TW202120580A - Epoxy resin composition, electronic component device and method of producing electronic component device - Google Patents
Epoxy resin composition, electronic component device and method of producing electronic component device Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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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
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- H—ELECTRICITY
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
Description
本揭示是有關於一種環氧樹脂組成物、電子零件裝置、及電子零件裝置的製造方法。The present disclosure relates to an epoxy resin composition, an electronic component device, and a manufacturing method of the electronic component device.
近年來，半導體元件的高密度安裝化不斷發展。伴隨於此，樹脂密封型半導體裝置中相對於先前的引腳***型封裝而表面安裝型封裝成為主流。表面安裝型積體電路（Integrated Circuit，IC）、大規模積體電路（Large Scale Integration，LSI）等為了提高安裝密度、降低安裝高度，成為薄型且小型的封裝。因此，元件相對於封裝的佔有面積變大，封裝的壁厚變得非常薄。In recent years, high-density mounting of semiconductor elements has continued to develop. Along with this, in the resin-sealed semiconductor device, the surface mount type package has become the mainstream compared to the conventional pin-insertion type package. Surface-mount integrated circuits (IC), large scale integrated circuits (Large Scale Integration, LSI), etc. have become thin and small packages in order to increase the mounting density and reduce the mounting height. Therefore, the area occupied by the component relative to the package becomes larger, and the wall thickness of the package becomes very thin.
進而，該些封裝的安裝方法與先前的引腳***型封裝不同。即，引腳***型封裝是將引腳***至配線板後，自配線板的背面進行焊接，因此封裝不會直接暴露在高溫下。但是，表面安裝型IC是於配線板表面進行暫時固定，並藉由焊料浴、回焊裝置等進行處理，故直接暴露於焊接溫度（回焊溫度）下。其結果，於IC封裝吸濕的情況下，於回焊時該吸濕水分蒸發，所產生的蒸氣壓作為剝離應力發揮作用，於元件、引線框架等***物與密封材之間產生剝離，成為封裝裂紋的產生及電性特性不良的原因。因此期望開發一種焊料耐熱性（耐回焊性）優異的密封材料。Furthermore, the mounting method of these packages is different from the previous pin insertion type packages. That is, the pin-insertion type package is to insert the pins into the wiring board and solder from the back of the wiring board, so the package is not directly exposed to high temperatures. However, surface mount ICs are temporarily fixed on the surface of the wiring board and processed with solder baths, reflow devices, etc., so they are directly exposed to the soldering temperature (reflow temperature). As a result, when the IC package absorbs moisture, the moisture evaporates during reflow, and the generated vapor pressure acts as a peeling stress, causing peeling between the interposer such as components and lead frames and the sealing material. The causes of package cracks and poor electrical characteristics. Therefore, it is desired to develop a sealing material excellent in solder heat resistance (reflow resistance).
作為耐回焊性優異的環氧樹脂組成物，提出如下環氧樹脂組成物，其含有：包含特定的環氧樹脂的環氧樹脂；以及包含選自由伸聯苯基型苯酚芳烷基樹脂、苯酚芳烷基樹脂、及三苯基甲烷型酚樹脂所組成的群組中的至少一種的硬化劑（例如，參照專利文獻1）。As an epoxy resin composition having excellent reflow resistance, the following epoxy resin composition is proposed, which contains: an epoxy resin containing a specific epoxy resin; and an epoxy resin containing a biphenyl type phenol aralkyl resin, At least one curing agent from the group consisting of phenol aralkyl resin and triphenylmethane type phenol resin (for example, refer to Patent Document 1).
另外，自先前以來，於電晶體、IC等電子零件密封的領域中廣泛使用環氧樹脂組成物。作為其原因，是由於環氧樹脂取得了電氣特性、耐濕性、耐熱性、機械特性、與***物的接著性等的平衡。In addition, epoxy resin compositions have been widely used in the field of sealing electronic parts such as transistors and ICs. The reason is that the epoxy resin balances electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to the insert.
作為使用環氧樹脂組成物密封電子零件的方法，最普通的是轉移成形。另一方面，於轉移成形中，藉由加壓使熔融的環氧樹脂組成物於模具內流動，因此有時藉由所述流動而產生線圈流動。相對於此，研究了環氧樹脂組成物的高流動化的方法，但線圈流動的抑制仍存在課題。作為代替轉移成形的成形方法，已知有壓縮成形。於壓縮成形中，於模具的腔內放入環氧樹脂組成物使其熔融，關閉模具並加壓，藉此密封元件。根據壓縮成形，幾乎不會引起環氧樹脂組成物的流動，因此可抑制線圈流動的產生。As a method of sealing electronic parts with epoxy resin composition, the most common method is transfer molding. On the other hand, in the transfer molding, the molten epoxy resin composition is caused to flow in the mold by pressurization, and therefore, coil flow may sometimes occur due to the flow. In contrast to this, a method of increasing the fluidity of the epoxy resin composition has been studied, but there are still problems in the suppression of coil flow. As a molding method that replaces the transfer molding, compression molding is known. In compression molding, an epoxy resin composition is put into the cavity of a mold to melt, the mold is closed and pressure is applied, thereby sealing the element. According to compression molding, there is almost no flow of the epoxy resin composition, so the occurrence of coil flow can be suppressed.
作為用以藉由壓縮成形密封半導體元件的環氧樹脂組成物，例如專利文獻2中提出了一種粒子狀的環氧樹脂組成物，其特徵在於含有環氧樹脂、硬化劑、硬化促進劑、無機填充材、熔點為70℃以下的脂肪酸、及沸點為200℃以上的矽烷偶合劑，粒徑分佈於100 μm～3 mm的範圍內佔85質量%以上。記載了藉由使用此種環氧樹脂組成物，可於壓縮成形中充分熔融，可提高填充性。As an epoxy resin composition for sealing semiconductor elements by compression molding, for example, Patent Document 2 proposes a particulate epoxy resin composition, which is characterized by containing epoxy resin, hardener, hardening accelerator, inorganic Fillers, fatty acids with a melting point of 70°C or lower, and a silane coupling agent with a boiling point of 200°C or higher, have a particle size distribution in the range of 100 μm to 3 mm, accounting for 85% by mass or more. It is described that by using such an epoxy resin composition, it can be sufficiently melted during compression molding, and the filling property can be improved.
進而，近年來於電子零件領域中，高速化及高密度化不斷發展，伴隨於此，電子零件的發熱量顯著增大。另外，對於在高溫下運作的電子零件的需求亦增加。因此，對於電子零件的密封中所使用的塑膠、特別是環氧樹脂的硬化物要求提高導熱性。Furthermore, in the field of electronic components in recent years, high-speed and high-density advances have been progressing, and along with this, the heat generation of electronic components has increased significantly. In addition, the demand for electronic components that operate at high temperatures has also increased. Therefore, there is a demand for improved thermal conductivity of plastics, particularly hardened epoxy resins, used in the sealing of electronic parts.
作為用以提高環氧樹脂的硬化物的導熱性的方法，報告有增加氧化鋁等高導熱性填料於環氧樹脂組成物中的填充量等方法（例如，參照專利文獻3）。 [現有技術文獻] [專利文獻]As a method for improving the thermal conductivity of a cured epoxy resin, a method for increasing the filling amount of a highly thermally conductive filler such as alumina in the epoxy resin composition has been reported (for example, refer to Patent Document 3). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2015-74703號公報 [專利文獻2]日本專利特開2011-153173號公報 [專利文獻3]日本專利特開2007-153969號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-74703 [Patent Document 2] Japanese Patent Laid-Open No. 2011-153173 [Patent Document 3] Japanese Patent Laid-Open No. 2007-153969
[發明所欲解決之課題] 例如，如專利文獻1般使用苯酚酚醛清漆樹脂作為硬化劑的密封材料中，耐回焊性存在改善的餘地。本揭示的第一實施形態是有關於提供一種耐回焊性優異的密封用環氧樹脂組成物、以及包括藉由其密封的元件的電子零件裝置。[The problem to be solved by the invention] For example, in a sealing material that uses a phenol novolak resin as a hardening agent as in Patent Document 1, there is room for improvement in reflow resistance. The first embodiment of the present disclosure relates to providing an epoxy resin composition for sealing with excellent reflow resistance and an electronic component device including an element sealed by the epoxy resin composition.
另外，對於壓縮成形中所使用的環氧樹脂組成物而言，為了達成硬化物的低吸濕性、高導熱率等各種特性，有時調整無機填充材的比例及粒度分佈。另外，就調整無機填充材的比例及粒度分佈，形成高填充的同時維持低黏度等而獲得所期望的各物性的觀點而言，對於環氧樹脂組成物期望設計的自由度高。因此，理想的是藉由專利文獻1中記載的方法以外的方法亦獲得容易熔融、適合於利用壓縮成形的元件密封的環氧樹脂組成物。 鑑於所述情況，本揭示的第二實施形態是有關於提供一種容易熔融的壓縮成形用環氧樹脂組成物、以及包括藉由其密封的元件的電子零件裝置。In addition, for the epoxy resin composition used in compression molding, in order to achieve various properties such as low moisture absorption and high thermal conductivity of the cured product, the ratio and particle size distribution of the inorganic filler may be adjusted. In addition, from the viewpoint of adjusting the ratio and particle size distribution of the inorganic filler to achieve high filling while maintaining low viscosity, etc., to obtain desired various physical properties, it is desirable for the epoxy resin composition to have a high degree of freedom in design. Therefore, it is desirable to obtain an epoxy resin composition that is easy to melt and suitable for element sealing by compression molding by a method other than the method described in Patent Document 1. In view of the foregoing, the second embodiment of the present disclosure relates to providing an epoxy resin composition for compression molding that is easy to melt, and an electronic component device including an element sealed by the epoxy resin composition.
另外，近年來高導熱化的要求越來越高，但於先前的方法中，由於伴隨高導熱性填料的填充量增加而環氧樹脂組成物進行高黏度化而無法混練等的制約，高導熱化存在極限。 另外，伴隨半導體裝置的薄型化及大型化的發展，存在施加至用於半導體裝置的密封的環氧樹脂組成物的硬化物上的應力增大的傾向。因此，期望開發一種除了顯示導熱，而且於硬化後顯示優異的強度的環氧樹脂組成物。此處，若增加氧化鋁等高導熱性填料的含有率，則彎曲強度存在上升至一定程度的傾向，但若超過一定的含有率，則存在硬化物變脆而彎曲強度降低的傾向。如此，難以達成高導熱化且維持高的彎曲強度。 鑑於所述情況，本揭示的第三實施形態是有關於提供一種能夠製作導熱性及彎曲強度優異的硬化物的密封用環氧樹脂組成物、以及包括該密封用環氧樹脂組成物的硬化物的電子零件裝置及其製造方法。 [解決課題之手段]In addition, in recent years, the demand for higher thermal conductivity has become higher. However, in the previous method, due to the increase in the filling amount of the high thermal conductivity filler, the epoxy resin composition becomes highly viscous and cannot be kneaded. There are limits to chemistry. In addition, with the advancement of thinning and large-scale semiconductor devices, the stress applied to the cured epoxy resin composition used for sealing of the semiconductor device tends to increase. Therefore, it is desired to develop an epoxy resin composition that not only exhibits thermal conductivity, but also exhibits excellent strength after curing. Here, if the content of high thermal conductivity fillers such as alumina is increased, the bending strength tends to rise to a certain extent, but if the content exceeds a certain content, the hardened material becomes brittle and the bending strength tends to decrease. As such, it is difficult to achieve high thermal conductivity and maintain high bending strength. In view of the foregoing circumstances, the third embodiment of the present disclosure relates to providing an epoxy resin composition for sealing that can produce a cured product with excellent thermal conductivity and bending strength, and a cured product including the epoxy resin composition for sealing Electronic component device and manufacturing method thereof. [Means to solve the problem]
用以達成所述課題的具體手段如以下般。
＜1＞ 一種密封用環氧樹脂組成物，含有：環氧樹脂；以及硬化劑，包含以下的通式（B）所表示的化合物。
[化1]
[化2]
（通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數） ＜7＞ 如＜6＞所述的壓縮成形用環氧樹脂組成物，其中所述硬化劑中的所述通式（B）所表示的化合物的含有率為30質量%～100質量%。 ＜8＞ 如＜6＞或＜7＞所述的壓縮成形用環氧樹脂組成物，其中所述通式（B）中，R1 為甲基。 ＜9＞ 如＜6＞至＜8＞中任一項所述的壓縮成形用環氧樹脂組成物，進而含有脫模劑，相對於所述壓縮成形用環氧樹脂組成物的總質量，所述脫模劑的含有率超過0質量%且為2.0質量%以下。 ＜10＞ 一種密封用環氧樹脂組成物，含有：環氧樹脂；無機填充材，包含氧化鋁；以及硬化劑，包含以下的通式（B）所表示的化合物。(In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 10) <7> The epoxy resin composition for compression molding as described in <6>, The content of the compound represented by the general formula (B) in the curing agent is 30% by mass to 100% by mass. <8> The epoxy resin composition for compression molding as described in <6> or <7>, wherein in the general formula (B), R 1 is a methyl group. <9> The epoxy resin composition for compression molding as described in any one of <6> to <8>, further containing a release agent, relative to the total mass of the epoxy resin composition for compression molding The content of the mold release agent exceeds 0% by mass and is 2.0% by mass or less. <10> An epoxy resin composition for sealing, containing an epoxy resin; an inorganic filler containing alumina; and a curing agent, containing a compound represented by the following general formula (B).
[化3]
（通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數） ＜11＞ 如＜10＞所述的密封用環氧樹脂組成物，其中相對於所述硬化劑的總質量而言的所述通式（B）所表示的化合物的含有率為30質量%～100質量%。 ＜12＞ 如＜10＞或＜11＞所述的密封用環氧樹脂組成物，其中所述通式（B）中，R1 為甲基。 ＜13＞ 如＜10＞至＜12＞中任一項所述的密封用環氧樹脂組成物，其中相對於密封用環氧樹脂組成物的總體積，所述無機填充材的含有率為75體積%以上。 ＜14＞ 如＜10＞至＜13＞中任一項所述的密封用環氧樹脂組成物，其中相對於所述無機填充材的總質量而言的氧化鋁的含有率為75質量%以上。 ＜15＞ 如＜10＞至＜14＞中任一項所述的密封用環氧樹脂組成物，其中所述無機填充材進而包含二氧化矽，所述二氧化矽的平均粒徑為2.0 μm以下。 ＜16＞ 一種電子零件裝置，包括：元件；以及密封所述元件的如＜1＞至＜15＞中任一項所述的環氧樹脂組成物的硬化物。 ＜17＞ 一種電子零件裝置的製造方法，包括：藉由如＜1＞至＜15＞中任一項所述的環氧樹脂組成物來密封元件。 ＜18＞ 如＜17＞所述的電子零件裝置的製造方法，其中所述元件的密封是藉由壓縮成形來進行。 [發明的效果](In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 10) <11> The epoxy resin composition for sealing as described in <10>, wherein The content rate of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% by mass to 100% by mass. <12> The epoxy resin composition for sealing as described in <10> or <11>, wherein in the general formula (B), R 1 is a methyl group. <13> The epoxy resin composition for sealing according to any one of <10> to <12>, wherein the content of the inorganic filler is 75 relative to the total volume of the epoxy resin composition for sealing Above volume %. <14> The epoxy resin composition for sealing as described in any one of <10> to <13>, wherein the content of alumina relative to the total mass of the inorganic filler is 75% by mass or more . <15> The epoxy resin composition for sealing according to any one of <10> to <14>, wherein the inorganic filler further contains silicon dioxide, and the average particle diameter of the silicon dioxide is 2.0 μm the following. <16> An electronic component device, including: an element; and a cured product of the epoxy resin composition according to any one of <1> to <15> that seals the element. <17> A method of manufacturing an electronic component device, including: sealing an element with the epoxy resin composition as described in any one of <1> to <15>. <18> The method of manufacturing an electronic component device as described in <17>, wherein the sealing of the component is performed by compression molding. [Effects of the invention]
根據本揭示的第一實施形態，可提供一種耐回焊性優異的密封用環氧樹脂組成物、以及包括藉由其密封的元件的電子零件裝置。According to the first embodiment of the present disclosure, it is possible to provide an epoxy resin composition for sealing with excellent reflow resistance, and an electronic component device including an element sealed by the epoxy resin composition.
根據本揭示的第二實施形態，可提供一種容易熔融的壓縮成形用環氧樹脂組成物、以及包括藉由其密封的元件的電子零件裝置。According to the second embodiment of the present disclosure, it is possible to provide an epoxy resin composition for compression molding that is easy to melt, and an electronic component device including an element sealed by the epoxy resin composition.
根據本揭示的第三實施形態，可提供一種能夠製作導熱性及彎曲強度優異的硬化物的密封用環氧樹脂組成物、以及包括該密封用環氧樹脂組成物的硬化物的電子零件裝置及其製造方法。According to the third embodiment of the present disclosure, it is possible to provide an epoxy resin composition for sealing that can produce a cured product having excellent thermal conductivity and bending strength, and an electronic component device including the cured product of the epoxy resin composition for sealing, and其制造方法。 Its manufacturing method.
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，其結構要素（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同樣如此，並不限制本發明。 於本揭示中，「步驟」的用語中，除與其他步驟獨立的步驟以外，即便於無法與其他步驟明確區別的情況下，只要達成該步驟的目的，則亦包含該步驟。 於本揭示中，使用「～」所表示的數值範圍中包含「～」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，各成分亦可包含多種相符的物質。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，則各成分的含有率或含量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，亦可包含多種相當於各成分的粒子。於在組成物中存在多種相當於各成分的粒子的情況下，只要無特別說明，則各成分的粒徑是指關於組成物中存在的該多種粒子的混合物的值。Hereinafter, the mode for implementing the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the structural elements (including element steps, etc.) are not essential unless otherwise specified. The same is true for the numerical value and its range, which does not limit the present invention. In the present disclosure, in the term "step", in addition to a step independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved, the step is also included. In this disclosure, the numerical values described before and after the "～" included in the numerical range indicated by "~" are used as the minimum and maximum values, respectively. In the numerical range described stepwise in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in the present disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also include a plurality of corresponding substances. When there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple types of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may also be included. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component refers to a value with respect to a mixture of the multiple types of particles present in the composition.
以下，對第一實施形態、第二實施形態、及第三實施形態進行詳細敘述。Hereinafter, the first embodiment, the second embodiment, and the third embodiment will be described in detail.
（1）第一實施形態 ＜密封用環氧樹脂組成物＞ 第一實施形態的密封用環氧樹脂組成物含有：環氧樹脂；以及硬化劑，包含以下的通式（B）所表示的化合物（以下，亦稱為「特定硬化劑」）。(1) The first embodiment ＜Epoxy resin composition for sealing＞ The epoxy resin composition for sealing of the first embodiment contains an epoxy resin; and a curing agent, and contains a compound represented by the following general formula (B) (hereinafter, also referred to as a "specific curing agent").
[化4]
通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數。第一實施形態的密封用環氧樹脂組成物由於含有特定硬化劑，故耐回焊性優異。In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0-10. Since the epoxy resin composition for sealing of 1st Embodiment contains a specific hardening agent, it is excellent in reflow resistance.
以下，對第一實施形態的密封用環氧樹脂組成物中可包含的成分進行詳細說明。Hereinafter, the components which can be contained in the epoxy resin composition for sealing of 1st Embodiment are demonstrated in detail.
[環氧樹脂] 第一實施形態的密封用環氧樹脂組成物含有環氧樹脂。環氧樹脂只要為於一分子中具有兩個以上環氧基者，則其種類並無特別限制。 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等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組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於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於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；使所述苯酚化合物及萘酚化合物與醛化合物於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合型環氧樹脂；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；作為烷基經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；作為二苯乙烯（stilbene）系酚化合物的二縮水甘油醚的二苯乙烯型環氧樹脂；作為雙酚S等的二縮水甘油醚的含硫原子型環氧樹脂；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；將二環戊二烯與苯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-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、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環氧樹脂。該些環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。[Epoxy resin] The epoxy resin composition for sealing of the first embodiment contains an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, examples include phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, At least one phenolic compound in the group consisting of naphthol compounds such as dihydroxynaphthalene is condensed or co-condensed with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolak resin and the phenolic compound Novolac type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) obtained by epoxidizing varnish resin; combining the phenolic compound with aromatics such as benzaldehyde and salicylaldehyde Triphenylmethane type epoxy resin obtained by condensing or co-condensing triphenylmethane type phenol resin under acidic catalyst and epoxidizing the triphenylmethane type phenol resin; making the phenol The compound and the naphthol compound and the aldehyde compound are co-condensed under an acidic catalyst to obtain a novolak resin and the novolak resin is epoxidized to obtain a copolymerized epoxy resin; as a two-component epoxy resin such as bisphenol A and bisphenol F Diphenylmethane type epoxy resin of glycidyl ether; biphenyl type epoxy resin of diglycidyl ether of biphenol with substituted or unsubstituted alkyl group; diphenyl epoxy resin of stilbene type phenol compound Stilbene type epoxy resin of glycidyl ether; sulfur atom-containing epoxy resin of diglycidyl ether such as bisphenol S; glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resins; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; aniline, diaminodiphenylmethane Glycidylamine type epoxy resin obtained by substituting glycidyl groups for active hydrogen bonded to nitrogen atoms such as isocyanuric acid; obtained by epoxidizing co-condensed resin of dicyclopentadiene and phenol compound Dicyclopentadiene type epoxy resin; Diepoxy vinylcyclohexene obtained by epoxidizing intramolecular olefin bonds, 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclic (3,4-epoxy)cyclohexane-m-dioxane and other alicyclic rings Oxygen resin; para-xylene-modified epoxy resin as glycidyl ether of para-xylene-modified phenol resin; meta-xylene-modified epoxy resin as glycidyl ether of meta-xylene-modified phenol resin; as terpene Modified epoxy resin with terpene modified by glycidyl ether of modified phenol resin; modified epoxy resin of dicyclopentadiene with glycidyl ether of modified phenol resin of dicyclopentadiene; modified by cyclopentadiene Cyclopentadiene-modified epoxy resin of glycidyl ether of phenol resin; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as polycyclic aromatic ring-modified phenol resin; glycidation of phenol resin containing naphthalene ring Glyceryl ether naphthalene type epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; obtained by oxidizing olefin bonds with peracetic acid and other peracids Linear aliphatic epoxy resin; aralkyl phenol resin such as phenol aralkyl resin and naphthol aralkyl resin Aralkyl type epoxy resin obtained by epoxidation and the like. Furthermore, epoxide of silicone resin, epoxide of acrylic resin, etc. can also be mentioned as an epoxy resin. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.
所述環氧樹脂中，就耐回焊性與流動性的平衡的觀點而言，較佳為選自由聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂及芳烷基型環氧樹脂所組成的群組中的環氧樹脂（將該些稱為「特定環氧樹脂」）。特定環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。Among the epoxy resins, from the viewpoint of the balance of reflow resistance and fluidity, they are preferably selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, and diphenylmethane type epoxy resins. , Sulfur atom type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymer type epoxy resin and aralkyl type epoxy resin The epoxy resins in the group of composition (these are called "specific epoxy resins"). A specific epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.
於環氧樹脂包含特定環氧樹脂的情況下，就發揮特定環氧樹脂的性能的觀點而言，其合計含有率較佳為環氧樹脂整體的30質量%以上，更佳為50質量%以上。When the epoxy resin contains a specific epoxy resin, from the viewpoint of exerting the performance of the specific epoxy resin, the total content is preferably 30% by mass or more of the entire epoxy resin, more preferably 50% by mass or more .
就流動性的觀點而言，特定環氧樹脂中更佳為聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂或含硫原子型環氧樹脂，就耐熱性的觀點而言，較佳為二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂或芳烷基型環氧樹脂。From the viewpoint of fluidity, among the specific epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, or sulfur atom-containing epoxy resin is more preferable. From the viewpoint of performance, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, or an aralkyl type epoxy resin is preferable.
該些中，就進一步提高流動性的觀點而言，環氧樹脂較佳為包含聯苯型環氧樹脂。於環氧樹脂包含聯苯型環氧樹脂的情況下，相對於環氧樹脂的總質量，聯苯型環氧樹脂的含有率較佳為30質量%～100質量%，更佳為50質量%～100質量%，進而佳為70質量%～100質量%。 以下表示較佳的環氧樹脂的具體例。Among these, from the viewpoint of further improving fluidity, the epoxy resin preferably contains a biphenyl type epoxy resin. When the epoxy resin contains a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin is preferably 30% by mass to 100% by mass, and more preferably 50% by mass relative to the total mass of the epoxy resin. ~100% by mass, more preferably 70% by mass to 100% by mass. Specific examples of preferable epoxy resins are shown below.
聯苯型環氧樹脂只要為具有聯苯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（II）所表示的環氧樹脂。下述通式（II）所表示的環氧樹脂中，R8 中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R8 為氫原子的YX-4000H（三菱化學股份有限公司，商品名），所有的R8 為氫原子的4,4'-雙(2,3-環氧基丙氧基)聯苯，所有的R8 為氫原子的情況以及R8 中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R8 為氫原子的情況下的混合品、即YL-6121H（三菱化學股份有限公司，商品名）等可作為市售品而獲取。The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. In the epoxy resin represented by the following general formula (II), the position where the oxygen atom in R 8 is substituted is set to the 4-position and the 4'position. When the 3, 3', 5, and 5'positions are methyl groups, except R 8 is other than a hydrogen atom YX-4000H (manufactured by Mitsubishi chemical Co., Ltd., trade name), all R 8 is a hydrogen atom, 4,4'-bis (2,3-epoxypropoxy) biphenyl , All the cases where R 8 is a hydrogen atom and the position where the oxygen atom in R 8 is substituted is set to 4 and 4'. When the 3, 3', 5, and 5'positions are methyl groups and the other R 8 In the case of a hydrogen atom, a mixed product, namely YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), etc., can be obtained as a commercial product.
[化5]
式（II）中，R8 表示氫原子、碳數1～12的烷基或碳數4～18的芳香族基，可分別均相同亦可不同。n為平均值，表示0～10的數。In the formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbons, or an aromatic group having 4 to 18 carbons, and each of them may be the same or different. n is an average value and represents a number from 0 to 10.
二苯乙烯型環氧樹脂只要為具有二苯乙烯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（III）所表示的環氧樹脂。下述通式（III）所表示的環氧樹脂中，R9 中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R9 為氫原子、R10 均為氫原子的情況，以及R9 中3,3',5,5'位中的三個為甲基、一個為第三丁基且除此以外的R9 為氫原子、R10 均為氫原子的情況下的混合品、即ESLV-210（住友化學股份有限公司，商品名）等可作為市售品而獲取。The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. In the epoxy resin represented by the following general formula (III), the position where the oxygen atom in R 9 is substituted is set to the 4 position and the 4'position. When the 3, 3', 5, and 5'positions are methyl groups, except Other than the case where R 9 is a hydrogen atom and R 10 is a hydrogen atom, and three of the 3, 3', 5, and 5'positions in R 9 are methyl groups, one is a tertiary butyl group, and others When R 9 is a hydrogen atom and R 10 is a hydrogen atom, a mixed product, that is, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., can be obtained as a commercially available product.
[化6]
式（III）中，R9 及R10 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，表示0～10的數。In the formula (III), R 9 and R 10 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is an average value and represents a number from 0 to 10.
二苯基甲烷型環氧樹脂只要為具有二苯基甲烷骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（IV）所表示的環氧樹脂。下述通式（IV）所表示的環氧樹脂中，R11 均為氫原子、R12 中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R12 為氫原子的YSLV-80XY（日鐵化學&材料股份有限公司，商品名）等可作為市售品而獲取。The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. In the epoxy resin represented by the following general formula (IV), each of R 11 is a hydrogen atom, and the position where the oxygen atom in R 12 is substituted is 3, 3', 5, 5'when the position 4 and 4'are substituted YSLV-80XY (Nippon Steel Chemical & Materials Co., Ltd., trade name), etc. whose position is a methyl group and whose other R 12 is a hydrogen atom can be obtained as a commercially available product.
[化7]
式（IV）中，R11 及R12 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，表示0～10的數。In the formula (IV), R 11 and R 12 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is an average value and represents a number from 0 to 10.
含硫原子型環氧樹脂只要為含有硫原子的環氧樹脂，則並無特別限定。例如可列舉下述通式（V）所表示的環氧樹脂。下述通式（V）所表示的環氧樹脂中，R13 中氧原子進行取代的位置設為4位及4'位時的3,3'位為第三丁基、6,6'位為甲基且除此以外的R13 為氫原子的YSLV-120TE（日鐵化學&材料股份有限公司，商品名）等可作為市售品而獲取。The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, the epoxy resin represented by the following general formula (V) is mentioned. In the epoxy resin represented by the following general formula (V), the position where the oxygen atom in R 13 is substituted is the 4th and 4'positions. When the 3,3' positions are the tertiary butyl and 6,6' positions YSLV-120TE (Nippon Steel Chemical & Materials Co., Ltd., trade name), etc., in which R 13 is a hydrogen atom and is a methyl group is available as a commercially available product.
