TWI742139B - Resin composition, resin sheet and semiconductor device - Google Patents

Resin composition, resin sheet and semiconductor device Download PDF

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TWI742139B
TWI742139B TW106128041A TW106128041A TWI742139B TW I742139 B TWI742139 B TW I742139B TW 106128041 A TW106128041 A TW 106128041A TW 106128041 A TW106128041 A TW 106128041A TW I742139 B TWI742139 B TW I742139B
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triazine compound
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柄澤泰紀
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日商琳得科股份有限公司
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Abstract

本發明係揭示一種樹脂組成物，其為含有熱硬化性成分、熱塑性樹脂、填料與三嗪化合物，前述三嗪化合物為下述一般式（1）所表示。一般式（1）中，R1 為氫原子或烷基，R2 為氫原子或烷基，X為含有由烷基、苯基、羥基、烷氧基及烷氧基矽烷基所成群中所選出之至少任一種的基。

Figure 106128041-A0101-11-0001-1
The present invention discloses a resin composition containing a thermosetting component, a thermoplastic resin, a filler, and a triazine compound. The triazine compound is represented by the following general formula (1). In general formula (1), R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, and X is a group consisting of an alkyl group, a phenyl group, a hydroxyl group, an alkoxy group, and an alkoxysilyl group. At least any one of the selected bases.
Figure 106128041-A0101-11-0001-1

Description

樹脂組成物、樹脂薄片及半導體裝置Resin composition, resin sheet and semiconductor device

本發明係有關樹脂組成物、樹脂薄片及半導體裝置。The present invention relates to a resin composition, a resin sheet, and a semiconductor device.

先前已知接著劑層係使用樹脂組成物之接著薄片。 　　例如文獻1（專利第5195454號公報）曾揭示，依序層合聚對苯二甲酸乙二醇酯等之支撐物，與形成於該支撐物物上之樹脂組成物層，與保護該樹脂組成物層之聚丙烯薄膜等之保護薄膜所得的接著薄膜。文獻1所記載之樹脂組成物為，含有多官能環氧樹脂、硬化劑、苯氧基樹脂，及無機填充材。 　　但要求接著劑層所使用之樹脂組成物為，降低吸水率且提升接著強度。It is known that the adhesive layer is an adhesive sheet using a resin composition. For example, Document 1 (Patent No. 5195454) disclosed that a support such as polyethylene terephthalate and a resin composition layer formed on the support are sequentially laminated to protect the resin composition. Adhesive film obtained from protective film such as polypropylene film of the object layer. The resin composition described in Document 1 contains a multifunctional epoxy resin, a curing agent, a phenoxy resin, and an inorganic filler. "However, the resin composition used in the adhesive layer is required to reduce the water absorption rate and increase the bonding strength.

發明之概要 　　本發明之目的為，提供可降低吸水率且提升接著強度之樹脂組成物，及樹脂薄片。又，本發明之目的為，提供具有使用該樹脂薄片密封之半導體元件的半導體裝置。 　　本發明之一態樣係有關樹脂組成物，其特徵為，含有熱硬化性成分、熱塑性樹脂、填料與三嗪化合物，前述三嗪化合物為下述一般式（1）所表示，

Figure 02_image003
（前述一般式（1）中， 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　X為含有由烷基、苯基、羥基、烷氧基、及烷氧基矽烷基所成群中所選出之至少任一種的基）。 　　本發明之態樣的樹脂組成物中，又以R1 及R2 為氫原子，X為含有烷氧矽烷基之基較佳。 　　本發明之一態樣的樹脂組成物中，又以R1 及R2 為烷基，X為含有羥基之基較佳。 　　本發明之一態樣的樹脂組成物中，又以前述三嗪化合物為下述一般式（2）所表示較佳，
Figure 02_image005
（前述一般式（2）中， 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　R3 為由烷基、羥基、烷氧基、及烷氧基矽烷基所成群中所選出之至少一種基， 　　n為1以上3以下之整數， 　　複數之R3 可相同或相異， 　　L1 為含有由伸烷基，及伸芳基所成群中所選出之至少一種基的鏈狀連結基）。 　　本發明之一態樣的樹脂組成物中，又以前述三嗪化合物為下述一般式（3）所表示較佳，
Figure 02_image007
（前述一般式（3） 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　R3 為羥基，或烷氧基矽烷基， 　　L2 為碳數1～8之有機鏈）。 　　本發明之一態樣的樹脂組成物又以R1 及R2 為氫原子，R3 為烷氧基矽烷基較佳。 　　本發明之一態樣的樹脂組成物又以R1 及R2 為烷基，R3 為羥基較佳。 　　本發明之一態樣的樹脂組成物又以前述樹脂組成物之全量基準下含有0.1質量%以上15質量%以下之前述三嗪化合物較佳。 　　本發明之一態樣的樹脂組成物又以前述熱硬化性成分含有環氧樹脂及硬化劑較佳。 　　本發明之一態樣的樹脂組成物又以前述熱塑性樹脂為苯氧基樹脂較佳。 　　本發明之一態樣的樹脂組成物又以前述填料為二氧化矽填料較佳。 　　本發明之一態樣的樹脂組成物較佳為，使用於動力半導體元件。 　　本發明之一態樣係有關樹脂薄片，其特徵為含有前述本發明之一態樣的樹脂組成物。 　　本發明之一態樣係有關半導體裝置，其特徵為具有以本發明之一態樣的樹脂薄片密封之半導體元件。 　　藉由本發明可提供降低吸水率且提升接著強度之樹脂組成物，及樹脂薄片。又，藉由本發明可提供具有以該樹脂薄片密封之半導體元件的半導體裝置。SUMMARY OF THE INVENTION The object of the present invention is to provide a resin composition and a resin sheet that can reduce water absorption and improve bonding strength. In addition, an object of the present invention is to provide a semiconductor device having a semiconductor element sealed with the resin sheet. One aspect of the present invention relates to a resin composition characterized by containing a thermosetting component, a thermoplastic resin, a filler, and a triazine compound. The triazine compound is represented by the following general formula (1):
Figure 02_image003
(In the foregoing general formula (1), R 1 is a hydrogen atom, or an alkyl group, R 2 is a hydrogen atom, or an alkyl group, and X is an alkyl group, a phenyl group, a hydroxyl group, an alkoxy group, and an alkoxysilane. At least any one selected from the group of bases). In the resin composition of the aspect of the present invention, it is preferable that R 1 and R 2 are hydrogen atoms, and X is a group containing an alkoxysilyl group. In the resin composition of one aspect of the present invention , it is preferable that R 1 and R 2 are alkyl groups, and X is a hydroxyl group-containing group. In the resin composition of one aspect of the present invention, the aforementioned triazine compound is preferably represented by the following general formula (2),
Figure 02_image005
(In the aforementioned general formula (2), R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, and R 3 is composed of an alkyl group, a hydroxyl group, an alkoxy group, and an alkoxysilyl group. At least one group selected from the group, n is an integer from 1 to 3, the plural R 3 may be the same or different, L 1 contains at least one group selected from the group consisting of an alkylene group and an aryl group The chain link base). In the resin composition of one aspect of the present invention, the aforementioned triazine compound is preferably represented by the following general formula (3),
Figure 02_image007
(The aforementioned general formula (3) R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, R 3 is a hydroxyl group or an alkoxysilyl group, and L 2 is an organic chain with 1 to 8 carbon atoms. ). In one aspect of the resin composition of the present invention, R 1 and R 2 are hydrogen atoms, and R 3 is preferably an alkoxysilyl group. In one aspect of the resin composition of the present invention, R 1 and R 2 are alkyl groups, and R 3 is a hydroxyl group. The resin composition of one aspect of the present invention preferably contains the triazine compound in an amount of 0.1% by mass to 15% by mass based on the total amount of the resin composition. The resin composition of one aspect of the present invention further preferably contains an epoxy resin and a curing agent as the aforementioned thermosetting component. In one aspect of the resin composition of the present invention, the aforementioned thermoplastic resin is preferably a phenoxy resin. In one aspect of the resin composition of the present invention, the aforementioned filler is preferably a silica filler. The resin composition of one aspect of the present invention is preferably used for power semiconductor devices. One aspect of the present invention relates to a resin sheet, which is characterized by containing the resin composition according to one aspect of the present invention. One aspect of the present invention relates to a semiconductor device, which is characterized by having a semiconductor element sealed with a resin sheet according to one aspect of the present invention. According to the present invention, it is possible to provide a resin composition that reduces water absorption and improves bonding strength, and a resin sheet. Furthermore, according to the present invention, a semiconductor device having a semiconductor element sealed with the resin sheet can be provided.

