TW202328333A - Resin composition, laminate, semiconductor chip with resin composition layer, mounting board for semiconductor chip with resin composition layer, and semiconductor device - Google Patents

Resin composition, laminate, semiconductor chip with resin composition layer, mounting board for semiconductor chip with resin composition layer, and semiconductor device Download PDF

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TW202328333A
TW202328333A TW111138419A TW111138419A TW202328333A TW 202328333 A TW202328333 A TW 202328333A TW 111138419 A TW111138419 A TW 111138419A TW 111138419 A TW111138419 A TW 111138419A TW 202328333 A TW202328333 A TW 202328333A
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resin composition
compound
group
mass
parts
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亀井孝幸
猪原勝利
杉山源希
高野健太郎
木田剛
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日商三菱瓦斯化學股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/42Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F271/00Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • C08F271/02Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415Five-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/30Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04Rosin
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

A resin composition containing: an aminotriazine novolac resin (A), at least one compound (B) selected from the group consisting of maleimide compounds (BA) and citraconimide compounds (BB), and an inorganic filler (D), wherein the inorganic filler (D) contains an inorganic filler (D1) having at least one functional group (d) selected from the group consisting of a (meth)acryl group, vinyl group, styryl group, and phenyl group, the compound (B) contains a compound (B1) and a compound (B2), the compound (B1) is at least one compound selected from the group consisting of maleimide compounds (BA-1) with a weight average molecular weight of at least 3,000 but not more than 9,500 and citraconimide compounds (BB-1) with a weight average molecular weight of at least 3,000 but not more than 9,500, the compound (B2) is at least one compound selected from the group consisting of maleimide compounds (BA-2) with a weight average molecular weight of at least 300 but less than 3,000 and citraconimide compounds (BB-2) with a weight average molecular weight of at least 300 but less than 3,000, and each of the above weight average molecular weights is a standard polystyrene equivalent value determined by gel permeation chromatography.

Description

樹脂組成物、疊層體、設有樹脂組成物層之半導體晶片、設有樹脂組成物層之半導體晶片搭載用基板、及半導體裝置Resin composition, laminate, semiconductor wafer provided with resin composition layer, substrate for mounting semiconductor wafer provided with resin composition layer, and semiconductor device

本發明關於樹脂組成物、疊層體、設有樹脂組成物層之半導體晶片、設有樹脂組成物層之半導體晶片搭載用基板、及半導體裝置。詳細而言,本發明關於作為底部填充材有用的樹脂組成物。The present invention relates to a resin composition, a laminate, a semiconductor wafer provided with a resin composition layer, a substrate for mounting a semiconductor wafer provided with a resin composition layer, and a semiconductor device. Specifically, the present invention relates to a resin composition useful as an underfill material.

近年,伴隨半導體裝置之小型化及高性能化,覆晶安裝作為將半導體晶片(以下有時省略稱為「晶片」)搭載於半導體晶片搭載用基板(以下有時省略稱為「基板」)之方法而受到關注。在覆晶安裝中,將晶片與基板接合後,於晶片與基板之間隙中填充底部填充材並使其硬化之工法係為一般。又,也有於晶片或基板填充底部填充材(也稱預塗型底部填充材)後,再使晶片、底部填充材、及基板進行接合之工法。In recent years, with the miniaturization and high performance of semiconductor devices, flip-chip mounting has become a method of mounting a semiconductor chip (hereinafter sometimes referred to as "chip") on a semiconductor chip mounting substrate (hereinafter sometimes referred to as "substrate"). method has received attention. In flip-chip mounting, after bonding the chip and the substrate, filling the gap between the chip and the substrate with an underfill material and curing it is common. In addition, there is also a method of bonding the wafer, the underfill material, and the substrate after the chip or the substrate is filled with an underfill material (also called a pre-coated underfill material).

在覆晶安裝中,就底部填充材所要求的重要特性而言,可列舉:保持絕緣可靠性。因此,在製造半導體裝置之步驟中,底部填充材與晶片及基板之間必須不產生空隙(氣泡),且必須抑制底部填充材硬化物從晶片及基板剝離。In flip-chip mounting, important characteristics required of underfill materials include maintaining insulation reliability. Therefore, in the steps of manufacturing a semiconductor device, it is necessary not to generate voids (bubbles) between the underfill material and the wafer and substrate, and it is necessary to suppress peeling of the cured underfill material from the wafer and substrate.

