TWI821184B - Epoxy resin composition for forming adhesion layer of semiconductor device - Google Patents

Epoxy resin composition for forming adhesion layer of semiconductor device Download PDF

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TWI821184B
TWI821184B TW107116294A TW107116294A TWI821184B TW I821184 B TWI821184 B TW I821184B TW 107116294 A TW107116294 A TW 107116294A TW 107116294 A TW107116294 A TW 107116294A TW I821184 B TWI821184 B TW I821184B
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epoxy resin
resin composition
semiconductor element
semiconductor device
epoxy
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TW201902976A (en
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諏訪剛史
上田祐揮
小出泰之
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日商日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/62—Alcohols or phenols
    • 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 potential barriers, e.g. a 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本發明之課題係提供一種環氧樹脂組成物，其係用來形成耐熱性、密著性為優異的半導體裝置用的密著層。 　　本發明之半導體裝置密著層形成用環氧樹脂組成物，其係在由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置中，用來形成在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分所具備的密著層之環氧樹脂組成物，包含：式[1]所表示的環氧化合物、及硬化劑。 (式中，R1 至R3 係分別獨立表示氫原子或甲基，L1 至L3 係分別獨立表示碳原子數1~7的伸烷基)。An object of the present invention is to provide an epoxy resin composition for forming an adhesive layer for a semiconductor device that is excellent in heat resistance and adhesiveness. The epoxy resin composition for forming an adhesive layer of a semiconductor device of the present invention is composed of a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a cured sealing resin for sealing these. In the semiconductor device configured, the epoxy resin composition for forming an adhesion layer provided in at least part of the interface between the cured sealing resin and the substrate and/or the lead electrode includes: Formula [1] Indicates epoxy compounds and hardeners. (In the formula, R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and L 1 to L 3 each independently represent an alkylene group having 1 to 7 carbon atoms).

Description

半導體裝置密著層形成用環氧樹脂組成物Epoxy resin composition for forming adhesive layer of semiconductor device

本發明係關於半導體裝置密著層形成用環氧樹脂組成物及使用此者的半導體裝置的製造方法。更詳細而言係關於可對於金屬或陶瓷基板形成高密著性、及優異耐熱性的密著層的環氧樹脂組成物、及使用此者的半導體裝置的製造方法。The present invention relates to an epoxy resin composition for forming an adhesive layer of a semiconductor device and a method of manufacturing a semiconductor device using the same. More specifically, the invention relates to an epoxy resin composition capable of forming an adhesive layer with high adhesion and excellent heat resistance on a metal or ceramic substrate, and a method of manufacturing a semiconductor device using the same.

時至今日，半導體裝置被使用在各種的電子機器中，擔任著機器的運作所需要的電流或信號的控制。一般而言構成半導體裝置之半導體元件、接合材、金屬電極、絕緣基板等的各構件，由於具有不同的熱膨脹率，故伴隨著加熱、冷卻而在元件的內部會產生應力，恐將有引起以材料間(特別是焊料(solder)等的接合材部)作為起點的剝離之虞。若發生如此般的事態時，將會對元件內的正常的電流控制造成妨礙，而使得元件的運作不良。 　　為了抑制該現象，一般而言係如下述般來設計：將半導體元件搭載在基板(substrate)或引線框(leadframe)並進行電連接後，藉由利用彈性率高的密封樹脂(sealing resin)進行密封，從而保護半導體元件以免於來自於外部的化學性、電學性、物理性的刺激之同時，限制了被層合的各層的熱變形以抑制上述的剝離。此時，就抑制上述剝離之點而言，因構成半導體裝置的各構件與密封樹脂之熱膨脹率差所伴隨的剝離，亦為重要之因素。Today, semiconductor devices are used in various electronic machines to control the current or signals required for the operation of the machines. Generally speaking, various components that make up a semiconductor device, such as semiconductor elements, bonding materials, metal electrodes, and insulating substrates, have different thermal expansion coefficients. Therefore, stress will be generated inside the element with heating and cooling, which may cause There is a risk of peeling off between materials (especially the joining material portion such as solder) as the starting point. If such a situation occurs, it will hinder the normal current control in the component and cause the component to malfunction. In order to suppress this phenomenon, the design is generally as follows: after mounting the semiconductor element on a substrate or a lead frame and electrically connecting it, the sealing resin with a high elastic modulus is used. The sealing protects the semiconductor element from external chemical, electrical, and physical stimulation, and at the same time limits the thermal deformation of each laminated layer to inhibit the above-mentioned peeling. At this time, in terms of suppressing the above-mentioned peeling, peeling caused by the difference in thermal expansion coefficient between each member constituting the semiconductor device and the sealing resin is also an important factor.

另一方面，近年來隨著控制的電流、信號的高電壓化或高頻化，正進行著碳化矽(SiC)、氮化鎵(GaN)之類的能帶隙為寬的半導體元件之開發，來替代以往的矽半導體。搭載如此般的寬能帶隙的半導體元件的半導體裝置，其設計是以較以往為更高溫度下的運作，故上述剝離的問題將成為更顯著的課題。 　　為了解決如此般的課題，已有如下述般之對策：藉由對密封樹脂添加填料(filler)來降低熱膨脹係數(CTE)，來使密封樹脂與周邊構件的CTE差變小。但，為了使CTE充分地降低，而需要添加大量的填料，此情形時，由於擔任與基板表面接著的樹脂成分的表面積減少，故本質上而言對於基材的密著性會降低。因此，將難以確保一定程度以上的密著性。On the other hand, in recent years, as the controlled currents and signals have become higher voltage or higher frequency, semiconductor devices with wide bandgaps such as silicon carbide (SiC) and gallium nitride (GaN) are being developed. , to replace previous silicon semiconductors. Semiconductor devices equipped with such wide bandgap semiconductor elements are designed to operate at higher temperatures than ever before, so the above-mentioned peeling problem will become a more significant issue. In order to solve such problems, there have been countermeasures such as adding a filler to the sealing resin to reduce the coefficient of thermal expansion (CTE), thereby reducing the CTE difference between the sealing resin and peripheral components. However, in order to sufficiently reduce the CTE, a large amount of filler needs to be added. In this case, the surface area of the resin component responsible for contacting the substrate surface is reduced, so the adhesion to the substrate is essentially reduced. Therefore, it will be difficult to ensure adhesion above a certain level.

於如此般的狀況中，揭示著藉由在搭載半導體元件的引線框上設置突起，從而使引線框與密封樹脂的密著性提升的方法(例如專利文獻1)。又，揭示著在線膨脹率為不同的構件間，設置擔任應力緩和的由聚醯胺醯亞胺樹脂所成的中間層，從而改善密著性的方法(例如專利文獻2)。 [先前技術文獻] [專利文獻]Under such circumstances, a method of improving the adhesion between the lead frame and the sealing resin by providing protrusions on the lead frame mounting the semiconductor element is disclosed (for example, Patent Document 1). Furthermore, a method of improving adhesion by providing an intermediate layer made of polyamideimide resin that serves as stress relaxation between members having different linear expansion rates is disclosed (for example, Patent Document 2). [Prior art documents] [Patent documents]

[專利文獻1]日本特開2000-150753號公報 　　[專利文獻2]日本特開2015-164165號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2000-150753 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-164165

[發明所欲解決之課題][Problem to be solved by the invention]

然而，專利文獻1所記載的方法中，必須事先將引線框或基板進行加工，故在成本方面、製程方面仍留有課題。又，專利文獻2所記載的方法中，具有如下述般之課題：聚醯胺醯亞胺樹脂之硬化溫度為高，而在半導體裝置之製造時需要大量的能量，此外，絕緣可靠性為差、或吸濕性為高而因此在後段步驟中吸濕的水分之揮發，容易造成構件間的剝離。 [解決課題之手段]However, in the method described in Patent Document 1, the lead frame or the substrate must be processed in advance, so there are still problems in terms of cost and manufacturing process. In addition, the method described in Patent Document 2 has the following problems: the curing temperature of the polyamideimide resin is high, a large amount of energy is required for manufacturing a semiconductor device, and the insulation reliability is poor. , or the hygroscopicity is high, so the volatilization of the absorbed moisture in the subsequent steps can easily cause peeling between components. [Means to solve the problem]