發明之實施形態 [樹脂組成物] 　　本實施形態之樹脂組成物為，含有熱硬化性成分、熱塑性樹脂、填料與三嗪化合物。 （三嗪化合物） 　　三嗪化合物為下述一般式（1）所表示。

Figure 02_image009
（前述一般式（1）中， 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　X為含有由烷基、苯基、羥基、烷氧基及烷氧基矽烷基所成群中所選出之至少一種的基）。 　　前述一般式（1）中，R1 及R2 可相同或相異。 　　前述一般式（1）中，R1 及R2 之烷基較佳如，由甲基、乙基、異丙基、丙基及丁基所成群中所選出之任一種基，更佳為甲基。 　　前述一般式（1）中，R1 及R2 更佳為氫原子。 　　前述一般式（1）中X所表示之基為，可另具有各種官能基。X所具有之官能基較佳為，由具有碳-碳雙鍵之官能基、具有醚鍵之基、醛基，及羧基所成群中所選出之至少一種的官能基。X為含有鏈狀連結基時較佳為，該連結基之主鏈及支鏈中至少任一方含有該官能基。X之鏈狀連結基較佳為，含有由伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基。X所表示之基可具有複數官能基、複數官能基可相同或相異。 　　又以X所表示之基的末端，鍵結由羥基及烷氧基矽烷基所成群中所選出之至少一種基較佳，更佳為鍵結由羥基、甲氧基矽烷基及三甲氧基矽烷基所成群中所選出之至少一種基。 　　前述一般式（1）更佳為，R1 及R2 為氫原子，X為含有烷氧基矽烷基之基。 　　前述一般式（1）更佳為，R1 及R2 為烷基，X為含有羥基之基。 　　本實施形態之三嗪化合物較佳為下述一般式（2）所表示。
Figure 02_image011
（前述一般式（2）中， 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　R3 為由烷基、羥基、烷氧基及烷氧基矽烷基所成群中所選出之至少一種基， 　　n為1以上3以下之整數， 　　複數之R3 可為相同或相異， 　　L1 為含有由伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基）。 　　前述一般式（2）中R1 及R2 可為相同或相異。 　　前述一般式（2）中R1 及R2 之烷基各自為，與前述一般式（1）之烷基同義。 　　L1 之伸烷基較佳為碳數1～10之伸基，L1 之伸芳基較佳為伸苯基。 　　L1 可另具有各種官能基。L1 所具有之官能基較佳為，由具有碳-碳雙鍵之官能基、羥基、烷氧基、烷氧基矽烷基、具有醚鍵之基、醛基、及羧基所成群中所選出之至少一種基。L1 為具有該類官能基時較佳為，L1 之主鏈及支鏈中至少任一方含有該官能基。L1 可具有複數之官能基，複數官能基可相同或相異。 　　前述一般式（2）中R3 較佳為，具有可與其他化合物反應之官能基的基，或可與其他化合物反應之官能基本身，該官能基無特別限制。R3 所具有之官能基較佳為，由羥基、烷氧基及烷氧基矽烷基所成群中所選出之至少一種基。烷氧基矽烷基較佳如甲氧基矽烷基、或三甲氧基矽烷基。具有羥基之基，更佳為具有伯醇或仲醇之官能基。 　　本實施形態之三嗪化合物較佳為下述一般式（3）所表示。
Figure 02_image013
（前述一般式（3）中， 　　R1 為氫原子，或烷基， 　　R2 為氫原子，或烷基， 　　R3 為羥基，或烷氧基矽烷基， 　　L2 為碳數1～8之有機鏈）。 　　前述一般式（3）中R1 及R2 可相同或相異。 　　前述一般式（3）中R1 及R2 之烷基為，各自與前述一般式（1）之烷基同義。 　　L2 之有機鏈較佳為，含有由碳數1～8之伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基，更佳為含有由碳數2～6之伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基。L2 之伸芳基較佳為伸苯基。 　　L2 可另具有各種官能基。L2 所具有之官能基較佳為，由具有碳-碳雙鍵之官能基、羥基、烷氧基、烷氧基矽烷基、具有醚鍵之基、醛基、及羧基所成群中所選出之至少一種基。L2 具有該類官能基時較佳為，L2 之主鏈及支鏈中至少任一方含有該官能基。L2 可具有複數之官能基，複數之官能可相同或相異。 　　前述一般式（3）中R3 較佳為，具有可與其他化合物反應之官能基的基，或可與其他化合物反應之官能基本身，該官能基無特別限定。R3 之末端所具有之官能基更佳為三甲氧基矽烷基。 　　前述一般式（3）中R1 及R2 為氫原子時（此時之化合物稱為三嗪化合物之第一態樣）。L2 之有機鏈較佳為碳數1～8之伸烷基，更佳為碳數2～6之伸烷基。三嗪化合物之第一態樣中，L2 可另具有各種層官能基，更佳為具有由具有碳-碳雙鍵之官能基、羥基、烷氧基、烷氧基矽烷基、具有醚鍵之基、醛基、及羧基所成群中所選出之至少一種基。另外三嗪化合物之第一態樣中，前述一般式（3）中R3 較佳為具有可與其他化合物反應之官能基，該官能基無特別限定。三嗪化合物之第一態樣中，R3 之末端所具有的官能基更佳為三甲氧基矽烷基。 　　前述一般式（3）中，R1 及R2 為烷基時（此時之化合物稱為三嗪化合物之第二態樣），R1 之烷基較佳為，由甲基、乙基、異丙基、丙基、及丁基所成群中所選出之任一種基，特佳為甲基。三嗪化合物之第二態樣中，前述一般式（3）中L2 較佳為，含有由碳數1～8之伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基，更佳為含有由碳數2～6之伸烷基及伸芳基所成群中所選出之至少一種基的鏈狀連結基。三嗪化合物之第二態樣中，L2 可另具有各種官能基，L2 所具有之官能基較佳為，由具有碳-碳雙鍵之官能基、羥基、烷氧基、烷氧基矽烷基、具有醚鍵之基、醛基、及羧基所成群中所選出之至少一種基。L2 具有該類官能基時較佳為，L2 之主鏈及支鏈中至少一方含有該官能基。另外三嗪化合物之第二態樣中，前述一般式（3）中R3 較佳為具有可與其他化合物反應之官能基，該官能基無特別限定。三嗪化合物之第二態樣中，R3 之末端所具有的官能基更佳為羥基。 　　又，上述三嗪化合物之第一態樣及第二態樣不過是本實施形態之三嗪化合物例，本發明非限定於使用該類態樣之三嗪化合物的樹脂組成物。 　　三嗪化合物之分子量較佳為150以上450以下。 　　又，三嗪化合物之分子量較佳為150以上300以下。 　　又，三嗪化合物之分子量較佳為300以上450以下。 　　本實施形態之三嗪化合物為，不具有環氧基。 　　樹脂組成物中三嗪化合物之含量，就降低吸水率及提升接著力之觀點較佳為，樹脂組成物之全量基準下0.1質量%以上15質量%以下。 　　樹脂組成物中三嗪化合物之含量就樹脂組成物之全量基準下更佳為0.4質量%以上12質量%以下，又以0.5質量%以上10質量%以下更佳，特佳為含有1.4質量%以上10質量%以下。 （熱硬化性成分） 　　熱硬化性成分為，具有受熱而三次元網狀化，而強固接著被著物之性質。本實施形態之熱硬化性成分無特別限制，可使用先前已知之各種熱硬化性成分。 　　本實施形態之熱硬化性成分為，含有熱硬化性樹脂與硬化劑。 　　熱硬化性樹脂較佳如，由環氧、苯酚、間苯二酚、脲醛、三聚氰胺、呋喃、不飽和聚酯、及聚矽氧等所成群中所選出之至少任一方樹脂，更佳為環氧樹脂。 　　本實施形態之熱硬化性成分較佳為，含有環氧樹脂及硬化劑。 　　所使用之環氧樹脂為先前已知之各種環氧樹脂。 　　就熱硬化後具有適度接著性之觀點較佳為，重量平均分子量300以上2000程度以下之環氧樹脂，又以重量平均分子量300以上500以下之環氧樹脂較佳。更佳為重量平均分子量330以上400以下之常態液狀的環氧樹脂，與重量平均分子量400以上2000以下（較佳為500以上1500以下）之常態固狀的環氧樹脂摻混所得之環氧樹脂。本說明書中重量平均分子量係藉由凝膠滲透色譜（Gel Permeation Chromatography；GPC）法測定之標準聚苯乙烯換算值。 　　本實施形態所適用之環氧樹脂的環氧當量一般為50～5000g/eq。 　　本實施形態之環氧樹脂具體如，苯酚類（例如苯酚A、雙酚F、間苯二酚、苯基酚醛清漆、及甲酚酚醛清漆等）之縮水二甘油醚、醇類（例如丁二醇、聚乙二醇、及聚丙二醇等）之縮水甘油醚、羧酸（例如酞酸、間苯二甲酸、四氫酞酸等）之縮水甘油醚、縮水甘油基型或烷基縮水甘油基型之環氧樹脂（例如苯胺三聚氰酸酯等之鍵結於氮原子之活性氫，被縮水甘油基取代之環氧樹脂等），及所謂的脂環型環氧化物等。 　　脂環型環氧化物如，分子內之碳-碳雙鍵例如係藉由氧化而導入之樹脂，具體如乙烯基環己烷二環氧化物、3,4-環氧環己基甲基-3,4-二環己烷羧酸酯、及2-（3,4-環氧基）環己基-5,5-螺（3,4-環氧）環己烷-m-二噁烷等。 　　又，本實施形態之環氧樹脂如，聯苯型環氧樹脂，及萘型環氧樹脂。 　　又，本實施形態之環氧樹脂可使用分子內具有二環戊二烯骨架，與反應性之環氧基的含二環戊二烯骨架之環氧樹脂。 　　該等環氧樹脂可單獨使用一種，或二種以上組合使用。例如本實施形態中環氧樹脂之一態樣為，組合使用雙酚A之縮水甘油醚（雙酚A型環氧樹脂）、聯苯型環氧樹脂，及萘型環氧樹脂之態樣。 　　熱硬化性樹脂為環氧樹脂時，硬化劑可為具有使環氧樹脂硬化之機能的硬化劑，無特別限定。環氧樹脂用之硬化劑如，由苯酚系硬化劑、胺系硬化劑、二氰二醯胺系硬化劑，及酸酐系硬化劑所成群中所選出之至少一種的硬化劑。又，環氧樹脂用之硬化劑較佳如，熱活性型潛在性環氧樹脂硬化劑。熱活性型潛在性環氧樹脂係指，室溫下不會與環氧樹脂反應，而藉由加熱至某種溫度以上，會與環氧樹脂反應之類型的硬化劑。 　　硬化劑可單獨使用一種，或二種以上組合使用。 　　使熱活性型潛在性環氧樹脂活性化之方法如下述方法（a）～（d）。 　　（a）「藉由加熱之化學反應而生成活性種（陰離子、陽離子）之方法」 　　（b）「高溫下與環氧樹脂相溶或溶解，而開始硬化反應之方法」（該方法時，於室溫附近熱活性型潛在性環氧樹脂硬化劑為，可安定分散於環氧樹脂中） 　　（c）「高溫下使分子篩封入型之硬化劑溶出而開始硬化反應之方法」 　　（d）「藉由微膠囊之方法」 　　該等熱活性型潛在性環氧樹脂硬化劑可單獨使用一種，或二種以上組合使用。上述熱活性型潛在性環氧樹脂硬化劑中更佳為二氰二醯胺、咪唑化合物、或該等之混合物。 　　上述般硬化劑較佳為，相對於環氧樹脂100質量份一般使用比例為0.1質量份以上20質量份以下，又以使用比例為0.5質量份以上15質量份以下較佳，更佳之使用比例為1質量份以上10質量份以下。 　　樹脂組成物較佳為，樹脂組成物之全量基準下含有1質量%以上30質量%以下之熱硬化性成分，更佳為含有2質量%以上20質量%以下。 （熱塑性樹脂） 　　熱塑性樹脂無特別限定。熱塑性樹脂較佳如，由苯氧樹脂、丙烯酸樹脂、甲基丙烯酸樹脂、聚酯樹脂、及胺基甲酸酯樹脂所成群中所選出之至少任一方的樹脂，更佳為苯氧樹脂。熱塑性樹脂可單獨使用一種，或二種以上組合使用。 　　熱塑性樹脂之重量平均分子量較佳為8000以上150000以下，又以10000以上100000以下較佳，更佳為20000以上80000以下。 　　苯氧樹脂較佳為，具有由雙酚A骨架、雙酚F骨架、聯苯骨架、及萘骨架所成群中所選出之一種以上的骨架之苯氧樹脂，更佳為具有雙酚A骨架及雙酚F骨架之苯氧樹脂。 　　樹脂組成物中熱塑性樹脂之含量較佳為，樹脂組成物之全量基準下1質量%以上30質量%以下，更佳為2質量%以上20質量%以下。 （填料） 　　填料較佳為無機填料。無機填料之材質如，二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、氧化鐵紅、碳化矽、及氮化硼等。無機填料之形狀如，粉末狀、球狀、粒狀、板狀、針狀、及纖維狀。其他之無機填料如玻璃纖維等。 　　該等填料中較佳為二氧化矽填料。 　　填料可單獨使用一種，或二種以上併用。 　　樹脂組成物中填料之含量較佳為，樹脂組成物之全量基準下5質量%以上75質量%以下，更佳為10質量%以上70質量%以下。 　　本實施形態中樹脂組成物之一例如，僅含有熱硬化性成分、熱塑性樹脂、填料、及三嗪化合物之樹脂組成物。 　　又，本實施形態中樹脂組成物之另一例如，如下述般含有熱硬化性成分、熱塑性樹脂、填料、三嗪化合物、及其他成分之樹脂組成物。 （其他成分） 　　本實施形態中樹脂組成物可另含有其他成分。 　　其他成分如偶合劑等。 　　偶合劑較佳為，具有與前述熱塑性樹脂，或熱硬化性成分所具有之官能基反應的基，更佳為具有與熱硬化性成分所具有之官能基反應的基。 　　偶合劑於硬化反應時，推斷偶合劑中之有機官能基會與熱硬化性成分（較佳為環氧樹脂）反應，可於無損硬化物之耐熱性下提升接著性及密合性，且可提升耐水性（耐濕熱性）。 　　偶合劑就其泛用性，及成本優勢等較佳為矽烷系（矽烷偶合劑）。又，上述般偶合劑相對於前述熱硬化性成分100質量份，一般添加比例為0.1質量份以上20質量份以下，較佳之添加比例為0.3質量份以上15質量份以下，更佳之添加比例為0.5質量份以上10質量份以下。 　　樹脂組成物為了調節硬化劑之初期接著性及凝聚性，可另含有交聯劑（例如有機多價異氰酸酯化合物，及有機多價亞胺化合物等）。 　　上述有機多價異氰酸酯化合物，例如芳香族多價異氰酸酯化合物、脂肪族多價異氰酯化合物、脂環族多價異氰酸酯化合物，及該等之多價異氰酸酯化合物的三聚物，以及該等多價異氰酸酯化合物與聚醇化合物反應所得之末端異氰酸酯胺基甲酸酯預聚物等。有機多價異氰酸酯化合物之另外具體例如，2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-二甲伸苯基二異氰酸酯、1,4-二甲伸苯基二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、二苯基甲烷-2,4’-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、六伸甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、二環己基甲烷-2,4-二異氰酸酯、及賴胺酸異氰酸酯等。 　　上述有機多價亞胺化合物之具體例如，N,N’-二苯基甲烷-4,4’-雙（1-氮雜環丙烷羧基醯胺）、三羥甲基丙烷-三-β-氮雜環丙基丙酸酯、四羥甲基甲烷-三-β-氮雜環丙基丙酸酯、及N,N’-甲苯-2,4-雙（1-氮雜環丙烷羧基醯胺）三伸乙基三聚氰胺等。上述般交聯劑相對於前述熱塑性樹脂100質量份，一般添加比例為0.1質量份以上20質量份以下，較佳之添加比例為0.2質量份以上10質量份以下。 　　本實施形態中樹脂組成物之另一例如，前述第一態樣或前述第二態樣之含有三嗪化合物、熱硬化性成分、熱塑性樹脂與填料、熱硬化性成分係含有環氧樹脂及硬化劑之樹脂組成物。 　　本實施形態中樹脂組成物之另一例如，前述第一態樣或前述第二態樣之含有三嗪化合物、熱硬化性成分、熱塑性樹脂與填料，熱塑性樹脂係含有苯氧基樹脂之樹脂組成物。 　　本實施形態中樹脂組成物之另一例如，前述第一態或前述第二態樣之含有三嗪化合物、熱硬化性成分、熱塑性樹脂與填料，熱硬化性成分係含有環氧樹脂及硬化劑，熱塑性樹脂係含有苯氧基樹脂之樹脂組成物。 　　本實施形態之樹脂組成物較佳為，使用於動力半導體元件。本實施形態之樹脂組成物更佳為，使用於使用氮化矽及氮化鎵中至少任一種之動力半導體元件。 [樹脂薄片] 　　本實施形態之樹脂薄片為，含有本實施形態之樹脂組成物。 　　藉由使本實施形態之樹脂組成物薄片化，可得本實施形態之樹脂薄片。使樹脂組成物薄片化之方法可採用先前已知之薄片化的方法，無特別限定。本實施形態之樹脂薄片可為長尺狀薄片，或以捲成滾筒狀之狀態提供。捲成滾筒狀之本實施形態之樹脂薄片可為，由滾筒滾出時切成所希望之尺寸等再使用。 　　本實施形態之樹脂薄片的厚度較佳如10μm以上，更佳為20μm以上。又，該厚度較佳為500μm以下，又以400μm以下較佳，更佳為300μm以下。 [層合體] 　　圖1為，表示本實施形態之層合體1的剖面概略圖。 　　本實施形態之層合體1為，具有第一剝離材2、第二剝離材4、與設置於第一剝離材2與第二剝離材4之間的樹脂薄片3。