TW201842052A - Epoxy resin composition and electronic component apparatus - Google Patents
Epoxy resin composition and electronic component apparatus Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Abstract
Description
本發明是有關於一種環氧樹脂組成物及電子零件裝置。The invention relates to an epoxy resin composition and an electronic component device.
伴隨近年來的電子機器的小型化、輕量化、高性能化等，安裝的高密度化正在推進。藉此，電子零件裝置的主流自現有的針腳***型的封裝向積體電路（Integrated Circuit，IC）、大規模積體電路（Large Scale Integration，LSI）等表面安裝型的封裝變化。With the recent miniaturization, weight reduction, and high performance of electronic devices, the mounting density has been increasing. As a result, the mainstream of electronic component devices has changed from the existing pin-plug-type packages to surface-mount packages such as integrated circuits (ICs) and large-scale integrated circuits (LSIs).
表面安裝型的封裝與現有的針腳***型的封裝的安裝方法不同。即，於將針腳安裝於配線板時，現有的針腳***型封裝於將針腳***至配線板中後，自配線板背面進行焊接，因此封裝不會直接暴露於高溫。但是，表面安裝型封裝中，電子零件裝置整體利用焊料浴、回焊裝置等進行處理，因此封裝會直接暴露於焊接溫度（回焊溫度）。其結果，於封裝吸濕的情況下，有時於焊接時吸濕所產生的水分劇烈膨脹，所產生的蒸氣壓作為剝離應力發揮作用，而於元件、引線框架等的***件與密封材之間產生剝離，從而成為封裝裂紋、電氣特性不良等的原因。因此，期望開發出對***件的接著性優異、進而焊料耐熱性（耐回焊性）優異的密封材料。The surface mounting type package is different from the conventional pin insertion type package. That is, when the pins are mounted on the wiring board, the conventional pin insertion type package is soldered from the back of the wiring board after the pins are inserted into the wiring board, so the package is not directly exposed to high temperatures. However, in the surface mount package, since the entire electronic component device is processed with a solder bath, a reflow device, etc., the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture generated by moisture absorption during soldering may swell sharply, and the generated vapor pressure acts as a peeling stress, and is applied to the inserts and sealing materials of components, lead frames, and the like. In some cases, peeling occurs, which can cause package cracks and poor electrical characteristics. Therefore, it is desired to develop a sealing material having excellent adhesiveness to the interposer and further excellent solder heat resistance (reflow resistance).
為了應對該些要求，至今為止對成為主材料的固體狀環氧樹脂進行了各種研究。例如，作為固形狀環氧樹脂，研究有使用聯苯型環氧樹脂或萘型環氧樹脂的方法（例如，參照日本專利特開昭64-65116號公報及日本專利特開2007-231159號公報）。In order to meet these requirements, various studies have been conducted on solid epoxy resins that have been used as main materials. For example, as a solid epoxy resin, a method using a biphenyl epoxy resin or a naphthalene epoxy resin has been studied (for example, refer to Japanese Patent Laid-Open No. Sho 64-65116 and Japanese Patent Laid-Open No. 2007-231159). ).
另外，關於各種環氧樹脂改質材的使用亦進行了研究，作為其中一例，著眼於元件與引線框架等的***件的密接力提高，而研究了矽烷偶合劑的使用。具體而言，有含環氧基的矽烷偶合劑或含胺基的矽烷偶合劑的使用（例如，參照日本專利特開平11-147939號公報）及含硫原子的矽烷偶合劑的使用（例如，參照日本專利特開2000-103940號公報）。In addition, the use of various epoxy resin modified materials has also been studied. As one example, the use of a silane coupling agent has been studied with a view to improving the adhesion between an element and an insert such as a lead frame. Specifically, there are the use of an epoxy group-containing silane coupling agent or an amine group-containing silane coupling agent (for example, refer to Japanese Patent Laid-Open No. 11-147939) and the use of a sulfur atom-containing silane coupling agent (for example, (Refer to Japanese Patent Laid-Open No. 2000-103940).
[發明所欲解決的課題] 然而，若僅使用聯苯型環氧樹脂或萘型環氧樹脂，則難以取得流動性及耐回焊性的平衡。 另外，若僅使用含環氧基的矽烷偶合劑或含胺基的矽烷偶合劑，則有時接著性提高效果並不充分。尤其，所述日本專利特開平11-147939號公報中記載的含胺基的矽烷偶合劑的反應性高，於用於密封用環氧樹脂組成物的情況下，密封時的流動性下降。進而，關於所述日本專利特開平11-147939號公報中記載的含環氧基的矽烷偶合劑及含胺基的矽烷偶合劑，矽烷偶合劑自身發生凝膠化等而流動性存在課題。 另外，於使用所述日本專利特開2000-103940號公報中記載的含硫原子的矽烷偶合劑的情況下，與Ag及Au之類的貴金屬的接著性提高效果不充分，耐回焊性的提高效果亦不充分。[Problems to be Solved by the Invention] However, if only a biphenyl type epoxy resin or a naphthalene type epoxy resin is used, it is difficult to achieve a balance between fluidity and reflow resistance. In addition, if only an epoxy group-containing silane coupling agent or an amine group-containing silane coupling agent is used, the effect of improving adhesion may not be sufficient in some cases. Particularly, the amine group-containing silane coupling agent described in Japanese Patent Application Laid-Open No. 11-147939 has high reactivity, and when it is used for an epoxy resin composition for sealing, the fluidity during sealing decreases. Furthermore, there is a problem regarding fluidity due to the epoxy group-containing silane coupling agent and the amine group-containing silane coupling agent described in Japanese Patent Application Laid-Open No. 11-147939, and the silane coupling agent itself gels. In addition, when the sulfur atom-containing silane coupling agent described in Japanese Patent Laid-Open No. 2000-103940 is used, the effect of improving adhesion with precious metals such as Ag and Au is insufficient, and reflow resistance The improvement effect is also insufficient.
如上所述，無法獲得充分滿足耐回焊性與流動性此兩者的環氧樹脂組成物成為現狀。 本揭示是鑒於所述狀況而成者，其課題在於提供一種維持流動性且耐回焊性優異的環氧樹脂組成物、以及具備所述環氧樹脂組成物的硬化物的電子零件裝置。 [解決課題之手段]As described above, it is a current situation that an epoxy resin composition that cannot sufficiently satisfy both reflow resistance and fluidity is obtained. The present disclosure has been made in view of the above circumstances, and an object thereof is to provide an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, and an electronic component device including the cured product of the epoxy resin composition. [Means for solving problems]
為了解決所述課題的手段包含以下實施態樣。 ＜1＞ 一種環氧樹脂組成物，其含有：熔點或軟化點超過40℃的環氧樹脂、硬化劑、以及具有縮水甘油基且熔點為40℃以下的化合物。 ＜2＞ 如＜1＞所述的環氧樹脂組成物，其中所述具有縮水甘油基且熔點為40℃以下的化合物具有二環戊二烯骨架。 ＜3＞ 如＜1＞或＜2＞所述的環氧樹脂組成物，其中所述具有縮水甘油基且熔點為40℃以下的化合物的含有率相對於所述環氧樹脂而言為5質量%以上且未滿45質量%。 ＜4＞ 如＜1＞～＜3＞中任一項所述的環氧樹脂組成物，其進一步含有硬化促進劑。 ＜5＞ 如＜1＞～＜4＞中任一項所述的環氧樹脂組成物，其進一步含有無機填充材。 ＜6＞ 如＜1＞～＜5＞中任一項所述的環氧樹脂組成物，其進一步含有矽烷化合物。 ＜7＞ 如＜1＞～＜6＞中任一項所述的環氧樹脂組成物，其中所述環氧樹脂的熔點或軟化點為80℃～130℃。 ＜8＞ 如＜1＞～＜7＞中任一項所述的環氧樹脂組成物，其中所述具有縮水甘油基且熔點為40℃以下的化合物的環氧當量為165 g/eq～365 g/eq。 ＜9＞ 如＜1＞～＜8＞中任一項所述的環氧樹脂組成物，其中所述具有縮水甘油基且熔點為40℃以下的化合物的含有率相對於所述環氧樹脂而言為20質量%以上且未滿45質量%。 ＜10＞ 一種電子零件裝置，其包括：元件；以及密封所述元件的如＜1＞～＜9＞中任一項所述的環氧樹脂組成物的硬化物。 [發明的效果]Means for solving the problems include the following implementation aspects. <1> An epoxy resin composition containing an epoxy resin having a melting point or softening point exceeding 40 ° C, a hardener, and a compound having a glycidyl group and a melting point of 40 ° C or lower. <2> The epoxy resin composition according to <1>, wherein the compound having a glycidyl group and having a melting point of 40 ° C. or lower has a dicyclopentadiene skeleton. <3> The epoxy resin composition according to <1> or <2>, wherein a content rate of the compound having a glycidyl group and a melting point of 40 ° C. or lower is 5 masses relative to the epoxy resin % Or more and less than 45% by mass. <4> The epoxy resin composition according to any one of <1> to <3>, further containing a hardening accelerator. <5> The epoxy resin composition according to any one of <1> to <4>, further containing an inorganic filler. <6> The epoxy resin composition according to any one of <1> to <5>, further containing a silane compound. <7> The epoxy resin composition according to any one of <1> to <6>, wherein the melting point or softening point of the epoxy resin is 80 ° C to 130 ° C. <8> The epoxy resin composition according to any one of <1> to <7>, wherein the epoxy equivalent of the compound having a glycidyl group and a melting point of 40 ° C or lower is 165 g / eq to 365 g / eq. <9> The epoxy resin composition according to any one of <1> to <8>, wherein a content rate of the compound having a glycidyl group and a melting point of 40 ° C or lower is relative to the epoxy resin. It is said to be 20% by mass or more and less than 45% by mass. <10> An electronic component device including: a component; and a cured product of the epoxy resin composition according to any one of <1> to <9> that seals the component. [Effect of the invention]
根據本揭示，可提供一種維持流動性且耐回焊性優異的環氧樹脂組成物、以及具備所述環氧樹脂組成物的硬化物的電子零件裝置。因此，其工業價值大。According to the present disclosure, it is possible to provide an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, and an electronic component device including the cured product of the epoxy resin composition. Therefore, its industrial value is great.
以下，對用以實施本發明的形態進行詳細說明。但是，本發明並不限定於以下的實施形態。於以下的實施形態中，其構成要素（亦包括要素步驟等）除了特別明示的情況，並非必須。關於數值及其範圍亦相同，並不限制本發明。Hereinafter, the form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not necessarily required except for the case where they are specifically stated. The same applies to numerical values and ranges, and does not limit the present invention.