本發明人為解決上述之課題經深入研究之結果發現，以包含在各種的環氧樹脂中為具有特定構造的三聚氰酸(cyanuric acid)系環氧化合物、及酚硬化劑而成的環氧樹脂組成物，由該環氧樹脂組成物的硬化物所成的密著層，對於金屬或陶瓷以及密封樹脂為具有高密著性，故作為半導體裝置用的密著層為優異，因而完成本發明。 　　即，本發明作為第1觀點係關於一種半導體裝置密著層形成用環氧樹脂組成物，其係在由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置中，用來形成在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分所具備的密著層之環氧樹脂組成物，包含：式[1]所表示的環氧化合物、及硬化劑，(式中，R1 至R3 係分別獨立表示氫原子或甲基，L1 至L3 係分別獨立表示碳原子數1~7的伸烷基)。 　　作為第2觀點係關於如第1觀點所記載之環氧樹脂組成物，其中，前述硬化劑係包含由苯酚酚醛清漆樹脂(phenol novolac resin)、甲酚酚醛清漆樹脂(cresol novolac resin)、萘酚醛清漆樹脂(naphthalene novolac resin)、蒽酚醛清漆樹脂(anthracene novolac resin)、伸聯苯酚醛清漆樹脂(biphenylene novolac resin)、伸二甲苯酚醛清漆樹脂(xylylene novolac resin)、三苯酚甲烷酚醛清漆樹脂(triphenolmethane novolac resin)、四苯酚酚醛清漆樹脂(tetrakisphenol novolac resin)及雙環戊二烯酚醛清漆樹脂(dicyclopentadiene novolac resin)所成之群中選出之至少1種。 　　作為第3觀點係關於如第2觀點所記載之環氧樹脂組成物，其中，前述硬化劑係包含三苯酚甲烷酚醛清漆樹脂。 　　作為第4觀點係關於如第1觀點至第3觀點中任1所記載之環氧樹脂組成物，其中，進而包含硬化觸媒。 　　作為第5觀點係關於一種半導體裝置，其係由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置，在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分具備由第1觀點~第4觀點中任1觀點所記載之環氧樹脂組成物的硬化物所成的密著層。 　　作為第6觀點係關於一種半導體裝置的製造方法，其係包含：將第1觀點~第4觀點中任1觀點所記載之環氧樹脂組成物塗佈至搭載半導體元件的基板及/或接合於半導體元件的引線電極之至少一部分的步驟、將前述塗膜硬化並形成密著層的步驟、在前述密著層上形成密封樹脂硬化物的步驟。 　　作為第7觀點係關於如第6觀點所記載之製造方法，其中，以清漆的形態來使用前述環氧樹脂組成物。 [發明的效果]In order to solve the above-mentioned problems, the present inventors conducted in-depth research and found that an epoxy resin containing a cyanuric acid-based epoxy compound with a specific structure and a phenol hardener is contained in various epoxy resins. The resin composition and the adhesive layer made of the cured product of the epoxy resin composition have high adhesion to metals, ceramics and sealing resins, and therefore are excellent as an adhesive layer for semiconductor devices. This led to the completion of the present invention. . That is, the present invention, as a first aspect, relates to an epoxy resin composition for forming an adhesive layer of a semiconductor device, which is composed of a semiconductor element, a substrate on which the semiconductor element is mounted, and/or a lead electrode bonded to the semiconductor element, and the An epoxy resin composition for forming an adhesion layer provided in at least part of the interface between the sealing resin cured material and the substrate and/or the lead electrode in a semiconductor device composed of a sealed sealing resin cured material. , including: an epoxy compound represented by formula [1] and a hardener, (In the formula, R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and L 1 to L 3 each independently represent an alkylene group having 1 to 7 carbon atoms). The second aspect relates to the epoxy resin composition as described in the first aspect, wherein the hardener is composed of phenol novolac resin, cresol novolac resin, naphthol novolac resin. Naphthalene novolac resin, anthracene novolac resin, biphenylene novolac resin, xylylene novolac resin, triphenolmethane novolac resin At least one selected from the group consisting of tetrakisphenol novolac resin and dicyclopentadiene novolac resin. A third aspect relates to the epoxy resin composition according to the second aspect, wherein the hardener contains trisphenolmethane novolak resin. The fourth aspect relates to the epoxy resin composition according to any one of the first to third aspects, further including a curing catalyst. The fifth aspect relates to a semiconductor device including a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a sealing resin cured material for sealing these. At least part of the interface between the cured sealing resin material and the substrate and/or the lead electrode is provided with an adhesion layer made of a cured material of the epoxy resin composition according to any one of the first to fourth aspects. A sixth aspect relates to a method for manufacturing a semiconductor device, which includes applying the epoxy resin composition described in any one of the first to fourth aspects to a substrate mounting a semiconductor element and/or bonding it to The steps of forming at least part of the lead electrode of the semiconductor element, curing the coating film to form an adhesion layer, and forming a cured sealing resin on the adhesion layer. A seventh aspect relates to the manufacturing method according to the sixth aspect, wherein the epoxy resin composition is used in the form of a varnish. [Effects of the invention]

環氧樹脂係由於耐熱性、耐絕緣性、密著性為優異，故已被廣泛使用作為電子材料用接著劑或半導體用密封樹脂。其中，作為本發明之特徵的三聚氰酸系環氧樹脂，由於該構造包含很多極性元素，故對於金屬或陶瓷等的各種基材的密著性為優異，藉由使用酚硬化劑來使其硬化，從而能夠得到耐熱性、密著性為優異的半導體裝置用的密著層。 　　因此，根據本發明可提供一種環氧樹脂組成物，其係用來形成耐熱性、密著性為優異的半導體裝置用的密著層。又，根據本發明可提供一種半導體裝置的製造方法，其具備構成半導體裝置的各構件與密封樹脂硬化物的密著層，即使是在高溫下運作的半導體裝置，也能防止密封樹脂硬化物從構成半導體裝置的各構件上剝離。Epoxy resins are widely used as adhesives for electronic materials and sealing resins for semiconductors because they have excellent heat resistance, insulation resistance, and adhesion. Among them, the cyanuric acid-based epoxy resin, which is a feature of the present invention, has excellent adhesion to various base materials such as metals and ceramics because its structure contains many polar elements. It is made possible by using a phenol hardener. By hardening, an adhesive layer for a semiconductor device having excellent heat resistance and adhesion can be obtained. Therefore, according to the present invention, it is possible to provide an epoxy resin composition for forming an adhesive layer for a semiconductor device that is excellent in heat resistance and adhesiveness. Furthermore, according to the present invention, it is possible to provide a method for manufacturing a semiconductor device, which includes an adhesion layer between each member constituting the semiconductor device and a cured sealing resin, and can prevent the cured sealing resin from being removed even in a semiconductor device that operates at a high temperature. Each component constituting the semiconductor device is peeled off.

[實施發明之最佳形態][The best way to implement the invention]

＜環氧樹脂組成物＞ 　　本發明之環氧樹脂組成物，其係在半導體裝置中，用來形成在密封樹脂硬化物、與基板及/或引線電極之界面之至少一部分所具備的密著層，環氧樹脂組成物係包含上述式[1]所表示的環氧化合物及硬化劑之組成物。<Epoxy resin composition> The epoxy resin composition of the present invention is used in a semiconductor device to form an adhesion layer provided on at least part of the interface between a sealing resin cured product and a substrate and/or a lead electrode. , the epoxy resin composition is a composition containing an epoxy compound represented by the above formula [1] and a hardener.

[式[1]所表示的環氧化合物] 　　上述式[1]中、R1 至R3 係分別獨立表示氫原子或甲基，L1 至L3 係分別獨立表示碳原子數1~7的伸烷基。 　　作為L1 至L3 所表示的碳原子數1~7的伸烷基，可舉例如亞甲基(methylene)、伸乙基(ethylene)、三亞甲基、1-甲基伸乙基、四亞甲基、1-甲基三亞甲基、1,1-二甲基伸乙基、五亞甲基、1-甲基四亞甲基、2-甲基四亞甲基、1,1-二甲基三亞甲基、1,2-二甲基三亞甲基、2,2-二甲基三亞甲基、1-乙基三亞甲基、六亞甲基、1-甲基五亞甲基、2-甲基五亞甲基、3-甲基五亞甲基、1,1-二甲基四亞甲基、1,2-二甲基四亞甲基、2,2-二甲基四亞甲基、1-乙基四亞甲基、1,1,2-三甲基三亞甲基、1,2,2-三甲基三亞甲基、1-乙基-1-甲基三亞甲基、1-乙基-2-甲基三亞甲基、環己烷-1,4-二基、七亞甲基等。較佳為亞甲基、三亞甲基、六亞甲基，又較佳為亞甲基、三亞甲基。[Epoxy compound represented by formula [1]] In the above formula [1], R 1 to R 3 each independently represents a hydrogen atom or a methyl group, and L 1 to L 3 each independently represents a carbon number of 1 to 7. Alkylene. Examples of the alkylene group having 1 to 7 carbon atoms represented by L 1 to L 3 include methylene, ethylene, trimethylene, 1-methylethylene, and tetramethylethylene. Methylene, 1-methyltrimethylene, 1,1-dimethylethylidene, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1- Dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, hexamethylene, 1-methylpentamethylene , 2-methylpentamethylene, 3-methylpentamethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyl Tetramethylene, 1-ethyltetramethylene, 1,1,2-trimethyltrimethylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1-methyltrimethylene Methyl, 1-ethyl-2-methyltrimethylene, cyclohexane-1,4-diyl, heptamethylene, etc. Preferred are methylene, trimethylene and hexamethylene, and further preferred are methylene and trimethylene.