樹脂薄片3為，含有本實施形態樹脂組成物。 　　第一剝離材2及第二剝離材4為，具有剝離性，且第一剝離2相對於樹脂薄片3之剝離力與第二剝離材4相對於樹脂薄片3之剝離力具有差值。第一剝離材2及第二剝離材4之材質無特別限定。第一剝離材2及第二剝離材4可為，例如剝離材本身具有剝離性之構件，或實施剝離處理後之構件，或層合剝離層之構件等。第一剝離材2及第二剝離材4未實施剝離處理時，第一剝離材2及第二剝離材4之材質具體如，烯烴系樹脂及氧樹脂等。 　　第一剝離材2及第二剝離材4可為，備有剝離基材，與將剝離劑塗佈於剝離基材上所形成之剝離劑層的剝離材。備有剝離基材與剝離劑層之剝離材較易處理。又，第一剝離材2及第二剝離材4可為，僅剝離基材之單面備有剝離劑層，或剝離基材雙面備有剝離劑層。 　　剝離基材如紙基材、將聚乙烯等之熱塑性樹脂層壓於該紙基材所得之層壓紙、及塑料薄膜等。紙基材如玻璃紙、塗紙、及鑄造塗紙等。塑料薄膜如聚酯薄膜（例如聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁醇酯，及聚萘二酸乙二醇酯等），及聚烯烴薄膜（例如聚丙烯，及聚乙烯等）等。該等之中較佳為聚酯薄膜。 　　剝離劑如，由聚矽氧樹脂所構成之聚矽氧系剝離劑；由聚乙烯基胺基甲酸酯，及烷基尿素衍生物等之含有長鏈烷基之化合物所構成的含有長鏈烷基化合物系剝離劑；由醇酸樹脂（例如不轉化性醇酸樹脂，及轉化性醇酸樹脂等）所構成的醇酸樹脂系剝離劑；由烯烴樹脂（例如聚乙烯（例如高密度聚乙烯、低密度聚乙烯、及直鏈狀低密度聚乙烯等）、具有等規結構或間規結構之丙烯單獨聚合物，及丙烯-α-烯烴共聚物等之結晶性聚丙烯樹脂等）所構成之烯烴樹脂系剝離劑；由天然橡膠、合成橡膠（例如丁二烯橡膠、異戊二烯橡膠、苯乙烯-丁二烯橡膠、甲基甲基丙烯酸酯-丁二烯橡膠、及丙烯腈-丁二烯橡膠等）等之橡膠所構成的橡膠系剝離劑；及由（甲基）丙烯酸酯系共聚物等之丙烯酸樹脂所構成的丙烯酸樹脂系剝離劑等之各種剝離劑，該等可單獨使用一種，或二種以上組合使用。該等之中較佳為聚矽氧系剝離劑及醇酸樹脂系剝離材。又以第一剝離材及第二剝離材使用不同之剝離劑較佳。 　　第一剝離材2及第二剝離材4之厚度無特別限定。一般為1μm以上500μm以下，較佳為3μm以上100μm以下。 　　剝離劑層之厚度無特別限定。塗佈含有剝離劑之溶液而形成剝離劑層時，剝離劑層之厚度較佳為0.01μm以上3μm以下，更佳為0.03μm以上1μm以下。 　　層合體1之製造方法無特別限定。例如層合體1係經由下述步驟製造。首先將樹脂組成物塗佈於第一剝離材2上，形成塗膜。其次將該塗膜乾燥，形成樹脂薄片3。接著以常溫貼合樹脂薄片3與第二剝離材4，得層合體1。 [半導體裝置] 　　本實施形態之半導體裝置為，具有本實施形態之樹脂組成物，或以樹脂薄片密封之半導體元件。 　　本實施形態中使用樹脂薄片之半導體元件的密封法如下述般進行。以被覆半導體元件般載置樹脂薄片後，藉由真空層壓法壓合，而密封半導體元件。 　　使用本實施形態之層合體1時，係於剝離層合體1之一方的剝離材後，以被覆半導體元件般載置樹脂薄片。其次剝離另一方。其係藉由真空層壓法壓合，而密封半導體元件。 　　藉由本實施形態之樹脂組成物，及樹脂薄片，可降低吸水率且提升接著強度。使用本實施形態之樹脂組成物，及樹脂薄片，可藉由吸水率較低之密封樹脂層密封半導體元件，而提升半導體元件與密封樹脂層之接著強度。本實施形態之樹脂組成物，及樹脂薄片特別適用於使用氮化矽及氮化鎵中至少任一種的動力半導體元件。 [實施形態之變更] 　　本發明非限定於前述實施形態，於可達成本發明之目的的範圍內進行變更或改良等，也包含於本發明。 　　前述實施形態係以具有第一剝離材2、第二剝離材4，與設置於第一剝離材2及第二剝離材4之間的樹脂薄片3之層合體1進行說明，又可為僅樹脂薄片之單方表面具有剝離材之層合體的其他實施形態。 　　前述實施形態中雖說明半導體密封用途，但本發明之樹脂組成物，及樹脂薄片也適用為其他，例如電路基板用絕緣材料（例如硬質印刷配線板材料、可撓性配線基板用材料，及堆疊基板用層間絕緣材料等）、堆疊用接著薄膜，及接著劑等。 實施例 　　下面將舉實施例更詳細說明本發明。但本發明非限定於該等實施例。 調製樹脂組成物 　　調製樹脂組成物所使用之材料如下所述。 （熱塑性樹脂） 　　苯氧基樹脂：雙酚A/雙酚F骨架混合型（重量平均分子量=60000～70000） （熱硬化性成分） •環氧樹脂 　　液狀雙酚A型環氧樹脂（環氧當量：189g/eq） 　　聯苯型環氧樹脂（環氧當量：272g/eq，軟化點：52℃） 　　萘型環氧樹脂（環氧當量：165g/eq，軟化點：92℃） •硬化劑 　　聯苯型苯酚樹脂（官能基當量：218g/eq，軟化點：82℃） 　　2-乙基-4-甲基咪唑 （填料） 　　•二氧化矽填料：ADMATECHS股份公司製SC-2050MA（平均粒徑：0.5μm） （三嗪化合物） 　　含有羥基之三嗪化合物：四國化成股份公司製VD-4（熔點：97℃，5%重量減少溫度：243℃） 　　含有三甲氧基矽烷基之三嗪化合物：四國化成股份公司製VD-5（熔點171℃，5%重量減少溫度：229℃） 　　依表1所示之添加比例調製實施例1～6及比較例1之樹脂組成物。
Figure 02_image015
•樹脂組成物之硬化條件 　　以100℃加熱調製所得之樹脂組成物30分鐘，再以180℃加熱30分鐘，得樹脂硬化物。 [剝離強度] 　　使用島津製作所股份公司製之拉伸試驗機（裝置名：auto glasc AG-IS），以下述條件測定。 　　測定剝離強度用之樣品為，首先將樹脂組成物貼合於二氧化矽晶片（12mm×12mm）之表面上，再將銅箔（JIS H3100 C1100P，0.15mm×10mm×50mm）貼合於樹脂組成物，其次以上述硬化條件使樹脂組成物硬化而得。 　　樣品構成：銅箔/樹脂硬化物/二氧化矽晶片 　　剝離速度：50mm/分 　　剝離角度：90度 　　溫度 ：23℃ 　　濕度 ：50%RH [吸水率] 　　以初期（試驗前）之樹脂硬化物的重量為a，以JEDEC Lv.1（85℃，85%RH，168小時）試驗後之樹脂硬化物的重量為b，藉由下述計算式算出吸水率（單位：%)。 吸水率={(b-a)/a}×100 　　剝離強度及吸水率之評估結果如表1所示。 　　實施例1～6之樹脂組成物比較比較例1之樹脂組成物時，可降低吸水率，且可提升剝離強度。Embodiment of the invention [Resin composition] The resin composition of this embodiment contains a thermosetting component, a thermoplastic resin, a filler, and a triazine compound. (Triazine compound) The triazine compound is represented by the following general formula (1).
Figure 02_image009
(In the aforementioned general formula (1), R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, and X is an alkyl group, a phenyl group, a hydroxyl group, an alkoxy group, and an alkoxysilyl group. At least one base selected from the group). In the aforementioned general formula (1), R 1 and R 2 may be the same or different. In the aforementioned general formula (1), the alkyl group of R 1 and R 2 is preferably any one selected from the group consisting of methyl, ethyl, isopropyl, propyl and butyl, and more preferably methyl. In the aforementioned general formula (1), R 1 and R 2 are more preferably hydrogen atoms. The group represented by X in the aforementioned general formula (1) may additionally have various functional groups. The functional group possessed by X is preferably at least one functional group selected from the group consisting of a functional group having a carbon-carbon double bond, a group having an ether bond, an aldehyde group, and a carboxyl group. When X contains a chain linking group, it is preferable that at least any one of the main chain and the branch chain of the linking group contains the functional group. The chain linking group of X is preferably a chain linking group containing at least one group selected from the group of an alkylene group and an arylene group. The group represented by X may have plural functional groups, and the plural functional groups may be the same or different. In addition, the terminal of the group represented by X is preferably bonded to at least one group selected from the group consisting of a hydroxyl group and an alkoxysilyl group, and more preferably is bonded to a hydroxyl group, a methoxysilyl group and a trimethoxy group. At least one group selected from the group of silyl groups. The aforementioned general formula (1) is more preferably that R 1 and R 2 are hydrogen atoms, and X is a group containing an alkoxysilyl group. It is more preferable that the aforementioned general formula (1) is that R 1 and R 2 are alkyl groups, and X is a hydroxyl group-containing group. The triazine compound of this embodiment is preferably represented by the following general formula (2).
Figure 02_image011
(In the foregoing general formula (2), R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, and R 3 is a group consisting of an alkyl group, a hydroxyl group, an alkoxy group and an alkoxysilyl group N is an integer from 1 to 3, the plural R 3 may be the same or different, and L 1 is a group containing at least one group selected from the group of alkylene and aryl Chain link base). In the aforementioned general formula (2), R 1 and R 2 may be the same or different. The alkyl groups of R 1 and R 2 in the aforementioned general formula (2) are each and have the same meaning as the alkyl groups of the aforementioned general formula (1). The alkylene group of L 1 is preferably a C 1-10 alkylene group, and the arylene group of L 1 is preferably a phenylene group. L 1 may additionally have various functional groups. The functional group possessed by L 1 is preferably a group consisting of a functional group having a carbon-carbon double bond, a hydroxyl group, an alkoxy group, an alkoxysilyl group, a group having an ether bond, an aldehyde group, and a carboxyl group. At least one base selected. When L 1 has such a functional group, it is preferable that at least any one of the main chain and the branch chain of L 1 contains the functional group. L 1 may have plural functional groups, and the plural functional groups may be the same or different. In the aforementioned general formula (2), R 3 is preferably a group having a functional group capable of reacting with other compounds, or a functional group itself capable of reacting with other compounds, and the functional group is not particularly limited. The functional group possessed by R 3 is preferably at least one group selected from the group consisting of a hydroxyl group, an alkoxy group, and an alkoxysilyl group. The alkoxysilyl group is preferably a methoxysilyl group or a trimethoxysilyl group. The group having a hydroxyl group is more preferably a functional group having a primary alcohol or a secondary alcohol. The triazine compound of this embodiment is preferably represented by the following general formula (3).