[化8]
式（V）中，R13 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，表示0～10的數。In the formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. n is an average value and represents a number from 0 to 10.
酚醛清漆型環氧樹脂只要為使酚醛清漆型酚樹脂進行環氧化而獲得的環氧樹脂，則並無特別限定。例如較佳為使用縮水甘油醚化等方法使苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、萘酚酚醛清漆樹脂等酚醛清漆型酚樹脂進行環氧化而獲得的環氧樹脂，更佳為下述通式（VI）所表示的環氧樹脂。下述通式（VI）所表示的環氧樹脂中，R14 均為氫原子、R15 為甲基、i=1的ESCN-190、ESCN-195（住友化學股份有限公司，商品名）；R14 均為氫原子、i=0的N-770、N-775（迪愛生（DIC）股份有限公司，商品名）；具有R14 均為氫原子、i=0的部分與i=1、R15 為-CH(CH3 )-Ph的部分的苯乙烯改質苯酚酚醛清漆型環氧樹脂、即YDAN-1000-10C（日鐵化學&材料股份有限公司，商品名）等可作為市售品而獲取。The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, etc., using glycidyl etherification, etc., is more preferably an epoxy resin obtained by epoxidizing novolac type phenol resins such as phenol novolak resin, cresol novolak resin, and naphthol novolak resin. The epoxy resin represented by formula (VI). In the epoxy resin represented by the following general formula (VI), R 14 is a hydrogen atom, R 15 is a methyl group, and ESCN-190 and ESCN-195 (Sumitomo Chemical Co., Ltd., trade name) with i=1; R 14 is a hydrogen atom, N-770, N-775 (DIC Co., Ltd., trade name) with i=0; the part with R 14 is a hydrogen atom, i=0 and i=1, A styrene-modified phenol novolak type epoxy resin whose R 15 is -CH(CH 3 )-Ph, that is, YDAN-1000-10C (Nippon Steel Chemical & Materials Co., Ltd., trade name), etc. are commercially available Product.
[化9]
式（VI）中，R14 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R15 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，表示0～10的數。In the formula (VI), R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R 15 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0-3. n is an average value and represents a number from 0 to 10.
二環戊二烯型環氧樹脂只要為將具有二環戊二烯骨架的化合物作為原料來進行環氧化而獲得的環氧樹脂，則並無特別限定。例如較佳為下述通式（VII）所表示的環氧樹脂。下述通式（VII）所表示的環氧樹脂中，i=0的HP-7200（迪愛生（DIC）股份有限公司，商品名）等可作為市售品而獲取。The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Co., Ltd., trade name) with i=0 can be obtained as a commercially available product.
[化10]
式（VII）中，R16 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，表示0～10的數。In the formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. i each independently represents an integer of 0-3. n is an average value and represents a number from 0 to 10.
三苯基甲烷型環氧樹脂只要為將具有三苯基甲烷骨架的化合物作為原料的環氧樹脂，則並無特別限制。例如較佳為將具有三苯基甲烷骨架的化合物與具有酚性羥基的化合物的酚醛清漆型酚樹脂等三苯基甲烷型酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式（VIII）所表示的環氧樹脂。下述通式（VIII）所表示的環氧樹脂中，i為0且k為0的1032H60（三菱化學股份有限公司，商品名）、EPPN-502H（日本化藥股份有限公司，商品名）等可作為市售品而獲取。The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherifying a triphenylmethane type phenol resin such as a compound having a triphenylmethane skeleton and a novolak type phenol resin of a compound having a phenolic hydroxyl group is preferable, and more preferably the following The epoxy resin represented by the general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name) where i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name), etc. It is available as a commercially available product.
[化11]
式（VIII）中，R17 及R18 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數，k各自獨立地表示0～4的整數。n為平均值，表示0～10的數。In the formula (VIII), R 17 and R 18 represent a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i each independently represents an integer of 0 to 3, and k each independently represents an integer of 0 to 4. n is an average value and represents a number from 0 to 10.
使由萘酚化合物及苯酚化合物與醛化合物所獲得的酚醛清漆樹脂進行環氧化而成的共聚合型環氧樹脂只要為將具有萘酚骨架的化合物及具有苯酚骨架的化合物作為原料的環氧樹脂，則並無特別限定。例如較佳為使利用具有萘酚骨架的化合物及具有苯酚骨架的化合物的酚醛清漆型酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式（IX）所表示的環氧樹脂。下述通式（IX）所表示的環氧樹脂中，R21 為甲基且i為1、j為0、k為0的NC-7300（日本化藥股份有限公司，商品名）等可作為市售品而獲取。Copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound and an aldehyde compound, as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials , There is no particular limitation. For example, it is preferably an epoxy resin obtained by glycidyl etherification of a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton, and more preferably a ring represented by the following general formula (IX) Oxy resin. In the epoxy resin represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) in which R 21 is a methyl group, i is 1, j is 0, and k is 0 can be used as Obtained from commercially available products.
[化12]
式（IX）中，R19 ～R21 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數，j各自獨立地表示0～2的整數，k各自獨立地表示0～4的整數。l及m分別為平均值，為0～10的數，（l+m）表示0～10的數。式（IX）所表示的環氧樹脂的末端為下述式（IX-1）或式（IX-2）的任一者。式（IX-1）及式（IX-2）中，R19 ～R21 中i、j及k的定義與式（IX）中的R19 ～R21 中的i、j及k的定義相同。n為1（經由亞甲基而鍵結的情況）或0（不經由亞甲基而鍵結的情況）。In the formula (IX), R 19 to R 21 represent a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different. i each independently represents an integer of 0 to 3, j each independently represents an integer of 0 to 2, and k each independently represents an integer of 0 to 4. l and m are average values, and are numbers from 0 to 10, and (l+m) represents a number from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either of the following formula (IX-1) or formula (IX-2). In formula (IX-1) and formula (IX-2), as defined for R 19 ~ R 21 are i, j, and k are as defined in formula (IX) R 19 ~ R 21 is i, j and k of . n is 1 (in the case of bonding via a methylene group) or 0 (in the case of not bonding via a methylene group).
[化13]
作為所述通式（IX）所表示的環氧樹脂，可列舉：無規地包含一個結構單元及m個結構單元的無規共聚物、交替地包含一個結構單元及m個結構單元的交替共聚物、有規則地包含一個結構單元及m個結構單元的共聚物、以嵌段狀包含一個結構單元及m個結構單元的嵌段共聚物等。可單獨使用該些的任一種，亦可將兩種以上組合而使用。Examples of the epoxy resin represented by the general formula (IX) include: a random copolymer including one structural unit and m structural units randomly, and an alternating copolymer including one structural unit and m structural units alternately A copolymer containing one structural unit and m structural units regularly, a block copolymer containing one structural unit and m structural units in a block form, and the like. Any one of these may be used alone, or two or more of them may be used in combination.
作為共聚合型環氧樹脂，另外亦較佳為以無規、交替或嵌段的順序包含下述兩種結構單元的甲氧基萘-甲酚甲醛共縮合型環氧樹脂、即下述通式所表示的艾比克隆（EPICLON）HP-5000（迪愛生（DIC）股份有限公司，商品名）。下述通式中，n及m分別為平均值，為1～10的數，（n+m）表示2～10的數，較佳為n及m分別為平均值，為1～9的數，（n+m）表示2～10的數。As the copolymerized epoxy resin, it is also preferably a methoxy naphthalene-cresol formaldehyde co-condensed epoxy resin containing the following two structural units in a random, alternating or block order, that is, the following general EPICLON HP-5000 (DIC Co., Ltd., trade name) represented by the formula. In the following general formula, n and m are average values and are numbers from 1 to 10, (n+m) are numbers from 2 to 10, preferably n and m are average values, and are numbers from 1 to 9 , (N+m) represents the number from 2 to 10.
[化14]
芳烷基型環氧樹脂只要為將由選自由苯酚、甲酚等苯酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種，與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂作為原料的環氧樹脂，則並無特別限定。例如較佳為使由選自由苯酚、甲酚等苯酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式（X）及通式（XI）所表示的環氧樹脂。The aralkyl type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethyl naphthol, and dimethoxy-p-xylene There are no particular limitations on the epoxy resin used as the raw material for the phenol resin synthesized from bis(methoxymethyl)biphenyl or these derivatives. For example, it is preferable to combine at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethyl naphthol with dimethoxy-p-xylene, bis(methoxy) An epoxy resin obtained by glycidyl etherification of a phenol resin synthesized from (methyl)biphenyl or these derivatives is more preferably an epoxy represented by the following general formula (X) and general formula (XI) Resin.
下述通式（X）所表示的環氧樹脂中，i為0且R38 為氫原子的NC-3000S（日本化藥股份有限公司，商品名），以質量比80：20將i為0且R38 為氫原子的環氧樹脂與通式（II）的所有的R8 為氫原子的環氧樹脂混合而成的CER-3000（日本化藥股份有限公司，商品名）等可作為市售品而獲取。另外，下述通式（XI）所表示的環氧樹脂中，i為0、j為0、k為0的ESN-175（日鐵化學&材料股份有限公司，商品名）等可作為市售品而獲取。In the epoxy resin represented by the following general formula (X), NC-3000S (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and R 38 is a hydrogen atom, i is 0 at a mass ratio of 80:20 And CER-3000 (Nippon Kayaku Co., Ltd., trade name), which is a mixture of epoxy resins in which R 38 is a hydrogen atom and all epoxy resins in the general formula (II), in which R 8 is a hydrogen atom, can be used as a market For sale. In addition, in the epoxy resin represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical & Materials Co., Ltd., trade name) with i being 0, j being 0, and k being 0 is commercially available as Product.
[化15]
式（X）及式（XI）中，R38 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R37 、R39 ～R41 表示碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，j分別獨立地為0～2的整數，k分別獨立地為0～4的整數，l分別獨立地表示0～6的整數。n為平均值，分別獨立地為0～10的數。In formula (X) and formula (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R 37 and R 39 to R 41 represent a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, and l each independently represents an integer of 0 to 6. n is an average value, and each independently is a number from 0 to 10.
關於所述通式（II）～通式（XI）中的R8 ～R21 及R37 ～R41 ，所謂「可分別均相同亦可不同」例如是指式（II）中的8個～88個R8 可均相同亦可不同。關於其他的R9 ～R21 及R37 ～R41 ，亦是指式中所含的各自的個數可均相同亦可不同。另外，R8 ～R21 及R37 ～R41 可分別相同亦可不同。例如，R9 與R10 可均相同亦可不同。 另外，通式（III）～通式（XI）中的碳數1～18的一價有機基較佳為烷基或芳基。 Regarding R 8 to R 21 and R 37 to R 41 in the general formula (II) to the general formula (XI), the term "may be all the same or different" means, for example, 8 to in the formula (II) The 88 R 8 may all be the same or different. Regarding the other R 9 to R 21 and R 37 to R 41 , it also means that the respective numbers contained in the formula may all be the same or different. In addition, R 8 to R 21 and R 37 to R 41 may be the same or different, respectively. For example, R 9 and R 10 may both be the same or different. In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formula (III) to the general formula (XI) is preferably an alkyl group or an aryl group.
所述通式（II）～通式（XI）中的n為平均值，較佳為分別獨立地為0～10的範圍。若n為10以下，則樹脂成分的熔融黏度不會過高，環氧樹脂組成物的熔融成形時的黏度降低，有抑制產生填充不良、接合線（連接元件與引線的金屬線）的變形等的傾向。n更佳為設定為0～4的範圍。The n in the general formula (II) to the general formula (XI) is an average value, and is preferably in the range of 0-10 each independently. If n is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the epoxy resin composition during melt molding will decrease, and the occurrence of filling defects and deformation of bonding wires (metal wires connecting components and leads) will be suppressed. Propensity. More preferably, n is set to the range of 0-4.
環氧樹脂的環氧當量並無特別限制。就成形性、耐回焊性及電性可靠性等各種特性平衡的觀點而言，環氧樹脂的環氧當量較佳為100 g/eq～1000 g/eq，更佳為150 g/eq～500 g/eq。環氧樹脂的環氧當量設為利用依據日本工業標準（Japanese Industrial Standards，JIS）K 7236：2009的方法而測定的值。The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq～1000 g/eq, more preferably 150 g/eq～ 500 g/eq. The epoxy equivalent of an epoxy resin shall be the value measured by the method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.
於環氧樹脂為固體的情況下，其軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物的製備時的操作性的觀點而言，更佳為50℃～130℃。環氧樹脂的熔點設為利用示差掃描熱量測定（differential scanning calorimetry，DSC）而測定的值，環氧樹脂的軟化點設為利用依據JIS K 7234：1986的方法（環球法）而測定的值。In the case where the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during the preparation of the epoxy resin composition, it is more preferably from 50°C to 130°C. The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with JIS K 7234:1986.
就強度、流動性、耐熱性、成形性等觀點而言，環氧樹脂組成物中的環氧樹脂的含有率較佳為0.5質量%～50質量%，更佳為2質量%～30質量%。From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the epoxy resin content in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass .
[硬化劑] 第一實施形態的密封用環氧樹脂組成物含有包含以下的通式（B）所表示的化合物（特定硬化劑）的硬化劑。[hardener] The epoxy resin composition for sealing of the first embodiment contains a curing agent containing a compound (specific curing agent) represented by the following general formula (B).
[化16]
通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數。 作為碳數1～6的烷基，可列舉：甲基、乙基、丙基、丁基、戊基、己基、異丙基、異丁基、第三丁基等。其中，較佳為甲基。In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0-10. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and tertiary butyl. Among them, methyl is preferred.
特定硬化劑的羥基當量較佳為100 g/eq～130 g/eq。特定硬化劑的羥基當量可利用後述的方法來測定。The hydroxyl equivalent of the specific hardener is preferably 100 g/eq to 130 g/eq. The hydroxyl equivalent of a specific hardening agent can be measured by the method mentioned later.
於特定硬化劑為固體的情況下，其軟化點或熔點並無特別限制，就成形性與耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物的製造時的操作性的觀點而言，更佳為50℃～130℃。就提高流動性的觀點及降低環氧樹脂組成物的硬化物的高溫彈性係數、提高耐回焊性的觀點而言，較佳為50℃～100℃，更佳為50℃～75℃，進而佳為50℃～70℃。When the specific hardener is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably 40°C to 180°C. For the production of epoxy resin composition From the viewpoint of operability at this time, it is more preferably 50°C to 130°C. From the viewpoint of improving fluidity, reducing the high-temperature elastic modulus of the cured epoxy resin composition, and improving the reflow resistance, it is preferably 50°C to 100°C, more preferably 50°C to 75°C, and further It is preferably 50°C to 70°C.
特定硬化劑可單獨使用任一種，亦可併用兩種以上。 硬化劑除了特定硬化劑以外亦可進一步併用其他硬化劑。硬化劑中的特定硬化劑的含有率較佳為30質量%～100質量%，更佳為50質量%～100質量%，進而佳為70質量%～100質量%。Any one of the specific curing agents may be used alone, or two or more of them may be used in combination. In addition to the specific hardener, the hardener may be further used in combination with other hardeners. The content of the specific curing agent in the curing agent is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and still more preferably 70% by mass to 100% by mass.
作為其他硬化劑，可列舉通式（B）所表示的化合物以外的、於分子中具有酚性羥基者（酚硬化劑）。Examples of other curing agents include those having a phenolic hydroxyl group in the molecule (phenol curing agent) other than the compound represented by the general formula (B).
作為通式（B）所表示的化合物以外的酚硬化劑，例如可列舉於一分子中具有兩個以上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、間甲酚、對甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組中的至少一種酚性化合物、與甲醛、乙醛、丙醛、苯甲醛、水楊醛等醛化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂（通式（B）所表示的化合物除外）；由所述酚性化合物與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯等所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂；對二甲苯及/或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；由所述酚性化合物與二環戊二烯藉由共聚合而合成的二環戊二烯型苯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、水楊醛等芳香族醛化合物於酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂；將該些的兩種以上共聚合而獲得的酚樹脂等。該些酚硬化劑可單獨使用一種，亦可將兩種以上組合而使用。As a phenol hardener other than the compound represented by general formula (B), the phenol resin and polyhydric phenol compound which have two or more phenolic hydroxyl groups in one molecule are mentioned, for example. Specifically, examples include: polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenols; selected from phenol, m-cresol, and p-cresol Phenol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthalenes Novolac type phenol resin obtained by condensation or co-condensation of at least one phenolic compound in the group of phenolic compounds with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. under an acidic catalyst (Except the compound represented by the general formula (B)); Phenol aralkyl resin, naphthol synthesized from the phenolic compound, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. Aralkyl phenol resin such as aralkyl resin; para-xylene and/or meta-xylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; from the phenolic compound and dicyclopentadiene Dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin ; Triphenylmethane type phenol resin obtained by condensation or co-condensation of the phenolic compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in an acidic catalyst; obtained by copolymerizing two or more of these The phenol resin and so on. These phenol hardeners may be used alone or in combination of two or more kinds.
通式（B）所表示的化合物以外的酚硬化劑中，就耐回焊性的觀點而言，較佳為選自由芳烷基型酚樹脂、二環戊二烯型酚樹脂、三苯基甲烷型酚樹脂、苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、及酚醛清漆型酚樹脂（通式（B）所表示的化合物除外）所組成的群組中的至少一種（將該些稱為「特定酚硬化劑」）。特定酚硬化劑可單獨使用一種，亦可將兩種以上組合而使用。Among the phenolic hardeners other than the compound represented by the general formula (B), from the viewpoint of reflow resistance, it is preferably selected from the group consisting of aralkyl type phenol resin, dicyclopentadiene type phenol resin, and triphenyl phenol resin. At least one of the group consisting of a methane-type phenol resin, a copolymerized phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin, and a novolak-type phenol resin (except the compound represented by the general formula (B)) One type (these are called "specific phenol hardeners"). The specific phenol hardener may be used alone or in combination of two or more kinds.
於硬化劑包含特定酚硬化劑的情況下，特定酚硬化劑的含有率可為硬化劑整體的5質量%～75質量%，亦可為5質量%～70質量%，亦可為10質量%～50質量%，亦可為15質量%～30質量%。When the curing agent contains a specific phenol curing agent, the content of the specific phenol curing agent may be 5 mass% to 75 mass% of the whole curing agent, may be 5 mass% to 70 mass %, or may be 10 mass% ~50% by mass, or 15% by mass to 30% by mass.
作為芳烷基型酚樹脂，可列舉由酚性化合物與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯等所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等。芳烷基型酚樹脂亦可進而與其他酚樹脂共聚合。作為共聚合的芳烷基型酚樹脂，可列舉：苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、水楊醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、酚醛清漆型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂等。Examples of aralkyl type phenol resins include phenol aralkyl resins, naphthol aralkyl resins synthesized from phenolic compounds, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. . The aralkyl type phenol resin may be further copolymerized with other phenol resins. Examples of the copolymerized aralkyl phenol resin include: a copolymerized phenol resin of a benzaldehyde type phenol resin and an aralkyl phenol resin, and a copolymerized type of a salicylaldehyde phenol resin and an aralkyl phenol resin. Phenolic resin, novolak type phenol resin and copolymerized phenol resin of aralkyl type phenol resin, etc.
芳烷基型酚樹脂只要為由選自由苯酚化合物及萘酚化合物所組成的群組中的至少一種與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂，則並無特別限定。例如較佳為下述通式（XII）～通式（XIV）所表示的酚樹脂。 其中，關於下述通式（XIII）所表示的酚樹脂，將所述通式（B）所表示的化合物除外。The aralkyl-type phenol resin is as long as it is derived from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxypara-xylene, bis(methoxymethyl)biphenyl, or these The phenol resin synthesized by the compound is not particularly limited. For example, the phenol resin represented by the following general formula (XII)-general formula (XIV) is preferable. However, regarding the phenol resin represented by the following general formula (XIII), the compound represented by the aforementioned general formula (B) is excluded.
[化17]
式（XII）～式（XIV）中，R23 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R22 、R24 、R25 及R28 表示碳數1～18的一價有機基，可分別均相同亦可不同。R26 及R27 表示羥基或碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，j分別獨立地為0～2的整數，k分別獨立地為0～4的整數，p分別獨立地為0～4的整數。n為平均值，分別獨立地為0～10的數。In formula (XII) to formula (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R 22 , R 24 , R 25 and R 28 represent a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different. R 26 and R 27 represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, and p is each independently an integer of 0 to 4. n is an average value, and each independently is a number from 0 to 10.
所述通式（XII）所表示的酚樹脂中，i為0且R23 均為氫原子的MEH-7851（明和化成股份有限公司，商品名）等可作為市售品而獲取。Among the phenol resins represented by the general formula (XII), MEH-7851 (Mingwa Chemical Co., Ltd., trade name) in which i is 0 and R 23 is a hydrogen atom can be obtained as a commercially available product.
所述通式（XIII）所表示的酚樹脂中，i為0且k為0的XL-225、XLC（三井化學股份有限公司，商品名）、MEH-7800（明和化成股份有限公司，商品名）等可作為市售品而獲取。Among the phenol resins represented by the general formula (XIII), XL-225, XLC (Mitsui Chemicals Co., Ltd., trade name), and MEH-7800 (Meiwa Chemicals Co., Ltd., trade name) where i is 0 and k is 0 ) Etc. can be obtained as commercially available products.
所述通式（XIV）所表示的酚樹脂中，j為0、k為0且p為0的SN-170（日鐵化學&材料股份有限公司，商品名）、j為0、k為1、R27 為羥基且p為0的SN-395（日鐵化學&材料股份有限公司，商品名）等可作為市售品而獲取。In the phenol resin represented by the general formula (XIV), SN-170 (Nippon Steel Chemical & Materials Co., Ltd., trade name) where j is 0, k is 0, and p is 0, j is 0, and k is 1. , SN-395 (Nippon Steel Chemical & Materials Co., Ltd., trade name) in which R 27 is a hydroxyl group and p is 0 can be obtained as a commercially available product.
二環戊二烯型酚樹脂只要為將具有二環戊二烯骨架的化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XV）所表示的酚樹脂。下述通式（XV）所表示的酚樹脂中，i為0的DPP（新日本石油化學股份有限公司，商品名）等可作為市售品而獲取。The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred. Among the phenol resins represented by the following general formula (XV), DPP (New Japan Petrochemical Co., Ltd., trade name) in which i is 0 can be obtained as a commercially available product.
[化18]
式（XV）中，R29 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，表示0～10的數。In the formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. i each independently represents an integer of 0-3. n is an average value and represents a number from 0 to 10.
三苯基甲烷型酚樹脂只要為將具有三苯基甲烷骨架的化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XVI）所表示的酚樹脂。The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.
下述通式（XVI）所表示的酚樹脂中，i為0且k為0的MEH-7500（明和化成股份有限公司，商品名）等可作為市售品而獲取。Among the phenol resins represented by the following general formula (XVI), MEH-7500 (Mingwa Chemical Co., Ltd., trade name) in which i is 0 and k is 0 can be obtained as a commercially available product.
[化19]
式（XVI）中，R30 及R31 表示碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，k分別獨立地為0～4的整數。n為平均值，為0～10的數。In formula (XVI), R 30 and R 31 represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer of 0-3, and k is each independently an integer of 0-4. n is an average value and is a number from 0 to 10.
苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂只要為將具有苯甲醛骨架的化合物作為原料而獲得的酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂，則並無特別限定。例如較佳為下述通式（XVII）所表示的酚樹脂。Copolymerization type phenol resin of benzaldehyde type phenol resin and aralkyl type phenol resin, as long as it is a copolymer type phenol resin of phenol resin and aralkyl type phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material, it is not There is no particular limitation. For example, a phenol resin represented by the following general formula (XVII) is preferred.
下述通式（XVII）所表示的酚樹脂中，i為0、k為0且q為0的HE-510（空氣水化學（Air Water Chemical）股份有限公司，商品名）等可作為市售品而獲取。Among the phenol resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) in which i is 0, k is 0, and q is 0 is commercially available as Product.
[化20]
式（XVII）中，R32 ～R34 表示碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，k分別獨立地為0～4的整數，q分別獨立地為0～5的整數。l及m分別為平均值，分別獨立地為0～11的數。其中，l與m的合計為1～11的數。In the formula (XVII), R 32 to R 34 represent a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i is an integer of 0-3 each independently, k is an integer of 0-4 each independently, and q is an integer of 0-5 each independently. l and m are the average values, and are independently numbers from 0 to 11. Among them, the total of l and m is a number from 1 to 11.
酚醛清漆型酚樹脂只要為使選自由苯酚化合物及萘酚化合物所組成的群組中的至少一種酚性化合物與醛化合物於酸性觸媒下縮合或共縮合而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XVIII）所表示的酚樹脂。Novolac-type phenol resin is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. limited. For example, a phenol resin represented by the following general formula (XVIII) is preferable.
下述通式（XVIII）所表示的酚樹脂中，i為0、R35 均為氫原子的特瑪諾爾（Tamanol）758、759（荒川化學工業股份有限公司，商品名）等可作為市售品而獲取。Among the phenol resins represented by the following general formula (XVIII), Tamanol 758, 759 (Arakawa Chemical Industry Co., Ltd., trade name), etc. whose i is 0 and R 35 are all hydrogen atoms are commercially available Product.
[化21]
式（XVIII）中，R35 表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R36 表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，表示0～10的數。In the formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. i each independently represents an integer of 0-3. n is an average value and represents a number from 0 to 10.
關於所述通式（XII）～通式（XVIII）中的R22 ～R36 所記載的「可分別均相同亦可不同」例如是指式（XII）中的i個R22 可均相同亦可相互不同。關於其他的R23 ～R36 ，亦是指式中所含的各自的個數可均相同亦可相互不同。另外，R22 ～R36 分別可相同亦可不同。例如，R22 及R23 可均相同亦可不同，R30 及R31 可均相同亦可不同。 Regarding the R 22 to R 36 in the general formula (XII) to the general formula (XVIII), the "may be all the same or different." For example, it means that the i R 22 in the formula (XII) may all be the same or Can be different from each other. Regarding other R 23 to R 36 , it also means that the respective numbers contained in the formula may all be the same or different from each other. In addition, R 22 to R 36 may be the same or different. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may be the same or different.
所述通式（XII）～通式（XVIII）中的n較佳為0～10的範圍。若為10以下，則樹脂成分的熔融黏度不會過高，環氧樹脂組成物的熔融成形時的黏度亦變低，難以產生填充不良、接合線（連接元件與引線的金屬線）的變形等。一分子中的平均n較佳為設定為0～4的範圍。Preferably, n in the general formula (XII) to (XVIII) is in the range of 0-10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the epoxy resin composition during melt molding will also be low, and poor filling, deformation of the bonding wire (the metal wire connecting the element and the lead), etc. are unlikely to occur. . The average n in one molecule is preferably set in the range of 0-4.
硬化劑的官能基當量（於分子中具有酚性羥基的硬化劑中，為羥基當量）並無特別限制。就成形性、耐回焊性、電性可靠性等各種特性平衡的觀點而言，較佳為70 g/eq～1000 g/eq，更佳為80 g/eq～500 g/eq。The functional group equivalent of the curing agent (in a curing agent having a phenolic hydroxyl group in the molecule, it is a hydroxyl equivalent) is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, it is preferably 70 g/eq to 1000 g/eq, and more preferably 80 g/eq to 500 g/eq.
硬化劑的官能基當量（於分子中具有酚性羥基的硬化劑中，為羥基當量）例如亦可為藉由依據JIS K 0070：1992的方法而測定的值。The functional group equivalent of the curing agent (in a curing agent having a phenolic hydroxyl group in the molecule, the hydroxyl equivalent) may be a value measured by a method based on JIS K 0070:1992, for example.
於硬化劑為固體的情況下，其軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物的製造時的操作性的觀點而言，更佳為50℃～130℃。另外，就降低熔融黏度的觀點或提高流動性的觀點、以及降低環氧樹脂組成物的硬化物的高溫彈性係數、提高耐回焊性的觀點而言，硬化劑的軟化點或熔點較佳為50℃～100℃，更佳為50℃～75℃，進而佳為50℃～65℃。In the case where the hardener is a solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during the production of the epoxy resin composition, it is more preferably from 50°C to 130°C. In addition, from the viewpoint of lowering melt viscosity or improving fluidity, lowering the high-temperature elastic modulus of the cured product of the epoxy resin composition, and improving the reflow resistance, the softening point or melting point of the hardener is preferably 50°C to 100°C, more preferably 50°C to 75°C, and still more preferably 50°C to 65°C.
硬化劑的熔點或軟化點設為與環氧樹脂的熔點或軟化點同樣地測定的值。The melting point or softening point of the hardener is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.