專利文獻1記載主樹脂使用了自由基聚合性單體之底部填充材。該專利文獻1中有關於為了改善和晶片之黏接性而摻合矽烷偶聯劑之記載。 [先前技術文獻] [專利文獻] Patent Document 1 describes an underfill material in which a radically polymerizable monomer is used as the main resin. This Patent Document 1 describes the addition of a silane coupling agent in order to improve the adhesion to a wafer. [Prior Art Literature] [Patent Document]

[專利文獻1]日本特表2015-503220號公報[Patent Document 1] Japanese National Publication No. 2015-503220

[發明所欲解決之課題][Problem to be Solved by the Invention]

但是,一般而言,自由基聚合性單體硬化快,故會在矽烷偶聯劑之反應部位和晶片表面之矽醇基形成足夠數量的鍵結前即硬化。因此,專利文獻1所記載之底部填充材並無法獲得樹脂組成物和晶片及印刷配線板等基板之充分的密合性及黏接性,結果會有產生空隙的傾向。又,由於樹脂組成物在填埋於晶片及基板表面所存在的凹凸前即硬化,故專利文獻1所記載之底部填充材還有無法充分獲得對黏接性有用的錨定效果之問題。However, generally speaking, radically polymerizable monomers harden quickly, so they harden before a sufficient number of bonds are formed between the reaction sites of the silane coupling agent and the silanol groups on the wafer surface. Therefore, the underfill material described in Patent Document 1 cannot obtain sufficient adhesiveness and adhesiveness between the resin composition and substrates such as chips and printed wiring boards, and as a result, voids tend to be generated. In addition, since the resin composition hardens before filling the unevenness existing on the surface of the wafer and the substrate, the underfill material described in Patent Document 1 has the problem of not being able to sufficiently obtain an anchoring effect useful for adhesion.

本發明係鑑於如此的課題而成者,係在於提供低空隙性及晶片黏接性優良的樹脂組成物、疊層體、設有樹脂組成物層之半導體晶片、設有樹脂組成物層之半導體晶片搭載用基板、及半導體裝置。 [解決課題之手段] The present invention is made in view of such problems, and aims to provide a resin composition, a laminate, a semiconductor wafer provided with a resin composition layer, and a semiconductor provided with a resin composition layer, which have low voids and excellent wafer adhesion. A substrate for mounting a chip, and a semiconductor device. [Means to solve the problem]

本發明人們為了解決習知技術所存在的上述課題而深入探討後結果發現,含有特定的成分之樹脂組成物可解決前述課題,乃至完成本發明。The inventors of the present invention have made in-depth studies in order to solve the above-mentioned problems existing in the prior art, and found that a resin composition containing a specific component can solve the above-mentioned problems, leading to the completion of the present invention.