Figure 02_image013
(In the foregoing general formula (3), R 1 is a hydrogen atom or an alkyl group, R 2 is a hydrogen atom or an alkyl group, R 3 is a hydroxyl group or an alkoxysilyl group, and L 2 is a carbon number of 1-8 Organic chain). In the aforementioned general formula (3), R 1 and R 2 may be the same or different. The alkyl groups of R 1 and R 2 in the aforementioned general formula (3) are each having the same meaning as the alkyl groups of the aforementioned general formula (1). The organic chain of L 2 is preferably a chain linking group containing at least one group selected from the group of alkylene groups with carbon numbers 1 to 8 and aryl group A chain linking group of at least one group selected from the group of alkylene and arylalkylene. The arylene group of L 2 is preferably a phenylene group. L 2 may additionally have various functional groups. The functional group possessed by L 2 is preferably a group consisting of a functional group having a carbon-carbon double bond, a hydroxyl group, an alkoxy group, an alkoxysilyl group, a group having an ether bond, an aldehyde group, and a carboxyl group. At least one base selected. When L 2 has such a functional group, it is preferable that at least any one of the main chain and the branch chain of L 2 contains the functional group. L 2 may have plural functional groups, and the plural functions may be the same or different. In the aforementioned general formula (3), R 3 is preferably a group having a functional group that can react with other compounds, or a functional group itself that can react with other compounds, and the functional group is not particularly limited. The functional group possessed at the end of R 3 is more preferably a trimethoxysilyl group. When R 1 and R 2 in the aforementioned general formula (3) are hydrogen atoms (the compound at this time is called the first aspect of the triazine compound). The organic chain of L 2 is preferably an alkylene having 1 to 8 carbons, and more preferably an alkylene having 2 to 6 carbons. In the first aspect of the triazine compound, L 2 may additionally have various layer functional groups, and more preferably have functional groups with carbon-carbon double bonds, hydroxyl groups, alkoxy groups, alkoxysilyl groups, and ether bonds. At least one group selected from the group consisting of aldehyde group, aldehyde group, and carboxyl group. In addition, in the first aspect of the triazine compound, R 3 in the aforementioned general formula (3) preferably has a functional group that can react with other compounds, and the functional group is not particularly limited. In the first aspect of the triazine compound, the functional group at the end of R 3 is more preferably a trimethoxysilyl group. In the aforementioned general formula (3), when R 1 and R 2 are alkyl groups (the compound at this time is referred to as the second aspect of triazine compounds), the alkyl group of R 1 is preferably a group consisting of methyl, ethyl, Any one selected from the group consisting of isopropyl, propyl, and butyl is particularly preferably methyl. In the second aspect of the triazine compound, L 2 in the aforementioned general formula (3) is preferably a chain containing at least one group selected from the group of alkylene groups and aryl groups having 1 to 8 carbon atoms. The linking group is more preferably a chain linking group containing at least one group selected from the group of alkylene groups and arylene groups having 2 to 6 carbon atoms. In the second aspect of the triazine compound, L 2 can additionally have various functional groups, and the functional groups possessed by L 2 are preferably functional groups with carbon-carbon double bonds, hydroxyl groups, alkoxy groups, and alkoxy groups. At least one group selected from the group consisting of a silyl group, a group having an ether bond, an aldehyde group, and a carboxyl group. When L 2 has such a functional group, it is preferable that at least one of the main chain and branch chain of L 2 contains the functional group. In addition, in the second aspect of the triazine compound, R 3 in the aforementioned general formula (3) preferably has a functional group that can react with other compounds, and the functional group is not particularly limited. In the second aspect of the triazine compound, the functional group at the end of R 3 is more preferably a hydroxyl group. In addition, the first aspect and the second aspect of the above-mentioned triazine compound are only examples of the triazine compound of the present embodiment, and the present invention is not limited to resin compositions using such a type of triazine compound. The molecular weight of the triazine compound is preferably 150 or more and 450 or less. In addition, the molecular weight of the triazine compound is preferably 150 or more and 300 or less. In addition, the molecular weight of the triazine compound is preferably 300 or more and 450 or less. The triazine compound of this embodiment does not have an epoxy group. The content of the triazine compound in the resin composition is preferably 0.1% by mass or more and 15% by mass or less on the basis of the total amount of the resin composition from the viewpoint of reducing the water absorption rate and enhancing the adhesive force. The content of the triazine compound in the resin composition is more preferably 0.4% by mass or more and 12% by mass or less based on the total amount of the resin composition, more preferably 0.5% by mass or more and 10% by mass or less, particularly preferably containing 1.4% by mass or more 10% by mass or less. (Thermosetting component) The thermosetting component has the properties of being heated to form a three-dimensional network and strengthening the adherend. The thermosetting component in this embodiment is not particularly limited, and various previously known thermosetting components can be used. The thermosetting component of this embodiment contains a thermosetting resin and a curing agent. The thermosetting resin is preferably at least one resin selected from the group consisting of epoxy, phenol, resorcinol, urea-formaldehyde, melamine, furan, unsaturated polyester, and silicone, and more preferably Epoxy resin. The thermosetting component of this embodiment preferably contains an epoxy resin and a curing agent. The epoxy resins used are various epoxy resins previously known. From the viewpoint of having moderate adhesiveness after thermal curing, epoxy resins