上述式[1]所表示的化合物，例如，將具有異三聚氰酸及脫離基X的烯烴化合物作為起始原料，藉由以往周知(例如國際公開第2010/092947號說明書、日本特開2012-25688號公報等所記載)的環氧化物的合成方法，而可製造。 　　具體而言，將異三聚氰酸、與CH2 =CR-L-X(式中，R及L係表示R1 及L1 、R2 及L2 或R3 及L3 )所表示的烯烴化合物進行反應，來製造具有不飽和鍵的烯烴取代異氰脲酸酯(中間物)後，將該化合物(中間物)與過氧化物進行反應，從而可製造上述式[1]所表示的環氧化合物。作為一例，將合成架構表示於以下。 　　尚，只要是能與異三聚氰酸的N-H基反應的基即可，脫離基X並無特別限定，可舉例如羥基、甲磺醯氧基、三氟甲磺醯氧基、甲苯磺醯氧基、硝苯磺醯氧基、乙醯氧基、三氟乙醯氧基、鹵素原子等。上述式中，R1 至R3 、L1 至L3 表示與前述為相同之意思。 　　又，若為R1 、R2 及R3 分別表示氫原子、且L1 、L2 及L3 分別表示亞甲基的環氧化合物，藉由將異三聚氰酸與環氧氯丙烷反應並進行閉環的方法亦能夠製造。The compound represented by the above formula [1], for example, is prepared by using an olefin compound having isocyanuric acid and a leaving group It can be produced by the epoxide synthesis method described in Publication No. 25688, etc.). Specifically, an olefin compound represented by isocycyanuric acid and CH 2 =CR-LX (in the formula, R and L represent R 1 and L 1 , R 2 and L 2 or R 3 and L 3 ) After carrying out the reaction to produce an olefin-substituted isocyanurate (intermediate) having an unsaturated bond, the compound (intermediate) is reacted with a peroxide to produce the epoxy represented by the above formula [1]. compound. As an example, the synthetic architecture is shown below. Furthermore, as long as it is a group that can react with the NH group of isocycyanuric acid, the leaving group Oxygen group, nitensulfonyloxy group, acetyloxy group, trifluoroacetyloxy group, halogen atom, etc. In the above formula, R 1 to R 3 and L 1 to L 3 have the same meanings as described above. Moreover, if it is an epoxy compound in which R 1 , R 2 and R 3 each represent a hydrogen atom, and L 1 , L 2 and L 3 each represent a methylene group, by reacting isocyanuric acid with epichlorohydrin And the closed-loop method can also be produced.

作為上述環氧化合物，可舉例如三縮水甘油基異氰脲酸酯、三(3,4-環氧基丁基)異氰脲酸酯、三(4,5-環氧基戊基)異氰脲酸酯、三(5,6-環氧基己基)異氰脲酸酯、三(6,7-環氧基庚基)異氰脲酸酯、三(7,8-環氧基辛基)異氰脲酸酯、三(8,9-環氧基壬基)異氰脲酸酯等。 　　又，上述環氧化合物係可適合使用市售品，可舉例如TEPIC(註冊商標)-G、同S、同SS、同SP、同L、同HP、同VL、同FL[皆為日產化學工業(股)製]等。該等的環氧化合物係可單獨或可以二種以上的混合物來使用。 　　藉由使用含有異氰脲酸酯環的環氧化合物，從而可得到用來形成與金屬或陶瓷等的半導體基板、半導體元件及接合於半導體元件的引線電極等、以及密封樹脂硬化物為具有優異的密著性的密著層的環氧樹脂組成物。Examples of the epoxy compound include triglycidyl isocyanurate, tris(3,4-epoxybutyl)isocyanurate, and tris(4,5-epoxypentyl)isocyanurate. Cyanurate, tris(5,6-epoxyhexyl)isocyanurate, tris(6,7-epoxyheptyl)isocyanurate, tris(7,8-epoxyoctyl) base) isocyanurate, tris(8,9-epoxynonyl)isocyanurate, etc. In addition, commercially available products can be suitably used as the above-mentioned epoxy compounds, and examples include TEPIC (registered trademark)-G, Same-S, Same-SS, Same-SP, Same-L, Same-HP, Same-VL, Same-FL [all manufactured by Nissan Chemical Co., Ltd. Industrial (stock) system] etc. These epoxy compounds can be used alone or in a mixture of two or more kinds. By using an epoxy compound containing an isocyanurate ring, it is possible to obtain a cured product having excellent properties for forming semiconductor substrates with metals, ceramics, etc., semiconductor elements, lead electrodes bonded to semiconductor elements, etc., and sealing resins. The epoxy resin composition of the adhesive layer has excellent adhesion.

本發明中，在不損及本發明之效果的範圍內，可併用上述式[1]所表示的環氧化合物、與和式[1]不同的其他的環氧化合物。上述式[1]所表示的環氧化合物與其他的環氧化合物，係能夠以環氧基的莫耳比計為1：0~1：2的範圍來使用。 　　作為上述其他的環氧化合物，並無特別限定而可使用各種的環氧化合物，特別是以多官能的環氧化合物為較佳。In the present invention, the epoxy compound represented by the above-mentioned formula [1] and other epoxy compounds different from the formula [1] can be used together in a range that does not impair the effects of the present invention. The epoxy compound represented by the above formula [1] and other epoxy compounds can be used with a molar ratio of the epoxy group in the range of 1:0 to 1:2. As the above-mentioned other epoxy compounds, there are no particular limitations and various epoxy compounds can be used. In particular, polyfunctional epoxy compounds are preferred.

作為本發明中能夠使用的其他的環氧化合物，可舉例如1,2,7,8-二環氧基辛烷、1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、1,6-二羥甲基全氟己烷二縮水甘油醚、(聚)乙二醇二縮水甘油醚、(聚)丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、丙三醇三縮水甘油醚、二丙三醇聚縮水甘油醚、三羥甲基乙烷三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇二縮水甘油醚、季戊四醇四縮水甘油醚、季戊四醇聚縮水甘油醚、山梨糖醇聚縮水甘油醚、1,4-環己烷二甲醇二縮水甘油醚、二溴苯基=縮水甘油基=醚、2,6-二縮水甘油基苯基=縮水甘油基=醚、間苯二酚二縮水甘油醚、雙(2,7-二縮水甘油氧基萘-1-基 )甲烷、1,1,2,2-四(4-縮水甘油基氧基苯基)乙烷、1,1,3-三(4-縮水甘油基氧基苯基)丙烷、雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、四溴雙酚A二縮水甘油醚、氫化雙酚A二縮水甘油醚、雙酚六氟丙酮二縮水甘油醚、雙(2,3-環氧基環戊基)醚、1,2-雙(3,4-環氧基環己基甲氧基)乙烷、乙二醇雙(3,4-環氧基環己烷羧酸酯)、3,4-環氧基環己烷羧酸(3,4-環氧基環己基)甲酯、4,5-環氧基-2-甲基環己烷羧酸4,5-環氧基-2-甲基環己基甲酯、己二酸雙(3,4-環氧基環己基甲基)、1,2-環氧基-4-(環氧基乙基)環己烷、4-(螺[3,4-環氧基環己烷-1,5’-[1,3]二噁烷]-2’-基)-1,2-環氧基環己烷、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、1,2-環己烷二羧酸二縮水甘油酯、三(2-縮水甘油氧基乙基)異氰脲酸酯、單烯丙基二縮水甘油基異氰脲酸酯、N,N’-二縮水甘油基N”-(2,3-二丙醯氧基丙基)異氰脲酸酯、N,N’-雙(2,3-二丙醯氧基丙基)N”-縮水甘油基異氰脲酸酯、三(2,2-雙(縮水甘油氧基甲基)丁基)3,3’,3”-(2,4,6-三氧-1,3,5-三嗪基-1,3,5-三基)三丙酸酯、N,N-二縮水甘油基-4-縮水甘油氧基苯胺、N,N,N’,N’-四縮水甘油基-m-伸二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、4,4’-亞甲基雙(N,N-二縮水甘油基苯胺)、2-(4,4-二甲基戊烷-2-基)-5,7,7-三甲基辛基=縮水甘油基=醚、2-(4,4-二甲基戊烷-2-基)-5,7,7-三甲基辛酸縮水甘油酯、2-(4,4-二甲基戊烷-2-基)-5,7,7-三甲基辛酸2,2-雙(縮水甘油氧基甲基)丁酯、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘酚醛清漆型環氧樹脂、蒽酚醛清漆型環氧樹脂、伸聯苯酚醛清漆型環氧樹脂、伸二甲苯酚醛清漆型環氧樹脂、三苯酚甲烷酚醛清漆型環氧樹脂、四苯酚酚醛清漆型環氧樹脂、雙環戊二烯酚醛清漆型環氧樹脂等，但並非被限定於該等。 　　又，上述環氧化合物係可適合使用市售品，可舉例如TEPIC(註冊商標)-PAS B22、同PAS B26、同PAS B26L、同UC、FOLDI(註冊商標)-E101、同E201[皆為日產化學工業(股)製]、jER(註冊商標)828、同807、同YX8000、同157S70[皆為三菱化學(股)製]、RIKARESIN(註冊商標) DME100[新日本理化(股)製]、Celoxide 2021P [(股)Daicel製]、EPICLON(註冊商標)HP-4700、同HP-4710、同HP-7200L[皆為DIC(股)製]、AV LITE(註冊商標)TEP-G[旭有機材(股)製]等。 　　該等的環氧化合物係可單獨或可以二種以上的混合物來使用。Examples of other epoxy compounds that can be used in the present invention include 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol. Diglycidyl ether, 1,6-dihydroxymethylperfluorohexane diglycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , Glycerol triglycidyl ether, diglycerol polyglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether , Pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, dibromophenyl=glycidyl=ether, 2,6-diglycidylphenyl =glycidyl=ether, resorcinol diglycidyl ether, bis(2,7-diglycidyloxynaphthalen-1-yl)methane, 1,1,2,2-tetrakis(4-glycidyl) Oxyphenyl)ethane, 1,1,3-tris(4-glycidyloxyphenyl)propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether Ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 1,2- Bis(3,4-epoxycyclohexylmethoxy)ethane, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexanecarboxylic acid (3,4-Epoxycyclohexyl)methyl ester, 4,5-epoxy-2-methylcyclohexanecarboxylic acid 4,5-epoxy-2-methylcyclohexylmethyl ester, hexanediamine Acid bis(3,4-epoxycyclohexylmethyl), 1,2-epoxy-4-(epoxyethyl)cyclohexane, 4-(spiro[3,4-epoxycyclohexane Hexane-1,5'-[1,3]dioxan]-2'-yl)-1,2-epoxycyclohexane, diglycidyl adipate, diglycidyl phthalate Ester, diglycidyl tetrahydrophthalate, diglycidyl 1,2-cyclohexanedicarboxylate, tris(2-glycidoxyethyl)isocyanurate, monoallyl di Glycidyl isocyanurate, N,N'-diglycidyl N"-(2,3-dipropyloxypropyl) isocyanurate, N,N'-bis(2,3 -Dipropyloxypropyl)N"-glycidyl isocyanurate, tris(2,2-bis(glycidyloxymethyl)butyl)3,3',3"-(2, 4,6-Trioxo-1,3,5-triazinyl-1,3,5-triyl)tripropionate, N,N-diglycidyl-4-glycidyloxyaniline, N, N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 4,4'-methylene Bis(N,N-diglycidylaniline), 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl=glycidyl=ether, 2-(4,4-Dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid glycidyl ester, 2-(4,4-dimethylpentan-2-yl)- 5,7,7-Trimethyloctanoic acid 2,2-bis(glycidyloxymethyl)butyl ester, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin , anthracene novolak type epoxy resin, diphenyl novolac type epoxy resin, diphenyl novolac type epoxy resin, trisphenolmethane novolak type epoxy resin, tetraphenol novolac type epoxy resin, dicyclopentadien Novolac type epoxy resin, etc., but are not limited to these. In addition, commercially available products can be suitably used as the above-mentioned epoxy compounds, and examples thereof include TEPIC (registered trademark)-PAS B22, synonymous with PAS B26, synonymous with PAS B26L, synonymous with UC, FOLDI (registered trademark)-E101, and synonymous with E201 [all Nissan Chemical Co., Ltd.], jER (registered trademark) 828, Domo 807, Domo YX8000, Domo 157S70 [all manufactured by Mitsubishi Chemical Co., Ltd.], RIKARESIN (registered trademark) DME100 [manufactured by Shin Nippon Chemical Co., Ltd.] , Celoxide 2021P [made by Daicel Co., Ltd.], EPICLON (registered trademark) HP-4700, same as HP-4710, same as HP-7200L [all made by DIC Co., Ltd.], AV LITE (registered trademark) TEP-G [Asahi Organic materials (stock) system] and so on. These epoxy compounds can be used alone or in a mixture of two or more.