環氧樹脂與硬化劑的當量比、即硬化劑中的官能基數相對於環氧樹脂中的環氧基數的比（硬化劑中的官能基數/環氧樹脂中的環氧基數）並無特別限制。就將各自的未反應成分抑制得少的觀點而言，較佳為設定為0.5～2.0的範圍，更佳為設定為0.6～1.3的範圍。就成形性與耐回焊性的觀點而言，進而佳為設定為0.7～1.2的範圍。The equivalent ratio of epoxy resin to hardener, that is, the ratio of the number of functional groups in the hardener to the number of epoxy groups in the epoxy resin (the number of functional groups in the hardener/the number of epoxy groups in the epoxy resin) is not particularly limited . From the viewpoint of reducing the respective unreacted components, it is preferably set to the range of 0.5 to 2.0, and more preferably set to the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferable to set it to the range of 0.7 to 1.2.
[硬化促進劑] 環氧樹脂組成物亦可包含硬化促進劑。硬化促進劑的種類並無特別限制，可根據環氧樹脂的種類、環氧樹脂組成物的所期望的特性等選擇。[Hardening accelerator] The epoxy resin composition may also contain a hardening accelerator. The type of hardening accelerator is not particularly limited, and can be selected according to the type of epoxy resin, the desired characteristics of the epoxy resin composition, and the like.
就硬化性及流動性或黏度的觀點而言，硬化促進劑較佳為包含鏻化合物。作為鏻化合物，具體而言，可列舉：三苯基膦、二苯基(對甲苯基)膦、三(烷基苯基)膦、三(烷氧基苯基)膦、三(烷基-烷氧基苯基)膦、三(二烷基苯基)膦、三(三烷基苯基)膦、三(四烷基苯基)膦、三(二烷氧基苯基)膦、三(三烷氧基苯基)膦、三(四烷氧基苯基)膦、三烷基膦、二烷基芳基膦、烷基二芳基膦、三萘基膦、三(苄基)膦等三級膦、與馬來酸酐、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、蒽醌等醌化合物、重氮苯基甲烷等具有π鍵的化合物加成而形成的具有分子內極化的化合物；於使所述三級膦或所述膦化合物與4-溴苯酚、3-溴苯酚、2-溴苯酚、4-氯苯酚、3-氯苯酚、2-氯苯酚、4-碘苯酚、3-碘苯酚、2-碘苯酚、4-溴-2-甲基苯酚、4-溴-3-甲基苯酚、4-溴-2,6-二甲基苯酚、4-溴-3,5-二甲基苯酚、4-溴-2,6-二-第三丁基苯酚、4-氯-1-萘酚、1-溴-2-萘酚、6-溴-2-萘酚、4-溴-4'-羥基聯苯等鹵化酚化合物反應後經過脫鹵化氫的步驟而獲得的具有分子內極化的化合物；四苯基鏻等四取代鏻、四苯基鏻四-對甲苯基硼酸鹽等四取代鏻的四苯基硼酸鹽、四取代鏻與酚化合物的鹽等四取代鏻化合物；四取代鏻與自酚化合物脫離質子後的陰離子的鹽、四取代鏻與自羧酸化合物脫離質子後的陰離子的鹽；磷酸酯甜菜鹼（phosphobetaine）化合物；鏻化合物與矽烷化合物的加成物等。From the viewpoint of curability and fluidity or viscosity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, and tris(alkyl- Alkoxyphenyl) phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, three (Trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl) Tertiary phosphine such as phosphine, and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzene Quinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthracene Compounds with intramolecular polarization formed by the addition of quinone compounds such as quinones and compounds with π bonds such as diazophenylmethane; to make the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol Phenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromophenol -3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4 -Chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and other halogenated phenol compounds are obtained by the step of dehydrohalogenation after the reaction Compounds with intramolecular polarization; tetra-substituted phosphonium such as tetraphenyl phosphonium, tetra-substituted phosphonium tetraphenyl borate such as tetraphenyl phosphonium tetra-p-tolyl borate, salts of tetra-substituted phosphonium and phenolic compounds, etc. Substituted phosphonium compounds; salts of tetra-substituted phosphonium and anions deprotonated from phenolic compounds, salts of tetra-substituted phosphonium and anions deprotonated from carboxylic acid compounds; phosphobetaine compounds; phosphonium compounds and silane compounds Additives, etc.
所述鏻化合物中，較佳為下述通式（I-1）所表示的化合物（以下，亦稱為特定硬化促進劑）。Among the above-mentioned phosphonium compounds, a compound represented by the following general formula (I-1) (hereinafter, also referred to as a specific hardening accelerator) is preferred.
[化22]
式（I-1）中，R1 ～R3 分別獨立地為碳數1～18的烴基，R1 ～R3 中兩個以上可相互鍵結而形成環狀結構，R4 ～R7 分別獨立地為氫原子、羥基或碳數1～18的一價有機基，R4 ～R7 中兩個以上可相互鍵結而形成環狀結構。In the formula (I-1), R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbons , two or more of R 1 to R 3 may be bonded to each other to form a cyclic structure, and R 4 to R 7 are each independently It is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 may be bonded to each other to form a cyclic structure.
作為通式（I-1）的R1 ～R3 而記載的「碳數1～18的烴基」包含碳數為1～18的脂肪族烴基及碳數為6～18的芳香族烴基。 The "hydrocarbon group having 1 to 18 carbon atoms" described as R 1 to R 3 of the general formula (I-1) includes aliphatic hydrocarbon groups having 1 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms.
就流動性或黏度的觀點而言，碳數1～18的脂肪族烴基的碳數較佳為1～8，更佳為2～6，進而佳為4～6。From the viewpoint of fluidity or viscosity, the carbon number of the aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferably 1-8, more preferably 2-6, and still more preferably 4-6.
碳數1～18的脂肪族烴基可為碳數1～18的直鏈或分支狀的脂肪族烴基，亦可為碳數3～18的脂環式烴基。就容易製造的觀點而言，較佳為直鏈或分支狀的脂肪族烴基。The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.
作為碳數1～18的直鏈或分支狀的脂肪族烴基，具體而言，可列舉：甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二烷基等烷基；烯丙基；乙烯基等。直鏈或分支狀的脂肪族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲氧基、乙氧基、丁氧基、第三丁氧基等烷氧基；苯基、萘基等芳基；羥基、胺基、鹵素原子等。直鏈或分支狀的脂肪族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於直鏈或分支狀的脂肪族烴基具有取代基的情況下，脂肪族烴基與取代基中所含的碳數的合計較佳為1～18。就硬化性的觀點而言，較佳為未經取代的烷基，更佳為碳數1～8的未經取代的烷基，進而佳為正丁基、異丁基、正戊基、正己基及正辛基。As the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and tertiary butyl. , Pentyl, hexyl, octyl, decyl, dodecyl and other alkyl groups; allyl groups; vinyl groups, etc. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. As a substituent, alkoxy groups, such as a methoxy group, an ethoxy group, a butoxy group, and a tertiary butoxy group, aryl groups, such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a halogen atom, etc. are mentioned. The linear or branched aliphatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbons contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of hardening properties, an unsubstituted alkyl group is preferred, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferred, and n-butyl, isobutyl, n-pentyl, and n-hexyl are more preferred. Base and n-octyl.
作為碳數3～18的脂環式烴基，具體而言，可列舉：環戊基、環己基、環庚基等環烷基、環戊烯基、環己烯基等環烯基等。脂環式烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、丁基、第三丁基等烷基、甲氧基、乙氧基、丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。脂環式烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於脂環式烴基具有取代基的情況下，脂環式烴基與取代基中所含的碳數的合計較佳為3～18。於脂環式烴基具有取代基的情況下，取代基的位置並無特別限定。就硬化性的觀點而言，較佳為未經取代的環烷基，更佳為碳數4～10的未經取代的環烷基，進而佳為環己基、環戊基及環庚基。Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of substituents include alkyl groups such as methyl, ethyl, butyl, and tertiary butyl, alkoxy groups such as methoxy, ethoxy, butoxy, and tertiary butoxy, phenyl, and naphthalene. Groups such as aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbons contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of hardening properties, an unsubstituted cycloalkyl group is preferred, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferred, and a cyclohexyl group, a cyclopentyl group, and a cycloheptyl group are further preferred.
碳數為6～18的芳香族烴基的碳數較佳為6～14，更佳為6～10。芳香族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、丁基、第三丁基等烷基；甲氧基、乙氧基、丁氧基、第三丁氧基等烷氧基；苯基、萘基等芳基；羥基；胺基；鹵素原子等。芳香族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於芳香族烴基具有取代基的情況下，芳香族烴基與取代基中所含的碳數的合計較佳為6～18。於芳香族烴基具有取代基的情況下，取代基的位置並無特別限定。The carbon number of the aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably 6-14, more preferably 6-10. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include: alkyl groups such as methyl, ethyl, butyl, and tertiary butyl; alkoxy groups such as methoxy, ethoxy, butoxy, and tertiary butoxy; phenyl, naphthalene, etc. Aryl groups such as groups; hydroxyl groups; amine groups; halogen atoms, etc. The aromatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbons contained in the aromatic hydrocarbon group and the substituent is preferably 6-18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.
作為碳數為6～18的芳香族烴基，具體而言，可列舉：苯基、1-萘基、2-萘基、甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基等。該些芳香族烴基中的取代基的位置可為鄰位、間位及對位中的任一種。就流動性或黏度的觀點而言，較佳為未經取代且碳數為6～12或包含取代基的碳數為6～12的芳基，更佳為未經取代且碳數為6～10或包含取代基的碳數為6～10的芳基，進而佳為苯基、對甲苯基及對甲氧基苯基。Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, and butylphenyl. , Tertiary butyl phenyl, methoxy phenyl, ethoxy phenyl, butoxy phenyl, tertiary butoxy phenyl, etc. The position of the substituent in these aromatic hydrocarbon groups may be any of ortho, meta, and para positions. From the viewpoint of fluidity or viscosity, it is preferably an unsubstituted aryl group having 6 to 12 carbon atoms or a substituent having 6 to 12 carbon atoms, and more preferably unsubstituted and 6 to 12 carbon atoms. 10 or a substituent-containing aryl group having 6 to 10 carbon atoms, more preferably a phenyl group, a p-tolyl group, and a p-methoxyphenyl group.
作為通式（I-1）的R1 ～R3 而記載的用語「R1 ～R3 中兩個以上可相互鍵結而形成環狀結構」是指R1 ～R3 中兩個或三個鍵結，整體成為一個二價或三價烴基的情況。作為此時的R1 ～R3 的例子，可列舉可與磷原子鍵結而形成環狀結構的伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基；伸乙烯基、伸丙烯基、伸丁烯基等伸烯基；亞甲基伸苯基等伸芳烷基；伸苯基、伸萘基、伸蒽基等伸芳基等可與磷原子鍵結而形成環狀結構的取代基。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。General formula (I-1) of R 1 ~ R 3 and described in terms of "two of R 1 ~ R 3 above may be bonded to each other to form a cyclic structure" refers to a R 1 ~ R 3 in two or three A case where a bond becomes a divalent or trivalent hydrocarbon group as a whole. As examples of R 1 to R 3 in this case, alkylene groups such as ethylene group, propylene group, butylene group, pentylene group, and hexylene group, which can be bonded to a phosphorus atom to form a cyclic structure; Vinyl, propenylene, butenylene and other alkenylene groups; methylene phenylene and other aralkylene groups; phenylene, naphthylene, anthrylene and other arylene groups can be bonded to phosphorus atoms And form the substituent of the ring structure. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, and the like.
作為所述通式（I-1）的R4 ～R7 而記載的「碳數1～18的一價有機基」，可列舉：碳數1～18且可經取代亦可未經取代的脂肪族烴基、芳香族烴基、脂肪族烴氧基、芳香族烴氧基、醯基、烴氧基羰基、以及醯氧基等。The "monovalent organic group having 1 to 18 carbons" described as R 4 to R 7 of the general formula (I-1) includes: 1 to 18 carbons and may be substituted or unsubstituted Aliphatic hydrocarbyl groups, aromatic hydrocarbyl groups, aliphatic hydrocarbyloxy groups, aromatic hydrocarbyloxy groups, acyl groups, hydrocarbyloxycarbonyl groups, acyloxy groups, and the like.
作為所述脂肪族烴基及芳香族烴基的例子，可列舉作為R1 ～R3 所表示的脂肪族烴基及芳香族烴基的例子而所述者。Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include those described as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R 1 to R 3.
作為所述脂肪族烴氧基，可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、2-丁氧基、第三丁氧基、環丙氧基、環己氧基、環戊氧基、烯丙氧基、乙烯基氧基等具有所述脂肪族烴基上鍵結有氧原子的結構的脂肪族烴氧基、該些脂肪族烴氧基進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代的基等。Examples of the aliphatic hydrocarbonoxy group include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tertiary butoxy, and cyclopropoxy , Cyclohexyloxy, cyclopentyloxy, allyloxy, vinyloxy and other aliphatic hydrocarbon oxy groups having a structure in which oxygen atoms are bonded to the aliphatic hydrocarbon groups, and these aliphatic hydrocarbon oxy groups are further Groups substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.
作為所述芳香族烴氧基，可列舉：苯氧基、甲基苯氧基、乙基苯氧基、甲氧基苯氧基、丁氧基苯氧基、苯氧基苯氧基等具有所述芳香族烴基上鍵結有氧原子的結構的芳香族烴氧基、該些芳香族烴氧基進一步經烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the aromatic hydrocarbonoxy group include: phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, phenoxyphenoxy, etc. The aromatic hydrocarbyloxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbyl group, and these aromatic hydrocarbyloxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, etc.的基等。 The base and so on.
作為所述醯基，可列舉：甲醯基、乙醯基、乙基羰基、丁醯基、環己基羰基、烯丙基羰基等脂肪族烴羰基；苯基羰基、甲基苯基羰基等芳香族烴羰基；該些脂肪族烴羰基或芳香族烴羰基進一步經烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as formyl, acetyl, ethylcarbonyl, butyryl, cyclohexylcarbonyl, and allylcarbonyl; aromatic hydrocarbons such as phenylcarbonyl and methylphenylcarbonyl Carbonyl group; these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, and the like.
作為所述烴氧基羰基，可列舉：甲氧基羰基、乙氧基羰基、丁氧基羰基、烯丙氧基羰基、環己氧基羰基等脂肪族烴氧基羰基；苯氧基羰基、甲基苯氧基羰基等芳香族烴氧基羰基；該些脂肪族烴羰氧基或芳香族烴羰氧基進一步經烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the hydrocarbyloxycarbonyl group include aliphatic hydrocarbyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, allyloxycarbonyl, and cyclohexoxycarbonyl; phenoxycarbonyl, Aromatic hydrocarbon oxycarbonyl groups such as methylphenoxycarbonyl group; these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further passed through alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, and halogen atoms. And other substituted groups.
作為所述醯氧基，可列舉：甲基羰氧基、乙基羰氧基、丁基羰氧基、烯丙基羰氧基、環己基羰氧基等脂肪族烴羰氧基；苯基羰氧基、甲基苯基羰氧基等芳香族烴羰氧基；該些脂肪族烴羰氧基或芳香族烴羰氧基進一步經烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, and cyclohexylcarbonyloxy; phenyl Aromatic hydrocarbon carbonyloxy groups such as carbonyloxy group and methylphenylcarbonyloxy group; these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further passed through alkyl groups, alkoxy groups, aryl groups, aryloxy groups, Amino groups, halogen atoms and other substituted groups.
作為所述通式（I-1）的R4 ～R7 而記載的用語「兩個以上的R4 ～R7 可相互鍵結而形成環狀結構」是指兩個～四個R4 ～R7 鍵結，作為整體可形成一個二價～四價的有機基。作為此時的R4 ～R7 ，可列舉：伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基；伸乙烯基、伸丙烯基、伸丁烯基等伸烯基；亞甲基伸苯基等伸芳烷基；伸苯基、伸萘基、伸蒽基等伸芳基等可形成環狀結構的取代基、該些的氧基或二氧基等。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。The term "two or more R 4 to R 7 may be bonded to each other to form a cyclic structure" described as R 4 to R 7 of the general formula (I-1) means two to four R 4 to R 7 is bonded to form a divalent to tetravalent organic group as a whole. Examples of R 4 to R 7 at this time include: ethylene, propylene, butylene, pentylene, hexylene, etc.; ethylene, propylene, butenylene, etc. Alkenyl; aralkylenes such as methylene phenylene; arylalkylenes such as phenylene, naphthylene, anthracenyl and the like substituents that can form a ring structure, these oxy or dioxy groups, etc. . These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, and the like.
作為所述通式（I-1）的R4 ～R7 ，並無特別限定。例如較佳為分別獨立地選自氫原子、羥基、經取代或未經取代的烷基、經取代或未經取代的芳基、經取代或未經取代的烷氧基、或者經取代或未經取代的芳氧基。其中，就原料的獲取容易性的觀點而言，較佳為氫原子、羥基、未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基、或者鏈狀或環狀的烷基。作為未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基，可列舉：苯基、對甲苯基、間甲苯基、鄰甲苯基、對甲氧基苯基等。作為鏈狀或環狀的烷基，可列舉：甲基、乙基、丙基、異丙基、丁基、2-丁基、第三丁基、辛基、環己基等。就硬化性的觀點而言，較佳為R4 ～R7 均為氫原子的情況、或者R4 ～R7 中的至少一個為羥基、其餘均為氫原子的情況。There are no particular limitations on R 4 to R 7 in the general formula (I-1). For example, it is preferably selected independently from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkoxy group. Substituted aryloxy. Among them, from the viewpoint of the availability of raw materials, a hydrogen atom, a hydroxyl group, an aryl group that is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a chain is preferred. Shaped or cyclic alkyl. Examples of unsubstituted or substituted aryl groups with at least one selected from the group consisting of alkyl and alkoxy include phenyl, p-tolyl, m-tolyl, o-tolyl, and p-methoxy Phenyl and so on. Examples of the chain or cyclic alkyl group include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, tertiary butyl, octyl, and cyclohexyl. From the viewpoint of curability, it is preferable that R 4 to R 7 are all hydrogen atoms, or that at least one of R 4 to R 7 is a hydroxyl group, and the rest are all hydrogen atoms.
通式（I-1）中，更佳為R1 ～R3 中兩個以上為碳數1～18的烷基或碳數3～18的環烷基，R4 ～R7 均為氫原子或至少一個為羥基，其餘均為氫原子。進而佳為R1 ～R3 均為碳數1～18的烷基或碳數3～18的環烷基，R4 ～R7 均為氫原子或至少一個為羥基，其餘均為氫原子。In the general formula (I-1), more preferably two or more of R 1 to R 3 are alkyl groups having 1 to 18 carbons or cycloalkyl groups having 3 to 18 carbons, and R 4 to R 7 are all hydrogen atoms Or at least one is a hydroxyl group, and the rest are hydrogen atoms. More preferably, R 1 to R 3 are all alkyl groups having 1 to 18 carbons or cycloalkyl groups having 3 to 18 carbons, R 4 to R 7 are all hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms.
就快速硬化性的觀點而言，特定硬化促進劑較佳為下述通式（I-2）所表示的化合物。From the viewpoint of rapid curing properties, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).
[化23]
式（I-2）中，R1 ～R3 分別獨立地為碳數1～18的烴基，R1 ～R3 中兩個以上可相互鍵結而形成環狀結構，R4 ～R6 分別獨立地為氫原子或碳數1～18的一價有機基，R4 ～R6 中兩個以上可相互鍵結而形成環狀結構。In formula (I-2), R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbons , two or more of R 1 to R 3 may be bonded to each other to form a cyclic structure, and R 4 to R 6 are each independently It is independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 may be bonded to each other to form a cyclic structure.
通式（I-2）中的R1 ～R6 的具體例分別與通式（I-1）中的R1 ～R6 的具體例相同，較佳範圍亦相同。The specific examples of R 1 to R 6 in the general formula (I-2) are the same as the specific examples of R 1 to R 6 in the general formula (I-1), and the preferred ranges are also the same.
作為特定硬化促進劑的具體例，可列舉：三苯基膦與1,4-苯醌的加成反應物、三正丁基膦與1,4-苯醌的加成反應物、三環己基膦與1,4-苯醌的加成反應物、二環己基苯基膦與1,4-苯醌的加成反應物、環己基二苯基膦與1,4-苯醌的加成反應物、三異丁基膦與1,4-苯醌的加成反應物、三環戊基膦與1,4-苯醌的加成反應物等。Specific examples of the specific hardening accelerator include: an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexyl The addition reaction product of phosphine and 1,4-benzoquinone, the addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, the addition reaction of cyclohexyldiphenylphosphine and 1,4-benzoquinone The addition reaction product of triisobutylphosphine and 1,4-benzoquinone, the addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone, etc.
特定硬化促進劑例如可作為第三膦化合物與醌化合物的加成物而獲得。 作為第三膦化合物，具體而言，可列舉：三苯基膦、三丁基膦、二丁基苯基膦、丁基二苯基膦、乙基二苯基膦、三苯基膦、三(4-甲基苯基)膦、三(4-乙基苯基)膦、三(4-丙基苯基)膦、三(4-丁基苯基)膦、三(異丙基苯基)膦、三(第三丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦等。就成形性的觀點而言，較佳為三苯基膦及三丁基膦。The specific hardening accelerator can be obtained as an adduct of a third phosphine compound and a quinone compound, for example. As the third phosphine compound, specifically, triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, triphenylphosphine (4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylphenyl) )Phosphine, tris(tertiary butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6- Trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl) Phosphine etc. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.
作為醌化合物，具體而言，可列舉：鄰苯醌、對苯醌、聯苯醌、1,4-萘醌、蒽醌等。就耐濕性與保存穩定性的觀點而言，較佳為對苯醌。Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.
環氧樹脂組成物亦可包含鏻化合物以外的硬化促進劑。 作為鏻化合物以外的硬化促進劑，具體而言，可列舉：乙基膦、苯基膦等一級膦、二甲基膦、二苯基膦等二級膦、所述三級膦等有機膦；1,5-二氮雜雙環[4.3.0]壬烯-5（1,5-Diazabicyclo[4.3.0]nonene-5，DBN）、1,8-二氮雜雙環[5.4.0]十一烯-7（1,8-Diazabicyclo[5.4.0]undecene-7，DBU）等二氮雜雙環烯烴、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等環狀脒化合物；所述環狀脒化合物的衍生物；所述環狀脒化合物或其衍生物的苯酚酚醛清漆鹽；於該些化合物上加成馬來酸酐、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-苯醌等醌化合物、重氮苯基甲烷等具有π鍵的化合物而形成的具有分子內極化的化合物；DBU的四苯基硼酸鹽、DBN的四苯基硼酸鹽、2-乙基-4-甲基咪唑的四苯基硼酸鹽、N-甲基嗎啉的四苯基硼酸鹽等環狀脒鎓化合物；吡啶、三乙胺、三乙二胺、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)苯酚等三級胺化合物；所述三級胺化合物的衍生物；乙酸四正丁基銨、磷酸四正丁基銨、乙酸四乙基銨、苯甲酸四正己基銨、氫氧化四丙基銨等銨鹽化合物等。The epoxy resin composition may contain a hardening accelerator other than the phosphonium compound. Specific examples of hardening accelerators other than phosphonium compounds include primary phosphines such as ethyl phosphine and phenyl phosphine, secondary phosphines such as dimethyl phosphine and diphenyl phosphine, and organic phosphines such as the tertiary phosphine; 1,5-Diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN), 1,8-diaazabicyclo[5.4.0] eleven Diazabicycloalkenes such as ene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, Cyclic amidine compounds such as 2-heptadecyl imidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof; maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy- Quinone compounds such as 5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazophenylmethane, etc. have a π bond Compounds with intramolecular polarization; DBU tetraphenylborate, DBN tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methyl Morpholine tetraphenylborate and other cyclic amidinium compounds; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylamino) (Methyl) phenol and other tertiary amine compounds; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetra-n-hexylammonium hydroxide Ammonium salt compounds such as propylammonium.
於環氧樹脂組成物包含特定硬化促進劑作為硬化促進劑的情況下，特定硬化促進劑的含有率較佳為硬化促進劑整體的30質量%以上，更佳為50質量%以上，進而佳為70質量%以上。In the case where the epoxy resin composition contains a specific hardening accelerator as the hardening accelerator, the content of the specific hardening accelerator is preferably 30% by mass or more of the entire hardening accelerator, more preferably 50% by mass or more, and still more preferably 70% by mass or more.
於環氧樹脂組成物包含硬化促進劑的情況下，相對於樹脂成分100質量份，硬化促進劑的量較佳為0.1質量份～30質量份，更佳為1質量份～15質量份。若硬化促進劑的量相對於樹脂成分100質量份而為0.1質量份以上，則存在短時間內良好地硬化的傾向。若硬化促進劑的量相對於樹脂成分100質量份而為30質量份以下，則存在可獲得硬化速度不會過快的良好的成形品的傾向。When the epoxy resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass relative to 100 parts by mass of the resin component. If the amount of the hardening accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency to harden well in a short time. If the amount of the hardening accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, there is a tendency that a good molded product with a hardening speed not too fast can be obtained.
[無機填充材] 環氧樹脂組成物亦可包含無機填充材。特別是於將環氧樹脂組成物用作半導體封裝的密封材的情況下，較佳為包含無機填充材。[Inorganic Filler] The epoxy resin composition may also contain an inorganic filler. In particular, when the epoxy resin composition is used as a sealing material for a semiconductor package, it is preferable to include an inorganic filler.
無機填充材的種類並無特別限制。具體而言，可列舉：熔融二氧化矽、晶體二氧化矽、玻璃、氧化鋁、碳酸鈣、矽酸鋯、矽酸鈣、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、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材。作為具有阻燃效果的無機填充材，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、硼酸鋅等。其中，就線膨脹係數減少的觀點而言，較佳為熔融二氧化矽，就高導熱性的觀點而言，較佳為氧化鋁。無機填充材可單獨使用一種，亦可將兩種以上組合而使用。作為無機填充材的狀態，可列舉粉末、將粉末球形化的顆粒、纖維等。The type of inorganic filler is not particularly limited. Specifically, include: fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconia , Zircon, forsterite, talc, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate. Among them, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferred, and from the viewpoint of high thermal conductivity, alumina is preferred. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the state of the inorganic filler include powder, particles formed by spheronizing powder, fibers, and the like.
再者，所謂「將兩種以上的無機填充材組合而使用」，例如可列舉：將成分相同且平均粒徑不同的無機填充材使用兩種以上的情況、將平均粒徑相同且成分不同的無機填充材使用兩種以上的情況以及將平均粒徑及種類不同的無機填充材使用兩種以上的情況。Furthermore, the so-called "combination of two or more inorganic fillers" includes, for example, the case where two or more inorganic fillers with the same composition and different average particle diameters are used, and those with the same average particle diameter and different components are used. The case where two or more types of inorganic fillers are used, and the case where two or more types of inorganic fillers with different average particle diameters and types are used.
於環氧樹脂組成物包含無機填充材的情況下，其含有率並無特別限制。就流動性及強度的觀點而言，較佳為環氧樹脂組成物整體的30體積%～90體積%，更佳為35體積%～88體積%，進而佳為40體積%～85體積%。若無機填充材的含有率為環氧樹脂組成物整體的30體積%以上，則存在硬化物的熱膨脹係數、導熱率、彈性係數等特性進一步提高的傾向。若無機填充材的含有率為環氧樹脂組成物整體的90體積%以下，則存在環氧樹脂組成物的黏度的上升得到抑制、流動性進一步提高且成形性變得更良好的傾向。When the epoxy resin composition contains an inorganic filler, the content rate is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume of the entire epoxy resin composition, more preferably 35% by volume to 88% by volume, and still more preferably 40% by volume to 85% by volume. When the content of the inorganic filler is 30% by volume or more of the entire epoxy resin composition, the thermal expansion coefficient, thermal conductivity, and elastic coefficient of the cured product tend to further improve. When the content of the inorganic filler is 90% by volume or less of the entire epoxy resin composition, the increase in the viscosity of the epoxy resin composition is suppressed, the fluidity is further improved, and the moldability tends to become better.
另外，於環氧樹脂組成物包含無機填充材的情況下，就耐回焊性及流動性的觀點而言，無機填充材的含有率較佳為環氧樹脂組成物整體的80質量%～95質量%，更佳為85質量%～94質量%，進而佳為88質量%～93質量%。若無機填充材的含有率為環氧樹脂組成物整體的80質量%以上，則存在耐回焊性提高的傾向。若無機填充材的含有率為環氧樹脂組成物整體的95質量%以下，則存在流動性優異的傾向。In addition, when the epoxy resin composition contains an inorganic filler, from the viewpoint of reflow resistance and fluidity, the content of the inorganic filler is preferably 80% to 95% by mass of the entire epoxy resin composition. % By mass, more preferably 85% by mass to 94% by mass, and still more preferably 88% by mass to 93% by mass. If the content of the inorganic filler is 80% by mass or more of the entire epoxy resin composition, the reflow resistance tends to improve. If the content of the inorganic filler is 95% by mass or less of the entire epoxy resin composition, the fluidity tends to be excellent.