with a weight average molecular weight of 300 or more and 2,000 or less are preferable, and epoxy resins with a weight average molecular weight of 300 or more and 500 or less are more preferable. More preferably, it is an epoxy resin obtained by blending a normal liquid epoxy resin with a weight average molecular weight of 330 or more and 400 or less and a normal solid epoxy resin with a weight average molecular weight of 400 or more and 2000 or less (preferably 500 or more and 1500 or less). Resin. The weight average molecular weight in this manual is the standard polystyrene conversion value measured by Gel Permeation Chromatography (GPC) method. The epoxy equivalent of the epoxy resin used in this embodiment is generally 50 to 5000 g/eq. The epoxy resin of this embodiment specifically includes glycidyl ethers of phenols (such as phenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac, etc.), alcohols (such as butadiene Alcohol, polyethylene glycol, polypropylene glycol, etc.) glycidyl ether, carboxylic acid (such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.) glycidyl ether, glycidyl type or alkyl glycidyl Type epoxy resins (such as aniline cyanurate and other active hydrogens bonded to nitrogen atoms, epoxy resins substituted by glycidyl groups, etc.), and so-called alicyclic epoxides, etc. Alicyclic epoxides such as carbon-carbon double bonds in the molecule are resins introduced by oxidation, such as vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3 ,4-Dicyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. In addition, the epoxy resin of this embodiment is a biphenyl type epoxy resin and a naphthalene type epoxy resin. In addition, as the epoxy resin of this embodiment, a dicyclopentadiene skeleton-containing epoxy resin having a dicyclopentadiene skeleton and a reactive epoxy group in the molecule can be used. These epoxy resins can be used alone or in combination of two or more. For example, one aspect of the epoxy resin in this embodiment is a combination of glycidyl ether of bisphenol A (bisphenol A epoxy resin), biphenyl epoxy resin, and naphthalene epoxy resin. When the thermosetting resin is an epoxy resin, the curing agent may be a curing agent having a function of curing the epoxy resin, and is not particularly limited. The hardener for epoxy resin is at least one hardener selected from the group of phenol hardeners, amine hardeners, dicyandiamide hardeners, and acid anhydride hardeners. In addition, the hardener for epoxy resin is preferably a thermally active latent epoxy resin hardener. Thermally active latent epoxy resin refers to a type of hardener that does not react with epoxy resin at room temperature, but will react with epoxy resin when heated to a certain temperature or higher. The hardener can be used alone or in combination of two or more. The method for activating the thermally active latent epoxy resin is as follows (a) to (d). (A) "Method of generating active species (anions, cations) by chemical reaction of heating" (b) "Method of dissolving or dissolving with epoxy resin at high temperature to start hardening reaction" (In this method, in The thermally active latent epoxy resin hardener near room temperature can be stably dispersed in the epoxy resin) (c) "The method of eluting the molecular sieve-enclosed hardener at high temperature to start the hardening reaction" (d) "By The method by microencapsulation" The thermally active latent epoxy resin hardeners can be used alone or in combination of two or more. The thermally active latent epoxy resin hardener is more preferably dicyandiamide, imidazole compounds, or a mixture of these. The above-mentioned general hardener is preferably, with respect to 100 parts by mass of epoxy resin, the general use ratio is 0.1 parts by mass or more and 20 parts by mass or less, and the use ratio is preferably 0.5 parts by mass or more and 15 parts by mass or less. More preferably, the use ratio is 1 part by mass or more and 10 parts by mass or less. The resin composition preferably contains 1% by mass or more and 30% by mass or less of the thermosetting component based on the total amount of the resin composition, more preferably 2% by mass or more and 20% by mass or less. (Thermoplastic resin) The thermoplastic resin is not particularly limited. The thermoplastic resin is preferably at least any one selected from the group consisting of phenoxy resin, acrylic resin, methacrylic resin, polyester resin, and urethane resin, and more preferably phenoxy resin. The thermoplastic resin may be used singly or in combination of two or more kinds. The weight average molecular weight of the thermoplastic resin is preferably 8,000 or more and 150,000 or less, more preferably 10,000 or more and 100,000 or less, and more preferably 20,000 or more and 80,000 or less. The phenoxy resin is preferably a phenoxy resin having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton, and naphthalene skeleton, and more preferably has a bisphenol A skeleton And phenoxy resin with bisphenol F skeleton. The content of the thermoplastic resin in the resin composition is preferably 1% by mass to 30% by mass based on the total amount of the resin composition, more preferably 2% by mass to 20% by mass. (Filler) The filler is preferably an inorganic filler. The materials of inorganic fillers include silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide red, silicon carbide, and boron nitride. The shapes of inorganic fillers include powder, spherical, granular, plate, needle, and fiber. Other inorganic fillers such as glass fiber, etc. Among these fillers, silica fillers are preferred. One kind of filler may be used alone, or two or more kinds may be used in combination. The content of the filler in the resin composition is preferably 5% by mass or more and 75% by mass or less based on the total amount of the resin composition, more preferably 10% by mass or more and 70% by mass or less. One of the resin compositions in this embodiment is, for example, a resin composition containing only a thermosetting component, a thermoplastic resin, a filler, and a triazine compound. In addition, another example of the resin composition in this embodiment is a resin composition containing a thermosetting component, a thermoplastic resin, a filler, a triazine compound, and other components as described below. (Other components) The resin composition in this embodiment may additionally contain other components. Other ingredients such as coupling agent and so on. The coupling agent preferably has a group reactive with the functional group of the thermoplastic resin or the thermosetting component, and more preferably has a group reactive with the functional group of the thermosetting component. During the curing reaction of the coupling agent, it is inferred that the organic functional group in the coupling agent will react with the