[硬化劑] 　　作為上述硬化劑並無特別限定，可使用例如酸酐、胺、酚樹脂(phenol resin)、聚醯胺樹脂、咪唑類、聚硫醇或該等的混合物。該等之中特別是以酚樹脂為較佳。 　　本發明之環氧樹脂組成物為藉由使用酚樹脂來作為硬化劑，以導入包含適度的酚骨架的交聯構造，從而可得到具有更加優異的耐熱性、耐龜裂性及密著性的密著層。[Hardening agent] The above-mentioned hardening agent is not particularly limited. For example, acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, polythiols, or mixtures thereof can be used. Among these, phenol resin is particularly preferred. The epoxy resin composition of the present invention uses a phenol resin as a hardener to introduce a cross-linked structure containing a moderate phenolic skeleton, thereby obtaining an epoxy resin composition with more excellent heat resistance, crack resistance and adhesion. Adhesion layer.

作為酚樹脂，可舉例如苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、萘酚醛清漆樹脂、蒽酚醛清漆樹脂、伸聯苯酚醛清漆樹脂、伸二甲苯酚醛清漆樹脂、三苯酚甲烷酚醛清漆樹脂、四苯酚酚醛清漆樹脂、雙環戊二烯酚醛清漆樹脂。特別是以苯酚酚醛清漆樹脂及三苯酚甲烷酚醛清漆樹脂為較佳。Examples of the phenol resin include phenol novolac resin, cresol novolac resin, naphthol novolac resin, anthracene novolak resin, diphenyl novolac resin, xylenol novolac resin, trisphenolmethane novolac resin, and tetraphenol. Novolac resin, dicyclopentadiene novolac resin. In particular, phenol novolak resin and trisphenolmethane novolak resin are preferred.

相對於環氧化合物的環氧基1當量，硬化劑為0.5~1.5當量，較佳可以0.8~1.2當量的比例來含有於環氧樹脂組成物中。相對於環氧化合物的硬化劑的當量，係以相對於環氧基的硬化劑的硬化性基的當量比來表示。尚，若在環氧樹脂組成物中，併用上述式[1]所表示的化合物與其他的環氧化合物之情形時，將相對於該全部環氧化合物的環氧基的當量設為前述範圍。 　　若硬化劑的當量少於該範圍時，硬化會變得不充分、硬化物的強度會降低，且密封樹脂硬化物與基板及/或引線電極有容易剝離之虞。The hardener is contained in the epoxy resin composition in a ratio of 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.8 to 1.2 equivalents. The equivalent weight of the curing agent with respect to the epoxy compound is represented by the equivalent ratio of the curing group of the curing agent with respect to the epoxy group. Incidentally, when the compound represented by the above formula [1] and other epoxy compounds are used together in the epoxy resin composition, the equivalent weight of the epoxy group relative to all the epoxy compounds is made into the aforementioned range. If the equivalent amount of the curing agent is less than this range, curing will be insufficient, the strength of the cured product will be reduced, and the sealing resin cured product may easily peel off from the substrate and/or lead electrodes.

[硬化觸媒] 　　又，本發明之環氧樹脂組成物中也可含有硬化觸媒。 　　作為硬化觸媒並無特別限定，可舉例如胺類、咪唑類、有機膦類、路易斯酸等。具體而言，可舉出1,8-二氮雜雙環(5.4.0)十一碳-7-烯(DBU)、三伸乙二胺、二甲苄胺、三乙醇胺、二甲胺乙醇、三(二甲胺甲基)苯酚等的三級胺類；2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、4-甲基-2-苯基咪唑、2-十七烷基咪唑等的咪唑類；三丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等的有機膦類；四苯基鏻四苯基硼酸酯、四苯基鏻乙基三苯基硼酸酯、四丁基鏻四丁基硼酸酯等的四取代鏻四取代硼酸酯類；2-乙基-4-甲基咪唑四苯基硼酸酯、N-甲基嗎福林四苯基硼酸酯等的四苯基硼鹽；四丁基鏻O,O-二乙基二硫代磷酸酯等。特別是以2-乙基-4-甲基咪唑為較佳。 　　作為添加量，相對於環氧樹脂100質量份，通常例如為0.001~5質量份，或0.001~1質量份、或0.05~1質量份、或0.05~0.3質量份的範圍。[Curing catalyst] In addition, the epoxy resin composition of the present invention may also contain a curing catalyst. The curing catalyst is not particularly limited, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acids. Specific examples include 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), triethylenediamine, dimethylbenzylamine, triethanolamine, dimethylamineethanol, Tertiary amines such as tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, Imidazoles such as 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc.; tetraphenylphosphonium tetraphenyl Tetrasubstituted phosphonium tetrasubstituted borate esters such as borate ester, tetraphenylphosphonium ethyl triphenylborate, tetrabutylphosphonium tetrabutylborate, etc.; 2-ethyl-4-methylimidazole tetraphenyl tetraphenylboron salts such as N-methylmorphine tetraphenylborate and N-methylmorphine tetraphenylborate; tetrabutylphosphonium O,O-diethyl dithiophosphate, etc. In particular, 2-ethyl-4-methylimidazole is preferred. The amount of addition is usually in the range of 0.001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.05 to 1 part by mass, or 0.05 to 0.3 parts by mass relative to 100 parts by mass of the epoxy resin.

[溶劑] 　　又，本發明之環氧樹脂組成物係可包含溶劑。又，本發明之環氧樹脂組成物，可溶解或分散於溶劑中而呈清漆(varnish)的形態。 　　作為溶劑，只要是可以溶解或分散式[1]所表示的環氧化合物及硬化劑、以及硬化觸媒等的其他的成分即可，並無特別限定。作為溶劑，可舉例如甲苯、二甲苯等的芳香族烴類；乙酸乙酯、乙酸丙酯、乙酸丁酯、γ-丁內酯(GBL)等的酯類；羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丙酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、2-羥基-3-甲基丁酸甲酯等的羥基酯類；甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、乙酸甲賽路蘇、乙酸乙賽路蘇、乙酸丁賽路蘇、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單甲基醚丙酸酯、丙二醇單乙基醚丙酸酯、丙二醇單丙基醚丙酸酯等的醚酯類；N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAc)、N-甲基-2-吡咯啶酮(NMP)等的醯胺類；甲基乙基酮(MEK)、甲基異丁酮(MIBK)、4-羥基-4-甲基-2-戊酮、環己酮等的酮類；乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇單甲基醚(PGME)、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等的醇類；四氫呋喃(THF)、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚等的醚類等、及該等的混合物。[Solvent] Furthermore, the epoxy resin composition of the present invention may contain a solvent. In addition, the epoxy resin composition of the present invention can be dissolved or dispersed in a solvent to take the form of a varnish. The solvent is not particularly limited as long as it can dissolve or disperse other components such as the epoxy compound represented by formula [1], the curing agent, and the curing catalyst. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate, propyl acetate, butyl acetate, and γ-butyrolactone (GBL); methyl glycolate and ethyl glycolate. Ester, propyl glycolate, methyl lactate, ethyl lactate, propyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 2-hydroxy-2-methyl Hydroxy esters such as methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate; methyl methoxyacetate, ethyl methoxyacetate , methoxypropyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, propoxymethyl acetate, propoxyethyl acetate, propoxypropyl acetate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropylpropionate, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid propyl ester, 3-ethoxypropionic acid methyl ester, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, Methylosal acetate, ethyl ether acetate, butylosal acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono Ether esters such as methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, etc.; N,N-dimethylformamide (DMF), N,N-dimethyl Acetamides (DMAc), N-methyl-2-pyrrolidone (NMP) and other amides; methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 4-hydroxy-4 - Ketones such as methyl-2-pentanone and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether , propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other alcohols; tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol Ethers such as diethyl ether and diethylene glycol ethyl methyl ether, and mixtures thereof.