於本揭示中，使用「～」而表示的數值範圍包括「～」的前後所記載的數值分別作為最小值及最大值。 於本揭示中階段性記載的數值範圍中，在一個數值範圍中所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。另外，於本揭示中所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 於本揭示中，關於組成物中的各成分的含有率或含量，於在組成物中存在多種相當於各成分的物質的情況下，只要無特別說明，則是指組成物中所存在的該多種物質的合計含有率或含量。 於本揭示中，關於「層」這一用語，於觀察該層所存在的區域時，除了形成於該區域的整個區域的情況以外，亦包含僅形成於該區域的一部分的情況。 於本揭示中，「積層」這一用語表示將層堆疊，可將兩層以上的層結合，亦可將兩層以上的層拆卸。In the present disclosure, the numerical ranges indicated using "~" include numerical values described before and after "~" as the minimum and maximum values, respectively. In the numerical range described in this disclosure stepwise, the upper limit value or lower limit value described in one numerical range may be replaced by the upper limit value or lower limit value in other numerical range described in stepwise. In addition, in the numerical range described in this disclosure, the upper limit value or lower limit value of this numerical range may be replaced with the value shown in an Example. In the present disclosure, regarding the content rate or content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means that the component is present in the composition. The total content or content of multiple substances. In the present disclosure, the term "layer" includes a case where a region existing in the layer is formed only in a part of the region, in addition to a case where the region is formed in the entire region. In the present disclosure, the term “lamination” means that the layers are stacked, and two or more layers can be combined or disassembled.
＜環氧樹脂組成物＞ 本發明的實施形態的環氧樹脂組成物含有：熔點或軟化點超過40℃的環氧樹脂（以下，亦稱為「（A）特定環氧樹脂」或「特定環氧樹脂」）、硬化劑（以下，亦稱為「（B）硬化劑」或「硬化劑」）、以及具有縮水甘油基且熔點為40℃以下的化合物（以下，亦稱為「（C）特定縮水甘油基化合物」或「特定縮水甘油基化合物」）。環氧樹脂組成物亦可視需要包含其他成分。再者，作為（C）特定縮水甘油基化合物，例如可列舉於常溫（例如25℃）下為液狀的化合物。 藉由所述構成，所述環氧樹脂組成物的耐回焊性優異。另外，所述環氧樹脂組成物的流動性良好。<Epoxy resin composition> The epoxy resin composition according to the embodiment of the present invention includes an epoxy resin having a melting point or a softening point exceeding 40 ° C. (hereinafter, also referred to as “(A) specific epoxy resin” or “specific ring Oxygen resin "), hardeners (hereinafter, also referred to as" (B) hardeners "or" hardeners "), and compounds with glycidyl groups and melting points below 40 ° C (hereinafter, also referred to as" (C) Specific glycidyl compounds "or" specific glycidyl compounds "). The epoxy resin composition may contain other components as needed. Moreover, as (C) specific glycidyl compound, the compound which is liquid at normal temperature (for example, 25 degreeC) is mentioned, for example. With this configuration, the epoxy resin composition is excellent in reflow resistance. In addition, the epoxy resin composition has good fluidity.
環氧樹脂組成物維持流動性且耐回焊性優異的理由雖不明確，但可如以下般考慮。具體而言，認為原因在於：藉由特定縮水甘油基化合物中的縮水甘油基與環氧樹脂組成物中的硬化劑結合，可獲得接著力的提高效果及彈性係數的減低效果，而維持高流動性且耐回焊性提高。Although the reason why the epoxy resin composition maintains fluidity and is excellent in reflow resistance is not clear, it can be considered as follows. Specifically, the reason is considered to be that the combination of the glycidyl group in the specific glycidyl compound and the hardener in the epoxy resin composition can obtain the effect of improving the adhesion and the effect of reducing the coefficient of elasticity while maintaining high flow. And improved reflow resistance.
所述環氧樹脂組成物例如可列舉於常溫常壓（例如25℃、1氣壓）下為固體者。固體的形狀並無限制，可為粉狀、粒狀、片狀等任意形狀。 另外，所述環氧樹脂組成物亦可用作密封用樹脂組成物、進而轉移模具用樹脂組成物。Examples of the epoxy resin composition are those which are solid at normal temperature and pressure (eg, 25 ° C., 1 atmosphere). The shape of the solid is not limited, and may be any shape such as powder, granular, and flake. The epoxy resin composition can also be used as a resin composition for sealing and a resin composition for transfer molds.
（C）特定縮水甘油基化合物 （C）特定縮水甘油基化合物是於分子結構中具有縮水甘油基且熔點為40℃以下的化合物。特定縮水甘油基化合物可單獨使用一種，亦可組合使用兩種以上。 藉由環氧樹脂組成物包含特定縮水甘油基化合物而維持流動性且耐回焊性優異。 再者，就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定縮水甘油基化合物的一分子所具有的縮水甘油基的數量較佳為1～6，更佳為2～4。(C) Specific glycidyl compound (C) The specific glycidyl compound is a compound having a glycidyl group in a molecular structure and a melting point of 40 ° C or lower. The specific glycidyl compound may be used singly or in combination of two or more kinds. When the epoxy resin composition contains a specific glycidyl compound, fluidity is maintained and reflow resistance is excellent. Furthermore, from the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the number of glycidyl groups per molecule of the specific glycidyl compound is preferably 1 to 6, and more preferably It is 2 to 4.
就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定縮水甘油基化合物較佳為於分子結構中進一步具有二環戊二烯骨架。推測藉由含有在分子結構中具有縮水甘油基及二環戊二烯骨架的特定縮水甘油基化合物，除了特定縮水甘油基化合物中的縮水甘油基與環氧樹脂組成物中的硬化劑結合以外，進而二環戊二烯結構在金屬表面相互作用，因此接著力進一步提高。 再者，就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定縮水甘油基化合物的一分子所具有的二環戊二烯骨架的數量較佳為1～4，更佳為1～2。From the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the specific glycidyl compound preferably has a dicyclopentadiene skeleton in the molecular structure. It is speculated that by including a specific glycidyl compound having a glycidyl group and a dicyclopentadiene skeleton in a molecular structure, in addition to the glycidyl group in the specific glycidyl compound being bonded to the hardener in the epoxy resin composition, Furthermore, the dicyclopentadiene structure interacts on the metal surface, so the adhesion force is further increased. Furthermore, from the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the number of dicyclopentadiene skeletons per molecule of the specific glycidyl compound is preferably 1 to 4 , More preferably 1 to 2.
作為特定縮水甘油基化合物的具體例，例如可列舉二環戊二烯二甲醇二縮水甘油醚。 另外，作為特定縮水甘油基化合物的具體例，除了所述化合物以外，例如亦可列舉橡膠交聯雙酚型環氧樹脂、螯合物改質型環氧樹脂。As a specific example of a specific glycidyl compound, a dicyclopentadiene dimethanol diglycidyl ether is mentioned, for example. Moreover, as a specific example of a specific glycidyl compound, in addition to the said compound, a rubber crosslinked bisphenol type epoxy resin, a chelate modification type epoxy resin can be mentioned, for example.
就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定縮水甘油基化合物的分子量較佳為100～600，更佳為200～400。 另外，特定縮水甘油基化合物的熔點為40℃以下，就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，較佳為0℃～35℃，更佳為0℃～30℃。 另外，特定縮水甘油基化合物的環氧當量較佳為165 g/eq～365 g/eq，更佳為165 g/eq～240 g/eq。From the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the molecular weight of the specific glycidyl compound is preferably 100 to 600, and more preferably 200 to 400. The melting point of the specific glycidyl compound is 40 ° C or lower, and from the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, it is preferably 0 ° C to 35 ° C, and more preferably 0 ° C. ～ 30 ℃. The epoxy equivalent of the specific glycidyl compound is preferably 165 g / eq to 365 g / eq, and more preferably 165 g / eq to 240 g / eq.
特定縮水甘油基化合物在環氧樹脂組成物中的含有率相對於（A）特定環氧樹脂的合計量而較佳為5質量%以上且未滿45質量%。藉由為5質量%以上，與未滿5質量%的情況相比，存在接著性提高、可獲得耐回焊性的提高效果的傾向。另外，藉由未滿45質量%，與為45質量%以上的情況相比，存在成形時的硬度的下降得到抑制的傾向。 再者，特定縮水甘油基化合物的含有率相對於（A）特定環氧樹脂的合計量而較佳為10質量%以上且未滿45質量%，進而佳為20質量%以上且未滿45質量%，尤佳為25質量%以上且未滿45質量%。 另外，特定縮水甘油基化合物的含有率相對於環氧樹脂組成物整體而較佳為1質量%以上。The content rate of the specific glycidyl compound in the epoxy resin composition is preferably 5% by mass or more and less than 45% by mass based on the total amount of the (A) specific epoxy resin. When it is 5 mass% or more, compared with the case where it is less than 5 mass%, there exists a tendency for adhesiveness to improve, and the improvement effect of reflow resistance may be acquired. Moreover, since it is less than 45 mass%, compared with the case where it is 45 mass% or more, the fall of the hardness at the time of shaping | molding tends to be suppressed. The content rate of the specific glycidyl compound is preferably 10% by mass or more and less than 45% by mass, and more preferably 20% by mass or more and less than 45% by mass with respect to the total amount of the (A) specific epoxy resin. %, Particularly preferably 25 mass% or more and less than 45 mass%. The content of the specific glycidyl compound is preferably 1% by mass or more with respect to the entire epoxy resin composition.
（A）特定環氧樹脂 環氧樹脂組成物包含熔點或軟化點超過40℃的環氧樹脂（即（A）特定環氧樹脂）的至少一種。 此處，環氧樹脂的熔點或軟化點設為藉由日本工業標準（Japanese Industrial Standards，JIS）K 7234:1986及JIS K 7233:1986中記載的單圓筒旋轉黏度計法測定而得的值。 特定環氧樹脂可為環氧樹脂組成物中通常所使用者，只要為熔點或軟化點超過40℃者，則並無特別限制。 就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定環氧樹脂的熔點或軟化點較佳為45℃～180℃，更佳為50℃～150℃，進而佳為80℃～130℃，尤佳為96℃～113℃。(A) Specific epoxy resin The epoxy resin composition contains at least one type of epoxy resin (ie, (A) specific epoxy resin) having a melting point or a softening point exceeding 40 ° C. Here, the melting point or softening point of the epoxy resin is a value measured by a single-cylinder rotary viscometer method described in Japanese Industrial Standards (JIS) K 7234: 1986 and JIS K 7233: 1986. . The specific epoxy resin may be generally used in epoxy resin compositions, and is not particularly limited as long as the melting point or softening point exceeds 40 ° C. From the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the melting point or softening point of the specific epoxy resin is preferably 45 ° C to 180 ° C, more preferably 50 ° C to 150 ° C, and furthermore The temperature is preferably 80 ° C to 130 ° C, and particularly preferably 96 ° C to 113 ° C.