亦即,本發明包含下列內容。 [1] 一種樹脂組成物,含有: 胺基三𠯤酚醛清漆樹脂(A), 選自由馬來醯亞胺化合物(BA)及檸康醯亞胺化合物(BB)構成之群組中之1種以上之化合物(B),及 無機填充材(D); 前述無機填充材(D)包含具有含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上之官能基(d)之無機填充材(D1), 前述化合物(B)包含化合物(B1)及化合物(B2), 前述化合物(B1)為選自由重量平均分子量為3,000以上且9,500以下之馬來醯亞胺化合物(BA-1)及重量平均分子量為3,000以上且9,500以下之檸康醯亞胺化合物(BB-1)構成之群組中之1種以上, 前述化合物(B2)為選自由重量平均分子量為300以上且未達3,000之馬來醯亞胺化合物(BA-2)及重量平均分子量為300以上且未達3,000之檸康醯亞胺化合物(BB-2)構成之群組中之1種以上, 各前述重量平均分子量為利用凝膠滲透層析法求得之以標準聚苯乙烯換算之值。 [2] 如[1]所記載之樹脂組成物,其中,前述官能基(d)更含有矽原子。 [3] 如[1]或[2]所記載之樹脂組成物,其中,前述無機填充材(D1)包含具有前述官能基(d)之化合物(d1)與不具有該官能基(d)之無機填充材(d2)之反應產物。 [4] 如[3]所記載之樹脂組成物,其中,前述具有官能基(d)之化合物(d1)包含選自由具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物以及具有苯乙烯基之矽烷化合物構成之群組中之1種以上。 [5] 如[3]或[4]所記載之樹脂組成物,其中,前述無機填充材(d2)包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石(boehmite)、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上。 [6] 如[3]~[5]中任一項所記載之樹脂組成物,其中,前述具有官能基(d)之化合物(d1)包含選自由具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物以及具有苯乙烯基之矽烷化合物構成之群組中之1種以上,且前述無機填充材(d2)包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上。 [7] 如[1]~[6]中任一項所記載之樹脂組成物,其中,前述無機填充材(D)的平均粒徑為3μm以下。 [8] 如[1]~[7]中任一項所記載之樹脂組成物,其中,前述無機填充材(D)的含量相對於前述胺基三𠯤酚醛清漆樹脂(A)與前述化合物(B)之合計100質量份,為20~500質量份。 [9] 如[1]~[8]中任一項所記載之樹脂組成物,其中,前述胺基三𠯤酚醛清漆樹脂(A)包含選自由下式(1)表示之化合物及下式(2)表示之化合物構成之群組中之1種以上。 [化1] 式(1)中,R 1各自獨立地表示氫原子、甲基、或乙基,l、m、及n各自獨立地表示0~10之整數,(l+m+n)表示1~20之整數。 [化2] 式(2)中,R 2各自獨立地表示氫原子、甲基、或乙基,o、p、q、r、及s各自獨立地表示0~10之整數,(o+p+q+r+s)表示1~20之整數。 [10] 如[1]~[9]中任一項所記載之樹脂組成物,其中,前述化合物(B1)的含量相對於前述化合物(B1)與前述化合物(B2)之合計100質量份,為45質量份以上且90質量份以下, 前述化合物(B2)的含量相對於前述化合物(B1)與前述化合物(B2)之合計100質量份,為10質量份以上且55質量份以下。 [11] 如[1]~[10]中任一項所記載之樹脂組成物,其中,前述馬來醯亞胺化合物(BA-1)包含選自由下式(3)表示之馬來醯亞胺化合物及含有下式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物構成之群組中之一種以上。 [化3] 式中,n3表示1~30之整數。 [化4] 式中,R 11表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基,R 12表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基,R 13各自獨立地表示氫原子、碳數1~16之直鏈狀或分支狀之烷基、或碳數2~16之直鏈狀或分支狀之烯基,n 5表示1以上且10以下之整數。 [12] 如[1]~[11]中任一項所記載之樹脂組成物,其中,前述馬來醯亞胺化合物(BA-2)包含選自由下式(5)表示之馬來醯亞胺化合物及下式(6)表示之馬來醯亞胺化合物構成之群組中之一種以上。 [化5] 式中,R 8各自獨立地表示氫原子、甲基、或乙基,R 9各自獨立地表示氫原子或甲基。 [化6] 式中,R 10各自獨立地表示氫原子、碳數1~5之烷基、或苯基,n4表示1~10之整數。 [13] 如[1]~[12]中任一項所記載之樹脂組成物,更含有助熔劑活性劑(C)。 [14] 如[13]所記載之樹脂組成物,其中,前述助熔劑活性劑(C)包含松香系樹脂。 [15] 如[1]~[14]中任一項所記載之樹脂組成物,更含有硬化觸媒(E)。 [16] 如[15]所記載之樹脂組成物,其中,前述硬化觸媒(E)包含選自由有機過氧化物及咪唑化合物構成之群組中之1種以上。 [17] 如[1]~[16]中任一項所記載之樹脂組成物,其中,前述胺基三𠯤酚醛清漆樹脂(A)的含量相對於前述胺基三𠯤酚醛清漆樹脂(A)與前述化合物(B)之合計100質量份,為1~60質量份。 [18] 如[1]~[17]中任一項所記載之樹脂組成物,其中,前述化合物(B)的含量相對於前述胺基三𠯤酚醛清漆樹脂(A)與前述化合物(B)之合計100質量份,為40~85質量份。 [19] 如[1]~[18]中任一項所記載之樹脂組成物,其係用於底部填充材。 [20] 一種疊層體,具備: 支持基材,及 疊層於前述支持基材上且含有如[1]~[19]中任一項所記載之樹脂組成物之樹脂組成物層。 [21] 如[20]所記載之疊層體,其中,前述樹脂組成物層的厚度為5~500μm之範圍。 [22] 一種設有樹脂組成物層之半導體晶片,具備: 半導體晶片,及 疊層於前述半導體晶片且使用如[1]~[19]中任一項所記載之樹脂組成物而形成的層。 [23] 一種設有樹脂組成物層之半導體晶片搭載用基板,具備: 半導體晶片搭載用基板,及 疊層於前述半導體晶片搭載用基板且使用如[1]~[19]中任一項所記載之樹脂組成物而形成的層。 [24] 一種半導體裝置,具備: 如[22]所記載之設有樹脂組成物層之半導體晶片。 [25] 一種半導體裝置,具備: 如[23]所記載之設有樹脂組成物層之半導體晶片搭載用基板。 [發明之效果] That is, the present invention includes the following. [1] A resin composition comprising: an aminotrisalpine novolak resin (A), one selected from the group consisting of a maleimide compound (BA) and a citraconamide compound (BB) The compound (B) above, and the inorganic filler (D); Inorganic filler (D1) having one or more functional groups (d), the compound (B) includes a compound (B1) and a compound (B2), and the compound (B1) is selected from the group having a weight average molecular weight of 3,000 to 9,500 One or more of the group consisting of a maleimide compound (BA-1) and a citraconamide compound (BB-1) having a weight average molecular weight of not less than 3,000 and not more than 9,500, and the aforementioned compound (B2) is Selected from the group consisting of maleimide compounds (BA-2) with a weight average molecular weight of 300 or more and less than 3,000 and citraconamide compounds (BB-2) with a weight average molecular weight of 300 or more and less than 3,000 One or more types in the group, each of the aforementioned weight average molecular weights is a value in terms of standard polystyrene obtained by gel permeation chromatography. [2] The resin composition as described in [1], wherein the functional group (d) further contains a silicon atom. [3] The resin composition according to [1] or [2], wherein the inorganic filler (D1) includes a compound (d1) having the