thermosetting component (preferably epoxy resin), which can improve the adhesion and adhesion without damaging the heat resistance of the cured product, and can Improve water resistance (heat and humidity resistance). The coupling agent is preferably a silane-based (silane coupling agent) in terms of its versatility and cost advantage. In addition, the above-mentioned general coupling agent is generally added at a ratio of 0.1 to 20 parts by weight relative to 100 parts by weight of the aforementioned thermosetting component, preferably at a ratio of 0.3 to 15 parts by weight, and more preferably at a ratio of 0.5. Parts by mass or more and 10 parts by mass or less. In order to adjust the initial adhesion and cohesiveness of the hardener, the resin composition may additionally contain a crosslinking agent (for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, etc.). The aforementioned organic polyvalent isocyanate compounds, such as aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and trimers of these polyvalent isocyanate compounds, and such polyvalent isocyanate compounds A terminal isocyanate urethane prepolymer obtained by reacting an isocyanate compound with a polyol compound, etc. Other specific examples of the organic polyvalent isocyanate compound include 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, 1,3-dimethylphenylene diisocyanate, and 1,4-dimethylphenylene diisocyanate. Phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4-diisocyanate, and lysine isocyanate, etc. Specific examples of the above-mentioned organic polyvalent imine compounds are N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxyamide), trimethylolpropane-tri-β-nitrogen Heterocyclyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, and N,N'-toluene-2,4-bis(1-aziridine carboxyamide ) Triethylene melamine, etc. The above-mentioned general crosslinking agent is generally added at a ratio of 0.1 part by mass to 20 parts by mass relative to 100 parts by mass of the aforementioned thermoplastic resin, and preferably at a ratio of 0.2 part by mass to 10 parts by mass. Another example of the resin composition in this embodiment is that the first aspect or the second aspect contains a triazine compound, a thermosetting component, a thermoplastic resin and a filler, and the thermosetting component contains an epoxy resin and a curing agent. The resin composition of the agent. Another example of the resin composition in this embodiment is a resin composition containing a triazine compound, a thermosetting component, a thermoplastic resin and a filler in the aforementioned first aspect or the aforementioned second aspect, and the thermoplastic resin is a resin composition containing phenoxy resin Things. Another example of the resin composition in this embodiment is that the first or second aspect contains a triazine compound, a thermosetting component, a thermoplastic resin, and a filler, and the thermosetting component contains an epoxy resin and a curing agent. , Thermoplastic resin is a resin composition containing phenoxy resin. The resin composition of this embodiment is preferably used for power semiconductor devices. The resin composition of this embodiment is more preferably used for power semiconductor devices using at least one of silicon nitride and gallium nitride. [Resin Sheet] The resin sheet of this embodiment contains the resin composition of this embodiment. By thinning the resin composition of this embodiment, the resin sheet of this embodiment can be obtained. The method of thinning the resin composition can be a previously known method of thinning, and it is not particularly limited. The resin sheet of this embodiment may be a long-length sheet or provided in a roll-like state. The resin sheet of this embodiment rolled into a roll shape can be cut into a desired size when rolled out from the roll and used. The thickness of the resin sheet of this embodiment is preferably 10 μm or more, more preferably 20 μm or more. Furthermore, the thickness is preferably 500 μm or less, more preferably 400 μm or less, and more preferably 300 μm or less. [Laminated body] Fig. 1 is a schematic cross-sectional view showing a laminated body 1 of the present embodiment. The laminate 1 of this embodiment has a first release material 2, a second release material 4, and a resin sheet 3 provided between the first release material 2 and the second release material 4. The resin sheet 3 contains the resin composition of this embodiment. The first peeling material 2 and the second peeling material 4 have peelability, and the peeling force of the first peeling 2 with respect to the resin sheet 3 and the peeling force of the second peeling material 4 with respect to the resin sheet 3 have a difference. The materials of the first release material 2 and the second release material 4 are not particularly limited. The first peeling material 2 and the second peeling material 4 may be, for example, a member in which the peeling material itself has peelability, or a member after a peeling treatment, or a member in which a peeling layer is laminated, or the like. When the first peeling material 2 and the second peeling material 4 are not subjected to the peeling treatment, the materials of the first peeling material 2 and the second peeling material 4 are specifically, for example, an olefin resin, an oxygen resin, and the like. The first release material 2 and the second release material 4 may be a release material provided with a release substrate and a release agent layer formed by applying a release agent on the release substrate. The release material with release substrate and release agent layer is easier to handle. In addition, the first release material 2 and the second release material 4 may have a release agent layer provided on only one side of the release substrate, or a release agent layer may be provided on both sides of the release substrate. Peeling substrates such as paper substrates, laminated paper obtained by laminating thermoplastic resins such as polyethylene on the paper substrate, and plastic films. Paper substrates such as cellophane, coated paper, and casting coated paper. Plastic films such as polyester films (such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, etc.), and polyolefin films (such as polypropylene, and poly Ethylene, etc.) and so on. Among them, a polyester film is preferred. Release agents such as silicone release agents composed of silicone resin; long-chain compounds composed of polyvinyl urethane, alkyl urea derivatives and other compounds containing long-chain alkyl groups Alkyd compound-based release agents; alkyd resin-based release agents composed of alkyd resins (such as non-convertible alkyd resins and conversion alkyd resins, etc.); and olefin resins (such as polyethylene (such as high-density poly) Ethylene, low-density polyethylene, and linear low-density