該等之中，以至少包含酯類、醚酯類、或醯胺類的溶劑為較佳，以至少包含醚酯類、或醯胺類的溶劑為又較佳，以至少包含醯胺類的溶劑為更佳。又，以至少包含GBL、PGMEA、或NMP的溶劑為較佳，以至少包含PGMEA、或NMP的溶劑為又較佳，以至少包含NMP的溶劑為更佳。Among these, a solvent containing at least esters, ether esters, or amides is preferred, a solvent containing at least ether esters, or amides is further preferred, and a solvent containing at least amides is preferred. Solvents are better. Furthermore, a solvent containing at least GBL, PGMEA, or NMP is preferred, a solvent containing at least PGMEA or NMP is further preferred, and a solvent containing at least NMP is even more preferred.

[其他的硬化性單體] 　　又，本發明之環氧樹脂組成物，以調整環氧樹脂組成物的黏度或提升硬化性之目的下，在不損及本發明的效果的範圍內，也可含有硬化性單體。 　　例如，作為陽離子硬化性單體，可使用含有乙烯基的化合物、含有氧雜環丁烷基(oxetanyl)的化合物等。[Other curable monomers] In addition, the epoxy resin composition of the present invention can also be used for the purpose of adjusting the viscosity of the epoxy resin composition or improving the curability within the scope that does not impair the effect of the present invention. Contains hardening monomers. For example, as the cationic curable monomer, vinyl-containing compounds, oxetanyl-containing compounds, etc. can be used.

作為含有乙烯基的化合物，只要是具有乙烯基的化合物即可並無特別限定，可舉例如2-羥基乙基乙烯基醚(HEVE)、二乙二醇單乙烯基醚(DEGV)、2-羥基丁基乙烯基醚(HBVE)、三乙二醇二乙烯基醚等的乙烯基醚化合物等。又，也可使用在α位及/或β位具有烷基、烯丙基等的取代基的乙烯基化合物。又，可使用包含環氧基及/或氧雜環丁烷基等的環狀醚基的乙烯基醚化合物，可舉例如氧基降莰烯二乙烯基醚、3,3-二甲醇氧雜環丁烷二乙烯基醚等。 　　又，可使用具有乙烯基與(甲基)丙烯醯基的化合物，可舉例如(甲基)丙烯酸2-(2-乙烯基氧基乙氧基)乙酯等。 　　該等含有乙烯基的化合物係可單獨或可組合二種以上來使用。The compound containing a vinyl group is not particularly limited as long as it is a compound having a vinyl group. Examples thereof include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2- Vinyl ether compounds such as hydroxybutyl vinyl ether (HBVE) and triethylene glycol divinyl ether. Furthermore, a vinyl compound having a substituent such as an alkyl group or allyl group at the α-position and/or β-position may also be used. Vinyl ether compounds containing a cyclic ether group such as an epoxy group and/or an oxetanyl group can be used, and examples thereof include oxynorbornene divinyl ether and 3,3-dimethanol oxa cyclobutane divinyl ether, etc. Furthermore, compounds having a vinyl group and a (meth)acrylyl group can be used, and examples thereof include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. These vinyl-containing compounds can be used alone or in combination of two or more.

作為含有氧雜環丁烷基的化合物，只要是具有氧雜環丁烷基的化合物即可並無特別限定，可舉出3-乙基-3-(羥基甲基)氧雜環丁烷(OXA)、3-乙基-3-(苯氧基甲基)氧雜環丁烷(POX)、雙((3-乙基-3-氧雜環丁烷)甲基)醚(DOX)、1,4-雙(((3-乙基-3-氧雜環丁烷)甲氧基)甲基)苯(XDO)、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷(EHOX)、3-乙基-3-((3-三乙氧基甲矽烷基丙氧基)甲基)氧雜環丁烷(TESOX)、苯酚酚醛清漆氧雜環丁烷(PNOX-1009)等的氧雜環丁烷化合物等。 　　又，可使用具有氧雜環丁烷基與(甲基)丙烯醯基的化合物，可舉例如(3-乙基-3-氧雜環丁烷)甲基(甲基)丙烯酸酯等。 　　該等的含有氧雜環丁烷基的化合物係可單獨或可組合二種以上來使用。The compound containing an oxetanyl group is not particularly limited as long as it is a compound having an oxetanyl group. Examples thereof include 3-ethyl-3-(hydroxymethyl)oxetane ( OXA), 3-ethyl-3-(phenoxymethyl)oxetane (POX), bis((3-ethyl-3-oxetane)methyl)ether (DOX), 1,4-Bis(((3-ethyl-3-oxetane)methoxy)methyl)benzene (XDO), 3-ethyl-3-(2-ethylhexyloxymethyl) )oxetane (EHOX), 3-ethyl-3-((3-triethoxysilylpropoxy)methyl)oxetane (TESOX), phenol novolac oxetane Oxetane compounds such as butane (PNOX-1009), etc. Furthermore, compounds having an oxetanyl group and a (meth)acrylyl group can be used, and examples thereof include (3-ethyl-3-oxetane)methyl(meth)acrylate. These oxetanyl group-containing compounds can be used alone or in combination of two or more.

[其他的成分] 　　又，本發明之環氧樹脂組成物，因應所需可包含慣用的添加劑。作為如此般的添加劑，可舉例如界面活性劑、密著促進劑、增稠劑、增感劑、消泡劑、調平劑、塗佈性改良劑、潤滑劑、穩定劑(抗氧化劑、熱穩定劑、耐光穩定劑等)、可塑劑、溶解促進劑、填充材(二氧化矽等)、抗靜電劑等。該等的添加劑係可單獨或可組合二種以上。[Other ingredients] In addition, the epoxy resin composition of the present invention may contain conventional additives as needed. Examples of such additives include surfactants, adhesion accelerators, thickeners, sensitizers, defoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, thermal Stabilizer, light stabilizer, etc.), plasticizer, dissolution accelerator, filler (silica, etc.), antistatic agent, etc. These additives may be used alone or in combination of two or more types.

本發明之環氧樹脂組成物中，就提升塗佈性之目的下，可添加界面活性劑。作為如此般之界面活性劑，可舉出氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等，特別是並非被限定於該等。前述界面活性劑係可單獨或可組合二種類以上來使用。 　　該等之界面活性劑之中，就塗佈性改善效果之程度而言，以氟系界面活性劑為較佳。作為氟系界面活性劑的具體例，可舉例如F-Top (註冊商標)EF-301、同EF-303、同EF-352[皆為Mitsubishi Materials Electronic Chemicals(股)製]、MegaFace(註冊商標)F-171、同F-173、同F-482、同R-08、同R-30、同R-90、同BL-20[皆為DIC(股)製]、Fluorad FC-430、同FC-431[皆為3M Japan(股)製]、AashiGuard(註冊商標)AG-710[旭硝子(股)製]、Surflon S-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106[皆為AGCSEIMI CHEMICAL (股)製]等，但並非被限定於該等。 　　本發明之環氧樹脂組成物中之界面活性劑的添加量，基於該環氧樹脂組成物的固形分的含有量為0.01~5質量%，較佳為0.01~3質量%，又較佳為0.01~2質量%。In the epoxy resin composition of the present invention, a surfactant may be added for the purpose of improving coatability. Examples of such surfactants include, but are not limited to, fluorine-based surfactants, polysiloxane-based surfactants, nonionic surfactants, and the like. The aforementioned surfactant can be used alone or in combination of two or more types. Among these surfactants, fluorine-based surfactants are preferred in terms of the degree of coating property improvement effect. Specific examples of the fluorine-based surfactant include F-Top (registered trademark) EF-301, Dodo EF-303, Dodo EF-352 [all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.], MegaFace (Registered Trademark) )F-171, same as F-173, same as F-482, same as R-08, same as R-30, same as R-90, same as BL-20 [all made by DIC (stock)], Fluorad FC-430, same as FC-431 [both manufactured by 3M Japan Co., Ltd.], AashiGuard (registered trademark) AG-710 [manufactured by Asahi Glass Co., Ltd.], Surflon S-382, same as SC-101, same as SC-102, same as SC-103, Same as SC-104, same as SC-105, same as SC-106 [all manufactured by AGCSEIMI CHEMICAL (stock)], etc., but not limited to them. The amount of surfactant added to the epoxy resin composition of the present invention is 0.01 to 5 mass % based on the solid content of the epoxy resin composition, preferably 0.01 to 3 mass %, and preferably 0.01 to 3 mass %. 0.01~2 mass%.