無機填充材的平均粒徑並無特別限制。例如，體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在模塑底部填充（mold underfill）用樹脂組成物的黏度的上升進一步得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性進一步提高的傾向。無機填充材的體積平均粒徑可藉由雷射繞射散射法粒度分佈測定裝置以體積平均粒徑（D50）的形式測定。The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the resin composition for mold underfill (mold underfill) tends to be further suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be further improved. The volume average particle size of the inorganic filler can be measured in the form of volume average particle size (D50) by a laser diffraction scattering method particle size distribution measuring device.
環氧樹脂組成物或其硬化物中的無機填充材的體積平均粒徑可利用公知的方法來進行測定。例如，使用有機溶劑、硝酸、王水等，或者對於環氧樹脂組成物或其硬化物的試樣於800℃等下進行加熱處理，使試樣灰化，自環氧樹脂組成物或硬化物中萃取無機填充材，利用超音波分散機等充分地分散而製備分散液。可使用該分散液，並根據利用雷射繞射散射法粒度分佈測定裝置而測定的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。或者，可將硬化物埋入至透明的環氧樹脂等中，進行研磨而獲得剖面，根據利用掃描式電子顯微鏡觀察所獲得的剖面而獲得的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。進而，亦可藉由如下方式來測定：使用FIB裝置（聚焦離子束SEM）等連續進行硬化物的二維的剖面觀察，並進行三維結構解析。The volume average particle diameter of the epoxy resin composition or the inorganic filler in the cured product can be measured by a known method. For example, use organic solvents, nitric acid, aqua regia, etc., or heat the sample of epoxy resin composition or its hardened product at 800°C to ash the sample, and make it from the epoxy resin composition or hardened product. Inorganic fillers are extracted in the medium, and the dispersion is prepared by fully dispersing it with an ultrasonic dispersion machine or the like. Using this dispersion liquid, the volume average particle diameter of the inorganic filler can be measured based on the volume-based particle size distribution measured by the laser diffraction scattering method particle size distribution measuring device. Alternatively, the cured product can be embedded in a transparent epoxy resin, etc., and polished to obtain a cross section, and the volume average of the inorganic filler can be measured based on the volume-based particle size distribution obtained by observing the obtained cross section with a scanning electron microscope Particle size. Furthermore, it is also possible to measure by continuously performing a two-dimensional cross-sectional observation of the cured product using a FIB device (focused ion beam SEM) or the like, and performing a three-dimensional structure analysis.
無機填充材的最大粒徑（亦稱為割點（cut point））並無特別限制。就對狹小的縫隙的填充性的觀點而言，無機填充材的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of the inorganic filler (also referred to as a cut point) is not particularly limited. From the viewpoint of filling properties for small gaps, the maximum particle size of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
就對狹小的縫隙的填充性及毛邊的抑制的觀點而言，環氧樹脂組成物較佳為混合體積平均粒徑為2.0 μm以下的無機填充材而成，更佳為混合體積平均粒徑為0.1 μm～2.0 μm的無機填充材而成，進而佳為混合體積平均粒徑為0.2 μm～1.5 μm的無機填充材而成，特佳為混合體積平均粒徑為0.3 μm～1.0 μm的無機填充材而成。From the viewpoints of filling of narrow gaps and suppression of burrs, the epoxy resin composition is preferably formed by mixing inorganic fillers with a volume average particle size of 2.0 μm or less, and more preferably the mixed volume average particle size is It is made of inorganic fillers of 0.1 μm to 2.0 μm, more preferably mixed with inorganic fillers with a volume average particle size of 0.2 μm to 1.5 μm, and particularly preferably mixed with inorganic fillers with a volume average particle size of 0.3 μm to 1.0 μm Material made.
於環氧樹脂組成物是混合體積平均粒徑為2.0 μm以下的無機填充材而成的情況下，亦可與體積平均粒徑超過2.0 μm的無機填充材一起混合而成。於環氧樹脂組成物中，相對於無機填充材的總質量，體積平均粒徑為2.0 μm以下的無機填充材的混合比例可為0.1質量%～10質量%，亦可為0.2質量%～5質量%，亦可為0.3質量%～2質量%。When the epoxy resin composition is mixed with an inorganic filler having a volume average particle diameter of 2.0 μm or less, it may be mixed with an inorganic filler having a volume average particle diameter of more than 2.0 μm. In the epoxy resin composition, relative to the total mass of the inorganic filler, the mixing ratio of the inorganic filler having a volume average particle diameter of 2.0 μm or less may be 0.1% by mass to 10% by mass, or 0.2% by mass to 5 The mass% may also be 0.3% to 2% by mass.
於環氧樹脂組成物中，就對狹小的縫隙的填充性及毛邊的抑制的觀點而言，相對於無機填充材的總量，粒徑為2.0 μm以下的無機填充材的含有率較佳為5質量%以上。相對於無機填充材的總量，粒徑為2.0 μm以下的無機填充材的含有率可為5質量%～30質量%，亦可為6質量%～20質量%，亦可為7質量%～15質量%。In the epoxy resin composition, from the viewpoints of filling properties for narrow gaps and suppression of burrs, the content of inorganic fillers having a particle size of 2.0 μm or less relative to the total amount of inorganic fillers is preferably Above 5 mass%. Relative to the total amount of inorganic fillers, the content of inorganic fillers with a particle size of 2.0 μm or less may be 5 mass% to 30 mass %, 6 mass% to 20 mass %, or 7 mass% to 15% by mass.
通常，若使環氧樹脂組成物含有粒徑小的無機填充材（微粒二氧化矽等），則存在黏度的上升及流動性的降低變得更顯著的傾向。另一方面，於第一實施形態的環氧樹脂組成物中使用特定硬化劑，因此存在即便於使用粒徑小的無機填充材的情況下，亦可抑制黏度的上升及流動性的降低的傾向。Generally, if the epoxy resin composition contains an inorganic filler (particulate silica, etc.) with a small particle size, the increase in viscosity and the decrease in fluidity tend to become more pronounced. On the other hand, since a specific curing agent is used in the epoxy resin composition of the first embodiment, there is a tendency to suppress the increase in viscosity and the decrease in fluidity even when an inorganic filler with a small particle size is used. .
就環氧樹脂組成物的流動性的觀點而言，關於無機填充材的粒子形狀，球形優於角形，且較佳為無機填充材的粒度分佈以廣範圍進行分佈。From the viewpoint of the fluidity of the epoxy resin composition, as for the particle shape of the inorganic filler, the spherical shape is better than the angular shape, and the particle size distribution of the inorganic filler is preferably distributed in a wide range.
於獲得高導熱性的硬化物的情況下，無機填充材較佳為包含氧化鋁，更佳為包含氧化鋁作為主成分。無機填充材包含氧化鋁時的氧化鋁的平均粒徑並無特別限制。例如氧化鋁的體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。In the case of obtaining a cured product with high thermal conductivity, the inorganic filler preferably contains alumina, and more preferably contains alumina as a main component. The average particle diameter of alumina when the inorganic filler contains alumina is not particularly limited. For example, the volume average particle size of alumina is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved.
氧化鋁的最大粒徑並無特別限制。就對狹小的縫隙的填充性的觀點而言，氧化鋁的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of alumina is not particularly limited. From the viewpoint of the filling properties of the narrow gaps, the maximum particle size of alumina is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
於較佳的一態樣中，亦可併用平均粒徑為0.1 μm～2.0 μm、較佳為0.2 μm～1.5 μm、更佳為0.3 μm～1.0 μm的氧化鋁、與平均粒徑超過2.0 μm且為75 μm以下、較佳為5.0 μm～55 μm、更佳為8.0 μm～20 μm的氧化鋁。藉由併用平均粒徑不同的兩種以上的氧化鋁，存在可使填充性變佳的傾向。In a preferred aspect, alumina having an average particle diameter of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, more preferably 0.3 μm to 1.0 μm, and an average particle diameter of more than 2.0 μm can also be used in combination. And it is 75 μm or less, preferably 5.0 μm to 55 μm, more preferably 8.0 μm to 20 μm alumina. By using two or more types of alumina with different average particle diameters in combination, there is a tendency that the filling properties can be improved.
氧化鋁的形狀並無特別限制。就環氧樹脂組成物的混練性的觀點而言，氧化鋁的粒子形狀較佳為球形。The shape of alumina is not particularly limited. From the viewpoint of the kneading property of the epoxy resin composition, the particle shape of alumina is preferably spherical.
於無機填充材包含氧化鋁的情況下，就高導熱化的觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為90質量%以上，更佳為95質量%以上，進而佳為98質量%以上。另外，就低黏度化、混練的作業性等觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為99.9質量%以下，更佳為99.8質量%以下，進而佳為99.7質量%以下。When the inorganic filler contains alumina, from the viewpoint of high thermal conductivity, the content of alumina relative to the total mass of the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and further Preferably, it is 98% by mass or more. In addition, from the viewpoints of low viscosity and kneading workability, the content of alumina relative to the total mass of the inorganic filler is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, and still more preferably 99.7 mass% %the following.
於無機填充材包含氧化鋁的情況下，無機填充材較佳為除包含氧化鋁以外亦包含二氧化矽。若無機填充材包含二氧化矽，則存在黏度下降，可提高混練性及流動性的傾向，特別是藉由併用微細的二氧化矽，存在可抑制製成硬化物時的毛邊的產生的傾向。特別是無機填充材較佳為包含微粒二氧化矽、例如平均粒徑為0.01 μm～2.0 μm、更佳為0.1 μm～1.5 μm、進而佳為0.2 μm～1.0 μm的二氧化矽。就彈性係數的減少、線膨脹係數的減少的觀點而言，無機填充材較佳為包含大粒徑二氧化矽。 作為大粒徑二氧化矽，可列舉較佳為超過2.0 μm且為75 μm以下、更佳為5.0 μm～55 μm、進而佳為8.0 μm～20 μm的二氧化矽。When the inorganic filler contains alumina, the inorganic filler preferably contains silica in addition to alumina. If the inorganic filler contains silica, there is a tendency that the viscosity is lowered and the kneading and fluidity can be improved. In particular, by using fine silica in combination, there is a tendency that the generation of burrs when the hardened product is formed can be suppressed. In particular, the inorganic filler preferably contains particulate silica, for example, silica having an average particle size of 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.5 μm, and still more preferably 0.2 μm to 1.0 μm. From the viewpoint of a decrease in the coefficient of elasticity and a decrease in the coefficient of linear expansion, the inorganic filler preferably contains large-particle silica. As the large particle size silicon dioxide, silicon dioxide preferably exceeding 2.0 μm and 75 μm or less, more preferably 5.0 μm to 55 μm, and still more preferably 8.0 μm to 20 μm can be cited.
就耐回焊性、抑制黏度的上升等觀點而言，無機填充材較佳為包含二氧化矽，亦可包含二氧化矽作為主成分。無機填充材包含二氧化矽時的二氧化矽的平均粒徑並無特別限制。例如二氧化矽的體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。另外，無機填充材較佳為包含微粒二氧化矽、例如平均粒徑為0.01 μm～2.0 μm、更佳為0.1 μm～1.5 μm、進而佳為0.2 μm～1.0 μm的二氧化矽。若無機填充材包含微粒二氧化矽，則存在對狹小的縫隙的填充性提高，可抑制製成硬化物時的毛邊的產生的傾向。From the viewpoints of reflow resistance and suppression of viscosity increase, the inorganic filler preferably contains silicon dioxide, and may contain silicon dioxide as a main component. When the inorganic filler contains silica, the average particle size of silica is not particularly limited. For example, the volume average particle size of silicon dioxide is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved. In addition, the inorganic filler preferably contains particulate silica, for example, silica having an average particle diameter of 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.5 μm, and still more preferably 0.2 μm to 1.0 μm. If the inorganic filler contains particulate silicon dioxide, the filling properties for narrow gaps are improved, and there is a tendency that the generation of burrs when used as a hardened product can be suppressed.
二氧化矽的最大粒徑並無特別限制。就對狹小的縫隙的填充性的觀點而言，二氧化矽的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of silicon dioxide is not particularly limited. From the viewpoint of filling properties for small gaps, the maximum particle size of silicon dioxide is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
二氧化矽的形狀並無特別限制。就環氧樹脂組成物的混練性的觀點而言，二氧化矽的粒子形狀較佳為球形。The shape of silicon dioxide is not particularly limited. From the viewpoint of the kneading property of the epoxy resin composition, the particle shape of the silicon dioxide is preferably spherical.
於無機填充材包含二氧化矽的情況下，二氧化矽的含有率並無特別限定，相對於無機填充材的總質量，可為70質量%～100質量%，亦可為80質量%～100質量%，亦可為90質量%～100質量%。另外，相對於無機填充材的總質量，將二氧化矽與氧化鋁併用時的二氧化矽的含有率可為0.1質量%～10質量%，亦可為0.2質量%～5質量%，亦可為0.3質量%～2質量%。In the case where the inorganic filler contains silicon dioxide, the content of silicon dioxide is not particularly limited. Relative to the total mass of the inorganic filler, it may be 70% to 100% by mass, or 80% to 100. The mass% may be 90% to 100% by mass. In addition, with respect to the total mass of the inorganic filler, the silica content when using silica and alumina in combination may be 0.1% by mass to 10% by mass, or 0.2% by mass to 5% by mass, or It is 0.3% by mass to 2% by mass.
[各種添加劑] 環氧樹脂組成物除了所述成分以外，亦可包含以下例示的偶合劑、離子交換體、脫模劑、阻燃劑、著色劑、應力緩和劑等各種添加劑。環氧樹脂組成物除了以下例示的添加劑以外，視需要亦可包含於本技術領域中周知的各種添加劑。[Various additives] The epoxy resin composition may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relievers exemplified below in addition to the above-mentioned components. In addition to the additives exemplified below, the epoxy resin composition may also contain various additives known in the technical field as necessary.
（偶合劑） 於環氧樹脂組成物包含無機填充材的情況下，為了提高樹脂成分與無機填充材的接著性，亦可包含偶合劑。作為偶合劑，可列舉：環氧基矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等矽烷系化合物、鈦系化合物、鋁螯合物化合物、鋁/鋯系化合物等公知的偶合劑。(Coupling agent) When an epoxy resin composition contains an inorganic filler, in order to improve the adhesiveness of a resin component and an inorganic filler, you may contain a coupling agent. Examples of coupling agents include epoxy silanes, mercapto silanes, amino silanes, alkyl silanes, ureido silanes, vinyl silanes and other silane-based compounds, titanium-based compounds, aluminum chelate compounds, and aluminum/zirconium-based compounds And other well-known coupling agents.
作為矽烷系化合物，可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷、辛烯基三甲氧基矽烷、縮水甘油氧基辛基三甲氧基矽烷、及甲基丙烯醯氧基辛基三甲氧基矽烷等。Examples of silane-based compounds include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -(2-Aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octene Trimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane, etc.
作為鈦系化合物，可列舉：異丙基三異硬脂醯基鈦酸酯、異丙基三(焦磷酸二辛基酯)鈦酸酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、四辛基雙(亞磷酸二-十三烷基酯)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(亞磷酸二-十三烷基酯)鈦酸酯、雙(焦磷酸二辛基酯)氧基乙酸酯鈦酸酯、雙(焦磷酸二辛基酯)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(磷酸二辛基酯)鈦酸酯、異丙基三枯基苯基鈦酸酯、四異丙基雙(磷酸二辛基酯)鈦酸酯等。Examples of titanium compounds include isopropyl triisostearyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-amine) Ethyl ethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, tetrakis (2,2-diallyloxymethyl-1-butyl) bis (phosphorous acid) Di-tridecyl ester) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl tris Octyl titanate, isopropyl isostearyl dimethacrylate titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacrylate titanate Esters, isopropyl tris(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis(dioctyl phosphate) titanate, etc.
於環氧樹脂組成物包含偶合劑的情況下，相對於無機填充材100質量份，偶合劑的量較佳為0.05質量份～5質量份，更佳為0.1質量份～2.5質量份。若偶合劑的量相對於無機填充材100質量份而為0.05質量份以上，則存在與框架（frame）的接著性進一步提高的傾向。若偶合劑的量相對於無機填充材100質量份而為5質量份以下，則存在封裝的成形性進一步提高的傾向。When the epoxy resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and more preferably 0.1 parts by mass to 2.5 parts by mass relative to 100 parts by mass of the inorganic filler. If the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be further improved. If the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
（離子交換體） 環氧樹脂組成物亦可包含離子交換體。特別是於將環氧樹脂組成物用作密封用成形材料的情況下，就提高包括進行了密封的元件的電子零件裝置的耐濕性及高溫放置特性的觀點而言，較佳為包含離子交換體。離子交換體並無特別限制，可使用先前公知者。具體而言，可列舉水滑石化合物、以及含有選自由鎂、鋁、鈦、鋯及鉍所組成的群組中的至少一種元素的氫氧化物等。離子交換體可單獨使用一種，亦可將兩種以上組合而使用。其中，較佳為下述通式（A）所表示的水滑石。(Ion Exchanger) The epoxy resin composition may also contain an ion exchanger. Particularly when the epoxy resin composition is used as the sealing molding material, it is preferable to include ion exchange from the viewpoint of improving the humidity resistance and high temperature storage characteristics of the electronic component device including the sealed element body. The ion exchanger is not particularly limited, and previously known ones can be used. Specifically, hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like can be cited. One kind of ion exchanger may be used alone, or two or more kinds may be used in combination. Among them, the hydrotalcite represented by the following general formula (A) is preferred.
Mg(1-X) AlX (OH)2 (CO3 )X/2 ·mH2 O······（A） （0＜X≦0.5，m為正數）Mg (1-X) Al X (OH) 2 (CO 3 ) X/2 ·mH 2 O······(A) (0＜X≦0.5, m is a positive number)
於環氧樹脂組成物包含離子交換體的情況下，只要離子交換體的含量為對於捕捉鹵素離子等離子而言充分的量，則並無特別限制。例如相對於樹脂成分100質量份，較佳為0.1質量份～30質量份，更佳為1質量份～15質量份。When the epoxy resin composition contains an ion exchanger, as long as the content of the ion exchanger is a sufficient amount for capturing halogen ion plasma, there is no particular limitation. For example, with respect to 100 parts by mass of the resin component, it is preferably from 0.1 part by mass to 30 parts by mass, and more preferably from 1 part by mass to 15 parts by mass.
（脫模劑） 就獲得成形時的與模具的良好的脫模性的觀點而言，環氧樹脂組成物亦可包含脫模劑。脫模劑並無特別限制，可使用先前公知者。具體而言，可列舉：棕櫚蠟（carnauba wax）、二十八酸、硬脂酸等高級脂肪酸、高級脂肪酸金屬鹽、二十八酸酯等酯系蠟、氧化聚乙烯、非氧化聚乙烯等聚烯烴系蠟等。脫模劑可單獨使用一種，亦可將兩種以上組合而使用。(Release agent) From the viewpoint of obtaining good releasability from the mold during molding, the epoxy resin composition may contain a mold release agent. The release agent is not particularly limited, and previously known ones can be used. Specifically, examples include: carnauba wax, higher fatty acids such as octadecanoic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octadecanoic acid, oxidized polyethylene, non-oxidized polyethylene, etc. Polyolefin waxes, etc. One type of release agent may be used alone, or two or more types may be used in combination.
於環氧樹脂組成物包含脫模劑的情況下，相對於樹脂成分100質量份，所述脫模劑的量較佳為0.01質量份～15質量份，更佳為0.1質量份～10質量份。若脫模劑的量相對於樹脂成分100質量份而為0.01質量份以上，則存在可充分獲得脫模性的傾向。若為15質量份以下，則存在可獲得更良好的接著性的傾向。When the epoxy resin composition contains a mold release agent, the amount of the mold release agent is preferably 0.01 parts by mass to 15 parts by mass, and more preferably 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the resin component . If the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that sufficient release properties can be obtained. If it is 15 parts by mass or less, there is a tendency that better adhesiveness can be obtained.
（阻燃劑） 環氧樹脂組成物亦可包含阻燃劑。阻燃劑並無特別限制，可使用先前公知者。具體而言，可列舉包含鹵素原子、銻原子、氮原子或磷原子的有機化合物或無機化合物、金屬氫氧化物等。阻燃劑可單獨使用一種，亦可將兩種以上組合而使用。(Flame retardant) The epoxy resin composition may also contain a flame retardant. The flame retardant is not particularly limited, and previously known ones can be used. Specifically, an organic compound or an inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, etc. can be mentioned. One kind of flame retardant may be used alone, or two or more kinds may be used in combination.
於環氧樹脂組成物包含阻燃劑的情況下，只要阻燃劑的量為對於獲得所期望的阻燃效果而言充分的量，則並無特別限制。例如相對於樹脂成分100質量份，較佳為1質量份～300質量份，更佳為2質量份～150質量份。In the case where the epoxy resin composition contains a flame retardant, as long as the amount of the flame retardant is an amount sufficient to obtain the desired flame retardant effect, there is no particular limitation. For example, with respect to 100 parts by mass of the resin component, it is preferably 1 part by mass to 300 parts by mass, and more preferably 2 parts by mass to 150 parts by mass.
（著色劑） 環氧樹脂組成物亦可進一步包含著色劑。作為著色劑，可列舉：碳黑、有機染料、有機顏料、氧化鈦、鉛丹、氧化鐵等公知的著色劑。著色劑的含量可根據目的等適宜選擇。著色劑可單獨使用一種，亦可將兩種以上組合而使用。(Colorant) The epoxy resin composition may further contain a coloring agent. Examples of the coloring agent include known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, plumbum, and iron oxide. The content of the coloring agent can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.
（應力緩和劑） 環氧樹脂組成物亦可包含矽酮油、矽酮橡膠粒子等應力緩和劑。藉由包含應力緩和劑，可進一步減少封裝的翹曲變形及封裝裂紋的產生。作為應力緩和劑，可列舉一般而言所使用的公知的應力緩和劑（可撓劑）。具體而言，可列舉：矽酮系、苯乙烯系、烯烴系、胺基甲酸酯系、聚酯系、聚醚系、聚醯胺系、聚丁二烯系等熱塑性彈性體、天然橡膠（natural rubber，NR）、丙烯腈-丁二烯橡膠（acrylonitrile butadiene rubber，NBR）、丙烯酸橡膠、胺基甲酸酯橡膠、矽酮粉末等橡膠粒子、甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物（methyl methacrylate butadiene styrene，MBS）、甲基丙烯酸甲酯-矽酮共聚物、甲基丙烯酸甲酯-丙烯酸丁酯共聚物等具有核-殼結構的橡膠粒子等。應力緩和劑可單獨使用一種，亦可將兩種以上組合而使用。其中，較佳為矽酮系應力緩和劑。作為矽酮系應力緩和劑，可列舉：具有環氧基者、具有胺基者、將該些進行聚醚改質而成者等。(Stress reliever) The epoxy resin composition may also contain stress relievers such as silicone oil and silicone rubber particles. By including the stress reliever, the warpage of the package and the generation of package cracks can be further reduced. As the stress relaxation agent, a well-known stress relaxation agent (flexible agent) generally used can be mentioned. Specifically, examples include: silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based thermoplastic elastomers, and natural rubber (Natural rubber, NR), acrylonitrile butadiene rubber (acrylonitrile butadiene rubber, NBR), acrylic rubber, urethane rubber, silicone powder and other rubber particles, methyl methacrylate-styrene-butadiene Rubber particles with core-shell structure such as methyl methacrylate butadiene styrene (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. One kind of stress reliever may be used alone, or two or more kinds may be used in combination. Among them, silicone-based stress relievers are preferred. Examples of the silicone-based stress reliever include those having epoxy groups, those having amine groups, and those having been modified by polyether.
〔環氧樹脂組成物的製備方法〕 環氧樹脂組成物的製備方法並無特別限制。作為一般的方法，可列舉如下方法：於藉由混合機等將規定調配量的成分充分混合後，藉由研磨輥、擠出機等熔融混練，進行冷卻並粉碎。更具體而言，例如可列舉如下方法：將所述成分的規定量均勻地攪拌及混合，利用預先加熱為70℃～140℃的捏合機、輥、擠壓機等進行混練並冷卻，進行粉碎。[Preparation method of epoxy resin composition] The preparation method of the epoxy resin composition is not particularly limited. As a general method, the following method is exemplified: after fully mixing the components in a predetermined amount with a mixer or the like, melt-kneading with a grinding roll, an extruder, etc., cooling and pulverizing. More specifically, for example, the following method can be cited: uniformly stirring and mixing predetermined amounts of the components, kneading with a kneader, roller, extruder, etc. heated to 70°C to 140°C in advance, cooling, and pulverizing .
環氧樹脂組成物較佳為於常溫常壓下（例如，25℃、大氣壓下）為固體。環氧樹脂組成物為固體時的形狀並無特別限制，可列舉：粉狀、粒狀、片狀等。就操作性的觀點而言，環氧樹脂組成物為片狀時的尺寸及質量較佳為成為與封裝的成形條件相符的尺寸及質量。The epoxy resin composition is preferably solid at normal temperature and pressure (for example, 25° C., atmospheric pressure). The shape of the epoxy resin composition when it is a solid is not particularly limited, and examples include powder, granules, and flakes. From the viewpoint of operability, the size and quality when the epoxy resin composition is in the form of a sheet are preferably those that match the molding conditions of the package.
（2）第二實施形態 ＜壓縮成形用環氧樹脂組成物＞ 第二實施形態的壓縮成形用環氧樹脂組成物（以下，亦稱為「環氧樹脂組成物」）含有：環氧樹脂；以及硬化劑，包含以下的通式（B）所表示的化合物（以下，為「特定硬化劑」）。(2) The second embodiment ＜Epoxy resin composition for compression molding＞ The epoxy resin composition for compression molding of the second embodiment (hereinafter also referred to as "epoxy resin composition") contains: epoxy resin; and a curing agent, and contains a compound represented by the following general formula (B) ( Hereinafter, it is the "specific hardener").
[化24]
通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數。第二實施形態的環氧樹脂組成物含有特定硬化劑，因此容易熔融，可較佳地用於壓縮成形。進而，第二實施形態的環氧樹脂組成物由於含有特定硬化劑，故耐回焊性優異。In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0-10. The epoxy resin composition of the second embodiment contains a specific curing agent, and therefore is easy to melt, and can be preferably used for compression molding. Furthermore, since the epoxy resin composition of 2nd Embodiment contains a specific hardening agent, it is excellent in reflow resistance.
以下，對第二實施形態的環氧樹脂組成物中可包含的成分進行詳細說明。Hereinafter, the components which can be contained in the epoxy resin composition of 2nd Embodiment are demonstrated in detail.
[環氧樹脂] 第二實施形態的環氧樹脂組成物含有環氧樹脂。環氧樹脂只要為於一分子中具有兩個以上環氧基者，則其種類並無特別限制。 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等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組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於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於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；使所述苯酚化合物及萘酚化合物與醛化合物於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合型環氧樹脂；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；作為烷基經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；作為二苯乙烯系酚化合物的二縮水甘油醚的二苯乙烯型環氧樹脂；作為雙酚S等的二縮水甘油醚的含硫原子型環氧樹脂；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；將二環戊二烯與苯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-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、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環氧樹脂。該些環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。[Epoxy resin] The epoxy resin composition of the second embodiment contains epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, examples include phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, At least one phenolic compound in the group consisting of naphthol compounds such as dihydroxynaphthalene is condensed or co-condensed with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolak resin and the phenolic compound Novolac type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) obtained by epoxidizing varnish resin; combining the phenolic compound with aromatics such as benzaldehyde and salicylaldehyde Triphenylmethane type epoxy resin obtained by condensing or co-condensing triphenylmethane type phenol resin under acidic catalyst and epoxidizing the triphenylmethane type phenol resin; making the phenol The compound and the naphthol compound and the aldehyde compound are co-condensed under an acidic catalyst to obtain a novolak resin and the novolak resin is epoxidized to obtain a copolymerized epoxy resin; as a two-component epoxy resin such as bisphenol A and bisphenol F Diphenylmethane type epoxy resin of glycidyl ether; Biphenyl type epoxy resin of diglycidyl ether of alkyl substituted or unsubstituted biphenol; Diglycidyl ether of stilbene-based phenol compound Stilbene epoxy resin; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Resins; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; Glycidylamine type epoxy resin obtained by substituting the active hydrogen bonded to the nitrogen atom such as polycyanic acid with a glycidyl group; a bicyclic ring obtained by epoxidizing a co-condensed resin of dicyclopentadiene and a phenol compound Pentadiene type epoxy resin; Diepoxy vinylcyclohexene obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene Alkyl carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclo(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; Para-xylene-modified epoxy resin as glycidyl ether of para-xylene-modified phenol resin; meta-xylene-modified epoxy resin as glycidyl ether of meta-xylene-modified phenol resin; as terpene-modified phenol The terpene-modified epoxy resin of glycidyl ether of the resin; the dicyclopentadiene-modified epoxy resin of the glycidyl ether of the dicyclopentadiene-modified phenol resin; the epoxy resin of the glycidyl-modified phenol resin of cyclopentadiene Cyclopentadiene-modified epoxy resin of glycidyl ether; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as polycyclic aromatic ring-modified phenol resin; as glycidyl ether of phenol resin containing naphthalene ring Naphthalene type epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear fat obtained by oxidizing olefin bonds with peracetic acid and other peracids Group epoxy resin; aromatic phenol resin obtained by epoxidizing aralkyl phenol resin such as phenol aralkyl resin and naphthol aralkyl resin Alkyl type epoxy resin, etc. Furthermore, epoxide of silicone resin, epoxide of acrylic resin, etc. can also be mentioned as an epoxy resin. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.
