracture due to the cured product being too hard, the bending strength of the cured resin composition at 25°C is preferably 250 MPa or less, more preferably 220 MPa or less, and even more preferably 180 MPa or less. The flexural modulus and flexural strength of the cured material are measured by the following method.

[0057] (Method for measuring flexural modulus and flexural strength) Using a transfer molding apparatus, the resin composition is injected and molded 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 product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm. The obtained molded product is then post-cured at 175°C for 4 hours to obtain a test specimen. The flexural modulus and flexural strength of the obtained test specimen at 25°C are measured in accordance with JIS K 6911.

[0058] The resin composition is preferably used for sealing wafer-level packages (WLP) or panel-level packages (PLP). WLP typically refers to a wafer process where all steps, including redistribution, electrode formation, resin encapsulation, and dicing, are performed, resulting in a package size that is directly proportional to the size of the semiconductor chip obtained by cutting the wafer. Furthermore, PLP is a technology that uses panel-shaped substrates, which are larger than the typical wafers used in WLP (for example, 12-inch wafers), to manufacture electronic devices in a single unit. Both WLP and PLP involve the bulk encapsulation of large-area substrates, rather than the encapsulation of individual, relatively small semiconductor chips.

[0059] Next, a method for producing the resin composition will be described. In this embodiment, the resin composition can be obtained, for example, by mixing the above-mentioned components by known means, further melt-kneading them in a kneader such as a roll, kneader, or extruder, cooling, and then grinding. Alternatively, if necessary, the mixture may be compressed into tablets after grinding in the above method. Furthermore, the degree of dispersion and fluidity of the obtained resin composition may be adjusted as appropriate.

[0060] (hardened body) This cured product is a cured product of the resin composition in this embodiment. The cured product is suitably used, for example, as a encapsulant. The cured body specifically includes a portion composed of component (C) and a portion composed of other organic components. Of these, the portion composed of organic components preferably has a domain containing a first low-stress material and a domain containing component (A), from the viewpoint of reducing the coefficient of linear expansion and the elastic modulus. The size of the domain containing the first low-stress material may be, for example, several μm to several tens of μm.

[0061] (WLP, PLP) In WLP and PLP, multiple electronic components are encapsulated together using the resin composition of this embodiment. Furthermore, the electronic device is made by individually packaging the above-mentioned WLP or PLP.

[0062] The following describes an example of a manufacturing method for an electronic device, with reference to the drawings. Figures 1(a) to 1(f) schematically show the process of obtaining a WLP or PLP in which multiple electronic components are encapsulated together using the resin composition of this embodiment, and then obtaining an electronic device 50 (Figure 1(f)) by individualizing the components.

[0063] As shown in Figure 1(a), first, as an arrangement step, multiple electronic components (not shown) are arranged on the substrate 10. This forms the circuit surface 21. The substrate 10 can be any substrate known in the field of electronic devices. Typically, SiN or the like is exposed on the circuit surface 21. The size and shape of the base material 10 are, for example, a circle with a diameter of 12 inches in the case of WLP, and for example, a roughly rectangular shape with dimensions of 300-800 mm in length and 300-800 mm in width in the case of PLP.

[0064] Next, bumps 22, such as metal posts, are formed on the circuit surface 21 to electrically connect the solder balls 96 (Figure 1(e)) described later with the electronic components (Figure 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 (Figure 1(c)). Then, the bumps 22 are exposed from the sealing layer 30 by scraping it (Figure 1(d)). Note that when forming the sealing layer 30, if the bumps 22 are exposed as shown in Figure 1(d), the sealing layer 30 does not need to be scraped. Next, as part of the wiring process, connect the solder ball 96 to the bump 22 (Figure 1(e)). Next, in the individualization process, the sealing material layer 30 and the substrate 10 are cut to obtain the electronic device 50 (Figure 1(f)). A dicing blade or a laser can be used for cutting. The number of bumps 22 and solder balls 96 connected to the individualized electronic device 50 is not limited and can be set according to the type of electronic device 50.

[0065] Figures 2(a) to 2(g) schematically illustrate the process for obtaining an electronic device 52 (Figure 2(g)) that is different from the electronic device 50 shown in Figure 1(f). This process is preferably applied to the manufacture of so-called FaN-Out type package electronic devices.