polyethylene, etc.), propylene single polymers with isotactic or syndiotactic structure, and crystalline polypropylene resins such as propylene-α-olefin copolymers, etc.) Composed of olefin resin release agent; composed of natural rubber, synthetic rubber (such as butadiene rubber, isoprene rubber, styrene-butadiene rubber, methacrylate-butadiene rubber, and acrylonitrile) -Butadiene rubber, etc.) rubber-based release agents; and various release agents such as acrylic resin-based release agents composed of acrylic resins such as (meth)acrylate copolymers, etc. One kind is used alone, or two or more kinds are used in combination. Among these, silicone-based release agents and alkyd resin-based release materials are preferred. It is better to use different release agents for the first release material and the second release material. The thickness of the first release material 2 and the second release material 4 is not particularly limited. Generally, it is 1 μm or more and 500 μm or less, preferably 3 μm or more and 100 μm or less. The thickness of the release agent layer is not particularly limited. When a solution containing a release agent is applied to form a release agent layer, the thickness of the release agent layer is preferably 0.01 μm or more and 3 μm or less, more preferably 0.03 μm or more and 1 μm or less. The manufacturing method of the laminated body 1 is not specifically limited. For example, the laminate 1 is manufactured through the following steps. First, the resin composition is applied on the first release material 2 to form a coating film. Next, the coating film is dried to form a resin sheet 3. Next, the resin sheet 3 and the second release material 4 were bonded together at room temperature to obtain a laminate 1. [Semiconductor device] The semiconductor device of this embodiment is a semiconductor element which has the resin composition of this embodiment or is sealed with a resin sheet. The sealing method of the semiconductor element using the resin sheet in this embodiment is performed as follows. After the resin sheet is placed to cover the semiconductor element, the semiconductor element is sealed by pressure bonding by the vacuum lamination method. When using the laminated body 1 of this embodiment, after peeling off the peeling material of one side of the laminated body 1, the resin sheet is mounted so that a semiconductor element may be covered. Then peel off the other party. It seals the semiconductor element by pressing and bonding by the vacuum lamination method. With the resin composition and resin sheet of this embodiment, the water absorption rate can be reduced and the bonding strength can be improved. Using the resin composition and resin sheet of this embodiment, the semiconductor element can be sealed by the sealing resin layer with a low water absorption rate, and the bonding strength between the semiconductor element and the sealing resin layer can be improved. The resin composition and resin sheet of this embodiment are particularly suitable for power semiconductor devices using at least one of silicon nitride and gallium nitride. [Modifications of Embodiments] The present invention is not limited to the foregoing embodiments, and changes, improvements, etc., are included in the present invention within the scope of achieving the object of the invention. The foregoing embodiment is described with the laminated body 1 having the first release material 2, the second release material 4, and the resin sheet 3 provided between the first release material 2 and the second release material 4, but it may be resin only Another embodiment of a laminate having a release material on one side of the sheet. Although the foregoing embodiments describe semiconductor sealing applications, the resin composition and resin sheet of the present invention are also applicable to other materials, such as insulating materials for circuit boards (such as materials for rigid printed wiring boards, materials for flexible wiring boards, and stacks). Interlayer insulating materials for substrates, etc.), adhesive films for stacking, and adhesives, etc. Examples The following examples will illustrate the present invention in more detail. However, the present invention is not limited to these embodiments. Preparation of the resin composition The materials used in the preparation of the resin composition are as follows. (Thermoplastic resin) Phenoxy resin: Bisphenol A/bisphenol F skeleton hybrid type (weight average molecular weight=60,000～70,000) (Thermosetting component) • Epoxy resin liquid bisphenol A epoxy resin (epoxy Equivalent: 189g/eq) Biphenyl type epoxy resin (Epoxy equivalent: 272g/eq, softening point: 52°C) Naphthalene type epoxy resin (Epoxy equivalent: 165g/eq, softening point: 92°C) • Hardener Biphenyl type phenol resin (functional group equivalent: 218g/eq, softening point: 82°C) 2-ethyl-4-methylimidazole (filler) • Silica filler: ADMATECHS Co., Ltd. SC-2050MA (average particle size) : 0.5μm) (Triazine compound) Triazine compound containing hydroxyl group: VD-4 manufactured by Shikoku Kasei Co., Ltd. (Melting point: 97°C, 5% weight reduction temperature: 243°C) Triazine compound containing trimethoxysilyl group : VD-5 manufactured by Shikoku Chemical Co., Ltd. (melting point 171°C, 5% weight reduction temperature: 229°C) The resin compositions of Examples 1 to 6 and Comparative Example 1 were prepared in accordance with the addition ratio shown in Table 1.
Figure 02_image015
• Curing conditions of the resin composition The resin composition obtained is heated at 100°C for 30 minutes, and then heated at 180°C for 30 minutes to obtain a cured resin. [Peel strength] A tensile testing machine (device name: auto glasc AG-IS) manufactured by Shimadzu Corporation was used to measure under the following conditions. The sample for measuring the peel strength is to first bond the resin composition on the surface of the silicon dioxide wafer (12mm×12mm), and then bond the copper foil (JIS H3100 C1100P, 0.15mm×10mm×50mm) to the resin composition Next, it is obtained by curing the resin composition under the above-mentioned curing conditions. Sample composition: Copper foil/cured resin/silicon dioxide wafer Peeling speed: 50mm/min Peeling angle: 90 degrees Temperature: 23°C Humidity: 50%RH [Water absorption] Based on the weight of the cured resin at the initial stage (before the test) As a, take the weight of the cured resin after the test of JEDEC Lv.1 (85°C, 85%RH, 168 hours) as b, and calculate the water absorption rate (unit: %) by the following calculation formula. Water absorption={(ba)/a}×100 The evaluation results of peel strength and water absorption are shown in Table 1. When the resin composition of Examples 1 to 6 is compared with the resin composition of Comparative Example 1, the water absorption rate can be reduced, and the peel strength can be improved.