所述環氧樹脂中，就耐回焊性與黏度的平衡的觀點而言，較佳為選自由聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂及芳烷基型環氧樹脂所組成的群組中的環氧樹脂（將該些稱為「特定環氧樹脂」）。特定環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。Among the epoxy resins, from the viewpoint of the balance of reflow resistance and viscosity, they are preferably selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, Sulfur-containing epoxy resin, novolac epoxy resin, dicyclopentadiene epoxy resin, triphenylmethane epoxy resin, copolymer epoxy resin and aralkyl epoxy resin Epoxy resins in the group (referred to as "specific epoxy resins"). A specific epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.
於環氧樹脂包含特定環氧樹脂的情況下，就發揮特定環氧樹脂的性能的觀點而言，其合計含有率較佳為環氧樹脂整體的30質量%以上，更佳為50質量%以上。When the epoxy resin contains a specific epoxy resin, from the viewpoint of exerting the performance of the specific epoxy resin, the total content is preferably 30% by mass or more of the entire epoxy resin, more preferably 50% by mass or more .
就黏度的觀點而言，特定環氧樹脂中更佳為聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂或含硫原子型環氧樹脂，就耐熱性的觀點而言，較佳為二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂或芳烷基型環氧樹脂。From the viewpoint of viscosity, among the specific epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, or sulfur atom-containing epoxy resin is more preferable. From the viewpoint of, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, or an aralkyl type epoxy resin is preferable.
可較佳地使用的聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂、及芳烷基型環氧樹脂的詳情如第一實施形態中記載般。Preferably used biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene The details of the type epoxy resin, the triphenylmethane type epoxy resin, the copolymer type epoxy resin, and the aralkyl type epoxy resin are as described in the first embodiment.
環氧樹脂的環氧當量並無特別限制。就成形性、耐回焊性及電性可靠性等各種特性平衡的觀點而言，環氧樹脂的環氧當量較佳為100 g/eq～1000 g/eq，更佳為150 g/eq～500 g/eq。環氧樹脂的環氧當量設為利用依據JIS K 7236：2009的方法而測定的值。The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq～1000 g/eq, more preferably 150 g/eq～ 500 g/eq. The epoxy equivalent of an epoxy resin shall be the value measured by the method based on JISK 7236:2009.
於環氧樹脂為固體的情況下，其軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物的製備時的操作性的觀點而言，更佳為50℃～130℃。環氧樹脂的熔點設為利用示差掃描熱量測定（DSC）而測定的值，環氧樹脂的軟化點設為利用依據JIS K 7234：1986的方法（環球法）而測定的值。In the case where the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during the preparation of the epoxy resin composition, it is more preferably from 50°C to 130°C. The melting point of the epoxy resin is taken as a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is taken as a value measured by a method (ring and ball method) conforming to JIS K 7234:1986.
就強度、黏度、耐熱性、成形性等觀點而言，環氧樹脂組成物中的環氧樹脂的含有率較佳為0.5質量%～50質量%，更佳為2質量%～30質量%。From the viewpoints of strength, viscosity, heat resistance, moldability, etc., the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass.
[硬化劑] 第二實施形態的環氧樹脂組成物含有包含所述的通式（B）所表示的化合物（特定硬化劑）的硬化劑。硬化劑除了特定硬化劑以外亦可進一步併用其他硬化劑。硬化劑的詳情與第一實施形態中的硬化劑的詳情相同。[hardener] The epoxy resin composition of the second embodiment contains a curing agent containing the compound (specific curing agent) represented by the aforementioned general formula (B). In addition to the specific hardener, the hardener may be further used in combination with other hardeners. The details of the curing agent are the same as those of the curing agent in the first embodiment.
[硬化促進劑] 環氧樹脂組成物亦可包含硬化促進劑。硬化促進劑的種類並無特別限制。硬化促進劑的詳情與第一實施形態中的硬化促進劑的詳情相同。[Hardening accelerator] The epoxy resin composition may also contain a hardening accelerator. The type of hardening accelerator is not particularly limited. The details of the hardening accelerator are the same as those of the hardening accelerator in the first embodiment.
[無機填充材] 第二實施形態的環氧樹脂組成物亦可包含無機填充材。特別是於將環氧樹脂組成物用作半導體封裝的密封材的情況下，較佳為包含無機填充材。[Inorganic Filler] The epoxy resin composition of the second embodiment may include an inorganic filler. In particular, when the epoxy resin composition is used as a sealing material for a semiconductor package, it is preferable to include an inorganic filler.
無機填充材的種類並無特別限制。具體而言，可列舉：熔融二氧化矽、晶體二氧化矽、玻璃、氧化鋁、碳酸鈣、矽酸鋯、矽酸鈣、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、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材。作為具有阻燃效果的無機填充材，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、硼酸鋅等。其中，就線膨脹係數減少的觀點而言，較佳為熔融二氧化矽，就高導熱性的觀點而言，較佳為氧化鋁。無機填充材可單獨使用一種，亦可將兩種以上組合而使用。作為無機填充材的狀態，可列舉粉末、將粉末球形化的顆粒、纖維等。The type of inorganic filler is not particularly limited. Specifically, include: fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconia , Zircon, forsterite, talc, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate. Among them, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferred, and from the viewpoint of high thermal conductivity, alumina is preferred. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the state of the inorganic filler include powder, particles formed by spheronizing powder, fibers, and the like.
再者，所謂「將兩種以上的無機填充材組合而使用」，例如可列舉：將成分相同且平均粒徑不同的無機填充材使用兩種以上的情況、將平均粒徑相同且成分不同的無機填充材使用兩種以上的情況以及將平均粒徑及種類不同的無機填充材使用兩種以上的情況。Furthermore, the so-called "combination of two or more inorganic fillers" includes, for example, the case where two or more inorganic fillers with the same composition and different average particle diameters are used, and those with the same average particle diameter and different components are used. The case where two or more types of inorganic fillers are used, and the case where two or more types of inorganic fillers with different average particle diameters and types are used.
於環氧樹脂組成物包含無機填充材的情況下，其含有率並無特別限制。就黏度及強度的觀點而言，較佳為環氧樹脂組成物整體的30體積%～90體積%，更佳為35體積%～88體積%，進而佳為40體積%～85體積%。若無機填充材的含有率為環氧樹脂組成物整體的30體積%以上，則存在硬化物的熱膨脹係數、導熱率、彈性係數等特性進一步提高的傾向。若無機填充材的含有率為環氧樹脂組成物整體的90體積%以下，則存在環氧樹脂組成物的黏度的上升得到抑制、黏度進一步提高且成形性變得更良好的傾向。When the epoxy resin composition contains an inorganic filler, the content rate is not particularly limited. From the viewpoint of viscosity and strength, it is preferably 30% by volume to 90% by volume of the entire epoxy resin composition, more preferably 35% by volume to 88% by volume, and still more preferably 40% by volume to 85% by volume. When the content of the inorganic filler is 30% by volume or more of the entire epoxy resin composition, the thermal expansion coefficient, thermal conductivity, and elastic coefficient of the cured product tend to further improve. If the content of the inorganic filler is 90% by volume or less of the entire epoxy resin composition, the increase in the viscosity of the epoxy resin composition is suppressed, the viscosity is further improved, and the moldability tends to become better.
另外，於環氧樹脂組成物包含無機填充材的情況下，就耐回焊性及黏度的觀點而言，無機填充材的含有率較佳為環氧樹脂組成物整體的80質量%～95質量%，更佳為85質量%～94質量%，進而佳為88質量%～93質量%。若無機填充材的含有率為環氧樹脂組成物整體的80質量%以上，則存在耐回焊性提高的傾向。若無機填充材的含有率為環氧樹脂組成物整體的95質量%以下，則存在黏度優異的傾向。In addition, when the epoxy resin composition contains an inorganic filler, from the viewpoint of reflow resistance and viscosity, the content of the inorganic filler is preferably 80% to 95% by mass of the entire epoxy resin composition. %, more preferably 85% by mass to 94% by mass, and still more preferably 88% by mass to 93% by mass. If the content of the inorganic filler is 80% by mass or more of the entire epoxy resin composition, the reflow resistance tends to improve. If the content of the inorganic filler is 95% by mass or less of the entire epoxy resin composition, the viscosity tends to be excellent.
無機填充材的平均粒徑並無特別限制。例如，體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升進一步得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性進一步提高的傾向。無機填充材的體積平均粒徑可藉由雷射繞射散射法粒度分佈測定裝置以體積平均粒徑（D50）的形式測定。The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be further suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be further improved. The volume average particle size of the inorganic filler can be measured in the form of volume average particle size (D50) by a laser diffraction scattering method particle size distribution measuring device.
環氧樹脂組成物或其硬化物中的無機填充材的體積平均粒徑可利用公知的方法來進行測定。例如，使用有機溶劑、硝酸、王水等，自環氧樹脂組成物或硬化物中萃取無機填充材，利用超音波分散機等充分地分散而製備分散液。可使用該分散液，並根據利用雷射繞射散射法粒度分佈測定裝置而測定的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。或者，可將硬化物埋入至透明的環氧樹脂等中，進行研磨而獲得剖面，根據利用掃描式電子顯微鏡觀察所獲得的剖面而獲得的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。進而，亦可藉由如下方式來測定：使用FIB裝置（聚焦離子束SEM）等連續進行硬化物的二維的剖面觀察，並進行三維結構解析。The volume average particle diameter of the epoxy resin composition or the inorganic filler in the cured product can be measured by a known method. For example, using an organic solvent, nitric acid, aqua regia, etc., the inorganic filler is extracted from the epoxy resin composition or hardened material, and the dispersion is prepared by fully dispersing it with an ultrasonic dispersion machine or the like. Using this dispersion liquid, the volume average particle diameter of the inorganic filler can be measured based on the volume-based particle size distribution measured by the laser diffraction scattering method particle size distribution measuring device. Alternatively, the cured product can be embedded in a transparent epoxy resin, etc., and polished to obtain a cross section, and the volume average of the inorganic filler can be measured based on the volume-based particle size distribution obtained by observing the obtained cross section with a scanning electron microscope Particle size. Furthermore, it is also possible to measure by continuously performing a two-dimensional cross-sectional observation of the cured product using a FIB device (focused ion beam SEM) or the like, and performing a three-dimensional structure analysis.
無機填充材的最大粒徑（亦稱為割點）並無特別限制。就對狹小的縫隙的填充性的觀點而言，無機填充材的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size (also called cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling properties for small gaps, the maximum particle size of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
就環氧樹脂組成物的混練性的觀點而言，關於無機填充材的粒子形狀，球形優於角形，且較佳為無機填充材的粒度分佈以廣範圍進行分佈。From the viewpoint of the kneading property of the epoxy resin composition, as for the particle shape of the inorganic filler, the spherical shape is better than the angular shape, and the particle size distribution of the inorganic filler is preferably distributed in a wide range.
於獲得高導熱性的硬化物的情況下，無機填充材較佳為包含氧化鋁，更佳為包含氧化鋁作為主成分。無機填充材包含氧化鋁時的氧化鋁的平均粒徑並無特別限制。例如氧化鋁的體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。In the case of obtaining a cured product with high thermal conductivity, the inorganic filler preferably contains alumina, and more preferably contains alumina as a main component. The average particle diameter of alumina when the inorganic filler contains alumina is not particularly limited. For example, the volume average particle size of alumina is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved.
氧化鋁的最大粒徑並無特別限制。就對狹小的縫隙的填充性的觀點而言，氧化鋁的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of alumina is not particularly limited. From the viewpoint of the filling properties of the narrow gaps, the maximum particle size of alumina is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
於較佳的一態樣中，亦可併用平均粒徑為0.1 μm～2.0 μm、較佳為0.2 μm～1.5 μm、更佳為0.3 μm～1.0 μm的氧化鋁、與平均粒徑超過2.0 μm且為75 μm以下、較佳為5.0 μm～55 μm、更佳為8.0 μm～20 μm的氧化鋁。藉由併用平均粒徑不同的兩種以上的氧化鋁，存在可使填充性變佳的傾向。In a preferred aspect, alumina having an average particle diameter of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, more preferably 0.3 μm to 1.0 μm, and an average particle diameter of more than 2.0 μm can also be used in combination. And it is 75 μm or less, preferably 5.0 μm to 55 μm, more preferably 8.0 μm to 20 μm alumina. By using two or more types of alumina with different average particle diameters in combination, there is a tendency that the filling properties can be improved.
氧化鋁的形狀並無特別限制。就環氧樹脂組成物的混練性的觀點而言，氧化鋁的粒子形狀較佳為球形。The shape of alumina is not particularly limited. From the viewpoint of the kneading property of the epoxy resin composition, the particle shape of alumina is preferably spherical.
於無機填充材包含氧化鋁的情況下，就高導熱化的觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為90質量%以上，更佳為95質量%以上，進而佳為98質量%以上。另外，就低黏度化、混練的作業性等觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為99.9質量%以下，更佳為99.8質量%以下，進而佳為99.7質量%以下。When the inorganic filler contains alumina, from the viewpoint of high thermal conductivity, the content of alumina relative to the total mass of the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and further Preferably, it is 98% by mass or more. In addition, from the viewpoints of low viscosity and kneading workability, the content of alumina relative to the total mass of the inorganic filler is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, and still more preferably 99.7 mass% %the following.
於無機填充材包含氧化鋁的情況下，無機填充材較佳為除包含氧化鋁以外亦包含二氧化矽。若無機填充材包含二氧化矽，則存在黏度下降，可提高混練性及流動性的傾向，特別是藉由併用微細的二氧化矽，存在可抑制製成硬化物時的毛邊的產生的傾向。特別是無機填充材較佳為包含微粒二氧化矽、例如平均粒徑為0.01 μm～2.0 μm、更佳為0.1 μm～1.5 μm、進而佳為0.2 μm～1.0 μm的二氧化矽。就彈性係數的減少、線膨脹係數的減少的觀點而言，無機填充材較佳為包含大粒徑二氧化矽。 作為大粒徑二氧化矽，可列舉較佳為超過2.0 μm且為75 μm以下、更佳為5.0 μm～55 μm、進而佳為8.0 μm～20 μm的二氧化矽。When the inorganic filler contains alumina, the inorganic filler preferably contains silica in addition to alumina. If the inorganic filler contains silica, there is a tendency that the viscosity is lowered and the kneading and fluidity can be improved. In particular, by using fine silica in combination, there is a tendency that the generation of burrs when the hardened product is formed can be suppressed. In particular, the inorganic filler preferably contains particulate silica, for example, silica having an average particle size of 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.5 μm, and still more preferably 0.2 μm to 1.0 μm. From the viewpoint of a decrease in the coefficient of elasticity and a decrease in the coefficient of linear expansion, the inorganic filler preferably contains large-particle silica. As the large particle size silicon dioxide, silicon dioxide preferably exceeding 2.0 μm and 75 μm or less, more preferably 5.0 μm to 55 μm, and still more preferably 8.0 μm to 20 μm can be cited.
就耐回焊性、抑制黏度的上升等觀點而言，無機填充材較佳為包含二氧化矽，亦可包含二氧化矽作為主成分。無機填充材包含二氧化矽時的二氧化矽的平均粒徑並無特別限制。例如二氧化矽的體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。另外，無機填充材較佳為包含微粒二氧化矽、例如平均粒徑為0.01 μm～2.0 μm、更佳為0.1 μm～1.5 μm、進而佳為0.2 μm～1.0 μm的二氧化矽。若無機填充材包含微粒二氧化矽，則存在對狹部的填充性提高，製成硬化物時的毛邊的產生得到抑制的傾向。From the viewpoints of reflow resistance and suppression of viscosity increase, the inorganic filler preferably contains silicon dioxide, and may contain silicon dioxide as a main component. When the inorganic filler contains silica, the average particle size of silica is not particularly limited. For example, the volume average particle size of silicon dioxide is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved. In addition, the inorganic filler preferably contains particulate silica, for example, silica having an average particle diameter of 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.5 μm, and still more preferably 0.2 μm to 1.0 μm. If the inorganic filler contains fine-particle silica, the fillability to the narrow part is improved, and the generation of burrs when it is made into a hardened product tends to be suppressed.
二氧化矽的最大粒徑並無特別限制。就對狹小的縫隙的填充性的觀點而言，二氧化矽的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of silicon dioxide is not particularly limited. From the viewpoint of filling properties for small gaps, the maximum particle size of silicon dioxide is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
二氧化矽的形狀並無特別限制。就環氧樹脂組成物的混練性的觀點而言，二氧化矽的粒子形狀較佳為球形。The shape of silicon dioxide is not particularly limited. From the viewpoint of the kneading property of the epoxy resin composition, the particle shape of the silicon dioxide is preferably spherical.
於無機填充材包含二氧化矽的情況下，二氧化矽的含有率並無特別限定，相對於無機填充材的總質量，可為70質量%～100質量%，亦可為80質量%～100質量%，亦可為90質量%～100質量%。另外，相對於無機填充材的總質量，將二氧化矽與氧化鋁併用時的二氧化矽的含有率可為0.1質量%～10質量%，亦可為0.2質量%～5質量%，亦可為0.3質量%～2質量%。In the case where the inorganic filler contains silicon dioxide, the content of silicon dioxide is not particularly limited. Relative to the total mass of the inorganic filler, it may be 70% to 100% by mass, or 80% to 100. The mass% may be 90% to 100% by mass. In addition, with respect to the total mass of the inorganic filler, the silica content when using silica and alumina in combination may be 0.1% by mass to 10% by mass, or 0.2% by mass to 5% by mass, or It is 0.3% by mass to 2% by mass.
[各種添加劑] 第二實施形態的環氧樹脂組成物除了所述成分以外，亦可包含偶合劑、離子交換體、脫模劑、阻燃劑、著色劑、應力緩和劑等各種添加劑。環氧樹脂組成物視需要亦可包含於本技術領域中周知的各種添加劑。各種添加劑的詳情與第一實施形態中的各種添加劑的詳情相同。[Various additives] The epoxy resin composition of the second embodiment may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a coloring agent, and a stress reliever in addition to the above-mentioned components. The epoxy resin composition may contain various additives well-known in this technical field as needed. The details of the various additives are the same as the details of the various additives in the first embodiment.
其中，第二實施形態的環氧樹脂組成物包含脫模劑，相對於環氧樹脂組成物的總質量，脫模劑的含有率較佳為超過0質量%且為2.0質量%以下，更佳為超過0質量%且為1.5質量%以下，進而佳為超過0質量%且為1.2質量%以下。藉由以所述含有率含有脫模劑，與比所述含有率多地含有脫模劑的情況相比，存在可抑制使外觀、接著力、及雷射打印性顯著下降的傾向。另外，根據第二實施形態的環氧樹脂組成物，存在即便脫模劑的含有率為所述範圍亦可維持良好的脫模性的傾向。Among them, the epoxy resin composition of the second embodiment includes a mold release agent, and the content of the mold release agent relative to the total mass of the epoxy resin composition is preferably more than 0% by mass and 2.0% by mass or less, more preferably It is more than 0% by mass and 1.5% by mass or less, and more preferably more than 0% by mass and 1.2% by mass or less. By containing the release agent at the above content rate, compared with the case where the release agent is contained more than the above content rate, there is a tendency that the appearance, adhesive force, and laser printability can be suppressed from significantly degrading. Moreover, according to the epoxy resin composition of 2nd Embodiment, even if the content rate of a mold release agent is said range, there exists a tendency which can maintain favorable mold release property.
〔環氧樹脂組成物的製備方法〕 第二實施形態的環氧樹脂組成物的製備方法並無特別限制。第二實施形態的環氧樹脂組成物的製備方法的詳情與第一實施形態的環氧樹脂組成物的製備方法的詳情相同。[Preparation method of epoxy resin composition] The method of preparing the epoxy resin composition of the second embodiment is not particularly limited. The details of the method of preparing the epoxy resin composition of the second embodiment are the same as those of the method of preparing the epoxy resin composition of the first embodiment.
於第二實施形態的環氧樹脂組成物的說明中，關於適用第一實施形態的說明的部位，將「第一實施形態」替換為「第二實施形態」。In the description of the epoxy resin composition of the second embodiment, the "first embodiment" is replaced with the "second embodiment" with respect to the parts where the description of the first embodiment is applied.
（3）第三實施形態 ＜密封用環氧樹脂組成物＞ 第三實施形態的密封用環氧樹脂組成物（以下，亦簡稱為環氧樹脂組成物）含有：環氧樹脂；無機填充材，包含氧化鋁；以及硬化劑，包含以下的通式（B）所表示的化合物（即，「特定硬化劑」）。(3) The third embodiment ＜Epoxy resin composition for sealing＞ The epoxy resin composition for sealing of the third embodiment (hereinafter also referred to as epoxy resin composition) contains: epoxy resin; inorganic filler containing alumina; and hardener, containing the following general formula (B) The compound represented (ie, "specific hardener").
[化25]
通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數。In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0-10.
發現根據第三實施形態的環氧樹脂組成物，可製作導熱性及彎曲強度優異的硬化物。其理由未必明確，但可如以下般考慮。第三實施形態的環氧樹脂組成物含有包含通式（B）所表示的化合物的硬化劑。認為該化合物相對於氧化鋁的潤濕性良好，將第三實施形態的環氧樹脂組成物製成硬化物時，氧化鋁與樹脂的界面的接合變得良好。其結果，認為可良好地發揮氧化鋁的散熱性。另外認為，同樣地氧化鋁與樹脂的界面的接合良好時亦有助於提高硬化物的彎曲強度。It was found that according to the epoxy resin composition of the third embodiment, a cured product having excellent thermal conductivity and bending strength can be produced. The reason is not necessarily clear, but it can be considered as follows. The epoxy resin composition of the third embodiment contains a curing agent containing a compound represented by general formula (B). It is considered that this compound has good wettability with respect to alumina, and when the epoxy resin composition of the third embodiment is used as a cured product, the bonding between the alumina and the resin at the interface becomes good. As a result, it is considered that the heat dissipation properties of alumina can be exhibited satisfactorily. In addition, it is considered that, similarly, when the bonding between the alumina and the resin interface is good, it also contributes to the improvement of the bending strength of the cured product.
第三實施形態的環氧樹脂組成物亦可進一步含有硬化促進劑、其他添加劑等。以下，對第三實施形態的環氧樹脂組成物中可包含的成分進行詳細說明。The epoxy resin composition of the third embodiment may further contain a hardening accelerator, other additives, and the like. Hereinafter, the components that can be contained in the epoxy resin composition of the third embodiment will be described in detail.
[環氧樹脂] 第三實施形態的環氧樹脂組成物包含環氧樹脂。環氧樹脂只要為於一分子中具有兩個以上環氧基者，則其種類並無特別限制。 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等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組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於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於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；使所述苯酚化合物及萘酚化合物與醛化合物於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合型環氧樹脂；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；作為烷基經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；作為二苯乙烯系酚化合物的二縮水甘油醚的二苯乙烯型環氧樹脂；作為雙酚S等的二縮水甘油醚的含硫原子型環氧樹脂；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；將二環戊二烯與苯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-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、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環氧樹脂。該些環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。[Epoxy resin] The epoxy resin composition of the third embodiment contains epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, examples include phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, At least one phenolic compound in the group consisting of naphthol compounds such as dihydroxynaphthalene is condensed or co-condensed with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolak resin and the phenolic compound Novolac type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) obtained by epoxidizing varnish resin; combining the phenolic compound with aromatics such as benzaldehyde and salicylaldehyde Triphenylmethane type epoxy resin obtained by condensing or co-condensing triphenylmethane type phenol resin under acidic catalyst and epoxidizing the triphenylmethane type phenol resin; making the phenol The compound and the naphthol compound and the aldehyde compound are co-condensed under an acidic catalyst to obtain a novolak resin and the novolak resin is epoxidized to obtain a copolymerized epoxy resin; as a two-component epoxy resin such as bisphenol A and bisphenol F Diphenylmethane type epoxy resin of glycidyl ether; Biphenyl type epoxy resin of diglycidyl ether of alkyl substituted or unsubstituted biphenol; Diglycidyl ether of stilbene-based phenol compound Stilbene epoxy resin; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Resins; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; Glycidylamine type epoxy resin obtained by substituting the active hydrogen bonded to the nitrogen atom such as polycyanic acid with a glycidyl group; a bicyclic ring obtained by epoxidizing a co-condensed resin of dicyclopentadiene and a phenol compound Pentadiene type epoxy resin; Diepoxy vinylcyclohexene obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene Alkyl carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclo(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; Para-xylene-modified epoxy resin as glycidyl ether of para-xylene-modified phenol resin; meta-xylene-modified epoxy resin as glycidyl ether of meta-xylene-modified phenol resin; as terpene-modified phenol The terpene-modified epoxy resin of glycidyl ether of the resin; the dicyclopentadiene-modified epoxy resin of the glycidyl ether of the dicyclopentadiene-modified phenol resin; the epoxy resin of the glycidyl-modified phenol resin of cyclopentadiene Cyclopentadiene-modified epoxy resin of glycidyl ether; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as polycyclic aromatic ring-modified phenol resin; as glycidyl ether of phenol resin containing naphthalene ring Naphthalene type epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear fat obtained by oxidizing olefin bonds with peracetic acid and other peracids Group epoxy resin; aromatic phenol resin obtained by epoxidizing aralkyl phenol resin such as phenol aralkyl resin and naphthol aralkyl resin Alkyl type epoxy resin, etc. Furthermore, epoxide of silicone resin, epoxide of acrylic resin, etc. can also be mentioned as an epoxy resin. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.
所述環氧樹脂中，就耐回焊性與流動性的平衡的觀點而言，較佳為選自由聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂及芳烷基型環氧樹脂所組成的群組中的環氧樹脂（將該些稱為「特定環氧樹脂」）。特定環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。Among the epoxy resins, from the viewpoint of the balance of reflow resistance and fluidity, they are preferably selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, and diphenylmethane type epoxy resins. , Sulfur atom type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymer type epoxy resin and aralkyl type epoxy resin The epoxy resins in the group of composition (these are called "specific epoxy resins"). A specific epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.
於環氧樹脂包含特定環氧樹脂的情況下，就發揮特定環氧樹脂的性能的觀點而言，其合計含有率較佳為環氧樹脂整體的30質量%以上，更佳為50質量%以上。When the epoxy resin contains a specific epoxy resin, from the viewpoint of exerting the performance of the specific epoxy resin, the total content is preferably 30% by mass or more of the entire epoxy resin, more preferably 50% by mass or more .
就流動性的觀點而言，特定環氧樹脂中更佳為聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、及含硫原子型環氧樹脂，就耐熱性的觀點而言，較佳為二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、及芳烷基型環氧樹脂。From the viewpoint of fluidity, among the specific epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, and sulfur atom-containing epoxy resin are more preferable. From the viewpoint of heat resistance, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and aralkyl type epoxy resins are preferred.
於較佳的一態樣中，環氧樹脂組成物可含有選自由二苯基甲烷型環氧樹脂及聯苯型環氧樹脂所組成的群組中的至少一種。 於環氧樹脂組成物含有二苯基甲烷型環氧樹脂的情況下，相對於環氧樹脂的總質量，二苯基甲烷型環氧樹脂的含有率可為40質量%～100質量%，亦可為50質量%～100質量%，亦可為60質量%～100質量%。 於環氧樹脂組成物含有聯苯型環氧樹脂的情況下，相對於環氧樹脂的總質量，聯苯型環氧樹脂的含有率可為20質量%～100質量%，亦可為25質量%～100質量%。In a preferred aspect, the epoxy resin composition may contain at least one selected from the group consisting of diphenylmethane type epoxy resin and biphenyl type epoxy resin. When the epoxy resin composition contains diphenylmethane type epoxy resin, relative to the total mass of epoxy resin, the content rate of diphenylmethane type epoxy resin may be 40% by mass to 100% by mass. It may be 50% by mass to 100% by mass, or 60% by mass to 100% by mass. When the epoxy resin composition contains a biphenyl epoxy resin, the content of the biphenyl epoxy resin may be 20% by mass to 100% by mass, or 25% by mass relative to the total mass of the epoxy resin. %～100% by mass.
於較佳的一態樣中，可將二苯基甲烷型環氧樹脂與聯苯型環氧樹脂組合而使用。於該情況下，相對於環氧樹脂的總質量而言的二苯基甲烷型環氧樹脂與聯苯型環氧樹脂的合計含有率較佳為70質量%以上，更佳為80質量%以上，進而佳為90質量%以上。 於將二苯基甲烷型環氧樹脂與聯苯型環氧樹脂組合而使用的情況下，二苯基甲烷型環氧樹脂與聯苯型環氧樹脂的含量比（二苯基甲烷型環氧樹脂：聯苯型環氧樹脂）以質量基準計，可為90：10～10：90，亦可為80：20～50：50。In a preferred aspect, a combination of diphenylmethane type epoxy resin and biphenyl type epoxy resin can be used. In this case, the total content of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin relative to the total mass of the epoxy resin is preferably 70% by mass or more, more preferably 80% by mass or more , More preferably 90% by mass or more. When the diphenylmethane type epoxy resin and the biphenyl type epoxy resin are used in combination, the content ratio of the diphenylmethane type epoxy resin to the biphenyl type epoxy resin (diphenylmethane type epoxy resin Resin: Biphenyl type epoxy resin) based on mass basis, it can be 90:10-10:90, or 80:20-50:50.