其中，特定環氧樹脂較佳為於一分子中含有兩個以上的環氧基者。 就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，特定環氧樹脂的環氧當量較佳為100 g/eq～1000 g/eq，更佳為150 g/eq～1000 g/eq，進而佳為150 g/eq～500 g/eq，尤佳為196 g/eq～245 g/eq。 環氧當量是在使所秤量的環氧樹脂溶解於甲基乙基酮等溶劑中並加入乙酸與四乙基溴化銨乙酸溶液後，藉由過氯酸乙酸標準液並利用電位差滴定來測定。所述滴定亦可使用指示劑。Among them, the specific epoxy resin preferably contains two or more epoxy groups in one molecule. From the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the epoxy equivalent of the specific epoxy resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq. ~ 1000 g / eq, more preferably 150 g / eq to 500 g / eq, and even more preferably 196 g / eq to 245 g / eq. The epoxy equivalent is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a tetraethylammonium bromide acetic acid solution, and using a perchloric acid acetic acid standard solution and potentiometric titration. . The titration may also use an indicator.
作為特定環氧樹脂，具體而言可列舉：使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F等酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群粗中的至少一種酚性化合物與甲醛、乙醛、丙醛等脂肪族醛化合物在酸性觸媒下縮合或共縮合而獲得酚醛清漆樹脂並將該酚醛清漆樹脂進行環氧化而獲得的酚醛清漆型環氧樹脂（苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂等）；使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物在酸性觸媒下縮合或共縮合而獲得三苯基甲烷型酚樹脂並將該三苯基甲烷型酚樹脂進行環氧化而獲得的三苯基甲烷型環氧樹脂；使所述酚化合物及萘酚化合物與醛化合物在酸性觸媒下共縮合而獲得酚醛清漆樹脂並將該酚醛清漆樹脂進行環氧化而獲得的共聚型環氧樹脂；作為雙酚A、雙酚F等的二縮水甘油醚的二苯基甲烷型環氧樹脂；作為烷基取代或未經取代的聯苯酚的二縮水甘油醚的聯苯型環氧樹脂；作為芪系酚化合物的二縮水甘油醚的芪型環氧樹脂；雙酚S的二縮水甘油醚、硫代二苯酚型環氧樹脂等含硫原子的環氧樹脂；作為丁二醇、聚乙二醇、聚丙二醇等醇類的縮水甘油醚的環氧樹脂；作為鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等多元羧酸化合物的縮水甘油酯的縮水甘油酯型環氧樹脂；將苯胺、二胺基二苯基甲烷、異三聚氰酸等的鍵結於氮原子的活性氫以縮水甘油基取代而獲得的縮水甘油胺型環氧樹脂；將二環戊二烯與酚化合物的共縮合樹脂進行環氧化而獲得的二環戊二烯型環氧樹脂；將分子內的烯烴鍵進行環氧化而獲得的二環氧化乙烯基環己烯、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺環(3,4-環氧基)環己烷-間二噁烷等脂環型環氧樹脂；作為對二甲苯改質酚樹脂的縮水甘油醚的對二甲苯改質環氧樹脂；作為間二甲苯改質酚樹脂的縮水甘油醚的間二甲苯改質環氧樹脂；作為萜烯改質酚樹脂的縮水甘油醚的萜烯改質環氧樹脂；作為二環戊二烯改質酚樹脂的縮水甘油醚的二環戊二烯改質環氧樹脂；作為環戊二烯改質酚樹脂的縮水甘油醚的環戊二烯改質環氧樹脂；作為多環芳香環改質酚樹脂的縮水甘油醚的多環芳香環改質環氧樹脂；作為含萘環的酚樹脂的縮水甘油醚的萘型環氧樹脂；鹵化苯酚酚醛清漆型環氧樹脂；對苯二酚型環氧樹脂；三羥甲基丙烷型環氧樹脂；利用過乙酸等過酸將烯烴鍵氧化而獲得的線狀脂肪族環氧樹脂；將含有伸聯苯基骨架的苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂進行環氧化而獲得的芳烷基型環氧樹脂等。進而，亦可列舉矽酮樹脂的環氧化物、丙烯酸樹脂的環氧化物等作為特定環氧樹脂。該些環氧樹脂可單獨使用一種，亦可組合使用兩種以上。Specific examples of the specific epoxy resin include phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and α-naphthol, At least one phenolic compound in a group consisting of naphthol compounds such as β-naphthol and dihydroxynaphthol, and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde are condensed or co-condensed under an acidic catalyst to obtain a novolac A novolac-type epoxy resin (phenol novolac-type epoxy resin, o-cresol novolac-type epoxy resin, etc.) obtained by epoxidizing the novolac resin; a phenolic compound, benzaldehyde, A triphenylmethane type epoxy resin obtained by condensing or co-condensing an aromatic aldehyde compound such as salicylaldehyde under an acidic catalyst and epoxidizing the triphenylmethane type phenol resin A copolymer epoxy resin obtained by co-condensing the phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst to obtain a novolak resin and epoxidizing the novolak resin; as bisphenol A, bisphenol F and other two Diphenylmethane type epoxy resin of glycidyl ether; biphenyl type epoxy resin of diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene type of diglycidyl ether of stilbene phenol compound Epoxy resins; bisphenol S diglycidyl ether, thiodiphenol-type epoxy resins and other sulfur atom-containing epoxy resins; as glyceryl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resins; glycidyl ester epoxy resins that are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; aniline, diaminodiphenylmethane, Glycidylamine type epoxy resin obtained by substituting glycidyl group with active hydrogen bonded to nitrogen atom such as isocyanuric acid; obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound Dicyclopentadiene epoxy resin; Diepoxidized vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl obtained by epoxidizing olefinic bonds in the molecule Alkyl carboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy ) Cyclohexane-dioxane and other alicyclic epoxy resins; p-xylene modified epoxy resins as glycidyl ethers of p-xylene modified phenol resins; glycidol as m-xylene modified phenol resins Ether meta-xylene modified epoxy resin; terpene modified epoxy resin as glycidyl ether of terpene modified phenol resin; dicyclopentadiene as glycidyl ether of dicyclopentadiene modified phenol resin Olefin modified epoxy resin; cyclopentadiene modified epoxy resin as glycidyl ether of cyclopentadiene modified phenol resin; polycyclic aromatic ring modified of glycidyl ether as polycyclic aromatic ring modified phenol resin Epoxy resin; naphthalene type epoxy resin as a glycidyl ether of a phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin ; Linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; aralkyl-type phenol resins such as phenol aralkyl resins containing naphthyl aralkyl resins and naphthol aralkyl resins An aralkyl-type epoxy resin and the like obtained by epoxidation. Further, as the specific epoxy resin, an epoxy resin of a silicone resin, an epoxy resin of an acrylic resin, or the like can be cited. These epoxy resins may be used singly or in combination of two or more.
作為特定環氧樹脂，所述環氧樹脂中，就流動性及耐回焊性的觀點而言，較佳為作為具有雙酚F骨架的環氧樹脂的雙酚F型環氧樹脂、芪型環氧樹脂及含硫原子的環氧樹脂，就硬化性的觀點而言，較佳為酚醛清漆型環氧樹脂，就低吸濕性的觀點而言，較佳為二環戊二烯型環氧樹脂，就耐熱性及低翹曲性的觀點而言，較佳為萘型環氧樹脂，就阻燃性的觀點而言，較佳為作為具有伸聯苯基骨架的環氧樹脂的伸聯苯基型環氧樹脂及將萘酚芳烷基樹脂進行環氧化而獲得的萘酚芳烷基型環氧樹脂。 特定環氧樹脂較佳為含有雙酚F型環氧樹脂、芪型環氧樹脂、含硫原子的環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、伸聯苯基型環氧樹脂及萘酚芳烷基型環氧樹脂中的至少一種。作為特定環氧樹脂，使用阻燃性良好的樹脂，就高溫放置特性提高的觀點而言，較佳為設為無鹵素及無銻（即，使用不含鹵素原子及銻原子此兩者的環氧樹脂）。As the specific epoxy resin, among the epoxy resins, bisphenol F-type epoxy resins and stilbene type epoxy resins, which are epoxy resins having a bisphenol F skeleton, are preferred from the viewpoint of fluidity and reflow resistance. The epoxy resin and the sulfur atom-containing epoxy resin are preferably a novolac-type epoxy resin in terms of hardenability, and a dicyclopentadiene-type ring in terms of low hygroscopicity. The oxyresin is preferably a naphthalene-type epoxy resin from the viewpoint of heat resistance and low warpage, and is more preferably an epoxy resin having an extended biphenyl group from the viewpoint of flame retardancy. A biphenyl type epoxy resin and a naphthol aralkyl type epoxy resin obtained by epoxidizing a naphthol aralkyl resin. The specific epoxy resin is preferably a bisphenol F-type epoxy resin, a stilbene-type epoxy resin, a sulfur atom-containing epoxy resin, a novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, or a naphthalene-type ring. At least one of an oxyresin, a stretched phenyl type epoxy resin, and a naphthol aralkyl type epoxy resin. As the specific epoxy resin, a resin having good flame retardancy is used, and from the viewpoint of improving the high-temperature storage characteristics, it is preferable to use halogen-free and antimony-free (that is, a ring containing neither a halogen atom nor an antimony atom. Oxygen resin).
再者，特定環氧樹脂可根據目的及製造條件等選擇使用。例如，作為特定環氧樹脂，可將作為含有伸聯苯基骨架的苯酚芳烷基樹脂的環氧化物的含伸聯苯基骨架的苯酚芳烷基型環氧樹脂、及作為具有甲氧基萘骨架的環氧樹脂的甲氧基萘型環氧樹脂等單獨使用或組合使用。The specific epoxy resin can be selected and used according to the purpose, production conditions, and the like. For example, as the specific epoxy resin, a phenol aralkyl type epoxy resin containing a biphenyl group, which is an epoxide of a phenol aralkyl resin containing a biphenyl group, and a methoxy group, A methoxynaphthalene type epoxy resin, etc. of a naphthalene skeleton epoxy resin is used individually or in combination.
相對於特定環氧樹脂整體而言的雙酚F型環氧樹脂、芪型環氧樹脂、含硫原子的環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、伸聯苯基型環氧樹脂及萘酚芳烷基型環氧樹脂的合計含有率較佳為20質量%以上，更佳為30質量%以上，進而佳為50質量%以上。Bisphenol F-type epoxy resin, stilbene-type epoxy resin, sulfur atom-containing epoxy resin, novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene with respect to the specific epoxy resin as a whole The total content of the epoxy resin, the stretched phenyl epoxy resin, and the naphthol aralkyl epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. .