本發明之環氧樹脂組成物中，就提升該塗佈膜的平坦性之目的下，可添加二氧化矽等的無機微粒子。作為如此般的無機微粒子係可適合使用市售品，可舉例如Snowtex(註冊商標)series、Organosilicasol series[皆為日產化學工業(股)製]等。前述無機微粒子係可單獨或可組合2種類以上來使用。 　　本發明之環氧樹脂組成物中之無機微粒子的添加量，基於該環氧樹脂組成物的固形分的含有量為0.1~20質量%，較佳為0.1~10質量%，又較佳為1~10質量%。In the epoxy resin composition of the present invention, inorganic fine particles such as silica may be added for the purpose of improving the flatness of the coating film. As such an inorganic fine particle system, commercially available products can be suitably used, and examples thereof include Snowtex (registered trademark) series, Organosilicasol series [all manufactured by Nissan Chemical Industry Co., Ltd.], and the like. The above-mentioned inorganic fine particles can be used alone or in combination of two or more types. The amount of inorganic fine particles added to the epoxy resin composition of the present invention is 0.1 to 20 mass % based on the solid content of the epoxy resin composition, preferably 0.1 to 10 mass %, and more preferably 1 ~10% by mass.

本發明之環氧樹脂組成物中，就提升密封樹脂硬化物、基板及/或與引線電極的密著性之目的下，可添加密著促進劑。作為該等的密著促進劑，可舉例如氯三甲基矽烷、三氯(乙烯基)矽烷、氯(二甲基)(乙烯基)矽烷、氯(甲基)(二苯基)矽烷、氯(氯甲基)(二甲基)矽烷等的氯矽烷類；甲氧基三甲基矽烷、二甲氧基二甲基矽烷、二乙氧基二甲基矽烷、乙氧基(二甲基)(乙烯基)矽烷、二甲氧基二苯基矽烷、三乙氧基(苯基)矽烷、3-氯丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、三甲氧基(3-(N-哌啶基)丙基)矽烷等的烷氧基矽烷類；六甲基二矽氮烷、N,N’-雙(三甲基甲矽烷基)脲、二甲基(三甲基甲矽烷基)胺、三甲基甲矽烷基咪唑等的矽氮烷類；咪唑、吲唑、苯并咪唑、苯并***、巰基咪唑、巰基嘧啶、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑、脲唑、硫尿嘧啶等的含氮雜環化合物；1,1-二甲基脲、1,3-二甲基脲等的脲類或硫脲類等。該等密著促進劑係可單獨或可組合二種類以上來使用。 　　本發明之環氧樹脂組成物中之密著促進劑的添加量，基於該環氧樹脂組成物的固形分的含有量通常為20質量%以下，較佳為0.01~10質量%，又較佳為0.05~5質量%。In the epoxy resin composition of the present invention, an adhesion accelerator may be added for the purpose of improving the adhesion between the cured sealing resin, the substrate, and/or the lead electrode. Examples of such adhesion accelerators include chlorotrimethylsilane, trichloro(vinyl)silane, chloro(dimethyl)(vinyl)silane, chloro(methyl)(diphenyl)silane, Chlorosilanes such as chloro(chloromethyl)(dimethyl)silane; methoxytrimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, ethoxy(dimethylsilane) (vinyl)silane, dimethoxydiphenylsilane, triethoxy(phenyl)silane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Alkoxysilane such as (meth)acryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, trimethoxy(3-(N-piperidyl)propyl)silane, etc. Silanes; hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyl(trimethylsilyl)amine, trimethylsilylimidazole, etc. Silazanes; imidazole, indazole, benzimidazole, benzotriazole, mercaptoimidazole, mercaptopyrimidine, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, ureazole, Nitrogen-containing heterocyclic compounds such as thiouracil; ureas or thioureas such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion accelerators can be used alone or in combination of two or more types. The amount of the adhesion accelerator added to the epoxy resin composition of the present invention is usually 20% by mass or less based on the solid content of the epoxy resin composition, preferably 0.01 to 10% by mass, and preferably 0.01 to 10% by mass. It is 0.05~5 mass%.

[環氧樹脂組成物的調製方法] 　　本發明之環氧樹脂組成物係藉由混合下述而得到：至少包含上述式[1]所表示的環氧化合物的環氧基成分、上述硬化劑、與依期望的硬化觸媒。又，依所需可添加上述溶劑。 　　只要可均勻地混合即可，該等之混合並無特別限定，例如，可使用反應燒瓶與攪拌翼或混合機等來進行。 　　混合係考量黏度並因應所需在加熱下來進行，可以10~100℃的溫度下進行0.5~1小時。[Preparation method of epoxy resin composition] The epoxy resin composition of the present invention is obtained by mixing the following: an epoxy group component containing at least the epoxy compound represented by the above formula [1], the above-mentioned hardener, With the desired hardening catalyst. Moreover, the above-mentioned solvent can be added as needed. The mixing is not particularly limited as long as it can be mixed uniformly. For example, a reaction flask and a stirring blade or a mixer can be used. The mixing system considers the viscosity and heats it as needed. It can be carried out at a temperature of 10~100℃ for 0.5~1 hour.

本發明之環氧樹脂組成物中之固形分濃度，例如可設為1~100質量%，或1~80質量%，或10~80質量%，或10~60質量%，或20~60質量%。於此，所謂的固形分係指環氧樹脂組成物中之溶劑以外的全部成分。 　　本發明之環氧樹脂組成物係能夠調整成為任意的黏度，故具有用來使用作為半導體裝置密著層形成用環氧樹脂組成物而言為適當的黏度。The solid content concentration in the epoxy resin composition of the present invention can be, for example, 1 to 100 mass %, or 1 to 80 mass %, or 10 to 80 mass %, or 10 to 60 mass %, or 20 to 60 mass %. %. Here, the so-called solid content refers to all components in the epoxy resin composition except the solvent. The epoxy resin composition of the present invention can be adjusted to any viscosity, so it has a suitable viscosity for use as an epoxy resin composition for forming an adhesive layer of a semiconductor device.

＜半導體裝置＞ 　　本發明之半導體裝置係由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置，在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分具備由上述環氧樹脂組成物的硬化物所成的密著層。<Semiconductor device> The semiconductor device of the present invention is a semiconductor device composed of a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a sealing resin cured product for sealing these. In the sealing resin At least part of the interface between the cured product and the substrate and/or the lead electrode is provided with an adhesive layer made of the cured product of the epoxy resin composition.

本發明之半導體裝置可藉由下述的半導體裝置的製造方法而得到，其係包含：將本發明相關的環氧樹脂組成物塗佈至搭載半導體元件的基板及/或接合於半導體元件的引線電極之至少一部分的步驟、將經塗佈的環氧樹脂組成物的塗膜硬化並形成密著層的步驟、及在密著層上形成密封樹脂硬化物的步驟。The semiconductor device of the present invention can be obtained by the following method of manufacturing a semiconductor device, which includes applying the epoxy resin composition related to the present invention to a substrate mounting a semiconductor element and/or a lead bonded to the semiconductor element. The steps of forming at least a part of the electrode, the step of curing the applied epoxy resin composition film to form an adhesion layer, and the step of forming a cured sealing resin on the adhesion layer.

在將本發明相關的環氧樹脂組成物塗佈至搭載半導體元件的基板及/或接合於半導體元件的引線電極之至少一部分的步驟中，塗佈環氧樹脂的方法並無特別限定，可舉例如流動塗佈法、旋轉塗佈法、噴塗塗佈法、網板印刷法、柔版印刷法、噴墨印刷法、澆鑄法、桿式塗佈法、簾流式塗佈法、輥式塗佈法、凹版塗佈法、浸漬法、狹縫法、點膠法等。 　　塗佈本發明之環氧樹脂組成物係可以是在基板的全面，也可以是在與密封樹脂硬化物接觸的基板及/或引線電極的全面或其一部分。以在與密封樹脂硬化物接觸的基板及/或引線電極的全面來進行塗佈為較佳。In the step of applying the epoxy resin composition related to the present invention to at least a part of a substrate mounting a semiconductor element and/or a lead electrode bonded to the semiconductor element, the method of applying the epoxy resin is not particularly limited, and examples thereof include Such as flow coating method, spin coating method, spray coating method, screen printing method, flexographic printing method, inkjet printing method, casting method, rod coating method, curtain flow coating method, roller coating method Cloth method, gravure coating method, dipping method, slit method, dispensing method, etc. The epoxy resin composition of the present invention may be applied to the entire surface of the substrate, or may be applied to the entire surface or part of the substrate and/or lead electrodes that are in contact with the cured sealing resin. It is preferable to apply the coating on the entire surface of the substrate and/or the lead electrode that is in contact with the cured sealing resin.

在將經塗佈的環氧樹脂組成物的塗膜硬化並形成密著層的步驟中，將環氧樹脂組成物的塗膜硬化的方法並無特別限定，可利用加熱、光照射、電子線照射等的周知的方法。塗膜的加熱係可以例如室溫(大約23℃)~250℃左右下來進行。加熱時間係可從3秒鐘以上(例如3秒鐘~5小時左右)的範圍來做選擇，例如為5秒鐘~2小時左右。又，藉由將塗膜予以預備加熱來使其乾燥後，可進行加熱硬化。In the step of hardening the coated film of the epoxy resin composition to form an adhesion layer, the method of hardening the coated film of the epoxy resin composition is not particularly limited, and heating, light irradiation, or electron beams can be used. Well-known methods of irradiation, etc. The coating film can be heated, for example, at room temperature (about 23°C) to about 250°C. The heating time can be selected from a range of more than 3 seconds (for example, about 3 seconds to about 5 hours), for example, about 5 seconds to about 2 hours. In addition, the coating film can be preliminarily heated and dried, and then heated and hardened.