可較佳地使用的聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂、及芳烷基型環氧樹脂的詳情如第一實施形態中記載般。Preferably used biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene The details of the type epoxy resin, the triphenylmethane type epoxy resin, the copolymer type epoxy resin, and the aralkyl type epoxy resin are as described in the first embodiment.
環氧樹脂的環氧當量並無特別限制。就成形性、耐回焊性及電性可靠性等各種特性平衡的觀點而言，環氧樹脂的環氧當量較佳為100 g/eq～1000 g/eq，更佳為150 g/eq～500 g/eq。環氧樹脂的環氧當量設為利用依據JIS K 7236：2009的方法而測定的值。The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq～1000 g/eq, more preferably 150 g/eq～ 500 g/eq. The epoxy equivalent of an epoxy resin shall be the value measured by the method based on JISK 7236:2009.
於環氧樹脂為固體的情況下，其軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃～180℃，就環氧樹脂組成物的製備時的操作性的觀點而言，更佳為50℃～130℃。環氧樹脂的熔點設為利用示差掃描熱量測定（DSC）而測定的值，環氧樹脂的軟化點設為利用依據JIS K 7234：1986的方法（環球法）而測定的值。In the case where the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during the preparation of the epoxy resin composition, it is more preferably from 50°C to 130°C. The melting point of the epoxy resin is taken as a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is taken as a value measured by a method (ring and ball method) conforming to JIS K 7234:1986.
就強度、流動性、耐熱性、成形性等觀點而言，環氧樹脂組成物中的環氧樹脂的含有率較佳為0.5質量%～50質量%，更佳為2質量%～30質量%。From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the epoxy resin content in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass .
[無機填充材] 第三實施形態的環氧樹脂組成物含有包含氧化鋁的無機填充材。作為無機填充材，可單獨使用氧化鋁，亦可併用氧化鋁與其他無機填充材。[Inorganic Filler] The epoxy resin composition of the third embodiment contains an inorganic filler containing alumina. As the inorganic filler, alumina may be used alone, or alumina and other inorganic fillers may be used in combination.
無機填充材的平均粒徑並無特別限制。例如，體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm，進而佳為1 μm～50 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。無機填充材的體積平均粒徑可藉由雷射繞射散射法粒度分佈測定裝置以體積平均粒徑（D50）的形式測定。就環氧樹脂組成物的流動性的觀點而言，無機填充材的粒徑較佳為以廣範圍進行分佈。The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and still more preferably 1 μm to 50 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved. The volume average particle size of the inorganic filler can be measured in the form of volume average particle size (D50) by a laser diffraction scattering method particle size distribution measuring device. From the viewpoint of the fluidity of the epoxy resin composition, the particle size of the inorganic filler is preferably distributed in a wide range.
環氧樹脂組成物或其硬化物中的無機填充材的體積平均粒徑具體而言可利用以下的方法來進行測定。 將放入有環氧樹脂組成物或其硬化物的坩堝放入蒙孚爐（muffle furnace）中，加熱至800℃。放置約4小時至試樣完全灰化為止。將試樣自然冷卻至恢復至常溫為止，並萃取灰分（無機填充材）。利用超音波分散機等充分地分散無機填充材而製備分散液。可使用該分散液，並根據利用雷射繞射散射法粒度分佈測定裝置而測定的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。Specifically, the volume average particle size of the inorganic filler in the epoxy resin composition or its cured product can be measured by the following method. The crucible containing the epoxy resin composition or its hardened substance is placed in a muffle furnace and heated to 800°C. Leave it for about 4 hours until the sample is completely ashed. Cool the sample naturally until it returns to room temperature, and extract the ash (inorganic filler). The inorganic filler is sufficiently dispersed using an ultrasonic disperser or the like to prepare a dispersion liquid. Using this dispersion liquid, the volume average particle diameter of the inorganic filler can be measured based on the volume-based particle size distribution measured by the laser diffraction scattering method particle size distribution measuring device.
無機填充材的最大粒徑（亦稱為割點）並無特別限制。就對狹小的縫隙的填充性的觀點而言，無機填充材的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size (also called cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling properties for small gaps, the maximum particle size of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
無機填充材的形狀並無特別限制。就環氧樹脂組成物的流動性的觀點而言，無機填充材的粒子形狀較佳為球形。The shape of the inorganic filler is not particularly limited. From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.
無機填充材的含有率並無特別限制。相對於環氧樹脂組成物的總體積，無機填充材的含有率較佳為50體積%以上，更佳為60體積%以上，進而佳為70體積%以上，特佳為75體積%以上，極佳為80體積%以上。若無機填充材的含有率為環氧樹脂組成物整體的50體積%以上，則存在硬化物的熱膨脹係數、導熱率、彈性係數等特性進一步提高的傾向。 另外，相對於環氧樹脂組成物的總體積，無機填充材的含有率較佳為95體積%以下，更佳為90體積%以下，進而佳為87體積%以下。若無機填充材的含有率為環氧樹脂組成物整體的95體積%以下，則存在環氧樹脂組成物的黏度的上升得到抑制、流動性進一步提高且成形性變得更良好的傾向。 就以上的觀點而言，相對於環氧樹脂組成物的總體積，無機填充材的含有率較佳為50體積%～95體積%，更佳為60體積%～95體積%，進而佳為70體積%～95體積%，特佳為75體積%～90體積%，極佳為80體積%～87體積%。The content rate of the inorganic filler is not particularly limited. Relative to the total volume of the epoxy resin composition, the content of the inorganic filler is preferably 50% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, particularly preferably 75% by volume or more. Preferably, it is more than 80% by volume. When the content of the inorganic filler is 50% by volume or more of the entire epoxy resin composition, the thermal expansion coefficient, thermal conductivity, and elastic coefficient of the cured product tend to further improve. In addition, the content of the inorganic filler relative to the total volume of the epoxy resin composition is preferably 95% by volume or less, more preferably 90% by volume or less, and still more preferably 87% by volume or less. When the content of the inorganic filler is 95% by volume or less of the entire epoxy resin composition, the increase in the viscosity of the epoxy resin composition is suppressed, the fluidity is further improved, and the moldability tends to become better. From the above viewpoints, relative to the total volume of the epoxy resin composition, the content of the inorganic filler is preferably 50% by volume to 95% by volume, more preferably 60% by volume to 95% by volume, and even more preferably 70% by volume. Volume%-95% by volume, particularly preferably 75% by volume to 90% by volume, and extremely preferably 80% by volume to 87% by volume.
另外，第三實施形態的環氧樹脂組成物中存在如下傾向：即便無機填充材的含有率為環氧樹脂組成物的例如82體積%以上、更佳為84體積%以上、進而佳為85體積%以上、特佳為86體積%以上、極佳為87體積%以上，亦可良好地混練。In addition, the epoxy resin composition of the third embodiment has a tendency that even if the content rate of the inorganic filler is, for example, 82 vol% or more of the epoxy resin composition, more preferably 84 vol% or more, and still more preferably 85 vol% % Or more, particularly preferably 86% by volume or more, and extremely preferably 87% by volume or more, and it can also be mixed well.
另外，第三實施形態的環氧樹脂組成物中存在如下傾向：即便無機填充材的含有率為環氧樹脂組成物的例如90質量%以上、更佳為92質量%以上、進而佳為94質量%以上、特佳為96質量%以上、極佳為98質量%以上，亦可良好地混練。In addition, the epoxy resin composition of the third embodiment has a tendency that even if the content of the inorganic filler is, for example, 90% by mass or more, more preferably 92% by mass or more, and still more preferably 94% by mass of the epoxy resin composition % Or more, particularly preferably 96% by mass or more, and extremely preferably 98% by mass or more, and it can also be mixed well.
-氧化鋁- 無機填充材包含氧化鋁。氧化鋁的平均粒徑並無特別限制。例如氧化鋁的體積平均粒徑較佳為0.2 μm～80 μm，更佳為0.5 μm～70 μm。若體積平均粒徑為0.2 μm以上，則存在環氧樹脂組成物的黏度的上升得到抑制的傾向。若體積平均粒徑為80 μm以下，則存在對狹小的縫隙的填充性提高的傾向。就環氧樹脂組成物的流動性的觀點而言，氧化鋁的粒徑較佳為以廣範圍進行分佈。-Alumina- The inorganic filler contains alumina. The average particle diameter of alumina is not particularly limited. For example, the volume average particle size of alumina is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm. If the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the volume average particle diameter is 80 μm or less, the filling properties of the narrow gaps tend to be improved. From the viewpoint of the fluidity of the epoxy resin composition, the particle size of alumina is preferably distributed in a wide range.
氧化鋁的最大粒徑（亦稱為割點）並無特別限制。就對狹小的縫隙的填充性的觀點而言，氧化鋁的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。The maximum particle size of alumina (also called cut point) is not particularly limited. From the viewpoint of the filling properties of the narrow gaps, the maximum particle size of alumina is preferably 150 μm or less, more preferably 75 μm or less, and still more preferably 55 μm or less.
於較佳的一態樣中，亦可併用平均粒徑為0.1 μm～2.0 μm、較佳為0.2 μm～1.5 μm、更佳為0.3 μm～1.0 μm的氧化鋁、與平均粒徑超過2.0 μm且為75 μm以下、較佳為5.0 μm～55 μm、更佳為8.0 μm～20 μm的氧化鋁。藉由併用平均粒徑不同的兩種以上的氧化鋁，存在可使填充性及流動性變佳的傾向。In a preferred aspect, alumina having an average particle diameter of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, more preferably 0.3 μm to 1.0 μm, and an average particle diameter of more than 2.0 μm can also be used in combination. And it is 75 μm or less, preferably 5.0 μm to 55 μm, more preferably 8.0 μm to 20 μm alumina. By using two or more types of alumina with different average particle diameters in combination, there is a tendency that the filling properties and fluidity can be improved.
氧化鋁的形狀並無特別限制。就環氧樹脂組成物的流動性的觀點而言，氧化鋁的粒子形狀較佳為球形。The shape of alumina is not particularly limited. From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of alumina is preferably spherical.
就高導熱化的觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為75質量%以上，更佳為80質量%以上，進而佳為85質量%以上，特佳為90質量%以上，極佳為95質量%以上。另外，就低黏度化、混練的作業性等觀點而言，氧化鋁相對於無機填充材的總質量的含有率較佳為99.9質量%以下，更佳為99.8質量%以下，進而佳為99.7質量%以下。From the viewpoint of high thermal conductivity, the content of alumina relative to the total mass of the inorganic filler is preferably 75% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90 Mass% or more, very preferably 95 mass% or more. In addition, from the viewpoints of low viscosity and kneading workability, the content of alumina relative to the total mass of the inorganic filler is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, and still more preferably 99.7 mass% %the following.
-其他無機填充材- 第三實施形態的環氧樹脂組成物亦可含有氧化鋁以外的無機填充材。氧化鋁以外的無機填充材的種類並無特別限制。具體而言，可列舉：二氧化矽（熔融二氧化矽、晶體二氧化矽等）、玻璃、碳酸鈣、矽酸鋯、矽酸鈣、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、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材。作為具有阻燃效果的無機填充材，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、硼酸鋅等。其中，就流動性、及線膨脹係數減少的觀點而言，較佳為二氧化矽，更佳為熔融二氧化矽。作為無機填充材的狀態，可列舉粉末、將粉末球形化的顆粒、纖維等。-Other inorganic fillers- The epoxy resin composition of the third embodiment may contain inorganic fillers other than alumina. The type of inorganic fillers other than alumina is not particularly limited. Specifically, it can include: silicon dioxide (fused silicon dioxide, crystalline silicon dioxide, etc.), glass, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide , Zirconia, zircon, forsterite, talc, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate. Among them, from the viewpoint of fluidity and reduction in linear expansion coefficient, silica is preferred, and fused silica is more preferred. Examples of the state of the inorganic filler include powder, particles formed by spheronizing powder, fibers, and the like.
無機填充材較佳為除包含氧化鋁以外亦包含二氧化矽。若無機填充材包含二氧化矽，則存在黏度下降，可提高混練性及流動性的傾向，特別是藉由併用微細的二氧化矽，存在可抑制製成硬化物時的毛邊的產生的傾向。特別是無機填充材較佳為包含微粒二氧化矽、例如平均粒徑2.0 μm以下、較佳為平均粒徑0.01 μm～2.0 μm、進而佳為0.1 μm～1.5 μm、特佳為0.2 μm～1.0 μm的二氧化矽。就彈性係數的減少及線膨脹係數的減少的觀點而言，無機填充材亦可包含大粒徑二氧化矽。作為大粒徑二氧化矽，可列舉平均粒徑超過2.0 μm且為75 μm以下、較佳為5.0 μm～55 μm、更佳為8.0 μm～20 μm的大粒徑二氧化矽。The inorganic filler preferably contains silica in addition to alumina. If the inorganic filler contains silica, there is a tendency that the viscosity is lowered and the kneading and fluidity can be improved. In particular, by using fine silica in combination, there is a tendency that the generation of burrs when the hardened product is formed can be suppressed. In particular, the inorganic filler preferably contains fine particles of silica, for example, the average particle size is 2.0 μm or less, preferably the average particle size is 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.5 μm, particularly preferably 0.2 μm to 1.0 μm silicon dioxide. From the viewpoint of the reduction of the coefficient of elasticity and the reduction of the coefficient of linear expansion, the inorganic filler may also include large particle size silica. Examples of the large particle size silica include those having an average particle size exceeding 2.0 μm and 75 μm or less, preferably 5.0 μm to 55 μm, and more preferably 8.0 μm to 20 μm.
於無機填充材包含二氧化矽的情況下，就混練性及填充性的觀點而言，二氧化矽的最大粒徑較佳為150 μm以下，更佳為75 μm以下，進而佳為55 μm以下。In the case where the inorganic filler contains silica, the maximum particle size of silica is preferably 150 μm or less, more preferably 75 μm or less, and more preferably 55 μm or less from the viewpoint of kneading and filling properties .
於無機填充材包含二氧化矽的情況下，相對於無機填充材的總質量，二氧化矽的含量較佳為0.1質量%～3.0質量%，更佳為0.1質量%～2.0質量%，進而佳為0.1質量%～1.0質量%。In the case where the inorganic filler contains silicon dioxide, the content of silicon dioxide is preferably 0.1% by mass to 3.0% by mass, more preferably 0.1% by mass to 2.0% by mass, and still more preferably, relative to the total mass of the inorganic filler. It is 0.1% by mass to 1.0% by mass.
一般而言，若環氧樹脂組成物含有微粒二氧化矽，則存在黏度上升的傾向。然而，發現第三實施形態的環氧樹脂組成物為低黏度，且存在如下傾向：即便含有微粒二氧化矽，亦可良好地抑制黏度的上升。In general, if the epoxy resin composition contains particulate silica, the viscosity tends to increase. However, it has been found that the epoxy resin composition of the third embodiment has a low viscosity and has a tendency that even if it contains fine silicon dioxide, the increase in viscosity can be suppressed satisfactorily.
[硬化劑] 第三實施形態的環氧樹脂組成物含有包含所述的通式（B）所表示的化合物（特定硬化劑）的硬化劑。硬化劑除了特定硬化劑以外亦可進一步併用其他硬化劑。硬化劑的詳情與第一實施形態中的硬化劑的詳情相同。[hardener] The epoxy resin composition of the third embodiment contains a curing agent containing the compound (specific curing agent) represented by the aforementioned general formula (B). In addition to the specific hardener, the hardener may be further used in combination with other hardeners. The details of the curing agent are the same as those of the curing agent in the first embodiment.
[硬化促進劑] 第三實施形態的環氧樹脂組成物亦可包含硬化促進劑。硬化促進劑的種類並無特別限制。硬化促進劑的詳情與第一實施形態中的硬化促進劑的詳情相同。[Hardening accelerator] The epoxy resin composition of the third embodiment may contain a hardening accelerator. The type of hardening accelerator is not particularly limited. The details of the hardening accelerator are the same as those of the hardening accelerator in the first embodiment.
[各種添加劑] 第三實施形態的環氧樹脂組成物除了所述成分以外，亦可包含偶合劑、離子交換體、脫模劑、阻燃劑、著色劑、應力緩和劑等各種添加劑。環氧樹脂組成物視需要亦可包含於本技術領域中周知的各種添加劑。各種添加劑的詳情與第一實施形態中的各種添加劑的詳情相同。[Various additives] The epoxy resin composition of the third embodiment may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a coloring agent, and a stress reliever in addition to the above-mentioned components. The epoxy resin composition may contain various additives well-known in this technical field as needed. The details of the various additives are the same as the details of the various additives in the first embodiment.
〔環氧樹脂組成物的製備方法〕 第三實施形態的環氧樹脂組成物的製備方法並無特別限制。第三實施形態的環氧樹脂組成物的製備方法的詳情與第一實施形態的環氧樹脂組成物的製備方法的詳情相同。[Preparation method of epoxy resin composition] The method of preparing the epoxy resin composition of the third embodiment is not particularly limited. The details of the method of preparing the epoxy resin composition of the third embodiment are the same as those of the method of preparing the epoxy resin composition of the first embodiment.
〔環氧樹脂組成物的用途〕 第三實施形態的環氧樹脂組成物可用於元件的密封用途。元件的密封方法並無特別限制，可為轉移成形法、噴射成形法、壓縮成形法等。〔Use of epoxy resin composition〕 The epoxy resin composition of the third embodiment can be used for sealing devices. The sealing method of the element is not particularly limited, and may be a transfer molding method, an injection molding method, a compression molding method, and the like.
〔環氧樹脂組成物的特性〕 發現第三實施形態的環氧樹脂組成物存在混練性優異的傾向。其理由未必明確，但可認為其原因在於：無機填充材的粒子的分散性良好，可抑制無機填充材彼此的摩擦，因此難以產生混練時的剪切發熱，從而可抑制由剪切發熱引起的環氧樹脂組成物的增稠。因而，存在即便提高無機填充材的含有率，亦可良好地製備環氧樹脂組成物的傾向。另外，特別是於將第三實施形態的環氧樹脂組成物供於壓縮成形的情況下，一般而言有時增加脫模劑的含量來維持混練性。然而，根據第三實施形態的環氧樹脂組成物，就減少成形物的表面的污垢、維持接著力、維持雷射打印性等觀點而言，存在如下傾向：即便減少脫模劑的含量（例如，相對於環氧樹脂的總質量而為3.0質量%以下，較佳為2.0質量%以下，更佳為1.5質量%以下），亦可良好地維持混練性。〔Characteristics of epoxy resin composition〕 It was found that the epoxy resin composition of the third embodiment tends to be excellent in kneading properties. The reason is not necessarily clear, but it can be considered that the dispersibility of the particles of the inorganic filler is good, and the friction between the inorganic fillers can be suppressed. Therefore, shear heat generation during kneading is difficult to generate, and the shear heat generation can be suppressed. Thickening of epoxy resin composition. Therefore, even if the content rate of the inorganic filler is increased, the epoxy resin composition tends to be prepared satisfactorily. In addition, especially when the epoxy resin composition of the third embodiment is provided for compression molding, generally, the content of the release agent may be increased to maintain the kneading property. However, according to the epoxy resin composition of the third embodiment, from the viewpoints of reducing dirt on the surface of the molded article, maintaining adhesive force, and maintaining laser printability, there is a tendency that even if the content of the release agent is reduced (for example, , Relative to the total mass of the epoxy resin, it is 3.0% by mass or less, preferably 2.0% by mass or less, more preferably 1.5% by mass or less), and the kneading property can also be maintained well.
（流動性） 發現第三實施形態的環氧樹脂組成物存在流動性優異的傾向。其理由未必明確，但可認為其原因在於：樹脂成分對無機填充材的潤濕性良好，因而微細的無機填充材的分散狀態良好，從而可抑制由摩擦引起的增稠。因而，例如於將第三實施形態的環氧樹脂組成物供於轉移成形的情況下，即便以高比例含有無機填充材，環氧樹脂組成物的流動性亦優異，因此有利。(fluidity) It was found that the epoxy resin composition of the third embodiment has a tendency to be excellent in fluidity. The reason is not necessarily clear, but it is thought that the reason is that the resin component has good wettability to the inorganic filler, and therefore the fine inorganic filler has a good dispersion state, so that thickening due to friction can be suppressed. Therefore, for example, when the epoxy resin composition of the third embodiment is used for transfer molding, even if an inorganic filler is contained in a high proportion, the epoxy resin composition has excellent fluidity, which is advantageous.
使用依據EMMI-1-66的旋流測定用模具，於模具溫度175℃、成形壓力6.9 MPa、硬化時間90秒的條件下將環氧樹脂組成物成形時的流動距離（吋（inch））較佳為40.0吋（1016 mm）以上，更佳為46.0吋（1168 mm）以上，進而佳為48.0吋（1219 mm）以上。另外，該流動距離可為70吋（1778 mm）以下。測定具體而言是利用實施例中記載的方法來進行。Using a mold for swirl flow measurement based on EMMI-1-66, the flow distance (inches) when the epoxy resin composition is molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds It is preferably 40.0 inches (1016 mm) or more, more preferably 46.0 inches (1168 mm) or more, and still more preferably 48.0 inches (1219 mm) or more. In addition, the flow distance can be 70 inches (1778 mm) or less. The measurement is specifically performed by the method described in the Example.
使用圓板流動測定用平板模具於180℃、負荷78 N、硬化時間90秒的條件下，對環氧樹脂組成物5 g進行壓縮成形時的圓盤流動（disk flow）較佳為80.0 mm以上，更佳為86.0 mm以上，進而佳為88.0 mm以上，特佳為90.0 mm以上。另外，圓盤流動亦可為160 mm以下。測定具體而言是利用實施例中記載的方法來進行。When using a plate mold for disk flow measurement at 180°C, a load of 78 N, and a curing time of 90 seconds, the disk flow when compressing 5 g of the epoxy resin composition is preferably 80.0 mm or more , More preferably 86.0 mm or more, still more preferably 88.0 mm or more, particularly preferably 90.0 mm or more. In addition, the disk flow can also be less than 160 mm. The measurement is specifically performed by the method described in the Example.
（熔解性） 發現第三實施形態的環氧樹脂組成物存在熔解性優異的傾向。因而，例如於將第三實施形態的環氧樹脂組成物供於壓縮成形的情況下，對狹路的填充性提高而較佳。(Solubility) It was found that the epoxy resin composition of the third embodiment has a tendency to be excellent in solubility. Therefore, for example, when the epoxy resin composition of the third embodiment is provided for compression molding, it is preferable to improve the filling property of the narrow path.
熔解性例如可利用實施例中記載的方法來評價。利用實施例中記載的方法所測定的熔解性較佳為40%以下，更佳為35%以下。The melting property can be evaluated, for example, by the method described in the examples. The melting property measured by the method described in the examples is preferably 40% or less, and more preferably 35% or less.
〔製成硬化物時的特性〕 （導熱率） 將環氧樹脂組成物製成硬化物時的導熱率並無特別限制。就獲得所期望的散熱性的觀點而言，導熱率於室溫（25℃）下可為3.0 W/（m·K）以上，亦可為4.0 W/（m·K）以上，亦可為5.0 W/（m·K）以上，亦可為5.4 W/（m·K）以上，亦可為6.0 W/（m·K）以上，亦可為7.0 W/（m·K）以上，亦可為8.0 W/（m·K）以上，亦可為9.0 W/（m·K）以上，亦可為10.0 W/（m·K）以上。硬化物的導熱率可利用氙閃光（Xe-flash）法（例如，耐馳（NETZSCH）公司製造，商品名：LFA467型 Hyper Flash裝置）來測定。〔Characteristics when made into hardened parts〕 (Thermal conductivity) The thermal conductivity when the epoxy resin composition is made into a hardened product is not particularly limited. From the viewpoint of obtaining the desired heat dissipation, the thermal conductivity can be 3.0 W/(m·K) or more at room temperature (25°C), or 4.0 W/(m·K) or more, or 5.0 W/(m·K) or more, or 5.4 W/(m·K) or more, or 6.0 W/(m·K) or more, or 7.0 W/(m·K) or more, also It can be 8.0 W/(m·K) or more, 9.0 W/(m·K) or more, or 10.0 W/(m·K) or more. The thermal conductivity of the cured product can be measured by the Xe-flash method (for example, manufactured by NETZSCH, trade name: LFA467 Hyper Flash device).
（彎曲強度） 將環氧樹脂組成物製成硬化物時的彎曲強度並無特別限定。例如硬化物的彎曲強度較佳為100 MPa以上，更佳為150 MPa以上，進而佳為160 MPa以上，特佳為165 MPa以上。彎曲強度的上限並無特別限制，例如可為250 MPa以下。硬化物的彎曲強度例如可利用實施例中記載的方法來測定。(Bending strength) The bending strength when the epoxy resin composition is made into a cured product is not particularly limited. For example, the bending strength of the cured product is preferably 100 MPa or more, more preferably 150 MPa or more, still more preferably 160 MPa or more, and particularly preferably 165 MPa or more. The upper limit of the bending strength is not particularly limited, and may be 250 MPa or less, for example. The bending strength of the cured product can be measured, for example, by the method described in the examples.
於第三實施形態的密封用環氧樹脂組成物的說明中，關於適用第一實施形態的說明的部位，將「第一實施形態」替換為「第三實施形態」。In the description of the epoxy resin composition for sealing of the third embodiment, the "first embodiment" is replaced with the "third embodiment" for the parts where the description of the first embodiment is applied.
＜電子零件裝置＞ 電子零件裝置包括：元件；以及密封所述元件的所述第一實施形態～第三實施形態的任一實施形態的環氧樹脂組成物的硬化物。 作為電子零件裝置，可列舉利用環氧樹脂組成物對如下元件部進行密封而得者，所述元件部是於引線框架、已配線的載帶、配線板、玻璃、矽晶圓、有機基板等支撐構件上搭載元件（半導體晶片、電晶體、二極體、閘流體等主動元件、電容器、電阻體、線圈等被動元件等）而獲得。 更具體而言，可列舉：雙列直插式封裝（Dual Inline Package，DIP）、塑膠引線晶片載體（Plastic Leaded Chip Carrier，PLCC）、四方扁平封裝（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）、薄型四方扁平封裝（Thin Quad Flat Package，TQFP）等一般的樹脂密封型IC，其具有在將元件固定在引線框架上且以打線接合、凸塊等連接接合墊等元件的端子部與引線部後，使用環氧樹脂組成物進行密封的結構；載帶封裝（Tape Carrier Package，TCP），其具有利用環氧樹脂組成物對以凸塊連接於載帶上的元件進行密封的結構；基板覆晶（Chip On Board，COB）模組、混合IC、多晶模組等，其具有利用環氧樹脂組成物對以打線接合、倒裝晶片接合、焊料等連接於支撐構件上所形成的配線上的元件進行密封的結構；球柵陣列（Ball Grid Array，BGA）、晶片尺寸封裝（Chip Size Package，CSP）、多晶片封裝（Multi Chip Package，MCP）等，其具有於背面形成配線板連接用端子的支撐構件的表面上搭載元件，並藉由凸塊或打線接合將元件與支撐構件上形成的配線連接後，利用環氧樹脂組成物密封元件的結構。另外，於印刷配線板中亦可較佳地使用環氧樹脂組成物。＜Electronic component device＞ The electronic component device includes: an element; and a cured product of the epoxy resin composition of any one of the first to third embodiments that seals the element. As an electronic component device, an epoxy resin composition can be used to seal the component parts such as lead frames, wired carrier tapes, wiring boards, glass, silicon wafers, organic substrates, etc. It is obtained by mounting components (active components such as semiconductor wafers, transistors, diodes, and thyristors, passive components such as capacitors, resistors, coils, etc.) on the supporting member. More specifically, it can include: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), small outline package (Small Outline Package, SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have an epoxy resin composition after the component is fixed to the lead frame and the terminal part and the lead part of the component such as a bonding pad are connected by wire bonding, bumps, etc. Structure; Tape Carrier Package (TCP), which has a structure that uses an epoxy resin composition to seal the components connected to the carrier tape by bumps; Chip On Board (COB) modules, Hybrid ICs, polycrystalline modules, etc., which have a structure that uses epoxy resin composition to seal components connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, etc.; ball grid array ( Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have components mounted on the surface of a supporting member that forms wiring board connection terminals on the back surface, and After connecting the element and the wiring formed on the supporting member by bumps or wire bonding, the structure of the element is sealed with an epoxy resin composition. In addition, an epoxy resin composition can also be preferably used in a printed wiring board.