就成形性、耐回焊性及電氣可靠性等各種特性平衡的觀點而言，特定環氧樹脂整體的含有率較佳為於環氧樹脂組成物中為0.4質量%～28質量%，更佳為1.1質量%～26質量%。若特定環氧樹脂在環氧樹脂組成物中的含有率為28質量%以下，則與超過28質量%的情況相比，存在耐回焊性得到良好地保持的傾向。另外，若為0.4質量%以上，則與未滿0.4質量%的情況相比存在流動性得到良好地保持的傾向。From the viewpoint of a balance of various properties such as formability, reflow resistance, and electrical reliability, the content of the specific epoxy resin as a whole is preferably 0.4% to 28% by mass in the epoxy resin composition, and more preferably It is 1.1% by mass to 26% by mass. When the content rate of a specific epoxy resin in an epoxy resin composition is 28 mass% or less, compared with the case where it exceeds 28 mass%, reflow resistance tends to be maintained favorably. Moreover, when it is 0.4 mass% or more, there exists a tendency for fluidity | liquidity to be maintained favorable compared with the case where it is less than 0.4 mass%.
（B）硬化劑 環氧樹脂組成物包含硬化劑的至少一種。硬化劑可為環氧樹脂組成物中通常使用者，並無特別限制。 作為（B）硬化劑，可列舉：酚硬化劑、胺硬化劑、酸酐硬化劑、聚硫醇硬化劑、聚胺基醯胺硬化劑、異氰酸酯硬化劑、嵌段異氰酸酯硬化劑等。就獲得維持流動性且耐回焊性優異的環氧樹脂組成物的觀點而言，硬化劑較佳為酚硬化劑、胺硬化劑及酸酐硬化劑，更佳為酚硬化劑。(B) Hardener The epoxy resin composition contains at least one kind of hardener. The hardener can be an ordinary user in the epoxy resin composition, and is not particularly limited. Examples of the (B) curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polythiol curing agent, a polyurethane curing agent, an isocyanate curing agent, and a block isocyanate curing agent. From the viewpoint of obtaining an epoxy resin composition that maintains fluidity and is excellent in reflow resistance, the hardener is preferably a phenol hardener, an amine hardener, and an acid anhydride hardener, and more preferably a phenol hardener.
作為酚硬化劑，例如可列舉於一分子中具有兩個以上的酚性羥基的酚樹脂及多元酚化合物。具體而言，可列舉：間苯二酚、鄰苯二酚、雙酚A、雙酚F、經取代或未經取代的聯苯酚等多元酚化合物；使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群粗中的至少一種酚性化合物與甲醛、乙醛、丙醛等醛化合物在酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由所述酚性化合物與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯等合成的芳烷基型酚樹脂（苯酚芳烷基樹脂、萘酚芳烷基樹脂等）；對二甲苯改質酚樹脂；間二甲苯改質酚樹脂；三聚氰胺改質酚樹脂；萜烯改質酚樹脂；藉由所述酚性化合物與二環戊二烯的共聚而合成的二環戊二烯型酚樹脂及二環戊二烯型萘酚樹脂；環戊二烯改質酚樹脂；多環芳香環改質酚樹脂；聯苯型酚樹脂；使所述酚性化合物與苯甲醛、柳醛等芳香族醛化合物在酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂；將該些兩種以上共聚而獲得的酚樹脂等。該些酚樹脂可單獨使用一種，亦可組合使用兩種以上。Examples of the phenol hardener include a phenol resin and a polyphenol compound having two or more phenolic hydroxyl groups in one molecule. Specific examples include polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; and selected from the group consisting of phenol, cresol, and xylenol. , Resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds Novolac-type phenol resin obtained by condensing or co-condensing at least one phenolic compound with formaldehyde, acetaldehyde, propionaldehyde and other aldehyde compounds under an acid catalyst; the phenolic compound and a dimethoxyl pair Xylene, bis (methoxymethyl) biphenyl and other synthetic aralkyl phenol resins (phenol aralkyl resin, naphthol aralkyl resin, etc.); p-xylene modified phenol resin; m-xylene modified Phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene type phenol resin and dicyclopentadiene type synthesized by copolymerization of the phenolic compound and dicyclopentadiene Naphthol resin; Cyclopentadiene modified phenol resin; Polycyclic aromatic ring modified phenol resin; Biphenyl type phenol resin; Phenolic compound with benzaldehyde, Liu aldehyde aromatic aldehyde compound under an acidic condensation or co-condensation catalyst triphenylmethane type phenol resin obtained; the more phenol resin obtained by copolymerization of two or more. These phenol resins may be used alone or in combination of two or more.
所述例示的硬化劑（即，酚醛清漆型酚樹脂、芳烷基型酚樹脂、對二甲苯改質酚樹脂、間二甲苯改質酚樹脂、三聚氰胺改質酚樹脂、萜烯改質酚樹脂、二環戊二烯型酚樹脂、二環戊二烯型萘酚樹脂、環戊二烯改質酚樹脂、多環芳香環改質酚樹脂、聯苯型酚樹脂及三苯基甲烷型酚樹脂以及將該些兩種以上共聚而獲得的酚樹脂）可單獨使用任一種，亦可組合使用兩種以上。所述例示的硬化劑（於使用兩種以上的情況下為其合計）的含有率較佳為於硬化劑總量中為50質量%以上，更佳為60質量%以上，進而佳為80質量%以上。The exemplified hardeners (ie, novolac-type phenol resin, aralkyl-type phenol resin, p-xylene modified phenol resin, m-xylene modified phenol resin, melamine-modified phenol resin, terpene-modified phenol resin , Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenol resin, polycyclic aromatic ring modified phenol resin, biphenyl type phenol resin and triphenylmethane type phenol The resin and the phenol resin obtained by copolymerizing these two or more kinds may be used singly or in combination of two or more kinds. The content rate of the exemplified hardener (total of two or more) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass of the total hardener. %the above.
硬化劑的官能基當量並無特別限制，就成形性、耐回焊性及電氣可靠性等的平衡的觀點而言，較佳為70 g/eq～1000 g/eq，更佳為80 g/eq～500 g/eq。再者，官能基當量是指依據JIS K0070:1992測定而得的值。 另外，硬化劑的軟化點或融點並無特別限制，就成形性及耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物製作時的操作性的觀點而言，更佳為50℃～130℃。再者，硬化劑的軟化點或融點的測定方法與特定環氧樹脂的軟化點或融點的測定方法相同。The functional group equivalent of the hardener is not particularly limited, and from the viewpoint of the balance of formability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq. eq ～ 500 g / eq. The functional group equivalent is a value measured in accordance with JIS K0070: 1992. In addition, the softening point or melting point of the hardener is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably from 40 ° C to 180 ° C, and from the viewpoint of operability during production of the epoxy resin composition. It is more preferably 50 ° C to 130 ° C. The method of measuring the softening or melting point of the hardener is the same as the method of measuring the softening or melting point of the specific epoxy resin.
環氧樹脂組成物中，（A）特定環氧樹脂及（C）特定縮水甘油基化合物與（B）硬化劑的當量比、即硬化劑中的官能基數相對於特定環氧樹脂及特定縮水甘油基化合物中的環氧基及縮水甘油基的總量的比（硬化劑中的官能基數/特定環氧樹脂及特定縮水甘油基化合物中的環氧基數及縮水甘油基數的合計）並無特別限制。為了將各未反應成分抑制得少，較佳為設定為0.5～2.0的範圍內，更佳為設定為0.6～1.3的範圍內。為了獲得成形性以及耐焊料性及耐回焊性更優異的環氧樹脂組成物，進而佳為設定為0.8～1.2的範圍內。藉由所述比率為0.5以上，與未滿0.5的情況相比，存在環氧樹脂組成物容易充分硬化，環氧樹脂組成物的硬化物的耐熱性、耐濕性及電氣特性變得良好的傾向。另一方面，藉由所述比率為2.0以下，與超過2.0的情況相比，存在硬化劑成分過剩所引起的硬化效率的下降、以及硬化物中殘留大量的官能基所引起的封裝的電氣特性及耐濕性的下降得到抑制的傾向。尤其是於使用酚硬化劑作為硬化劑的情況下，藉由所述比率為2.0以下，與超過2.0的情況相比，存在酚樹脂成分過剩所引起的硬化效率的下降、以及硬化物中殘留大量的酚性羥基所引起的封裝的電氣特性及耐濕性的下降得到抑制的傾向。In the epoxy resin composition, (A) the specific epoxy resin and (C) the specific glycidyl compound to (B) the equivalent ratio of the hardener, that is, the number of functional groups in the hardener relative to the specific epoxy resin and specific glycidol The ratio of the total number of epoxy groups and glycidyl groups in the base compound (the total number of functional groups in the hardener / the total number of epoxy groups and glycidyl groups in the specific epoxy resin and the specific glycidyl compound) is not particularly limited . In order to suppress each unreacted component to a small extent, it is preferably set in a range of 0.5 to 2.0, and more preferably set in a range of 0.6 to 1.3. In order to obtain an epoxy resin composition which is more excellent in moldability, solder resistance, and reflow resistance, it is more preferably set within a range of 0.8 to 1.2. When the ratio is 0.5 or more, compared with the case where the ratio is less than 0.5, the epoxy resin composition is easily cured sufficiently, and the cured product of the epoxy resin composition has good heat resistance, humidity resistance, and electrical characteristics. tendency. On the other hand, when the ratio is 2.0 or less, compared with the case where the ratio is more than 2.0, there is a decrease in curing efficiency due to an excessive amount of hardener component, and electrical characteristics of the package due to a large number of functional groups remaining in the cured material. And the decline in moisture resistance tends to be suppressed. In particular, when a phenol hardener is used as the hardener, when the ratio is 2.0 or less, compared with a case where the ratio exceeds 2.0, there is a decrease in hardening efficiency due to an excessive amount of phenol resin component, and a large amount of residual in the hardened material The decrease in the electrical characteristics and moisture resistance of the package caused by the phenolic hydroxyl group tends to be suppressed.