[0066] First, a sacrificial material 70 is prepared, on which a release layer 71 is provided on a base material 10. Then, as a placement step, multiple electronic components 20 are placed on the release layer 71 of the sacrificial material 70 so as to be spaced apart from each other (Figure 2(a)). For example, the release layer 71 can be an adhesive with low adhesive strength or a resin containing a foaming agent. This allows the release layer 71 to be easily separated from the electronic component 20 and the sealing material layer 30 in the peeling process described later.

[0067] Next, in the sealing step, the resin composition of this embodiment is used to fill the gaps between adjacent electronic components, and further seal the electronic components so as to cover the release layer 71 and the surface of all electronic components 20. This forms a sealing material layer 30 (Figure 2(b)).

[0068] Next, in the peeling process, the peeling layer 71 is peeled off from the sealing material layer 30 (Figure 2(c)). The release method can be carried out by, for example, foaming the release layer 71, which is made of a heat-expandable adhesive, through heat treatment, electron beam irradiation, ultraviolet irradiation, etc. Furthermore, if the release layer 71 is made of an adhesive with low adhesive strength, the release process can be performed without foaming.

[0069] Next, as a wiring process, a rewiring insulating resin layer 80 is formed on the side of the sealing material layer 30 facing the electronic component 20 (Figure 2(d)). The rewiring insulating resin layer 80 is formed by creating a pattern using, for example, a photolithography method with a photosensitive resin composition, and then performing a curing treatment. The photosensitive resin composition can include polyimide resin, polybenzooxide resin, benzocyclobutene resin, and the like. Via holes 82 may also be formed in the rewiring insulating resin layer 80.

[0070] Furthermore, as part of the wiring process, for example, as shown in Figure 2(e), a power supply layer can be formed on the entire surface of the rewiring insulating resin layer 80 by sputtering or the like, then a resist layer can be formed on the power supply layer, exposed and developed in a predetermined pattern, and then 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 Figure 2(f), for example, solder balls 96 can be mounted on the rewiring circuit 94 as part of the wiring process. Then, a solder resist layer 98 can be formed to cover the rewiring circuit 94 and a portion of the solder balls 96.

[0071] Next, as a fragmentation process, the sealing material layer 30, the rewiring insulating resin layer 80, and the solder resist layer 98 are cut to obtain fragmented electronic devices, thereby obtaining the electronic device 52 (Figure 2(g)). The number of electronic components 20 included in the electronic device 52 is not limited and can be set according to the type of electronic device 52.

[0072] The embodiments of the present invention have been described above with reference to the drawings, but these are merely examples of the present invention, and various other configurations can also be adopted. Examples of reference formats are provided below. 1. (A) Epoxy resin, (B) Hardener, (C) Inorganic fillers, and (D) Low stress material Includes, The Hansen solubility parameter distance between component (D) and component (A) is 8.5 MPa. 1 / 2 9.9 MPa 1 / 2 A sealing resin composition comprising one or more of the following first low-stress materials. 2. The sealing resin composition according to 1, wherein the first low-stress material contains a triglyceride. 3. The sealing resin composition according to 2., wherein all three fatty acid residues in the triglyceride are the same. 4. The sealing resin composition according to any one of 1 to 3, wherein the content of component (D) in the sealing resin composition is 0.1% by mass or more and 2.5% by mass or less of the total sealing resin composition. 5. The sealing resin composition according to any one of 1 to 3, wherein component (A) comprises at least one selected from the group consisting of biphenylaralkyl type epoxy resins and triphenylmethane type epoxy resins. 6. A sealing resin composition according to any one of 1 to 3, used for sealing wafer-level packages (WLPs) or panel-level packages (PLPs). 7. A granular encapsulating resin composition according to any one of 1 to 3. 8. A cured body which is a cured product of any one of the sealing resin compositions described in 1 to 3. 9. A wafer-level package in which multiple electronic components are collectively sealed with a sealing resin composition described in any one of items 1 to 3. 10. A panel-level package in which multiple electronic components are collectively sealed with the sealing resin composition described in any one of items 1 to 3. 11. Electronic devices in which wafer-level packages as described in 9. have been separated into individual pieces. 12. Electronic devices in which the panel-level packages described in 10. are individually packaged. [Examples]

[0073] The embodiment will be described in detail below with reference to examples, but this embodiment is not limited to these examples.

[0074] (Examples 1-4 and Comparative Examples 1-3) For each example, the components shown in Table 1 were mixed using a mixer. The resulting mixture was then roll-kneaded, cooled, and pulverized to obtain a granular resin composition.

[0075] For each example, the coefficient of linear thermal expansion (CTE1), flexural modulus at 25°C, and flexural strength of the resin composition or its cured product were measured, and the appearance of the cured product was evaluated. The measurement results are shown in Table 1.