作為使用環氧樹脂組成物來密封電子零件裝置的方法，可列舉：低壓轉移成形法、噴射成形法、壓縮成形法等。該些中一般而言為低壓轉移成形法。其中，於第二實施形態中電子零件裝置的密封是利用壓縮成形法來進行。As a method of sealing an electronic component device using an epoxy resin composition, a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like can be cited. These are generally low-pressure transfer molding methods. Among them, in the second embodiment, the sealing of the electronic component device is performed by the compression molding method.
《電子零件裝置的製造方法》 電子零件裝置的製造方法包括利用第一實施形態～第三實施形態的任一實施形態的環氧樹脂組成物密封元件。元件的密封方法並無特別限制，可列舉所述成形方法。其中，於第二實施形態中電子零件裝置的密封是利用壓縮成形法來進行。 [實施例]"Manufacturing Method of Electronic Component Device" The method of manufacturing an electronic component device includes sealing the element with the epoxy resin composition of any one of the first embodiment to the third embodiment. The sealing method of the element is not particularly limited, and the above-mentioned forming method can be mentioned. Among them, in the second embodiment, the sealing of the electronic component device is performed by the compression molding method. [Example]
以下，藉由實施例對本揭示的實施形態進行具體說明，但本揭示的實施形態並不限定於該些實施例。Hereinafter, the embodiments of the present disclosure will be described in detail through examples, but the embodiments of the present disclosure are not limited to these examples.
1.第一實施形態的實施例 〔環氧樹脂組成物的製備〕 ＜實施例1-1～實施例1-8及比較例1-1～比較例1-5＞ 將下述材料以表1中記載的組成（質量份）混合，於混練溫度80℃下進行輥混練，藉此分別製備實施例1-1～實施例1-8及比較例1-1～比較例1-5的環氧樹脂組成物。再者，表1中的「-」是指未調配所述成分。1. Examples of the first embodiment [Preparation of epoxy resin composition] <Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-5> The following materials were mixed with the composition (parts by mass) described in Table 1, and roll kneading was carried out at a kneading temperature of 80°C to prepare Example 1-1 to Example 1-8 and Comparative Example 1-1 to comparison. The epoxy resin composition of Examples 1-5. In addition, the "-" in Table 1 means that the ingredients are not formulated.
（環氧樹脂） 環氧樹脂1：環氧當量197 g/eq的鄰甲酚酚醛清漆型環氧樹脂（長春塑膠公司（Chang Chun Plastic Co., Ltd.），商品名「CNE-195LLB」） 環氧樹脂2：環氧當量250 g/eq、軟化點58℃的甲氧基萘-甲酚甲醛共縮合型環氧樹脂（迪愛生（DIC）股份有限公司，商品名「HP-5000」）(Epoxy resin) Epoxy resin 1: o-cresol novolak type epoxy resin with epoxy equivalent of 197 g/eq (Chang Chun Plastic Co., Ltd., trade name "CNE-195LLB") Epoxy resin 2: Methoxy naphthalene-cresol formaldehyde co-condensed epoxy resin with epoxy equivalent of 250 g/eq and softening point of 58°C (DIC Co., Ltd., trade name "HP-5000")
（硬化劑） 硬化劑1：羥基當量116 g/eq、軟化點64℃的鄰甲酚酚醛清漆樹脂（明和化成股份有限公司，商品名「MEH-5100-5S」） 硬化劑2：羥基當量117 g/eq、軟化點70℃的鄰甲酚酚醛清漆樹脂（明和化成股份有限公司，試製品） 硬化劑3：羥基當量117 g/eq、軟化點81℃的鄰甲酚酚醛清漆樹脂（迪愛生（DIC）股份有限公司，商品名「KA-1160」） 硬化劑A：羥基當量103 g/eq～107 g/eq、軟化點67℃～75℃的酚醛清漆型酚樹脂（明和化成股份有限公司，商品名「H-4」）(hardener) Hardener 1: Ortho-cresol novolac resin with a hydroxyl equivalent of 116 g/eq and a softening point of 64°C (Mingwa Chemical Co., Ltd., trade name "MEH-5100-5S") Hardener 2: Ortho-cresol novolak resin with a hydroxyl equivalent of 117 g/eq and a softening point of 70°C (Minghe Chemical Co., Ltd., trial product) Hardener 3: o-cresol novolak resin with hydroxyl equivalent of 117 g/eq and softening point of 81°C (DIC Co., Ltd., trade name "KA-1160") Hardener A: Novolac-type phenol resin with hydroxyl equivalent weight of 103 g/eq～107 g/eq and softening point of 67℃～75℃ (Mingwa Chemical Co., Ltd., trade name "H-4")
（硬化促進劑） 硬化促進劑：三苯基膦與1,4-苯醌的加成反應物 （無機填充材） 熔融二氧化矽（球狀熔融二氧化矽，平均粒徑17.5 μm，比表面積3.8 m2 /g） （偶合劑） 偶合劑：環氧基矽烷（γ-縮水甘油氧基丙基三甲氧基矽烷） （著色劑） 碳黑（三菱化學股份有限公司，商品名「MA-100」） （脫模劑） 棕櫚蠟（Cerarica NODA股份有限公司）(Hardening accelerator) Hardening accelerator: addition reactant of triphenylphosphine and 1,4-benzoquinone (inorganic filler) fused silica (spherical fused silica, average particle size 17.5 μm, specific surface area) 3.8 m 2 /g) (Coupling agent) Coupling agent: Epoxysilane (γ-glycidoxypropyltrimethoxysilane) (colorant) Carbon black (Mitsubishi Chemical Co., Ltd., trade name "MA-100 ") (Release agent) Carnauba wax (Cerarica NODA Co., Ltd.)
[表1]
〔環氧樹脂組成物的評價〕 藉由以下的特性試驗來評價實施例1-1～實施例1-8及比較例1-1～比較例1-5中製備的環氧樹脂組成物的特性。將評價結果示於下述表2中。再者，只要未標明，則環氧樹脂組成物的成形是藉由轉移成形機並於模具溫度175℃、成形壓力6.9 MPa、硬化時間90秒的條件下成形。另外，視需要於175℃、5小時的條件下進行後硬化。[Evaluation of epoxy resin composition] The characteristics of the epoxy resin compositions prepared in Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-5 were evaluated by the following characteristic test. The evaluation results are shown in Table 2 below. In addition, unless otherwise specified, the epoxy resin composition is molded by a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. In addition, post-curing is performed at 175°C for 5 hours as necessary.
（1）旋流 使用依據EMMI-1-66的旋流測定用模具，於所述條件下將環氧樹脂組成物成形並求出流動距離（cm）。(1) Swirl Using a mold for swirling flow measurement based on EMMI-1-66, the epoxy resin composition was molded under the conditions described above, 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，成形後立即使用蕭氏D型硬度計（上島製作所股份有限公司，HD-1120（D型））來進行測定。(2) Hardness when hot The epoxy resin composition was molded into a circular plate with a diameter of 50 mm × a thickness of 3 mm under the above-mentioned conditions, and immediately after the molding, a Shore D hardness tester (Ueshima Manufacturing Co., Ltd., HD-1120 (D type)) Perform the measurement.
（3）260℃彈性係數測定 將環氧樹脂組成物於所述條件下成形為長度50 mm×寬度5 mm×厚度2 mm的尺寸，並於所述條件下進行後硬化。之後，使用黏彈性測定裝置RSA-3（TA儀器（TA Instruments）公司），利用三點彎曲模式於升溫速度10℃/min、頻率1 Hz的條件下進行測定。根據測定結果，讀取260℃下的彈性係數（GPa）。(3) Determination of the coefficient of elasticity at 260°C The epoxy resin composition was molded into a size of 50 mm in length × 5 mm in width × 2 mm in thickness under the conditions, and post-curing was performed under the conditions. After that, the viscoelasticity measuring device RSA-3 (TA Instruments) was used to perform the measurement under the conditions of a temperature increase rate of 10°C/min and a frequency of 1 Hz in a three-point bending mode. According to the measurement results, read the coefficient of elasticity (GPa) at 260°C.
（4）吸水率 於所述條件下對所述（2）中成形的圓板進行後硬化。之後，將所獲得的圓板於85℃、60%RH（相對濕度）的條件下放置168小時，並測定放置前後的質量變化。根據測定結果並藉由下述式來計算吸水率。 吸水率（質量%）=[（放置後的圓板質量-放置前的圓板質量）/放置前的圓板質量]×100(4) Water absorption The round plate formed in (2) is post-cured under the conditions. After that, the obtained disc was left under the conditions of 85° C. and 60% RH (relative humidity) for 168 hours, and the mass change before and after being left was measured. Based on the measurement results, the water absorption is calculated by the following formula. Water absorption (mass%)=[(the mass of the disc after placement-the mass of the disc before placement)/the mass of the disc before placement]×100
（5）耐回焊性 針對搭載有8 mm×10 mm×0.4 mm的矽晶片的外形尺寸20 mm×14 mm×2 mm的80引腳扁平封裝（QFP）（引線框架材質：銅合金，晶片墊部上表面及引線前端鍍銀的處理品），使用環氧樹脂組成物於所述條件下進行成形，於所述條件下進行後硬化。將所獲得的封裝於85℃、60%RH的條件下加濕168小時。之後，於規定溫度（250℃、260℃、270℃）、10秒的條件下分別進行回焊處理，以目視觀察封裝外部的裂紋的有無，並利用超音波探傷裝置（日立建機股份有限公司，HYE-FOCUS）觀察封裝內部的剝離產生的有無。以相對於試驗封裝數（10）的產生裂紋及剝離的至少一者的封裝數的總和來評價耐回焊性。(5) Reflow resistance For an 80-pin flat package (QFP) with an external size of 20 mm×14 mm×2 mm mounted with a silicon chip of 8 mm×10 mm×0.4 mm (lead frame material: copper alloy, the upper surface of the chip pad and the tip of the lead) Silver-plated processed product), molded under the above conditions using an epoxy resin composition, and post-cured under the above conditions. The obtained package was humidified for 168 hours under the conditions of 85° C. and 60% RH. After that, reflow treatment was performed under the conditions of predetermined temperature (250°C, 260°C, 270°C) for 10 seconds, and the presence or absence of cracks on the outside of the package was visually observed, and ultrasonic flaw detection equipment (Hitachi Construction Machinery Co., Ltd.) , HYE-FOCUS) Observe whether there is peeling inside the package. The reflow resistance was evaluated by the sum of the number of packages in which at least one of cracks and peeling occurred relative to the number of test packages (10).
[表2]
如表1及表2所示，藉由使用含有硬化劑1～硬化劑3的實施例1-1～實施例1-8的環氧樹脂組成物，與使用不含有硬化劑1～硬化劑3的比較例1-1～比較例1-5的環氧樹脂組成物的情況相比，高溫的彈性係數下降，耐回焊性亦提高。高溫彈性係數的下降程度是超出根據樹脂的結構或羥基當量預測的結果。藉此，認為顯示出超出預測的耐回焊性。另外，使用硬化劑1作為硬化劑的一部分的實施例1-5的彈性係數下降率超出根據調配比率假定的值，即便使用特定硬化劑作為硬化劑的一部分，亦超出預測地發揮良好的耐回焊性。As shown in Table 1 and Table 2, by using the epoxy resin composition of Example 1-1 to Example 1-8 containing hardener 1 to hardener 3, and using the epoxy resin composition that does not contain hardener 1 to hardener 3 Compared with the epoxy resin composition of Comparative Example 1-1 to Comparative Example 1-5, the high-temperature elastic modulus is lowered, and the reflow resistance is also improved. The degree of decrease in the high-temperature elasticity coefficient is beyond the result predicted based on the structure of the resin or the hydroxyl equivalent. As a result, it is considered that the reflow resistance exceeding the prediction is exhibited. In addition, the modulus of elasticity reduction rate of Examples 1-5 using hardener 1 as a part of the hardener exceeds the value assumed based on the blending ratio, and even if a specific hardener is used as part of the hardener, it exhibits good resistance to aging beyond the predicted value. Weldability.
＜實施例1-9～實施例1-10及比較例1-6～比較例1-10＞ 〔環氧樹脂組成物的製備〕 將下述材料以表3及表4中記載的組成混合，於混練溫度100℃的條件下使用雙軸混練機進行混練，藉此分別製備實施例及比較例的環氧樹脂組成物。再者，以下的表中的「-」是指未調配所述成分。<Example 1-9 to Example 1-10 and Comparative Example 1-6 to Comparative Example 1-10> [Preparation of epoxy resin composition] The following materials were mixed with the compositions described in Tables 3 and 4, and kneaded using a biaxial kneader at a kneading temperature of 100°C to prepare epoxy resin compositions of Examples and Comparative Examples, respectively. In addition, "-" in the following table means that the above-mentioned ingredients are not blended.
（環氧樹脂） 環氧樹脂1：二苯基甲烷型環氧樹脂（商品名：YSLV-80XY，日鐵化學&材料股份有限公司，環氧當量190 g/eq） 環氧樹脂2：聯苯型環氧樹脂（商品名：YX-4000，三菱化學股份有限公司，環氧當量190 g/eq） 環氧樹脂3：三苯基甲烷型環氧樹脂（多官能型（商品名：1032H60，三菱化學股份有限公司，環氧當量170 g/eq））(Epoxy resin) Epoxy resin 1: Diphenylmethane type epoxy resin (trade name: YSLV-80XY, Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 190 g/eq) Epoxy resin 2: Biphenyl type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent 190 g/eq) Epoxy resin 3: Triphenylmethane type epoxy resin (multifunctional type (trade name: 1032H60, Mitsubishi Chemical Corporation, epoxy equivalent 170 g/eq))
（硬化劑） ·硬化劑1：酚醛清漆型酚樹脂（商品名：H-4，明和化成股份有限公司，羥基當量103 g/eq～107 g/eq，軟化點67℃～75℃） ·硬化劑2：芳烷基型酚樹脂（商品名：MEHC7800-4S，明和化成股份有限公司，羥基當量167 g/eq～179 g/eq，軟化點61℃～65℃） ·硬化劑3：鄰甲酚酚醛清漆樹脂（商品名：MEH5100-5S，明和化成股份有限公司，羥基當量116 g/eq，軟化點65℃；通式（B）所表示的化合物） ·硬化劑4：芳烷基型酚樹脂（商品名：MEHC7851-SS，明和化成股份有限公司，羥基當量201 g/eq～205 g/eq，軟化點64℃～69℃） ·硬化劑5：三苯基甲烷型酚樹脂（商品名：MEH-7500-3S，明和化成股份有限公司，羥基當量103 g/eq）(hardener) · Hardener 1: Novolac type phenol resin (trade name: H-4, Minghe Chemical Co., Ltd., hydroxyl equivalent 103 g/eq～107 g/eq, softening point 67℃～75℃) · Hardener 2: Aralkyl phenol resin (trade name: MEHC7800-4S, Minghe Chemical Co., Ltd., hydroxyl equivalent 167 g/eq～179 g/eq, softening point 61℃～65℃) · Hardener 3: o-cresol novolac resin (trade name: MEH5100-5S, Minghe Chemical Co., Ltd., hydroxyl equivalent 116 g/eq, softening point 65°C; compound represented by general formula (B)) · Hardener 4: Aralkyl phenol resin (trade name: MEHC7851-SS, Minghe Chemical Co., Ltd., hydroxyl equivalent 201 g/eq～205 g/eq, softening point 64℃～69℃) · Hardener 5: Triphenylmethane type phenol resin (trade name: MEH-7500-3S, Minghe Chemical Co., Ltd., hydroxyl equivalent 103 g/eq)
（無機填充材） ·無機填充材1：微粒子氧化鋁（平均粒徑0.4 μm，最大粒徑2.0 μm） ·無機填充材2：大粒子氧化鋁（平均粒徑10 μm，最大粒徑75 μm） ·無機填充材3：超微細二氧化矽（平均粒徑0.1 μm） ·無機填充材4：微粒子二氧化矽（平均粒徑0.4 μm，最大粒徑2.0 μm） ·無機填充材5：大粒子二氧化矽（平均粒徑12 μm，最大粒徑75 μm）(Inorganic filler) ·Inorganic filler 1: Fine particle alumina (average particle size 0.4 μm, maximum particle size 2.0 μm) ·Inorganic filler 2: Large particle alumina (average particle size 10 μm, maximum particle size 75 μm) ·Inorganic filler 3: Ultra-fine silica (average particle size 0.1 μm) ·Inorganic filler 4: Micro-particle silica (average particle size 0.4 μm, maximum particle size 2.0 μm) ·Inorganic filler 5: Large particles of silicon dioxide (average particle size 12 μm, maximum particle size 75 μm)
（硬化促進劑） ·硬化促進劑：三苯基膦與1,4-苯醌的加成反應物(Hardening accelerator) · Hardening accelerator: addition reactant of triphenylphosphine and 1,4-benzoquinone
（其他添加劑） ·偶合劑：N-苯基-3-胺基丙基三甲氧基矽烷（商品名：KBM-573，信越化學工業股份有限公司） ·脫模劑：棕櫚蠟 ·著色劑：碳黑 ·離子交換體：商品名：DHT-4A，協和化學工業股份有限公司(Other additives) ·Coupling agent: N-phenyl-3-aminopropyl trimethoxysilane (trade name: KBM-573, Shin-Etsu Chemical Industry Co., Ltd.) ·Release agent: palm wax ·Coloring agent: carbon black ·Ion Exchanger: Trade name: DHT-4A, Xiehe Chemical Industry Co., Ltd.
〔環氧樹脂組成物的評價〕 藉由以下的特性試驗來評價實施例及比較例中製備的環氧樹脂組成物的特性。再者，只要未標明，則環氧樹脂組成物的成形是藉由轉移成形機並於模具溫度175℃、成形壓力6.9 MPa、硬化時間90秒的條件下成形。另外，視需要於175℃、5小時的條件下進行後硬化。[Evaluation of epoxy resin composition] The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests. In addition, unless otherwise specified, the epoxy resin composition is molded by a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. In addition, post-curing is performed at 175°C for 5 hours as necessary.
（1）旋流 使用依據EMMI-1-66的旋流測定用模具，於所述條件下將環氧樹脂組成物成形並求出流動距離（吋）。關於流動距離為40.0吋以上者，判斷為流動性良好。(1) Swirl Using a mold for swirl flow measurement based on EMMI-1-66, the epoxy resin composition was molded under the conditions described above, and the flow distance (inch) was calculated. If the flow distance is 40.0 inches or more, it is judged that the flowability is good.
（2）熱時硬度 利用高溫真空成型機，並於175℃、600秒、壓力7 MPa的條件下將環氧樹脂組成物加以成形，使用蕭氏D型硬度計（上島製作所股份有限公司，HD-1120（D型））進行測定，將所得的值設為硬度。於熱時硬度為70以上的情況下，判斷為硬化性良好。(2) Hardness when hot Using a high-temperature vacuum molding machine, the epoxy resin composition was molded under the conditions of 175°C, 600 seconds, and a pressure of 7 MPa, using a Shore D hardness tester (Ueshima Manufacturing Co., Ltd., HD-1120 (D type) ) Perform measurement, and set the obtained value as hardness. When the hardness during heat is 70 or more, it is judged that the hardenability is good.
（3）圓板流動 使用具有200 mm（W）×200 mm（D）×25 mm（H）的上模具與200 mm（W）×200 mm（D）×15 mm（H）的下模具的圓板流動測定用平板模具，將利用盤式天平秤秤量的環氧樹脂組成物5 g載置於加熱為180℃的下模具的中心部，於5秒後關閉加熱為180℃的上模具，於負荷78 N、硬化時間90秒的條件下進行壓縮成形，利用游標卡尺測定成形品的長徑（mm）及短徑（mm），將其平均值（mm）設為圓盤流動。關於圓盤流動為80 mm以上者，判斷為流動性良好。(3) Circular plate flow Use a circular plate for flow measurement with an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H) In the mold, 5 g of the epoxy resin composition weighed by a pan balance is placed in the center of the lower mold heated to 180°C, and the upper mold heated to 180°C is closed after 5 seconds, and cured under a load of 78 N Compression molding was performed under the condition of a time of 90 seconds, the long diameter (mm) and short diameter (mm) of the molded product were measured with a vernier caliper, and the average value (mm) was set as a disk flow. When the disk flow is 80 mm or more, it is judged that the flowability is good.
（4）175℃下的熔融黏度（ηFT） 對環氧樹脂組成物進行加熱而使其熔融，使用高化型流動度試驗儀（Koka-type flow tester）測定175℃下的熔融黏度。 關於熔融黏度為250 Pa·s以下者，判斷為低黏度。(4) Melt viscosity (ηFT) at 175℃ The epoxy resin composition was heated to melt, and the melt viscosity at 175°C was measured using a Koka-type flow tester (Koka-type flow tester). If the melt viscosity is 250 Pa·s or less, it is judged to be a low viscosity.
（5）導熱率 使用環氧樹脂組成物，藉由壓縮成形機，於模具溫度175℃～180℃、成形壓力7 MPa、硬化時間150秒的條件下密封半導體元件，製作導熱率評價用試驗片。繼而，藉由氙閃光（Xe-flash）法測定試驗片的導熱率。關於導熱率（λ）為5.0 W/（m·℃）者，判斷為導熱率優異。(5) Thermal conductivity Using an epoxy resin composition, the semiconductor element was sealed with a compression molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a curing time of 150 seconds to prepare a test piece for thermal conductivity evaluation. Then, the thermal conductivity of the test piece was measured by the Xe-flash method. With regard to the thermal conductivity (λ) of 5.0 W/(m·°C), it is judged that the thermal conductivity is excellent.
（6）彎曲強度 將實施例及比較例中所獲得的環氧樹脂組成物的硬化物切成2.0 mm×5.0 mm×40 mm的長方體，製作彎曲強度評價用試驗片。使用該試驗片，利用騰喜龍（Tensilon）萬能材料試驗機（英斯特朗（Instron）5948，英斯特朗（Instron）公司）於支點間距離32 mm、十字頭速度1 mm/min的條件下進行彎曲試驗。使用測定的結果，根據式（1）製成彎曲應力-位移曲線，將所述最大應力設為彎曲強度。 σ=3FL/2bh2 ···式（1） σ：彎曲應力（MPa） F：彎曲負荷（N） L：支點間距離（mm） b：試驗片寬度（mm） h：試驗片厚度（mm）(6) Bending strength The cured product of the epoxy resin composition obtained in the Examples and Comparative Examples was cut into a rectangular parallelepiped of 2.0 mm×5.0 mm×40 mm to prepare a test piece for bending strength evaluation. Using this test piece, use Tensilon universal material testing machine (Instron 5948, Instron) at a distance of 32 mm between fulcrums and a crosshead speed of 1 mm/min. Perform a bending test under. Using the result of the measurement, a bending stress-displacement curve was created according to formula (1), and the maximum stress was set as the bending strength. σ=3FL/2bh 2 ···Formula (1) σ: bending stress (MPa) F: bending load (N) L: distance between fulcrums (mm) b: test piece width (mm) h: test piece thickness (mm) )
[表3]
[表4]
根據表3及表4可知，與比較例的環氧樹脂組成物相比，實施例的環氧樹脂組成物的流動性高，即便於使用粒徑較小的無機填充材的情況下亦可抑制黏度的上升及流動性的降低。另外，實施例的環氧樹脂組成物中亦可維持良好的硬化性。From Tables 3 and 4, it can be seen that, compared with the epoxy resin composition of the comparative example, the epoxy resin composition of the example has higher fluidity, and it can be suppressed even when an inorganic filler with a smaller particle size is used. Increase in viscosity and decrease in fluidity. In addition, the epoxy resin composition of the examples can also maintain good curability.
2.第二實施形態的實施例2. Example of the second embodiment
〔環氧樹脂組成物的製備〕 將下述材料以表5及表6中記載的組成混合，於混練溫度100℃的條件下使用雙軸混練機進行混練，藉此分別製備實施例及比較例的環氧樹脂組成物。再者，以下的表中的「-」是指未調配所述成分。[Preparation of epoxy resin composition] The following materials were mixed with the compositions described in Table 5 and Table 6, and kneaded using a biaxial kneader under the condition of a kneading temperature of 100° C., to prepare epoxy resin compositions of Examples and Comparative Examples, respectively. In addition, "-" in the following table means that the above-mentioned ingredients are not blended.
（環氧樹脂） 環氧樹脂1：二苯基甲烷型環氧樹脂（商品名：YSLV-80XY，日鐵化學&材料股份有限公司，環氧當量190 g/eq） 環氧樹脂2：聯苯型環氧樹脂（商品名：YX-4000，三菱化學股份有限公司，環氧當量190 g/eq） 環氧樹脂3：三苯基甲烷型環氧樹脂（多官能型（商品名：1032H60，三菱化學股份有限公司，環氧當量170 g/eq））(Epoxy resin) Epoxy resin 1: Diphenylmethane type epoxy resin (trade name: YSLV-80XY, Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 190 g/eq) Epoxy resin 2: Biphenyl type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent 190 g/eq) Epoxy resin 3: Triphenylmethane type epoxy resin (multifunctional type (trade name: 1032H60, Mitsubishi Chemical Corporation, epoxy equivalent 170 g/eq))
（硬化劑） ·硬化劑1：酚醛清漆型酚樹脂（商品名：H-4，明和化成股份有限公司，羥基當量103 g/eq～107 g/eq，軟化點67℃～75℃） ·硬化劑2：芳烷基型酚樹脂（商品名：MEHC7800-4S，明和化成股份有限公司，羥基當量167 g/eq～179 g/eq，軟化點61℃～65℃） ·硬化劑3：鄰甲酚酚醛清漆樹脂（商品名：MEH5100-5S，明和化成股份有限公司，羥基當量116 g/eq，軟化點65℃；通式（B）所表示的化合物） ·硬化劑4：芳烷基型酚樹脂（商品名：MEHC7851-SS，明和化成股份有限公司，羥基當量201 g/eq～205 g/eq，軟化點64℃～69℃） ·硬化劑5：三苯基甲烷型酚樹脂（商品名：MEH-7500-3S，明和化成股份有限公司，羥基當量103 g/eq）(hardener) · Hardener 1: Novolac type phenol resin (trade name: H-4, Minghe Chemical Co., Ltd., hydroxyl equivalent 103 g/eq～107 g/eq, softening point 67℃～75℃) · Hardener 2: Aralkyl phenol resin (trade name: MEHC7800-4S, Minghe Chemical Co., Ltd., hydroxyl equivalent 167 g/eq～179 g/eq, softening point 61℃～65℃) · Hardener 3: o-cresol novolac resin (trade name: MEH5100-5S, Minghe Chemical Co., Ltd., hydroxyl equivalent 116 g/eq, softening point 65°C; compound represented by general formula (B)) · Hardener 4: Aralkyl phenol resin (trade name: MEHC7851-SS, Minghe Chemical Co., Ltd., hydroxyl equivalent 201 g/eq～205 g/eq, softening point 64℃～69℃) · Hardener 5: Triphenylmethane type phenol resin (trade name: MEH-7500-3S, Minghe Chemical Co., Ltd., hydroxyl equivalent 103 g/eq)
（無機填充材） ·無機填充材1：微粒子氧化鋁（平均粒徑0.4 μm，最大粒徑2.0 μm） ·無機填充材2：大粒子氧化鋁（平均粒徑10 μm，最大粒徑75 μm） ·無機填充材3：超微細二氧化矽（平均粒徑0.1 μm） ·無機填充材4：微粒子二氧化矽（平均粒徑0.4 μm，最大粒徑2.0 μm） ·無機填充材5：大粒子二氧化矽（平均粒徑12 μm，最大粒徑75 μm）(Inorganic filler) ·Inorganic filler 1: Fine particle alumina (average particle size 0.4 μm, maximum particle size 2.0 μm) ·Inorganic filler 2: Large particle alumina (average particle size 10 μm, maximum particle size 75 μm) ·Inorganic filler 3: Ultra-fine silica (average particle size 0.1 μm) ·Inorganic filler 4: Micro-particle silica (average particle size 0.4 μm, maximum particle size 2.0 μm) ·Inorganic filler 5: Large particles of silicon dioxide (average particle size 12 μm, maximum particle size 75 μm)
（硬化促進劑） ·硬化促進劑：三苯基膦與1,4-苯醌的加成反應物(Hardening accelerator) · Hardening accelerator: addition reactant of triphenylphosphine and 1,4-benzoquinone
（其他添加劑） ·偶合劑：N-苯基-3-胺基丙基三甲氧基矽烷（商品名：KBM-573，信越化學工業股份有限公司） ·脫模劑：棕櫚蠟 ·著色劑：碳黑 ·離子交換體：商品名：DHT-4A，協和化學工業股份有限公司(Other additives) ·Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (trade name: KBM-573, Shin-Etsu Chemical Industry Co., Ltd.) ·Release agent: palm wax ·Coloring agent: carbon black ·Ion Exchanger: Trade name: DHT-4A, Xiehe Chemical Industry Co., Ltd.
〔環氧樹脂組成物的評價〕 藉由以下的特性試驗來評價實施例及比較例中製備的環氧樹脂組成物的特性。[Evaluation of epoxy resin composition] The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests.