（D）硬化促進劑 環氧樹脂組成物除了（A）特定環氧樹脂、（B）硬化劑及（C）特定縮水甘油基化合物以外，亦可視需要包含（D）硬化促進劑的至少一種。作為硬化促進劑，只要為促進（A）特定環氧樹脂與（B）硬化劑的反應的化合物，則並無特別限定。 作為（D）硬化促進劑，例如可列舉：1,8-二氮雜-雙環(5.4.0)十一烯-7、1,5-二氮雜-雙環(4.3.0)壬烯、5,6-二丁基胺基-1,8-二氮雜-雙環(5.4.0)十一烯-7等環脒（cycloamidine）化合物；於所述環脒化合物中加成馬來酸酐、醌化合物（例如，1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌）、重氮苯基甲烷、酚樹脂等具有π鍵的化合物而成的具有分子內分極的化合物；苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺類及該些的衍生物；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑類及該些的衍生物；三丁基膦、甲基二苯基膦、三苯基膦、三(4-甲基苯基)膦、二苯基膦、苯基膦等膦化合物；於所述膦化合物中加成馬來酸酐、所述醌化合物、重氮苯基甲烷、酚樹脂等具有π鍵的化合物而成的具有分子內分極的磷化合物；四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽、2-乙基-4-甲基咪唑四苯基硼酸鹽、N-甲基嗎啉四苯基硼酸鹽等四苯基硼鹽及該些的衍生物等。該些硬化促進劑可單獨使用一種，亦可組合使用兩種以上。(D) Hardening accelerator The epoxy resin composition may contain at least one of (D) a hardening accelerator, in addition to (A) a specific epoxy resin, (B) a hardener, and (C) a specific glycidyl compound. The curing accelerator is not particularly limited as long as it is a compound that accelerates the reaction between the specific epoxy resin (A) and the curing agent (B). Examples of the (D) hardening accelerator include 1,8-diaza-bicyclo (5.4.0) undecene-7, 1,5-diaza-bicyclo (4.3.0) nonene, 5 Cycloamidine compounds such as 1,6-dibutylamino-1,8-diaza-bicyclo (5.4.0) undecene-7; maleic anhydride and quinone are added to the cycloamidine compounds Compounds (for example, 1,4-benzoquinone, 2,5-toluone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-bis Methoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone), diazophenylmethane, phenol Compounds with a π bond such as resins that have intramolecular polarization; tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol And these derivatives; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and other imidazoles and these derivatives; tributylphosphine, methyldiphenylphosphine , Triphenylphosphine, tri (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and other phosphine compounds; add maleic anhydride, quinone compound, diazophenyl to the phosphine compound Methane Phosphorus compounds with intramolecular polarization made of compounds with π bond such as phenol resin, phenol resin; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole Tetraphenylborates such as tetraphenylborate, N-methylmorpholine tetraphenylborate, and derivatives thereof. These hardening accelerators may be used alone or in combination of two or more.
（D）硬化促進劑的含有率只要為可達成硬化促進效果的量，則並無特別限制，較佳為於環氧樹脂組成物中為0.005質量%～2質量%，更佳為0.01質量%～0.5質量%。藉由環氧樹脂組成物中的硬化促進劑的含有率為0.005質量%以上，與未滿0.005質量%的情況相比，存在短時間下的硬化性變得良好的傾向，藉由為2質量%以下，與超過2質量%的情況相比，由於硬化速度不會過快，因此存在容易獲得良好的成形品的傾向。(D) The content of the hardening accelerator is not particularly limited as long as it is an amount capable of achieving a hardening promoting effect. It is preferably 0.005% to 2% by mass, and more preferably 0.01% by mass in the epoxy resin composition. ～ 0.5% by mass. When the content of the hardening accelerator in the epoxy resin composition is 0.005% by mass or more, compared with the case where the content is less than 0.005% by mass, the curing property tends to be good in a short time, and is 2 mass. % Or less, as compared with the case where it exceeds 2% by mass, since the curing rate is not too fast, there is a tendency that a good molded product is easily obtained.
（E）無機填充劑 環氧樹脂組成物除了（A）特定環氧樹脂、（B）硬化劑及（C）特定縮水甘油基化合物以外，亦可視需要包含（E）無機填充劑的至少一種。無機填充劑例如可以吸濕性、線膨脹係數減低、熱傳導性提高及強度提高為目的而使用。(E) Inorganic filler In addition to (A) the specific epoxy resin, (B) the hardener, and (C) the specific glycidyl compound, the epoxy resin composition may optionally include at least one of (E) an inorganic filler. The inorganic filler can be used, for example, for the purpose of hygroscopicity, reduction in linear expansion coefficient, improvement in thermal conductivity, and improvement in strength.
無機填充劑的種類並無特別限制。具體而言，可列舉：球狀二氧化矽（例如熔融二氧化矽）、結晶二氧化矽、玻璃、氧化鋁、碳酸鈣、矽酸鋯、矽酸鈣、鈦酸鉀、碳化矽、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石（forsterite）、滑石（steatite）、尖晶石、莫來石（mullite）、氧化鈦、滑石、黏土、雲母等無機材料。亦可使用具有阻燃效果的無機填充劑。作為具有阻燃效果的無機填充劑，可列舉：氫氧化鋁、氫氧化鎂、鎂與鋅的複合氫氧化物等複合金屬氫氧化物、硼酸鋅、鉬酸鋅等。 作為無機填充劑的形狀，可列舉粉末、對粉末進行了球形化的顆粒、纖維等。The type of the inorganic filler is not particularly limited. Specific examples include spherical silica (for example, fused silica), crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, potassium titanate, silicon carbide, and nitride. Silicon, aluminum nitride, boron nitride, beryllium oxide, zirconia, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica And other inorganic materials. It is also possible to use an inorganic filler having a flame retardant effect. Examples of the inorganic filler having a flame-retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and a composite hydroxide of magnesium and zinc, zinc borate, zinc molybdate, and the like. Examples of the shape of the inorganic filler include powder, spheroidized particles, and fibers.
該些無機填充劑可單獨使用一種，亦可組合使用兩種以上。其中，就填充性、線膨脹係數的減低的觀點而言，較佳為球狀二氧化矽，就高熱傳導性的觀點而言，較佳為氧化鋁。就填充性及模具磨耗性的方面而言，無機填充劑的形狀較佳為球形。These inorganic fillers may be used alone or in combination of two or more. Among these, spherical silicon dioxide is preferred from the viewpoint of filling properties and reduction in linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. In terms of filling properties and mold wearability, the shape of the inorganic filler is preferably spherical.
就阻燃性、成形性、吸濕性、線膨脹係數減低、強度提高及耐回焊性的觀點而言，環氧樹脂組成物中的無機填充劑的含有率較佳為60質量%以上，就阻燃性的觀點而言，更佳為60質量%~95質量%，進而佳為70質量%~90質量%。藉由環氧樹脂組成物中的無機填充劑的含有率為60質量%以上，與未滿60質量%的情況相比，存在阻燃性及耐回焊性提高的傾向。若環氧樹脂組成物中的無機填充劑的含有率為95質量%以下，與超過95質量%的情況相比，存在流動性提高的傾向，且存在阻燃性亦提高的傾向。From the viewpoints of flame retardancy, moldability, hygroscopicity, reduced linear expansion coefficient, increased strength, and reflow resistance, the content of the inorganic filler in the epoxy resin composition is preferably 60% by mass or more. From the viewpoint of flame retardancy, it is more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass. Since the content of the inorganic filler in the epoxy resin composition is 60% by mass or more, the flame retardancy and reflow resistance tend to be improved as compared with the case where the content is less than 60% by mass. When the content rate of the inorganic filler in the epoxy resin composition is 95% by mass or less, the fluidity tends to be improved and the flame retardancy tends to be improved as compared with the case where the content exceeds 95% by mass.
環氧樹脂組成物除了所述成分（A）特定環氧樹脂、（B）硬化劑及（C）特定縮水甘油基化合物以外，亦可視需要包含以下例示的偶合劑、阻燃劑、陰離子交換體、脫模劑、著色劑、應力緩和劑等各種添加劑。另外，於環氧樹脂組成物中，並不限定於以下的添加劑，亦可視需要添加該技術領域中周知的各種添加劑。The epoxy resin composition may include the following coupling agents, flame retardants, and anion exchangers as required, in addition to the components (A) specific epoxy resin, (B) hardener, and (C) specific glycidyl compound. , Release agents, colorants, stress relief agents and other additives. In addition, the epoxy resin composition is not limited to the following additives, and various additives known in the technical field may be added as necessary.
（F）偶合劑 為了提高樹脂成分與填充劑的接著性，環氧樹脂組成物亦可視需要包含偶合劑的至少一種。 作為偶合劑，只要為環氧樹脂組成物中通常使用者，則並無特別限制，例如可列舉：具有一級胺基、二級胺基及三級胺基中的至少一種的矽烷化合物，環氧基矽烷、巰基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等各種矽烷系化合物（例如，下述矽烷偶合劑）、鈦系化合物（例如，下述鈦酸酯系偶合劑）、鋁螯合物類、鋁/鋯系化合物等。 就耐回焊性的觀點而言，作為偶合劑，較佳為使用所述矽烷化合物。(F) Coupling agent In order to improve the adhesion between the resin component and the filler, the epoxy resin composition may optionally include at least one type of coupling agent. The coupling agent is not particularly limited as long as it is an ordinary user in an epoxy resin composition, and examples thereof include a silane compound having at least one of a primary amine group, a secondary amine group, and a tertiary amine group, and an epoxy resin. Various silane-based compounds (for example, the following silane coupling agents), titanium-based compounds (for example, the following titanate-based coupling agents), and aluminum chelate Compounds, aluminum / zirconium compounds, etc. From the viewpoint of reflow resistance, it is preferable to use the silane compound as the coupling agent.
作為偶合劑的具體例，可列舉：乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基三甲氧基矽烷、γ-(N,N-二乙基)胺基丙基三甲氧基矽烷、γ-(N,N-二丁基)胺基丙基三甲氧基矽烷、γ-(N-甲基)苯胺基丙基三甲氧基矽烷、γ-(N-乙基)苯胺基丙基三甲氧基矽烷、γ-(N,N-二甲基)胺基丙基三乙氧基矽烷、γ-(N,N-二乙基)胺基丙基三乙氧基矽烷、γ-(N,N-二丁基)胺基丙基三乙氧基矽烷、γ-(N-甲基)苯胺基丙基三乙氧基矽烷、γ-(N-乙基)苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二乙基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二丁基)胺基丙基甲基二甲氧基矽烷、γ-(N-甲基)苯胺基丙基甲基二甲氧基矽烷、γ-(N-乙基)苯胺基丙基甲基二甲氧基矽烷、N-(三甲氧基矽烷基丙基)乙二胺、N-(二甲氧基甲基矽烷基異丙基)乙二胺、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷等矽烷系偶合劑；異丙基三異硬脂醯基鈦酸酯、異丙基三(二辛基焦磷酸酯)鈦酸酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、四辛基雙(二-十三烷基亞磷酸酯)鈦酸酯、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基亞磷酸酯)鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、雙(二辛基焦磷酸酯)伸乙基鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯酸異硬脂醯基鈦酸酯、異丙基三-十二烷基苯磺醯基鈦酸酯、異丙基異硬脂醯基二丙烯酸鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、異丙基三枯基苯基鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯等鈦酸酯系偶合劑等，可單獨使用該些中的一種，亦可組合使用兩種以上。Specific examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethylsilane. Oxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxy Silane, vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amine Propyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinepropyltrimethoxysilane, γ-anilinepropyltriethoxysilane, γ- (N , N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyl Trimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinepropyltrimethoxysilane, γ- (N, N-dimethyl ) Aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane , Γ- (N, N-dibutyl) aminopropyltriethoxysilane, γ- (N-methyl) anilinepropyltriethoxysilane, γ- (N-ethyl) aniline Propyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethyl Oxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinepropylmethyldimethoxysilane, γ- ( N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine , Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilanes, vinyltrimethoxysilane, γ- Silane-based coupling agents such as mercaptopropylmethyldimethoxysilane; isopropyltriisostearylfluorenyl titanate, isopropyltris (dioctyl pyrophosphate) titanate, isopropyltris ( N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl- 1-butyl) bis ( -Tridecyl phosphite) Titanate, Bis (dioctyl pyrophosphate) oxyacetate Titanate, Bis (dioctyl pyrophosphate) Ethyl titanate, Isopropyl Trioctylfluorenyl titanate, isostearyl isopropyl dimethacrylate, titanyl isopropyl, isotris-dodecylbenzenesulfonyl titanate, titanium isopropyl isostearyl diacrylate Esters, titanates such as isopropyltri (dioctyl phosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctyl phosphite) titanate As the coupling agent, one of these may be used alone, or two or more of them may be used in combination.