由本發明之環氧樹脂組成物所形成的塗膜的厚度，因應硬化物之用途，可從0.01μm~10mm左右的範圍來做選擇，例如，使用於半導體裝置的密著層之情形時，例如可設為0.1~20μm，例如可設為0.2~15μm，例如可設為0.3~10μm，例如0.5~7μm左右。若厚度較該範圍為薄之情形時，密著力會降低，維持密封樹脂硬化物與基板及/或引線電極的接著的效果將會有降低之虞。又，若厚度較該範圍為厚之情形時，溶劑難以乾燥，而在密著層上會殘留溶劑等，將會有無法發揮充分的密著性之情形。The thickness of the coating film formed by the epoxy resin composition of the present invention can be selected from the range of about 0.01 μm to 10 mm according to the use of the cured product. For example, when it is used as an adhesive layer of a semiconductor device, for example It can be set to 0.1~20 μm, for example, it can be set to 0.2~15 μm, for example, it can be set to 0.3~10 μm, for example, it can be set to about 0.5~7 μm. If the thickness is thinner than this range, the adhesion force will be reduced, and the effect of maintaining the bonding between the cured sealing resin material and the substrate and/or the lead electrode may be reduced. In addition, if the thickness is thicker than this range, the solvent will be difficult to dry, and the solvent will remain on the adhesive layer, so that sufficient adhesiveness may not be exerted.

本發明之在密著層上形成密封樹脂硬化物的步驟中，形成所使用的密封樹脂及密封樹脂硬化物的方法並無特別限定，可使用周知的密封樹脂及其硬化物形成方法。 [產業利用性]In the step of forming the sealing resin cured product on the adhesion layer of the present invention, the sealing resin and the method of forming the sealing resin cured product are not particularly limited, and well-known sealing resin and cured product forming methods can be used. [Industrial Applicability]

本發明之包含環氧化合物及硬化劑的環氧樹脂組成物係具有硬化性，可廣泛利用在半導體裝置，例如半導體元件、金屬電極、及/或基板與半導體基板的密封樹脂硬化物的密著層等的電子材料領域中。特別是可適合利用在元件溫度為高溫的次世代功率半導體裝置等之中。 [實施例]The epoxy resin composition containing an epoxy compound and a hardener of the present invention has curability and can be widely used in semiconductor devices, such as semiconductor elements, metal electrodes, and/or the close adhesion of sealing resin cured materials between substrates and semiconductor substrates. In the field of electronic materials such as layers. In particular, it can be suitably used in next-generation power semiconductor devices with high element temperatures. [Example]

以下，舉出實施例更具體的說明本發明，但本發明並非被限定於下述之實施例。 　　尚，實施例中使用於樣品的調製及物性的分析之裝置及條件係如以下般。Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Note that the equipment and conditions used for sample preparation and physical property analysis in the examples are as follows.

(1)接合強度試驗 　　裝置：Nordson Advanced Technology(股)製萬能型黏結強度試驗機 series4000 　　探針位置：從底面起100μm 　　探針速度：100μm/秒(1) Bonding strength test Equipment: Universal bonding strength testing machine series4000 manufactured by Nordson Advanced Technology Co., Ltd. Probe position: 100 μm from the bottom Probe speed: 100 μm/second

又，代號係表示以下之意思。 　　BPA：雙酚A型環氧樹脂[三菱化學(股)製jER(註冊商標)828] 　　CEL：3,4-環氧基環己烷羧酸(3,4-環氧基環己基)甲酯[(股)Daicel製Celoxide 2021P] 　　DCPN：雙環戊二烯酚醛清漆型環氧樹脂[DIC(股)製EPICLON(註冊商標)HP-7200L] 　　Nap：萘型4官能環氧樹脂[DIC(股)製EPICLON(註冊商標)HP-4700] 　　TEPeIC：三(4,5-環氧基戊基)異氰脲酸酯[日產化學工業(股)製TEPIC(註冊商標)-VL] 　　TGIC：三縮水甘油基異氰脲酸酯[日產化學工業(股)製TEPIC(註冊商標)-L] 　　BPNv：伸聯苯酚醛清漆樹脂[明和化成(股)製MEHC-7851H] 　　PNv：苯酚酚醛清漆樹脂[DIC(股)製PHENOLITE(註冊商標)TD-2131] 　　TPMNv：三苯酚甲烷酚醛清漆樹脂[明和化成(股)製MEH-7500] 　　2E4MZ：2-乙基-4-甲基咪唑[東京化成工業(股)製] 　　MH700：4-甲基六氫鄰苯二甲酸酐/六氫鄰苯二甲酸酐混合物(莫耳比70：30)[新日本理化(股)製Rikacid(註冊商標)MH-700] 　　PX4ET：四丁基鏻O,O-二乙基二硫代磷酸酯[日本化學工業(股)製HISHICOLIN(註冊商標)PX-4ET] 　　ST：膠質二氧化矽[預先利用NMP來取代日產化學工業(股)製Organosilicasol MEK-ST-40的分散媒，固形分：40質量%] 　　BCA：乙酸丁賽路蘇(butyl cellosolve acetate) 　　NMP：N-甲基-2-吡咯啶酮 　　PGMEA：丙二醇單甲基醚乙酸酯In addition, the code names represent the following meanings. BPA: Bisphenol A type epoxy resin [jER (registered trademark) 828 manufactured by Mitsubishi Chemical Co., Ltd.] CEL: 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl) methyl ester [Celoxide 2021P manufactured by Daicel Co., Ltd.] DCPN: Dicyclopentadiene novolak type epoxy resin [EPICLON (registered trademark) HP-7200L manufactured by DIC Co., Ltd.] Nap: Naphthalene type 4-functional epoxy resin [DIC Co., Ltd. EPICLON (registered trademark) HP-4700] TEPeIC: Tris(4,5-epoxypentyl) isocyanurate [TEPIC (registered trademark)-VL manufactured by Nissan Chemical Industry Co., Ltd.] TGIC: Triglycidyl Isocyanurate [TEPIC (registered trademark)-L manufactured by Nissan Chemical Industry Co., Ltd.] BPNv: Diphenyl novolac resin [MEHC-7851H manufactured by Meiwa Kasei Co., Ltd.] PNv: Phenol novolac resin [DIC ( PHENOLITE (registered trademark) TD-2131] manufactured by Meiwa Chemical Industry Co., Ltd.] TPMNv: Trisphenolmethane novolak resin [MEH-7500 manufactured by Meiwa Chemical Co., Ltd.] 2E4MZ: 2-ethyl-4-methylimidazole [Tokyo Chemical Industry Co., Ltd. [Manufactured] MH700: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride mixture (mol ratio 70:30) [Rikacid (registered trademark) MH-700 manufactured by New Nippon Rika Co., Ltd.] PX4ET : Tetrabutylphosphonium O,O-diethyl dithiophosphate [HISHICOLIN (registered trademark) PX-4ET manufactured by Nippon Chemical Industry Co., Ltd.] ST: Colloidal silica [Use NMP in advance to replace Nippon Chemical Industry Co., Ltd. (Nihon Chemical Industry Co., Ltd.) Dispersion medium of Organosilicasol MEK-ST-40 manufactured by Co., Ltd., solid content: 40% by mass] BCA: butyl cellosolve acetate NMP: N-methyl-2-pyrrolidinone PGMEA: propylene glycol monomethyl Ether acetate

[實施例1] 　　混合作為環氧化合物的TGIC 100質量份、作為硬化劑的TPMNv 98質量份、作為硬化觸媒的2E4MZ 0.1質量份、及作為溶劑的NMP 462質量份，以調製密著層形成用組成物。 　　將該組成物澆鑄塗佈至鍍銀的銅基板[長40mm×寬10mm×厚0.5mm]的鍍銀面上。藉由將該塗膜以180℃的加熱板乾燥5分鐘後，再以220℃的加熱板加熱3小時來使其硬化，以形成密著層。 　　在該基板上所形成的密著層上，藉由轉印成形來將半導體密封用環氧樹脂成形為上底Φ2.90mm、下底Φ3.57mm、高度4.00mm的圓錐台形狀。測定所得到的成形體在室溫(大約23℃)及225℃下的與基板的接合強度。將結果表示於表1。[Example 1] 100 parts by mass of TGIC as an epoxy compound, 98 parts by mass of TPMNv as a hardener, 0.1 parts by mass of 2E4MZ as a hardening catalyst, and 462 parts by mass of NMP as a solvent were mixed to prepare an adhesive layer. Use composition. The composition was cast and coated on the silver-plated surface of a silver-plated copper substrate [length 40 mm × width 10 mm × thickness 0.5 mm]. The coating film was dried on a hot plate at 180° C. for 5 minutes, and then heated on a hot plate at 220° C. for 3 hours to harden it to form an adhesive layer. On the adhesive layer formed on the substrate, the epoxy resin for semiconductor sealing is molded by transfer molding into a truncated cone shape with an upper base of Φ2.90mm, a lower base of Φ3.57mm, and a height of 4.00mm. The bonding strength between the obtained molded body and the substrate was measured at room temperature (about 23°C) and 225°C. The results are shown in Table 1.

[實施例2~5、比較例1~3] 　　除了將密著層形成用組成物的各組成、乾燥條件、硬化條件、及接合強度測定溫度分別變更成如表1所記載般以外，與實施例1以相同方式來製作成形體並測定接合強度。將結果合併表示於表1。[Examples 2 to 5, Comparative Examples 1 to 3] Except for changing each composition of the adhesive layer forming composition, drying conditions, hardening conditions, and joint strength measurement temperature to those described in Table 1, the same procedures were carried out. Example 1 A molded body was produced in the same manner and the joint strength was measured. The results are combined and shown in Table 1.