[0076] The details of each component in Table 1 are as follows: (Inorganic filler) (C) Inorganic filler 1: Silica, MUF-4, manufactured by Ryusen Co., Ltd., 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. Coupling agent 2: Hydrolyzate of γ-glycidoxypropylmethyldimethoxysilane, KE-6137, manufactured by Kyushu Sumitomo Bakelite Co., Ltd. (Epoxy resin) (A) Epoxy resin 1: Biphenyl aralkyl type epoxy resin represented by the following general formula, NC3000, manufactured by Nippon Kayaku Co., Ltd.

[0077] [ka]

[0078] (In the general formula above, n = 1 to 10.)

[0079] (A) Epoxy resin 2: A mixture of trisphenylmethane-type epoxy resin and biphenyl-type epoxy resin, YL6677, manufactured by Mitsubishi Chemical Corporation. (B) Hardener 1: Trisphenylmethane mixed phenolic resin, HE910-20, manufactured by Airweter. (B) Hardener 2: Biphenyl aralkyl type 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. (Coloring agent) Coloring agent 1: Carbon black, manufactured by Mitsubishi Chemical Corporation, Carbon #5 (Aeon Catcher) Ion Catcher 1: Hydrotalcite, DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd. (Stress-reducing agent) (D) Triglyceride 1: Caprylic acid triglyceride, manufactured by Kao Corporation (D) Triglyceride 2:2-Ethylhexanoate triglyceride, manufactured by Kao Corporation (D) Triglyceride 3: Oleate triglyceride, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 4:12-hydroxystearate triglyceride, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 5: Triglyceride stearate, manufactured by Riken Vitamin Co., Ltd. (D) Triglyceride 6: Soybean oil, manufactured by Nisshin Oillio Group Co., Ltd.

[0080] (Method for calculating ΔHSP) The structural formulas for HSP calculation of each component (A) or low-stress agent were converted to SMILES notation using editor software (Chem Draw). When these SMILES formulas were entered into the Y-MB calculation software included with HSPiP, the HSP (δd, δp, δh) of each component was calculated. ΔHSP is the R shown in formula (1) above. 2It is represented by [this formula]. Table 2 shows the SMILES formula and HSP for each component.

[0081] Here, the HSP of triglyceride 6 (soybean oil) was determined using the following procedure. 1. We listed the combinations of the five main fatty acids contained in soybean oil and calculated their probability of existence. Then, we proceeded with the calculations for the triglycerides that accounted for the top 75.8% of the probabilities of existence. 2. Each of the listed triglycerides was expressed using the SMILES formula, and HSP(δd, δp, δh) was calculated using the HSPiP software. 3. The probability of existence of each HSP component of the listed triglycerides was multiplied, and the sum of these components was calculated to determine the HSP. The following provides a more detailed explanation of each step.

[0082] The "five major fatty acids" in step 1 above refer to the five major 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 set to palmitic acid 11.0%, stearic acid 4.7%, oleic acid 23.7%, linoleic acid 53.5%, and linolenic acid 7.1%. Since three molecules of any of the above fatty acids are bound to one molecule of glycerol in soybean oil, all combinations of the five fatty acids were listed. The method for calculating the probability of existence of the listed triglycerides is shown below with a specific example. (Example) In the case of a triglyceride formed by the bonding of three molecules of linoleic acid. 0.53 × 0.53 × 0.53 = 0.149 Similarly, the probability of existence was calculated for other triglycerides. These were then arranged in descending order of probability, and calculations were continued 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) In the case of a triglyceride formed by the bonding of three molecules of linoleic acid. SMILES formula: CCCCC / C=C / C / C=C / CCCCCCCC(OCC(COC(CCCCCC / C=C / C / C=C / CCCCC)=O)OC(CCCCCC / C=C / C / C=C / CCCCC)=O)=O HSP(δd, δp, δh)=(16.6, 1.7, 4.1) The same method was used to calculate the HSP for other triglycerides.