其中，就流動性、阻燃性的觀點而言，較佳為具有二級胺基的矽烷偶合劑。具有二級胺基的矽烷偶合劑只要為分子內具有二級胺基的矽烷化合物，則並無特別限制，作為具體例，可列舉：γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、γ-苯胺基丙基甲基二甲氧基矽烷、γ-苯胺基丙基甲基二乙氧基矽烷、γ-苯胺基丙基乙基二乙氧基矽烷、γ-苯胺基丙基乙基二甲氧基矽烷、γ-苯胺基甲基三甲氧基矽烷、γ-苯胺基甲基三乙氧基矽烷、γ-苯胺基甲基甲基二甲氧基矽烷、γ-苯胺基甲基甲基二乙氧基矽烷、γ-苯胺基甲基乙基二乙氧基矽烷、γ-苯胺基甲基乙基二甲氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基三甲氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基三乙氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基甲基二甲氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基甲基二乙氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基乙基二乙氧基矽烷、N-(對甲氧基苯基)-γ-胺基丙基乙基二甲氧基矽烷、γ-(N-甲基)胺基丙基三甲氧基矽烷、γ-(N-乙基)胺基丙基三甲氧基矽烷、γ-(N-丁基)胺基丙基三甲氧基矽烷、γ-(N-苄基)胺基丙基三甲氧基矽烷、γ-(N-甲基)胺基丙基三乙氧基矽烷、γ-(N-乙基)胺基丙基三乙氧基矽烷、γ-(N-丁基)胺基丙基三乙氧基矽烷、γ-(N-苄基)胺基丙基三乙氧基矽烷、γ-(N-甲基)胺基丙基甲基二甲氧基矽烷、γ-(N-乙基)胺基丙基甲基二甲氧基矽烷、γ-(N-丁基)胺基丙基甲基二甲氧基矽烷、γ-(N-苄基)胺基丙基甲基二甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-(β-胺基乙基)胺基丙基三甲氧基矽烷、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷等。Among these, a silane coupling agent having a secondary amine group is preferred from the viewpoint of fluidity and flame retardancy. The silane coupling agent having a secondary amine group is not particularly limited as long as it is a silane compound having a secondary amine group in the molecule. Specific examples include γ-anilinopropyltrimethoxysilane and γ-anilino Propyltriethoxysilane, γ-anilinepropylmethyldimethoxysilane, γ-anilinepropylmethyldiethoxysilane, γ-anilinepropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane , Γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxy (Phenyl) -γ-aminopropyltrimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ -Aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldiethoxysilane, N- (p-methoxyphenyl) -γ -Aminopropylethyldiethoxysilane, N- (p-methoxyphenyl)- -Aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxysilane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- ( N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyltriethoxysilane, γ -(N-ethyl) aminopropyltriethoxysilane, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxy Silane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropylmethyldimethoxysilane, γ- (N-butyl ) Aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl Trimethoxysilane, γ- (β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxy Silane, etc.
環氧樹脂組成物中的偶合劑的含有率較佳為0.037質量%～4.75質量%，更佳為0.05質量%～5質量%，進而佳為0.1質量%～2.5質量%。藉由環氧樹脂組成物中的偶合劑的含有率為0.037質量%以上，與未滿0.037質量%的情況相比，存在與框架的接著性提高的傾向，藉由為4.75質量%以下，與超過4.75質量%的情況相比，存在封裝的成形性提高的傾向。The content of the coupling agent in the epoxy resin composition is preferably 0.037% to 4.75% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 2.5% by mass. When the content of the coupling agent in the epoxy resin composition is 0.037% by mass or more, compared with the case where the content is less than 0.037% by mass, the adhesion to the frame tends to be improved, and when it is 4.75% by mass or less, When it exceeds 4.75 mass%, the moldability of a package tends to improve.
為了賦予阻燃性，可於環氧樹脂組成物中視需要調配阻燃劑的至少一種。作為阻燃劑，並無特別限制，例如可列舉包含鹵素原子、銻原子、氮原子或磷原子的公知的有機或無機的化合物、金屬氫氧化物等，可單獨使用該些的一種，亦可組合使用兩種以上。阻燃劑的含有率只要達成阻燃效果，則並無特別限制，相對於（A）特定環氧樹脂而言較佳為1質量%～30質量%，更佳為2質量%～15質量%。In order to impart flame retardancy, at least one kind of flame retardant may be blended in the epoxy resin composition as necessary. The flame retardant is not particularly limited, and examples thereof include known organic or inorganic compounds and metal hydroxides containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom. These may be used alone or in combination. Use two or more kinds in combination. The content of the flame retardant is not particularly limited as long as the flame retardant effect is achieved, and it is preferably 1% to 30% by mass, and more preferably 2% to 15% by mass relative to the specific epoxy resin (A). .
可於環氧樹脂組成物中視需要調配陰離子交換體的至少一種。尤其，關於環氧樹脂組成物，由於將環氧樹脂組成物用作密封用成形材料，因此就使具備經密封的元件的電子零件裝置的耐濕性及高溫放置特性提高的觀點而言，較佳為含有陰離子交換體。 作為陰離子交換體，並無特別限制，可使用先前公知者，作為具體例，可列舉：水滑石類；選自鎂、鋁、鈦、鋯及鉍中的元素的含水氧化物等。陰離子交換體可單獨使用一種或組合使用兩種以上。其中，陰離子交換體較佳為下述通式（1）所表示的水滑石。At least one kind of anion exchanger can be blended in the epoxy resin composition as needed. In particular, since the epoxy resin composition is used as a molding material for sealing, the epoxy resin composition is more effective in terms of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed component. It preferably contains an anion exchanger. The anion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcites; hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. An anion exchanger can be used individually by 1 type or in combination of 2 or more types. Among them, the anion exchanger is preferably a hydrotalcite represented by the following general formula (1).
Mg1-X AlX (OH)2 (CO3 )X/2 ･mH2 O （1） （式（1）中，0＜X≦0.5，m為正數）Mg 1-X Al X (OH) 2 (CO 3 ) X / 2 ･ mH 2 O (1) (In the formula (1), 0 <X ≦ 0.5, m is a positive number)
所述陰離子交換體的含有率只要為可捕捉鹵素陰離子等陰離子的充分量，則並無特別限制，相對於（A）特定環氧樹脂而較佳為0.1質量%～30質量%，更佳為1質量%～5質量%。The content of the anion exchanger is not particularly limited as long as it is a sufficient amount to capture anions such as halogen anions, and is preferably 0.1% to 30% by mass, and more preferably (A) specific epoxy resin. 1 mass% to 5 mass%.
進而，於環氧樹脂組成物中可視需要而調配高級脂肪酸、高級脂肪酸金屬鹽、酯系蠟、聚烯烴系蠟、聚乙烯、氧化聚乙烯等脫模劑；碳黑等著色劑；矽油、矽橡膠粉末等應力緩和劑等作為其他添加劑。Further, in the epoxy resin composition, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, and oxidized polyethylene; colorants such as carbon black; As other additives, stress relaxation agents such as rubber powder are used.
環氧樹脂組成物只要可分散混合各種原材料，則亦可使用任意方法來製備，作為通常的方法，可列舉利用混合機等將原材料充分混合後，利用混合輥、擠出機、擂潰機、行星式混合機等進行混合或熔融混練後進行冷卻，視需要而進行脫泡及粉碎的方法等。另外，亦可視需要而以符合成形條件的尺寸及重量進行錠化。The epoxy resin composition may be prepared by any method as long as it can disperse and mix various raw materials. As a general method, after the raw materials are sufficiently mixed by a mixer or the like, a mixing roll, an extruder, a crusher, A planetary mixer or the like is mixed or melt-kneaded, and then cooled, and a method such as defoaming and pulverizing is performed as necessary. In addition, if necessary, the ingot can be formed into a size and weight that meet the molding conditions.
＜電子零件裝置＞ 本發明的實施形態的電子零件裝置包括：元件；以及密封所述元件的所述環氧樹脂組成物的硬化物。 作為電子零件裝置，可列舉於引線框架、已配線的帶載體、配線板、玻璃、矽晶圓等支撐構件或安裝基板上搭載元件（半導體晶片、電晶體、二極管、閘流體等主動元件，電容器、電阻體、線圈等被動元件），並利用所述環氧樹脂組成物密封所需部分而成的電子零件裝置等。<Electronic component device> The electronic component device according to the embodiment of the present invention includes a component and a cured product of the epoxy resin composition that seals the component. Examples of electronic component devices include components (active components such as semiconductor wafers, transistors, diodes, thyristors, and capacitors) mounted on support members such as lead frames, wired tape carriers, wiring boards, glass, and silicon wafers or mounting substrates. Passive components such as resistors, resistors, coils, etc.), and electronic component devices made by sealing the required parts with the epoxy resin composition.
此處，作為安裝基板，並無特別限制，作為具體例，可列舉：有機基板、有機膜、陶瓷基板、玻璃基板等***物基板，液晶用玻璃基板，多晶片模組（Multi Chip Module，MCM）用基板、混合IC用基板等。Here, the mounting substrate is not particularly limited, and specific examples include an insertion substrate such as an organic substrate, an organic film, a ceramic substrate, and a glass substrate, a glass substrate for a liquid crystal, and a multi-chip module (MCM). ) Substrates, hybrid IC substrates, etc.