[比較例4] 　　未形成密著層而直接在鍍銀的銅基板的鍍銀面上，與實施例1以相同方式來製作成形體，並測定接合強度。將結果合併表示於表1。[Comparative Example 4] Without forming an adhesion layer, a molded body was produced directly on the silver-plated surface of a silver-plated copper substrate in the same manner as in Example 1, and the bonding strength was measured. The results are combined and shown in Table 1.

如表1所表示般，相較於具有由比較例1、2的環氧樹脂組成物(該等係未包含具有三聚氰酸骨架的環氧化合物)所得到的密著層而成的成形體、及比較例4的成形體(其係不具有密著層)，具有由實施例1~5的環氧樹脂組成物所得到的密著層而成的成形體為展現出更高的接合強度(密著性)。 　　又，相較於比較例4的不具有密著層的成形體、及具有由比較例1的環氧樹脂所得到的密著層而成的成形體，具有由實施例1的環氧樹脂組成物所得到的密著層而成的成形體在225℃下展現出更高的接合強度(密著性)，故可確認耐熱性為優異。As shown in Table 1, compared with the molding having an adhesion layer obtained from the epoxy resin compositions of Comparative Examples 1 and 2 (these do not contain an epoxy compound having a cyanuric acid skeleton) body, and the molded body of Comparative Example 4 (which does not have an adhesion layer), the molded body having an adhesion layer obtained from the epoxy resin composition of Examples 1 to 5 exhibits higher bonding. Strength (adhesion). Furthermore, compared to the molded article without an adhesive layer of Comparative Example 4 and the molded article having an adhesive layer obtained from the epoxy resin of Comparative Example 1, the composition of the epoxy resin of Example 1 is Since the molded body formed by the obtained adhesive layer exhibited higher joint strength (adhesion) at 225°C, it was confirmed that the heat resistance was excellent.

[實施例6~8] 　　除了將鍍銀的銅基板變更成氮化鋁基板、並將密著層形成用組成物的各組成、乾燥條件、硬化條件、及接合強度測定溫度分別變更成如表2所記載般以外，與實施例1以相同方式來製作成形體並測定接合強度。將結果合併表示於表2。[Examples 6 to 8] In addition to changing the silver-plated copper substrate to an aluminum nitride substrate, and changing the compositions, drying conditions, hardening conditions, and joint strength measurement temperatures of the adhesion layer forming composition to the following table: Except as described in 2, a molded body was produced in the same manner as in Example 1, and the bonding strength was measured. The results are combined and shown in Table 2.

[比較例5] 　　未形成密著層而直接在氮化鋁基板上，與實施例1以相同方式來製作成形體，並測定接合強度。將結果合併表示於表2。[Comparative Example 5] Without forming an adhesion layer, a molded body was produced directly on the aluminum nitride substrate in the same manner as in Example 1, and the bonding strength was measured. The results are combined and shown in Table 2.

如表2所表示般，因由實施例6~8的環氧樹脂組成物所得到的密著層，可發現半導體密封用環氧樹脂對氮化鋁基板的接合強度(密著性)為提升。As shown in Table 2, it was found that the bonding strength (adhesion) of the semiconductor sealing epoxy resin to the aluminum nitride substrate was improved due to the adhesive layer obtained from the epoxy resin composition of Examples 6 to 8.

[實施例9~11、比較例6] 　　除了將鍍銀的銅基板變更成氮化鋁基板、並將密著層形成用組成物的各組成、乾燥條件、硬化條件、及接合強度測定溫度分別變更成如表3所記載般以外，與實施例1以相同方式來製作成形體並測定接合強度。將結果合併表示於表3。[Examples 9 to 11, Comparative Example 6] In addition to changing the silver-plated copper substrate to an aluminum nitride substrate, and changing the compositions, drying conditions, hardening conditions, and joint strength measurement temperatures of the adhesive layer forming composition, respectively Except for changing to what is described in Table 3, in the same manner as in Example 1, a molded body was produced and the joint strength was measured. The results are combined and shown in Table 3.

如表3所表示般，相較於具有由比較例6的環氧樹脂組成物(其係未包含具有三聚氰酸骨架的環氧化合物)所得到的密著層而成的成形體，具有由實施例9~11的環氧樹脂組成物所得到的密著層而成的成形體為在室溫(大約23℃)及175℃下展現出更高的接合強度(密著性)。As shown in Table 3, compared with the molded article having the adhesion layer obtained from the epoxy resin composition of Comparative Example 6 (which does not contain an epoxy compound having a cyanuric acid skeleton), it has The molded article formed from the adhesion layer obtained from the epoxy resin compositions of Examples 9 to 11 exhibits higher joint strength (adhesion) at room temperature (about 23°C) and 175°C.

Claims (6)

一種半導體裝置密著層形成用環氧樹脂組成物，其係在由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置中，用來形成在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分所具備的密著層之環氧樹脂組成物，以清漆的形態來使用前述環氧樹脂組成物，前述環氧樹脂組成物包含：式[1]所表示的環氧化合物、硬化劑、及溶劑，前述硬化劑係包含三苯酚甲烷酚醛清漆樹脂，相對於前述環氧化合物的環氧基1當量，前述硬化劑為以0.5~1.5當量含有於前述環氧樹脂組成物中，前述溶劑包含酯類、醚酯類或醯胺類之至少1種，
Figure 107116294-A0305-02-0030-1
 (式中，R1至R3係分別獨立表示氫原子或甲基，L1至L3係分別獨立表示碳原子數1~7的伸烷基)。 An epoxy resin composition for forming an adhesive layer of a semiconductor device, which is composed of a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a cured sealing resin for sealing these. In a semiconductor device, an epoxy resin composition for forming an adhesion layer provided in at least part of the interface between the cured sealing resin and the substrate and/or the lead electrode is used in the form of a varnish. Resin composition, the aforementioned epoxy resin composition includes: an epoxy compound represented by formula [1], a hardener, and a solvent; the aforementioned hardener is a trisphenolmethane novolak resin; The aforementioned hardener is contained in the aforementioned epoxy resin composition in an amount of 0.5 to 1.5 equivalents based on 1 equivalent, and the aforementioned solvent includes at least one of esters, ether esters or amides,
Figure 107116294-A0305-02-0030-1
 (In the formula, R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and L 1 to L 3 each independently represent an alkylene group having 1 to 7 carbon atoms). 如請求項1之環氧樹脂組成物，其中，進而包含硬化觸媒。 The epoxy resin composition according to claim 1, further comprising a curing catalyst. 一種半導體裝置，其係由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置，在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分具備由請求項1或請求項2之環氧樹脂組成物的硬化物所成的密著層。 A semiconductor device consisting of a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a cured sealing resin for sealing these, wherein the cured sealing resin and At least part of the interface between the substrate and/or the lead electrode is provided with an adhesive layer made of a cured product of the epoxy resin composition of Claim 1 or Claim 2. 一種半導體裝置的製造方法，其係包含：將請求項1或請求項2之環氧樹脂組成物塗佈至搭載半導體元件的基板及/或接合於半導體元件的引線電極之至少一部分的步驟、將前述塗膜硬化並形成密著層的步驟、在前述密著層上形成密封樹脂硬化物的步驟。 A method for manufacturing a semiconductor device, which includes the steps of applying the epoxy resin composition of Claim 1 or Claim 2 to at least a part of a substrate mounting a semiconductor element and/or a lead electrode bonded to the semiconductor element, and applying The steps of curing the coating film to form an adhesion layer, and forming a cured sealing resin on the adhesion layer. 一種環氧樹脂組成物作為半導體裝置密著層之用途，該密著層係在由半導體元件、搭載半導體元件的基板及/或接合於半導體元件的引線電極、以及將該等密封的密封樹脂硬化物所構成的半導體裝置中，形成在前述密封樹脂硬化物、與前述基板及/或前述引線電極之界面之至少一部分，該環氧樹脂組成物係以清漆的形態來使用，該環氧樹脂組成物包含：式[1]所表示的環氧化合物、硬化劑、及溶劑，前述溶劑包含酯類、醚酯類或醯胺類之至少1種，
Figure 107116294-A0305-02-0032-2
 (式中，R1至R3係分別獨立表示氫原子或甲基，L1至L3係分別獨立表示碳原子數1~7的伸烷基)。 An epoxy resin composition is used as an adhesive layer of a semiconductor device. The adhesive layer is composed of a semiconductor element, a substrate mounting the semiconductor element and/or a lead electrode bonded to the semiconductor element, and a sealing resin that hardens these seals. In the semiconductor device composed of the sealing resin cured product, at least a part of the interface with the substrate and/or the lead electrode is formed, and the epoxy resin composition is used in the form of a varnish, and the epoxy resin composition The substance includes: an epoxy compound represented by formula [1], a hardener, and a solvent, and the aforementioned solvent includes at least one of esters, ether esters, or amides,
Figure 107116294-A0305-02-0032-2
 (In the formula, R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and L 1 to L 3 each independently represent an alkylene group having 1 to 7 carbon atoms). 如請求項5之用途，其中，前述硬化劑係包含由苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、萘酚醛清漆樹脂、蒽酚醛清漆樹脂、伸聯苯酚醛清漆樹脂、伸二甲苯酚醛清漆樹脂、三苯酚甲烷酚醛清漆樹脂、四苯酚酚醛清漆樹脂及雙環戊二烯酚醛清漆樹脂所成之群中選出之至少1種。 Such as the use of claim 5, wherein the aforementioned hardener is composed of phenol novolac resin, cresol novolac resin, naphthol novolac resin, anthracene novolac resin, diphenyl novolac resin, xylylene novolac resin, At least one selected from the group consisting of phenolmethane novolac resin, tetraphenol novolac resin and dicyclopentadiene novolac resin.
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