1‧‧‧層合體2‧‧‧第一剝離材3‧‧‧樹脂薄片4‧‧‧第二剝離材1‧‧‧Laminated body 2.‧‧First release material 3.‧‧‧Resin sheet 4‧‧‧Second release material

圖1為，一實施形態之層合體的剖面概略圖。Fig. 1 is a schematic cross-sectional view of a laminated body according to an embodiment.

1‧‧‧層合體 1‧‧‧Laminated body

2‧‧‧第一剝離材 2‧‧‧First peeling material

3‧‧‧樹脂薄片 3‧‧‧Resin sheet

4‧‧‧第二剝離材 4‧‧‧Second peeling material

Claims (10)

一種樹脂組成物，其特徵為含有熱硬化性成分、熱塑性樹脂、填料，與三嗪化合物，前述三嗪化合物為下述一般式(1)所表示，
Figure 106128041-A0305-02-0029-1
 (前述一般式(1)中，R1為氫原子，R2為氫原子，X為含有烷氧基矽烷基的基)。 A resin composition characterized by containing a thermosetting component, a thermoplastic resin, a filler, and a triazine compound. The triazine compound is represented by the following general formula (1),
Figure 106128041-A0305-02-0029-1
 (In the aforementioned general formula (1), R 1 is a hydrogen atom, R 2 is a hydrogen atom, and X is a group containing an alkoxysilyl group). 如請求項1之樹脂組成物，其中前述三嗪化合物為下述一般式(2)所表示，
Figure 106128041-A0305-02-0029-2
 (前述一般式(2)中，R1為氫原子，R2為氫原子，R3為烷氧基矽烷基，n為1以上3以下之整數，複數之R3可相同或相異，L1為含有伸烷基，及伸芳基所成群中所選出之至少一種基的鏈狀連結基)。 The resin composition of claim 1, wherein the aforementioned triazine compound is represented by the following general formula (2),
Figure 106128041-A0305-02-0029-2
 (In the aforementioned general formula (2), R 1 is a hydrogen atom, R 2 is a hydrogen atom, R 3 is an alkoxysilyl group, n is an integer of 1 to 3, and the plural R 3 may be the same or different, L 1 is a chain linking group containing an alkylene group and at least one selected from the group of arylalkylene groups). 如請求項1之樹脂組成物，其中前述三嗪化合物為下述一般式(3)所表示，
Figure 106128041-A0305-02-0030-3
 (前述一般式(3)中，R1為氫原子，R2為氫原子，R3為烷氧基矽烷基，L2為碳數1~8之有機鏈)。 The resin composition of claim 1, wherein the aforementioned triazine compound is represented by the following general formula (3),
Figure 106128041-A0305-02-0030-3
 (In the aforementioned general formula (3), R 1 is a hydrogen atom, R 2 is a hydrogen atom, R 3 is an alkoxysilyl group, and L 2 is an organic chain with 1 to 8 carbon atoms). 如請求項1之樹脂組成物，其中前述樹脂組成物之全量基準下含有0.1質量%以上15質量%以下之前述三嗪化合物。 The resin composition of claim 1, wherein the total amount of the resin composition contains the triazine compound in an amount of 0.1% by mass or more and 15% by mass or less. 如請求項1之樹脂組成物，其中前述熱硬化性成分為，含有環氧樹脂及硬化劑。 The resin composition of claim 1, wherein the thermosetting component contains an epoxy resin and a curing agent. 如請求項1之樹脂組成物，其中前述熱塑性樹脂為苯氧基樹脂。 The resin composition of claim 1, wherein the aforementioned thermoplastic resin is a phenoxy resin. 如請求項1之樹脂組成物，其中前述填料為二氧化矽填料。 The resin composition of claim 1, wherein the aforementioned filler is silica filler. 如請求項1之樹脂組成物，其為使用於動力半導體元件。 Such as the resin composition of claim 1, which is used in power semiconductor devices. 一種樹脂薄片，其特徵為含有如請求項1之樹脂組成物。 A resin sheet characterized by containing the resin composition of claim 1. 一種半導體裝置，其特徵為具有以如請求項9之樹脂薄片密封的半導體元件。 A semiconductor device characterized by having a semiconductor element sealed with a resin sheet as in Claim 9.
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