[0083] 3. The probability of existence of each HSP component of the triglycerides listed in step 2 above was multiplied, and the sum of these components was obtained as the HSP. (Example) In the case of a triglyceride formed by the bonding of three molecules of linoleic acid. (δd, δp, δh)=(16.6×0.149, 1.7×0.149, 4.1×0.149)=(2.47, 0.253, 0.611)

[0084] The HSP components calculated in step 3 above were added together to determine the HSP of soybean oil. HSP(δd, δp, δh)=(15.77, 1.61, 3.45)

[0085] (Measurement method and evaluation method) (Coefficient of linear expansion) The resin compositions obtained in each example were 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 test specimens measuring 15 mm (long side) x 4.5 mm (short side) x 3 mm (thickness). The obtained test specimens were post-cured at 175°C for 4 hours, and then measured using a thermomechanical analyzer (Hitachi High-Tech Science, TMA7100) in compression mode under conditions of a measurement temperature range of -60°C to 400°C and a heating rate of 5°C / min. Based on the measurement results, the average coefficient of linear expansion from 50°C to 70°C was calculated and defined as CTE1. Products with a CTE1 level of less than 9.3 ppm / ℃ were deemed acceptable.

[0086] (Flexural modulus and flexural strength) The resin compositions obtained in each example were injected and molded using a transfer molding apparatus at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds to obtain molded products measuring 10 mm in width, 4 mm in thickness, and 80 mm in length. The obtained molded products were post-cured at 175°C for 4 hours to obtain test specimens. The flexural modulus and flexural strength of the obtained test specimens at 25°C were measured in accordance with JIS K 6911. Materials with a bending modulus of less than 22.5 GPa were deemed acceptable.

[0087] (exterior) The resin compositions obtained in each example were injected and molded using a transfer molding apparatus at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 180 seconds to obtain disc-shaped molded products with a diameter of 90 mm and a thickness of 5 mm. The obtained molded products were post-cured at 175°C for 4 hours to obtain test specimens. The appearance of the obtained test specimens was visually observed and evaluated according to the following criteria. A: No surface contamination, or slight surface contamination. B: Surface contamination present throughout the entire specimen.

[0088] [Table 1]

[0089] [Table 2]

[0090] As shown in Table 1, in each example, the ΔHSP between the epoxy resin and the low-stress material was within a suitable range, and there was an excellent balance between the reduction of CTE1 and the reduction of elastic modulus. Furthermore, in each example, deterioration of appearance was also suitably suppressed. [Explanation of symbols]

[0091] 10 Base material 20 Electronic Components 21 Circuit side 22 Bump 30 Encapsulant layer 50 Electronic equipment 52 Electronic equipment 70 Sacrificial materials 71 Exfoliation layer 80 Insulating resin layer for rewiring 82 Beer Hall 92 Beer 94 Rewiring circuit 96 Solder Ball 98 Solder Resist Layers

Claims

1. (A) Epoxy resin, (B) Hardener, (C) Inorganic fillers, and (D) One or more low-stress materials selected from the group consisting of triglycerides and silicone oils. A sealing resin composition comprising, The above component (A) contains a biphenyl aralkyl type epoxy resin, The aforementioned component (B) comprises a trisphenylmethane mixed-type phenolic resin and a biphenylaralkyl-type phenolic resin. The Hansen solubility parameter distance of component (D) to component (A) is 8.5 MPa. 1 / 2 The above is 9.9 MPa. 1 / 2 The following are included, and also contains one or more first low-stress materials that are triglycerides: A sealing resin composition in which the content of the first low-stress material in the sealing resin composition is 1.5% by mass or more and 3.0% by mass or less of the total sealing resin composition.

2. The sealing resin composition according to Claim 1, wherein the average particle size d50 of (C) measured by a laser particle size distribution analyzer is 0.5 μm or more and 5 μm or less.

3. The sealing resin composition according to claim 2, wherein all three fatty acid residues in the triglyceride are the same.

4. The sealing resin composition according to any one of claims 1 to 3, wherein the content of component (D) in the sealing resin composition is 1.5% by mass or more and 2.5% by mass or less of the total sealing resin composition.

5. The sealing resin composition according to any one of claims 1 to 3, wherein the content of component (C) in the sealing resin composition is 86.5% by mass or more and 90% by mass or less of the total sealing resin composition.

6. A sealing resin composition according to any one of claims 1 to 3, used for sealing wafer-level packages (WLPs) or panel-level packages (PLPs).

7. A encapsulating resin composition according to any one of claims 1 to 3, wherein the composition is granular.

8. A cured body which is a cured product of the sealing resin composition according to any one of claims 1 to 3.

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 claims 1 to 3.

10. A panel-level package in which a plurality of electronic components are collectively sealed with the sealing resin composition described in any one of claims 1 to 3.

11. An electronic device in which the wafer-level package according to claim 9 is divided into individual pieces.

12. An electronic device in which the panel-level package according to claim 10 is divided into individual pieces.

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