（1）熔解性 準備約1.5 g的環氧樹脂組成物的粉末（通過3.5 mm篩目（mesh-pass）、不通過1.0 mm篩目（mesh-on））。於加熱為175℃的熱板上，以成為面內圓形形狀且高度約3 mm的方式設置環氧樹脂組成物的粉末。於其上使同樣加熱為175℃的200 g的模具於水平方向上自由落下。上模具由下模具與垂直支柱支撐，因此可於面內施加一定的負荷。將上模具的落下的時間點（上模具到達粉末上表面的時間點）設為測定0秒，藉由雷射位移計測定自粉末開始熔解後的上模具的落下距離。將0秒時間點的高度設為A，將一秒後的高度設為B，利用（B/A）×100（%）計算，評價粉末的熔解性。 於一秒內環氧樹脂組成物的高度為40%以下的情況下，判斷為熔解性良好。(1) Meltability Prepare about 1.5 g of epoxy resin composition powder (passing 3.5 mm mesh-pass, but not 1.0 mm mesh-on). On a hot plate heated at 175°C, the epoxy resin composition powder was placed so as to have an in-plane circular shape and a height of about 3 mm. A 200 g mold, also heated to 175°C, was freely dropped on it in the horizontal direction. The upper mold is supported by the lower mold and the vertical pillars, so a certain load can be applied in the plane. The time point when the upper mold fell (the time point when the upper mold reached the upper surface of the powder) was set to 0 seconds for measurement, and the distance of the upper mold falling after the powder began to melt was measured with a laser displacement meter. The height at the time point of 0 seconds was set to A, and the height after one second was set to B, and the powder was calculated by (B/A)×100 (%) to evaluate the solubility of the powder. When the height of the epoxy resin composition is 40% or less in one second, it is judged that the meltability is good.
（2）熱時硬度 利用高溫真空成型機將環氧樹脂組成物於175℃、90秒、壓力7 MPa的條件下成形，使用蕭氏D型硬度計（上島製作所股份有限公司，HD-1120（D型））來進行測定，將所得的值設為硬度。於熱時硬度為70以上的情況下，判斷為硬化性良好。(2) Hardness when hot The epoxy resin composition is molded by a high-temperature vacuum molding machine at 175°C, 90 seconds, and a pressure of 7 MPa, using a Shore D hardness tester (Ueshima Seisakusho Co., Ltd., HD-1120 (D type)) It is measured, and the obtained value is made into hardness. When the hardness during heat is 70 or more, it is judged that the hardenability is good.
（3）圓板流動 使用具有200 mm（W）×200 mm（D）×25 mm（H）的上模具與200 mm（W）×200 mm（D）×15 mm（H）的下模具的圓板流動測定用平板模具，將利用盤式天平秤秤量的環氧樹脂組成物5 g載置於加熱為180℃的下模具的中心部，於5秒後關閉加熱為180℃的上模具，於負荷78 N、硬化時間90秒的條件下進行壓縮成形，利用游標卡尺測定成形品的長徑（mm）及短徑（mm），將其平均值（mm）設為圓盤流動。關於圓盤流動為80 mm以上者，判斷為流動性良好。(3) Circular plate flow Use a circular plate for flow measurement with an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H) In the mold, 5 g of the epoxy resin composition weighed by a pan balance is placed in the center of the lower mold heated to 180°C, and the upper mold heated to 180°C is closed after 5 seconds, and cured under a load of 78 N Compression molding was performed under the condition of a time of 90 seconds, the long diameter (mm) and short diameter (mm) of the molded product were measured with a vernier caliper, and the average value (mm) was set as a disk flow. When the disk flow is 80 mm or more, it is judged that the flowability is good.
（4）175℃下的熔融黏度（ηFT） 對環氧樹脂組成物進行加熱而使其熔融，使用高化型流動度試驗儀測定175℃下的熔融黏度。 關於熔融黏度為250 Pa·s以下者，判斷為低黏度。(4) Melt viscosity (ηFT) at 175℃ The epoxy resin composition was heated to melt, and the melt viscosity at 175°C was measured using a Koka type fluidity tester. If the melt viscosity is 250 Pa·s or less, it is judged to be a low viscosity.
（5）導熱率 使用環氧樹脂組成物，藉由壓縮成形機，於模具溫度175℃～180℃、成形壓力7 MPa、硬化時間150秒的條件下密封半導體元件，製作導熱率評價用試驗片。繼而，藉由氙閃光（Xe-flash）法測定試驗片的導熱率。關於導熱率（λ）為5.0 W/（m·℃）者，判斷為導熱率優異。(5) Thermal conductivity Using an epoxy resin composition, the semiconductor element was sealed with a compression molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a curing time of 150 seconds to prepare a test piece for thermal conductivity evaluation. Then, the thermal conductivity of the test piece was measured by the Xe-flash method. With regard to the thermal conductivity (λ) of 5.0 W/(m·°C), it is judged that the thermal conductivity is excellent.
[表5]
[表6]
根據表5及表6可知，實施例的環氧樹脂組成物的熔解性優異。另外，實施例的環氧樹脂組成物中亦可維持良好的硬化性。 另外，實施例的環氧樹脂組成物中圓板流動、熔融黏度的評價的任一者中亦可獲得良好的結果。From Table 5 and Table 6, it can be seen that the epoxy resin composition of the example has excellent melting properties. In addition, the epoxy resin composition of the examples can also maintain good curability. In addition, in the epoxy resin composition of the examples, good results were also obtained in any of the evaluation of the flow of the disk and the melt viscosity.
3.第三實施形態的實施例 〔環氧樹脂組成物的製備〕 將下述材料以表7中記載的組成混合，於混練溫度100℃的條件下利用雙軸混練機分別製備實施例及比較例的環氧樹脂組成物。再者，表7中的「-」是指未調配所述成分。3. Examples of the third embodiment [Preparation of epoxy resin composition] The following materials were mixed with the composition described in Table 7, and the epoxy resin compositions of the Examples and Comparative Examples were prepared using a biaxial kneader under the condition of a kneading temperature of 100°C. In addition, "-" in Table 7 means that the above-mentioned ingredients are not blended.
（環氧樹脂） 環氧樹脂1：二苯基甲烷型環氧樹脂（雙酚型環氧樹脂）（商品名：YSLV-80XY，日鐵化學&材料股份有限公司，環氧當量190 g/eq） 環氧樹脂2：聯苯型環氧樹脂（商品名：YX-4000，三菱化學股份有限公司，環氧當量190 g/eq）(Epoxy resin) Epoxy resin 1: Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (trade name: YSLV-80XY, Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 190 g/eq) Epoxy resin 2: Biphenyl type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent 190 g/eq)
（硬化劑） ·硬化劑1：酚醛清漆型酚樹脂（商品名：H-4，明和化成股份有限公司，羥基當量103 g/eq～107 g/eq，軟化點67℃～75℃） ·硬化劑2：鄰甲酚酚醛清漆樹脂（商品名：MEH5100-5S，明和化成股份有限公司，羥基當量116 g/eq，軟化點65℃；通式（B）所表示的化合物） ·硬化劑3：芳烷基型酚樹脂（商品名：MEHC7800-4S，羥基當量167 g/eq～179 g/eq，軟化點61℃～65℃） ·硬化劑4：芳烷基型酚樹脂（商品名：MEHC7851-SS，明和化成股份有限公司，羥基當量201 g/eq～205 g/eq，軟化點64℃～69℃）(hardener) · Hardener 1: Novolac type phenol resin (trade name: H-4, Minghe Chemical Co., Ltd., hydroxyl equivalent 103 g/eq～107 g/eq, softening point 67℃～75℃) · Hardener 2: o-cresol novolac resin (trade name: MEH5100-5S, Minghe Chemical Co., Ltd., hydroxyl equivalent 116 g/eq, softening point 65°C; compound represented by general formula (B)) · Hardener 3: Aralkyl phenol resin (trade name: MEHC7800-4S, hydroxyl equivalent 167 g/eq～179 g/eq, softening point 61℃～65℃) · Hardener 4: Aralkyl phenol resin (trade name: MEHC7851-SS, Minghe Chemical Co., Ltd., hydroxyl equivalent 201 g/eq～205 g/eq, softening point 64℃～69℃)
（無機填充材） ·無機填充材1：微粒子氧化鋁（平均粒徑0.4 μm，最大粒徑2.0 μm左右） ·無機填充材2：大粒子氧化鋁（平均粒徑10 μm，最大粒徑75 μm） ·無機填充材3：超微細二氧化矽（平均粒徑0.1 μm，最大粒徑2.0 μm左右）(Inorganic filler) ·Inorganic filler 1: Microparticle alumina (average particle size 0.4 μm, maximum particle size about 2.0 μm) ·Inorganic filler 2: Large particle alumina (average particle size 10 μm, maximum particle size 75 μm) ·Inorganic filler 3: Ultra-fine silica (average particle size of 0.1 μm, maximum particle size of about 2.0 μm)
（硬化促進劑） ·硬化促進劑：磷系硬化促進劑(Hardening accelerator) · Hardening accelerator: Phosphorus-based hardening accelerator
（其他添加劑） ·偶合劑：N-苯基-3-胺基丙基三甲氧基矽烷（商品名：KBM-573，信越化學工業股份有限公司） ·脫模劑：棕櫚蠟 ·著色劑：碳黑 ·離子交換體：水滑石類化合物（商品名：DHT-4A，協和化學工業股份有限公司）(Other additives) ·Coupling agent: N-phenyl-3-aminopropyl trimethoxysilane (trade name: KBM-573, Shin-Etsu Chemical Industry Co., Ltd.) ·Release agent: palm wax ·Coloring agent: carbon black ·Ion exchanger: Hydrotalcite compounds (trade name: DHT-4A, Xiehe Chemical Industry Co., Ltd.)
〔評價〕 藉由以下的特性試驗來評價實施例及比較例中製備的環氧樹脂組成物的特性。再者，只要未標明，則環氧樹脂組成物的成形是藉由轉移成形機並於模具溫度175℃、成形壓力6.9 MPa、硬化時間90秒的條件下成形。另外，視需要於175℃、5小時的條件下進行後硬化。〔Evaluation〕 The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests. In addition, unless otherwise specified, the epoxy resin composition is molded by a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. In addition, post-curing is performed at 175°C for 5 hours as necessary.
（1）旋流 使用依據EMMI-1-66的旋流測定用模具，於所述條件下將環氧樹脂組成物成形並求出流動距離（吋）。(1) Swirl Using a mold for swirl flow measurement based on EMMI-1-66, the epoxy resin composition was molded under the conditions described above, and the flow distance (inch) was calculated.
（2）圓板流動 使用具有200 mm（W）×200 mm（D）×25 mm（H）的上模具與200 mm（W）×200 mm（D）×15 mm（H）的下模具的圓板流動測定用平板模具，將利用盤式天平秤秤量的環氧樹脂組成物5 g載置於加熱為180℃的下模具的中心部，於5秒後關閉加熱為180℃的上模具，於負荷78 N、硬化時間90秒的條件下進行壓縮成形，利用游標卡尺測定成形品的長徑（mm）及短徑（mm），將其平均值（mm）設為圓盤流動。(2) Circular plate flow Use a circular plate for flow measurement with an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H) In the mold, 5 g of the epoxy resin composition weighed by a pan balance is placed in the center of the lower mold heated to 180°C, and the upper mold heated to 180°C is closed after 5 seconds, and cured under a load of 78 N Compression molding was performed under the condition of a time of 90 seconds, the long diameter (mm) and short diameter (mm) of the molded product were measured with a vernier caliper, and the average value (mm) was set as a disk flow.
（3）毛邊的評價 將環氧樹脂組成物15 g載置於壓製熱板上的180℃的模具上，以硬化時間90秒進行成形。於成形後使用游標卡尺測定環氧樹脂組成物於在模具上製作的50 μm、30 μm、20 μm、10 μm、5 μm及2 μm的狹縫流經最長的部分的長度，將所述測定值設為毛邊的長度。(3) Evaluation of burrs 15 g of the epoxy resin composition was placed on a 180°C mold on a pressing hot plate, and molded with a curing time of 90 seconds. After molding, use a vernier caliper to measure the length of the epoxy resin composition at the longest part of the 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm slits made on the mold. Set as the length of the burr.
（4）熔融黏度（ηFT） 使用流動度試驗儀測定加熱至175℃的環氧樹脂組成物的熔融黏度。(4) Melt viscosity (ηFT) The melt viscosity of the epoxy resin composition heated to 175°C was measured using a fluidity tester.
（5）彎曲強度 將實施例及比較例中所獲得的環氧樹脂組成物的硬化物切成2.0 mm×5.0 mm×40 mm的長方體，製作彎曲強度評價用試驗片。使用該試驗片，利用騰喜龍（Tensilon）萬能材料試驗機（英斯特朗（Instron）5948，英斯特朗（Instron）公司）於支點間距離32 mm、十字頭速度1 mm/min的條件下進行彎曲試驗。使用測定的結果，根據式（A）製成彎曲應力-位移曲線，將所述最大應力設為彎曲強度。(5) Bending strength The cured products of the epoxy resin compositions obtained in the Examples and Comparative Examples were cut into a rectangular parallelepiped of 2.0 mm×5.0 mm×40 mm to prepare test pieces for bending strength evaluation. Using this test piece, use Tensilon universal material testing machine (Instron 5948, Instron) at a distance of 32 mm between fulcrums and a crosshead speed of 1 mm/min. Perform a bending test under. Using the results of the measurement, a bending stress-displacement curve was created according to the formula (A), and the maximum stress was defined as the bending strength.
σ=3FL/2bh2 ···式（A）σ=3FL/2bh 2 ···Formula (A)
σ：彎曲應力（MPa） F：彎曲負荷（N） L：支點間距離（mm） b：試驗片寬度（mm） h：試驗片厚度（mm）σ: bending stress (MPa) F: bending load (N) L: Distance between fulcrums (mm) b: width of test piece (mm) h: thickness of test piece (mm)
（6）導熱率 使用環氧樹脂組成物，藉由壓縮成形機，於模具溫度175℃～180℃、成形壓力7 MPa、硬化時間150秒的條件下密封半導體元件，製作導熱率評價用試驗片。繼而，藉由氙閃光（Xe-flash）法測定試驗片的導熱率。(6) Thermal conductivity Using an epoxy resin composition, the semiconductor element was sealed with a compression molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a curing time of 150 seconds to prepare a test piece for thermal conductivity evaluation. Then, the thermal conductivity of the test piece was measured by the Xe-flash method.
（7）熔解性 準備約1.5 g的環氧樹脂組成物粉末（通過3.35 mm篩目、不通過1.0 mm篩目）。於加熱為175℃的熱板（下模具）上，以高度約3 mm的方式將環氧樹脂組成物粉末設置於面內圓形。於設置的環氧樹脂組成物上使同樣加熱為175℃的200 g的上模具於水平方向上自由落下。上模具由下模具與垂直支柱支撐，因此以施加一定的負荷的方式設置於面內。將上模具的落下的時間點（即，上模具到達粉末上表面的時間點）設為測定0秒，藉由雷射位移計測定自環氧樹脂組成物粉末開始熔解後的上模具的落下距離。將環氧樹脂組成物的上表面的0秒時間點的高度設為A，將一秒後的高度設為B，利用B/A×100（%）計算，調查粉末的熔解性。(7) Meltability Prepare about 1.5 g of epoxy resin composition powder (passing 3.35 mm mesh, not 1.0 mm mesh). On a hot plate (lower mold) heated to 175°C, the epoxy resin composition powder was set in a circular shape in the plane with a height of about 3 mm. A 200 g upper mold heated to 175°C was also freely dropped in the horizontal direction on the epoxy resin composition set. The upper mold is supported by the lower mold and the vertical pillars, so it is set in the plane by applying a certain load. The time point when the upper mold falls (that is, the time point when the upper mold reaches the upper surface of the powder) is set to 0 seconds, and the distance of the upper mold after the epoxy resin composition powder starts to melt is measured by a laser displacement meter. . The height of the upper surface of the epoxy resin composition at a time point of 0 seconds is set to A, and the height after one second is set to B, and the powder is calculated by B/A×100 (%) to investigate the solubility of the powder.
（8）混練性 將經混練的環氧樹脂組成物於模具的噴出口的設定溫度設為60℃，測定噴出的混練物的溫度，將溫度上升的程度作為混練性的指標。(8) Mixability The set temperature of the kneaded epoxy resin composition in the ejection port of the mold was set to 60°C, the temperature of the ejected kneaded product was measured, and the degree of temperature increase was used as an index of the kneading property.
[表7]
根據表7可知，實施例的環氧樹脂組成物製成硬化物時的導熱率為5.4 W/（m·K）以上，且彎曲強度為168 MPa以上，兼顧高的導熱率與良好的彎曲強度。According to Table 7, when the epoxy resin composition of the example is made into a cured product, the thermal conductivity is 5.4 W/(m·K) or more, and the bending strength is 168 MPa or more, which combines high thermal conductivity and good bending strength. .
另外，根據旋流及圓板流動的評價可知，實施例的環氧樹脂組成物具有優異的流動性。In addition, it can be seen from the evaluation of swirl flow and disk flow that the epoxy resin composition of the example has excellent fluidity.
於混練中將環氧樹脂組成物的噴出口溫度設定為60℃，但由於槳葉與環氧樹脂組成物產生的剪切發熱，混練物的溫度較設定溫度而言上升。然而，可知若測定噴出的混練物的溫度，則於實施例的環氧樹脂組成物中可保持最接近設定值的溫度，藉由使用實施例的環氧樹脂組成物，可抑制過度的剪切發熱。During the kneading, the temperature of the ejection port of the epoxy resin composition was set to 60°C, but the temperature of the kneaded product increased from the set temperature due to shear heat generated by the blade and the epoxy resin composition. However, it can be seen that if the temperature of the sprayed kneaded product is measured, the epoxy resin composition of the example can maintain the temperature closest to the set value. By using the epoxy resin composition of the example, excessive shear can be suppressed fever.
根據毛邊的評價可知，於使用超微細二氧化矽的實施例中可較佳地抑制毛邊。另外，即便於使用超微細二氧化矽的情況下，實施例的環氧樹脂組成物亦維持優異的流動性。According to the evaluation of the burrs, it can be known that the burrs can be suppressed better in the examples using ultra-fine silica. In addition, even in the case of using ultrafine silica, the epoxy resin composition of the example maintained excellent fluidity.
根據熔融黏度的評價可知，實施例的環氧樹脂組成物的熔融黏度低。According to the evaluation of the melt viscosity, the epoxy resin composition of the example has a low melt viscosity.
實施例的環氧樹脂組成物的熔解性亦優異。因此，認為亦可較佳地用作壓縮成形用環氧樹脂組成物。The epoxy resin composition of the example is also excellent in meltability. Therefore, it is considered that it can also be suitably used as an epoxy resin composition for compression molding.
（附加說明） 本揭示包含以下的態樣。 ＜1＞ 一種密封用環氧樹脂組成物，含有：環氧樹脂；以及硬化劑，包含以下的通式（B）所表示的化合物。(Additional information) This disclosure includes the following aspects. <1> An epoxy resin composition for sealing, which contains: an epoxy resin; and a hardener, and contains a compound represented by the following general formula (B).
[化26]
（通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數） ＜2＞ 如＜1＞所述的密封用環氧樹脂組成物，其中所述硬化劑中的所述通式（B）所表示的化合物的含有率為30質量%～100質量%。 ＜3＞ 如＜1＞或＜2＞所述的密封用環氧樹脂組成物，其中所述通式（B）中，R1 為甲基。 ＜4＞ 如＜1＞至＜3＞中任一項所述的密封用環氧樹脂組成物，其是將體積平均粒徑為2.0 μm以下的無機填充材混合而成。 ＜5＞ 如＜1＞至＜3＞中任一項所述的密封用環氧樹脂組成物，進而包含無機填充材，相對於所述無機填充材的總量，粒徑為2.0 μm以下的無機填充材的含有率為5質量%以上。 ＜6＞ 一種電子零件裝置，包括：元件；以及密封所述元件的如＜1＞至＜5＞中任一項所述的密封用環氧樹脂組成物的硬化物。(In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 10) <2> The epoxy resin composition for sealing as described in <1>, wherein The content rate of the compound represented by the general formula (B) in the curing agent is 30% by mass to 100% by mass. <3> The epoxy resin composition for sealing as described in <1> or <2>, wherein in the general formula (B), R 1 is a methyl group. <4> The epoxy resin composition for sealing as described in any one of <1> to <3>, which is obtained by mixing an inorganic filler having a volume average particle diameter of 2.0 μm or less. <5> The epoxy resin composition for sealing as described in any one of <1> to <3>, further comprising an inorganic filler, and having a particle size of 2.0 μm or less with respect to the total amount of the inorganic filler The content of the inorganic filler is 5% by mass or more. <6> An electronic component device, including: an element; and a cured product of the sealing epoxy resin composition according to any one of <1> to <5> that seals the element.
本揭示包含以下的態樣。 ＜1＞ 一種壓縮成形用環氧樹脂組成物，含有：環氧樹脂；以及硬化劑，包含以下的通式（B）所表示的化合物。This disclosure includes the following aspects. <1> An epoxy resin composition for compression molding, containing: an epoxy resin; and a hardener, and containing a compound represented by the following general formula (B).
[化27]
（通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數） ＜2＞ 如＜1＞所述的壓縮成形用環氧樹脂組成物，其中所述硬化劑中的所述通式（B）所表示的化合物的含有率為30質量%～100質量%。 ＜3＞ 如＜1＞或＜2＞所述的壓縮成形用環氧樹脂組成物，其中所述通式（B）中，R1 為甲基。 ＜4＞ 如＜1＞至＜3＞中任一項所述的壓縮成形用環氧樹脂組成物，進而含有脫模劑，相對於所述壓縮成形用環氧樹脂組成物的總質量，所述脫模劑的含有率超過0質量%且為2.0質量%以下。 ＜5＞ 一種電子零件裝置，包括：元件；以及密封所述元件的如＜1＞至＜3＞中任一項所述的壓縮成形用環氧樹脂組成物的硬化物。(In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 10) <2> The epoxy resin composition for compression molding as described in <1>, The content of the compound represented by the general formula (B) in the curing agent is 30% by mass to 100% by mass. <3> The epoxy resin composition for compression molding as described in <1> or <2>, wherein in the general formula (B), R 1 is a methyl group. <4> The epoxy resin composition for compression molding as described in any one of <1> to <3>, further containing a mold release agent, relative to the total mass of the epoxy resin composition for compression molding, The content of the mold release agent exceeds 0% by mass and is 2.0% by mass or less. <5> An electronic component device, comprising: an element; and a cured product of the epoxy resin composition for compression molding according to any one of <1> to <3> that seals the element.
本揭示包含以下的態樣。 ＜1＞ 一種密封用環氧樹脂組成物，含有：環氧樹脂；無機填充材，包含氧化鋁；以及硬化劑，包含以下的通式（B）所表示的化合物。This disclosure includes the following aspects. <1> An epoxy resin composition for sealing, containing an epoxy resin; an inorganic filler containing alumina; and a curing agent, containing a compound represented by the following general formula (B).
[化28]
（通式（B）中，R1 分別獨立地表示碳數1～6的烷基。n表示0～10的整數） ＜2＞ 如＜1＞所述的密封用環氧樹脂組成物，其中相對於所述硬化劑的總質量而言的所述通式（B）所表示的化合物的含有率為30質量%～100質量%。 ＜3＞ 如＜1＞或＜2＞所述的密封用環氧樹脂組成物，其中所述通式（B）中，R1 為甲基。 ＜4＞ 如＜1＞至＜3＞中任一項所述的密封用環氧樹脂組成物，其中所述無機填充材的含有率為75體積%以上。 ＜5＞ 如＜1＞至＜4＞中任一項所述的密封用環氧樹脂組成物，其中相對於所述無機填充材的總質量而言的氧化鋁的含有率為75質量%以上。 ＜6＞ 如＜1＞至＜5＞中任一項所述的密封用環氧樹脂組成物，其中所述無機填充材進而包含二氧化矽，所述二氧化矽的平均粒徑為2.0 μm以下。 ＜7＞ 一種電子零件裝置，包括：元件；以及密封所述元件的如＜1＞至＜6＞中任一項所述的密封用環氧樹脂組成物的硬化物。 ＜8＞ 一種電子零件裝置的製造方法，包括：藉由如＜1＞至＜6＞中任一項所述的密封用環氧樹脂組成物來密封元件。 ＜9＞ 如＜8＞所述的電子零件裝置的製造方法，其中所述元件的密封是藉由壓縮成形來進行。(In the general formula (B), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 10) <2> The epoxy resin composition for sealing as described in <1>, wherein The content rate of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% by mass to 100% by mass. <3> The epoxy resin composition for sealing as described in <1> or <2>, wherein in the general formula (B), R 1 is a methyl group. <4> The epoxy resin composition for sealing as described in any one of <1> to <3>, wherein the content of the inorganic filler is 75% by volume or more. <5> The epoxy resin composition for sealing according to any one of <1> to <4>, wherein the content of alumina relative to the total mass of the inorganic filler is 75% by mass or more . <6> The epoxy resin composition for sealing according to any one of <1> to <5>, wherein the inorganic filler further contains silicon dioxide, and the average particle diameter of the silicon dioxide is 2.0 μm the following. <7> An electronic component device, including: an element; and a cured product of the sealing epoxy resin composition according to any one of <1> to <6> that seals the element. <8> A method of manufacturing an electronic component device, including: sealing an element with the epoxy resin composition for sealing as described in any one of <1> to <6>. <9> The method of manufacturing an electronic component device as described in <8>, wherein the sealing of the element is performed by compression molding.
日本專利申請案第2019-189706號、日本專利申請案第2020-020134號、及日本專利申請案第2020-020135號的揭示的全部內容藉由參照而併入至本說明書中。 本說明書中記載的所有文獻、專利申請案、以及技術規格是與具體且分別記載各個文獻、專利申請案、以及技術規格藉由參照而併入的情況相同程度地引用並併入至本說明書中。The entire contents of the disclosures of Japanese Patent Application No. 2019-189706, Japanese Patent Application No. 2020-020134, and Japanese Patent Application No. 2020-020135 are incorporated into this specification by reference. All the documents, patent applications, and technical specifications described in this specification are cited and incorporated into this specification to the same extent as when each document, patent application, and technical specifications are specifically and separately described and incorporated by reference .
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| JP2019189706 | 2019-10-16 | ||
| JP2019-189706 | 2019-10-16 | ||
| JP2020020135 | 2020-02-07 | ||
| JP2020-020134 | 2020-02-07 | ||
| JP2020020134 | 2020-02-07 | ||
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| KR (1) | KR20220084073A (en) |
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| WO2023032971A1 (en) * | 2021-09-02 | 2023-03-09 | 株式会社レゾナック | Epoxy resin composition for compression molding and electronic component device |
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| JP2001106875A (en) * | 1999-10-08 | 2001-04-17 | Kashima Oil Co Ltd | Flame-retardant epoxy resin composition for semiconductor sealing and semiconductor device |
| JP4639439B2 (en) * | 2000-08-04 | 2011-02-23 | 住友ベークライト株式会社 | Epoxy resin composition, prepreg, and copper-clad laminate using the same |
| JP3944736B2 (en) * | 2003-02-06 | 2007-07-18 | 信越化学工業株式会社 | Epoxy resin composition and semiconductor device |
| JP2007153969A (en) | 2005-12-02 | 2007-06-21 | Showa Denko Kk | Highly heat-conductive resin composition and substrate for wiring |
| JP5189606B2 (en) | 2010-01-26 | 2013-04-24 | パナソニック株式会社 | Epoxy resin composition for semiconductor encapsulation, and semiconductor device |
| KR101735983B1 (en) * | 2013-03-07 | 2017-05-15 | 스미또모 베이크라이트 가부시키가이샤 | Adhesive film, adhesive film integrated with dicing sheet, adhesive film integrated with back grind tape, adhesive film integrated with back grind tape cum dicing sheet, laminate, cured product of laminate, semiconductor device, and process for producing semiconductor device |
| JP2015074703A (en) | 2013-10-08 | 2015-04-20 | 日立化成株式会社 | Epoxy resin composition and electronic part device |
| JP6770793B2 (en) * | 2015-08-19 | 2020-10-21 | 日鉄ケミカル＆マテリアル株式会社 | Flame-retardant epoxy resin composition and its cured product |
| JP7066975B2 (en) * | 2017-03-10 | 2022-05-16 | 味の素株式会社 | Resin composition, resin sheet, circuit board and semiconductor chip package |
| JP6859916B2 (en) * | 2017-10-13 | 2021-04-14 | 味の素株式会社 | Resin composition layer |
| JP7169076B2 (en) * | 2018-03-22 | 2022-11-10 | 太陽インキ製造株式会社 | Thermosetting resin composition, dry film, cured product, and electronic component |
| JP2019176023A (en) * | 2018-03-28 | 2019-10-10 | 京セラ株式会社 | Semiconductor-sealing resin composition and semiconductor device |
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