作為電子零件裝置的具體例，例如可列舉半導體裝置，更具體而言，可列舉：於引線框架(島(island)、片(tab))上配置半導體晶片等元件，將接合墊等元件的端子部與引線部以打線接合、凸塊等連接後，使用所述環氧樹脂組成物，藉由轉移成形等進行密封而成的雙列直插式封裝(Dual Inline Package，DIP)、塑膠引線晶片載體(Plastic Leaded Chip Carrier，PLCC)、四面扁平封裝(Quad Flat Package，QFP)、小外型封裝(Small Outline Package，SOP)、小外型J引線封裝(Small Outline J-lead Package，SOJ)、薄小外型封裝(Thin Small Outline Package，TSOP)、薄型四面扁平封裝(Thin Quad Flat Package，TQFP)等樹脂密封型IC；利用所述環氧樹脂組成物將引線接合於帶載體的半導體晶片密封而成的帶載體封裝(Tape Carrier Package，TCP)；利用所述環氧樹脂組成物將以打線接合、倒裝晶片接合、焊料等連接於形成於配線板或玻璃上的配線而成的半導體晶片密封而獲得的基板覆晶(Chip On Board，COB)、玻璃覆晶(Chip On Glass，COG)等安裝有裸晶片的半導體裝置；利用所述環氧樹脂組成物將以打線接合、倒裝晶片接合、焊料等連接於形成於配線板或玻璃上的配線而成的主動元件(半導體晶片、電晶體、二極管、閘流體等)及被動元件(電容器、電阻體、線圈等)中的至少一者密封而成的混合IC、MCM(Multi Chip Module)；於形成有母板連接用的端子的***物基板上搭載半導體晶片，並藉由凸塊或打線接合將所述半導體晶片與形成於***物基板上的配線連接後，利用所述環氧樹脂組成物將半導體晶片搭載側密封而獲得的球柵陣列(Ball Grid Array，BAG)、晶片尺寸封裝(Chip Size Package，CSP)、MCP(Multi Chip Package)等。另外，該些半導體裝置亦可為於安裝基板上以重疊的形式搭載有兩個以上的元件的堆積(積層)型封裝，亦可為利用環氧樹脂組成物一次性密封兩個以上的元件的成批模組型封裝。Specific examples of the electronic component device include a semiconductor device, and more specifically, a semiconductor device such as a semiconductor wafer is arranged on a lead frame (island, tab), and a terminal of a component such as a bonding pad is provided. And the lead part are connected by wire bonding, bumps, and the like, and a dual inline package (DIP), a plastic lead chip formed by using the epoxy resin composition and sealed by transfer molding, etc. Carrier (Plastic Leaded Chip Carrier (PLCC)), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead Package (SOJ), Resin-sealed ICs such as Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), etc .; use the epoxy resin composition to seal leads with semiconductor wafers with carriers and seal The tape carrier package (TCP) is formed, and the epoxy resin composition is used to connect wire bonding, flip chip bonding, solder, etc. to a wiring board or glass. A semiconductor device mounted with a bare wafer, such as a Chip On Board (COB), a Chip On Glass (COG), and the like, obtained by sealing a semiconductor wafer formed by wiring on the above; using the epoxy resin composition Active components (semiconductor wafers, transistors, diodes, thyristors, etc.) and passive components (capacitors, resistors, etc.) that are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. A hybrid IC or MCM (Multi Chip Module) formed by sealing at least one of the coils, etc .; a semiconductor chip is mounted on an insert substrate having terminals for mother board connection, and the semiconductor chip is connected by bumps or wire bonding. After the semiconductor wafer is connected to the wiring formed on the interposer substrate, a ball grid array (BAG), a chip size package obtained by sealing the semiconductor wafer mounting side with the epoxy resin composition, and a chip size package are obtained. , CSP), MCP (Multi Chip Package), etc. In addition, these semiconductor devices may be a stacked (stacked) type package in which two or more components are mounted on the mounting substrate in an overlapping form, or may be one in which two or more components are sealed at one time by an epoxy resin composition. Bulk modular package.
再者，作為將所述環氧樹脂組成物用作密封材而獲得元件經密封的半導體裝置等電子零件裝置的方法，最通常的是低壓轉移成形法，亦可列舉注射成形法、壓縮成形法等。作為獲得元件經密封的半導體裝置等電子零件裝置的方法，亦可使用點膠法、注型方式、印刷方式等。 [實施例]In addition, as a method for obtaining an electronic component device such as a semiconductor device with a sealed element by using the epoxy resin composition as a sealing material, a low-pressure transfer molding method is most commonly used, and an injection molding method and a compression molding method may also be cited. Wait. As a method of obtaining an electronic component device such as a sealed semiconductor device, a dispensing method, a casting method, a printing method, or the like may be used. [Example]
以下，藉由實施例對所述實施形態進行具體說明，但所述實施形態的範圍並不限定於該些實施例。再者，只要無特別說明，則「份」及「%」為質量基準。Hereinafter, the embodiments will be described in detail with examples, but the scope of the embodiments is not limited to these examples. In addition, unless otherwise specified, "part" and "%" are quality standards.
將以下的成分分別以下述表1及表2所示的質量份調配，利用擠出機在混煉溫度135℃下進行熔融混煉，而製作實施例及比較例的環氧樹脂組成物。再者，表中的空欄表示「未調配」。The following components were blended in parts by mass shown in Tables 1 and 2 below, and melt-kneaded at a kneading temperature of 135 ° C using an extruder to prepare epoxy resin compositions of Examples and Comparative Examples. In addition, the empty column in the table indicates "not deployed".
作為（A）特定環氧樹脂，使用 環氧樹脂1：硫代二苯酚型環氧樹脂（新日鐵住金化學股份有限公司製造、商品名：YSLV-120TE、環氧當量245、軟化點113℃） 環氧樹脂2：將含有伸聯苯基骨架的苯酚芳烷基樹脂進行環氧化而獲得的芳烷基型環氧樹脂（日本化藥股份有限公司製造、商品名：CER-3000L、環氧當量240、軟化點96℃） 環氧樹脂3：聯苯型環氧樹脂（三菱化學股份有限公司製造、商品名：YX-4000、環氧當量196、熔點106℃）。As (A) specific epoxy resin, epoxy resin 1: thiodiphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YSLV-120TE, epoxy equivalent 245, and softening point 113 ° C ) Epoxy resin 2: An aralkyl-type epoxy resin obtained by epoxidizing a phenol aralkyl resin containing a stretched phenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name: CER-3000L, epoxy Equivalent 240, softening point 96 ° C) Epoxy resin 3: Biphenyl epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX-4000, epoxy equivalent 196, melting point 106 ° C).
作為（B）硬化劑，使用 硬化劑1：羥基當量176、軟化點70℃的苯酚芳烷基樹脂（三井化學股份有限公司製造、商品名：米勒斯（MILEX）XLC） 硬化劑2：羥基當量120、軟化點85℃的三聚氰胺改質酚樹脂（日立化成股份有限公司製造、商品名：HPM-J3）。As the (B) curing agent, a curing agent 1: a phenol aralkyl resin having a hydroxyl equivalent of 176 and a softening point of 70 ° C. (manufactured by Mitsui Chemicals Co., Ltd., trade name: MILEX XLC), curing agent 2: hydroxyl Melamine modified phenol resin with an equivalent weight of 120 and a softening point of 85 ° C (manufactured by Hitachi Chemical Co., Ltd., trade name: HPM-J3).
作為（C）特定縮水甘油基化合物（於結構中具有縮水甘油基的化合物），使用 液狀樹脂1：二環戊二烯二甲醇二縮水甘油醚（艾迪科（ADEKA）股份有限公司製造、商品名：EP-4088L、環氧當量165、熔點：25℃以下） 液狀樹脂2：橡膠交聯雙酚型環氧樹脂（艾迪科（ADEKA）股份有限公司製造、商品名：EPR-4030、環氧當量365、熔點：25℃以下） 液狀樹脂3：螯合物改質型環氧樹脂（艾迪科（ADEKA）股份有限公司製造、商品名：EP-49-10N、環氧當量220、熔點：25℃以下）。As the specific glycidyl compound (a compound having a glycidyl group in the structure) (C), a liquid resin 1: dicyclopentadiene dimethanol diglycidyl ether (manufactured by ADEKA Corporation, Product name: EP-4088L, epoxy equivalent 165, melting point: 25 ° C or lower) Liquid resin 2: Rubber crosslinked bisphenol epoxy resin (made by ADEKA), product name: EPR-4030 Epoxy equivalent 365, Melting point: 25 ° C or less) Liquid resin 3: Chelate modified epoxy resin (made by ADEKA), trade name: EP-49-10N, epoxy equivalent 220, melting point: below 25 ° C).
作為（D）硬化促進劑，使用 硬化促進劑1：三苯基膦與苯醌的加成反應物 硬化促進劑2：三-對甲苯基膦·對苯醌的混合物。As the (D) hardening accelerator, a hardening accelerator 1: an addition reaction product of triphenylphosphine and benzoquinone is used. A hardening accelerator 2: a mixture of tri-p-tolylphosphine and p-benzoquinone.
作為（E）無機填充劑，使用 熔融二氧化矽：體積平均粒徑18 μm、比表面積1.5 m2 /g的球狀熔融二氧化矽。As the (E) inorganic filler, fused silica: spherical fused silica having a volume average particle diameter of 18 μm and a specific surface area of 1.5 m 2 / g was used.
作為（F）偶合劑，使用 偶合劑1：γ-巰基丙基三甲氧基矽烷（信越化學工業股份有限公司製造、商品名：KBM-803） 偶合劑2：N-苯基-γ-胺基丙基三甲氧基矽烷（信越化學工業股份有限公司製造、商品名：KBM-573） 偶合劑3：甲基三甲氧基矽烷（信越化學工業股份有限公司製造、商品名：KBM-13）。As (F) coupling agent, coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) coupling agent 2: N-phenyl-γ-amino group Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-573) Coupling agent 3: methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-13).
除此以外，作為各種添加劑，使用 著色劑：碳黑（三菱化學股份有限公司製造、商品名：MA100） 脫模劑：二十八酸酯（日本科萊恩（Clariant Japan）股份有限公司製造、商品名：HW-E） 添加劑：鎂·鋁·氫氧化物·碳酸酯·水合物（陰離子交換體、水滑石類、堺化學工業股份有限公司製造、商品名：HT-P）。In addition, as various additives, a colorant is used: carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: MA100). Release agent: octadecanoate (manufactured by Clariant Japan Co., Ltd., product) Name: HW-E) Additive: Magnesium, Aluminum, Hydroxide, Carbonate, Hydrate (anion exchanger, hydrotalcite, manufactured by Sakai Chemical Industry Co., Ltd., trade name: HT-P).
藉由以下的（1）～（5）的各種特性試驗評價實施例及比較例的環氧樹脂組成物。將評價結果匯總示於下述表1及表2中。再者，環氧樹脂組成物的成形只要未明示，則是藉由轉移成形機，在模具溫度180℃、成形壓力6.9 MPa、硬化時間90秒的條件下進行。另外，視需要於175℃下進行6小時後硬化。The epoxy resin compositions of Examples and Comparative Examples were evaluated by various characteristic tests (1) to (5) below. The evaluation results are collectively shown in Tables 1 and 2 below. The molding of the epoxy resin composition is performed using a transfer molding machine under conditions of a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, unless otherwise specified. In addition, if necessary, post-curing was performed at 175 ° C for 6 hours.
（1）螺旋流動 使用依據EMMI-1-66的螺旋流動測定用模具，在所述條件下將環氧樹脂組成物成形，並求出流動距離（cm）。(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin composition was molded under the above conditions, and the flow distance (cm) was determined.
（2）熱時硬度 將環氧樹脂組成物於所述條件下成形為直徑50 mm、厚度3 mm的圓板，成形後立即使用蕭耳(Shore)D型硬度計(上島製作所股份有限公司製造、商品編號：HD-1120(型號D))測定熱時硬度。(2) Hardness under heat The epoxy resin composition was formed into a circular plate with a diameter of 50 mm and a thickness of 3 mm under the above conditions, and a Shore D-type hardness tester (manufactured by Ueshima Manufacturing Co., Ltd.) was used immediately after forming. Product No .: HD-1120 (Model D)) Determine the hardness under heat.
（3）260℃下的彎曲彈性係數（高溫彎曲試驗） 將環氧樹脂組成物於所述條件下成形為10 mm×70 mm×3 mm，進行後硬化而製作試驗片。對於所得的試驗片，使用彎曲試驗機（A&D股份有限公司製造、品名：滕喜龍（Tensilon））在恆溫槽中一面保持為260℃，一面進行依照JIS K6911:2006的三點彎曲試驗，藉由下述式求出260℃下的彎曲彈性係數（MPa）。 其中，下述式中，「E」表示彎曲彈性係數(Pa)，「ΔP」表示負載單元的值(N)，「Δy」表示位移量(mm)，「l」表示跨距(=48 mm)，「w」表示試驗片寬度(=10 mm)，「h」表示試驗片厚度(=3 mm)。(3) Bending elastic coefficient (high temperature bending test) at 260 ° C. The epoxy resin composition was formed into 10 mm × 70 mm × 3 mm under the above conditions, and was post-cured to produce a test piece. The obtained test piece was subjected to a three-point bending test in accordance with JIS K6911: 2006 while maintaining the temperature at 260 ° C in a thermostatic bath using a bending tester (manufactured by A & D Co., Ltd., Tensilon). The flexural modulus (MPa) at 260 ° C was determined by the following formula. Among them, in the following formula, "E" represents the bending elastic coefficient (Pa), "ΔP" represents the value of the load unit (N), "Δy" represents the displacement amount (mm), and "l" represents the span (= 48 mm ), "W" indicates the width of the test piece (= 10 mm), and "h" indicates the thickness of the test piece (= 3 mm).
[數1] [Number 1]
（4）接著力試驗 將進行了鍍鈀的銅板放置於設置有9 mm×9 mm的狹縫的模具中，於其中將環氧樹脂組成物於所述條件下成形為底表面的直徑4 mm、上表面的直徑3 mm、高度4 mm的尺寸，進行後硬化，藉由黏結強度試驗機（諾信高科技（Nordson Advanced Technology）股份有限公司製造的系列4000），於室溫（25℃）下、以剪切速度50 μm/s測定剪切接著力（MPa）。(4) Force test Next, a copper plate subjected to palladium plating was placed in a mold provided with a slit of 9 mm × 9 mm, and an epoxy resin composition was formed under the above conditions to a diameter of a bottom surface of 4 mm. Dimensions of the upper surface with a diameter of 3 mm and a height of 4 mm are post-cured, using a bond strength tester (series 4000 manufactured by Nordson Advanced Technology Co., Ltd.) at room temperature (25 ° C) Next, the shear adhesion force (MPa) was measured at a shear rate of 50 μm / s.
（5）耐回焊性 針對搭載有8 mm×10 mm×0.4 mm的矽晶片的20 mm×14 mm×2 mm的80針腳扁平封裝（四面扁平封裝（QFP））（引線框架材質：銅合金，沖模墊部上表面及引線前端部鍍銀的處理品（表中的「Cu-Ag」）、以及鍍鈀合金的處理品（表中的「PPF」）），使用環氧樹脂組成物於所述條件下進行成形及後硬化而製作，於125℃、24小時的條件下進行烘烤後，於60℃、60%RH的條件下進行40小時加濕後，在260℃、30秒的條件下分別進行3次回焊處理，利用超音波探傷裝置觀察樹脂與框架的界面有無剝離，以相對於試驗封裝數（20個）的剝離產生封裝數來評價耐回焊性。(5) Reflow resistance for a 20 mm × 14 mm × 2 mm 80-pin flat package (Quad Flat Package (QFP)) equipped with a silicon wafer of 8 mm × 10 mm × 0.4 mm (lead frame material: copper alloy) For the silver-plated processed product ("Cu-Ag" in the table) on the upper surface of the die pad and the lead tip, and the processed product ("PPF") in the palladium alloy plate, an epoxy resin composition was used. It is made by forming and post-hardening under the above conditions. After baking at 125 ° C for 24 hours, it is humidified at 60 ° C and 60% RH for 40 hours and then at 260 ° C for 30 seconds. Reflow treatment was performed three times under the conditions, and the interface between the resin and the frame was observed for peeling with an ultrasonic flaw detection device, and the number of packages generated by peeling relative to the number of test packages (20) was used to evaluate the reflow resistance.
[表1]
[表2]
根據表1及表2而明確，不含（C）特定縮水甘油基化合物的比較例的耐回焊性差。對此，含有（C）特定縮水甘油基化合物的實施例1～實施例7與比較例相比耐回焊性優異。其理由雖不明確，但如上所述推測由彈性係數減低效果及接著力的提高效果所引起。 根據實施例1～實施例3及比較例的結果，可知具有二環戊二烯結構的多環芳香環化合物的耐回焊性更優異。 根據實施例4～實施例7及比較例的結果，可知與液狀樹脂1相對於環氧組成物整體的比例為1質量%以下的實施例4及實施例5相比，液狀樹脂1相對於環氧組成物整體的比例為1質量%以上的實施例6及實施例7的耐回焊性更優異。It is clear from Table 1 and Table 2 that the comparative example which does not contain (C) a specific glycidyl compound is inferior in reflow resistance. In contrast, Examples 1 to 7 containing the specific glycidyl compound (C) have better reflow resistance than Comparative Examples. Although the reason is not clear, it is estimated that it is caused by the effect of reducing an elastic coefficient and the effect of improving an adhesive force as mentioned above. From the results of Examples 1 to 3 and Comparative Examples, it is found that the polycyclic aromatic ring compound having a dicyclopentadiene structure is more excellent in reflow resistance. From the results of Examples 4 to 7 and Comparative Examples, it can be seen that compared with Examples 4 and 5 in which the ratio of the liquid resin 1 to the entire epoxy composition is 1% by mass or less, the liquid resin 1 is relatively The reflow resistance of Examples 6 and 7 in which the proportion of the entire epoxy composition was 1% by mass or more was more excellent.
於2017年3月31日提出申請的日本專利申請2017-072889號的揭示藉由參照而將其整體併入至本說明書中。 本說明書中所記載的所有文獻、專利申請及技術規格與各個文獻、專利申請及技術規格藉由參照而併入的情況下具體且分別記載的情況相同程度地，併入至本說明書中。The disclosure of Japanese Patent Application No. 2017-072889 filed on March 31, 2017 is incorporated herein by reference in its entirety. All the documents, patent applications, and technical specifications described in this specification are incorporated into this specification to the same extent as when the individual documents, patent applications, and technical specifications are incorporated by reference and specifically and individually described.
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| JP7415961B2 (en) * | 2021-01-14 | 2024-01-17 | 信越化学工業株式会社 | Rubber composition containing organosilicon compound |
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| JPH0551435A (en) * | 1991-08-23 | 1993-03-02 | Mitsui Toatsu Chem Inc | Epoxy resin composition |
| JPH1121426A (en) * | 1997-07-02 | 1999-01-26 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| JP2001131393A (en) * | 1999-10-29 | 2001-05-15 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing and electronic part device |
| JP2002128868A (en) * | 2000-10-24 | 2002-05-09 | Japan Epoxy Resin Kk | Epoxy resin composition for sealing semiconductor |
| JP4096806B2 (en) * | 2003-05-13 | 2008-06-04 | ジャパンエポキシレジン株式会社 | Phenol resin, epoxy resin curing agent, and epoxy resin composition |
| JP2007031698A (en) * | 2005-06-21 | 2007-02-08 | Hitachi Chem Co Ltd | Epoxy resin composition and electronic part device |
| KR101752222B1 (en) * | 2009-12-14 | 2017-06-29 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product |
| WO2011129272A1 (en) * | 2010-04-13 | 2011-10-20 | 積水化学工業株式会社 | Attachment material for semiconductor chip bonding, attachment film for semiconductor chip bonding, semiconductor device manufacturing method, and semiconductor device |
| TW201235402A (en) * | 2011-01-07 | 2012-09-01 | Ajinomoto Kk | Resin composition for release film |
| JP5768529B2 (en) * | 2011-06-24 | 2015-08-26 | 三菱化学株式会社 | Interlayer filler composition for three-dimensional stacked semiconductor device and coating solution thereof |
| US20130026660A1 (en) * | 2011-07-29 | 2013-01-31 | Namics Corporation | Liquid epoxy resin composition for semiconductor encapsulation, and semiconductor device using the same |
| KR101480178B1 (en) * | 2011-12-20 | 2015-01-09 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same |
| CN103819870B (en) * | 2012-11-16 | 2016-06-15 | 株式会社田村制作所 | Resin molding, metal forming, copper-clad plate and the multilayer laminated boards substrate on compositions of thermosetting resin, B rank |
| KR101518502B1 (en) * | 2012-12-26 | 2015-05-11 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same |
| JP6198483B2 (en) * | 2013-06-28 | 2017-09-20 | 太陽インキ製造株式会社 | Thermosetting resin composition and printed wiring board |
| JP6315170B2 (en) * | 2013-09-30 | 2018-04-25 | ナガセケムテックス株式会社 | Epoxy resin composition for semiconductor encapsulation, semiconductor packaging structure, and method for producing the same |
| JP6398824B2 (en) * | 2015-03-23 | 2018-10-03 | 味の素株式会社 | Resin sheet |
| JP6555042B2 (en) * | 2015-09-17 | 2019-08-07 | 味の素株式会社 | Granular resin composition |
| KR102637946B1 (en) * | 2015-09-30 | 2024-02-20 | 세키스이가가쿠 고교가부시키가이샤 | Resin compositions and multilayer substrates |
| CN106398112B (en) * | 2016-05-31 | 2019-09-13 | 江苏华海诚科新材料股份有限公司 | A kind of composition epoxy resin suitable for ESOP encapsulation |
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2018
- 2018-03-29 CN CN201880021249.7A patent/CN110461938A/en active Pending
- 2018-03-29 WO PCT/JP2018/013454 patent/WO2018181813A1/en active Application Filing
- 2018-03-29 JP JP2019510186A patent/JP7212830B2/en active Active
- 2018-03-30 TW TW107111320A patent/TW201842052A/en unknown
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| JPWO2018181813A1 (en) | 2020-02-06 |
| JP2023030182A (en) | 2023-03-07 |
| JP7212830B2 (en) | 2023-01-26 |
| WO2018181813A1 (en) | 2018-10-04 |
| CN110461938A (en) | 2019-11-15 |
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