functional group (d) and a compound not having the functional group (d). The reaction product of the inorganic filler (d2). [4] The resin composition as described in [3], wherein the compound (d1) having the functional group (d) is selected from silane compounds having (meth)acrylic and/or vinyl groups and styrene compounds having One or more of the group consisting of silane compounds based on the group. [5] The resin composition as described in [3] or [4], wherein the inorganic filler (d2) contains silicon dioxide, aluminum hydroxide, alumina, boehmite, nitride One or more species selected from the group consisting of boron, aluminum nitride, magnesium oxide, and magnesium hydroxide. [6] The resin composition as described in any one of [3] to [5], wherein the compound (d1) having a functional group (d) includes a compound selected from the group having a (meth)acrylic group and/or ethylene One or more of the group consisting of silane compounds having styryl groups and silane compounds having styryl groups, and the aforementioned inorganic filler (d2) includes silicon dioxide, aluminum hydroxide, alumina, boehmite, nitride One or more species selected from the group consisting of boron, aluminum nitride, magnesium oxide, and magnesium hydroxide. [7] The resin composition according to any one of [1] to [6], wherein the average particle diameter of the inorganic filler (D) is 3 μm or less. [8] The resin composition according to any one of [1] to [7], wherein the content of the inorganic filler (D) is relative to the amount of the amino trisanthene novolak resin (A) and the compound ( The total of 100 parts by mass of B) is 20 to 500 parts by mass. [9] The resin composition as described in any one of [1] to [8], wherein the above-mentioned aminotrisium novolac resin (A) comprises a compound selected from the following formula (1) and the following formula ( 2) One or more of the group consisting of the compounds represented. [chemical 1] In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group, 1, m, and n each independently represent an integer of 0 to 10, and (l+m+n) represents an integer of 1 to 20 integer. [Chem 2] In formula (2), R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, o, p, q, r, and s each independently represent an integer of 0 to 10, (o+p+q+r +s) means an integer from 1 to 20. [10] The resin composition according to any one of [1] to [9], wherein the content of the compound (B1) is 100 parts by mass of the total of the compound (B1) and the compound (B2), 45 to 90 parts by mass, and the content of the compound (B2) is 10 to 55 parts by mass based on 100 parts by mass of the compound (B1) and the compound (B2) in total. [11] The resin composition according to any one of [1] to [10], wherein the maleimide compound (BA-1) contains maleimide compounds represented by the following formula (3). One or more of the group consisting of an amine compound and a bismaleimide compound having a constitutional unit represented by the following formula (4) and a maleimide group at both ends of a molecular chain. [Chem 3] In the formula, n3 represents an integer of 1 to 30. [chemical 4] In the formula, R11 represents a linear or branched alkylene group with 1 to 16 carbons, or a linear or branched alkenylene group with 2 to 16 carbons, and R12 represents a linear or branched alkenyl group with 1 to 16 carbons. A linear or branched alkylene group, or a linear or branched alkenylene group with 2 to 16 carbons, R13 each independently represents a hydrogen atom, a straight or branched chain with 1 to 16 carbons An alkyl group, or a linear or branched alkenyl group with 2 to 16 carbons, n 5 represents an integer of 1 to 10. [12] The resin composition according to any one of [1] to [11], wherein the maleimide compound (BA-2) contains maleimide compounds represented by the following formula (5). One or more of the group consisting of an amine compound and a maleimide compound represented by the following formula (6). [chemical 5] In the formula, R 8 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R 9 each independently represent a hydrogen atom or a methyl group. [chemical 6] In the formula, R 10 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, or a phenyl group, and n4 represents an integer of 1 to 10. [13] The resin composition described in any one of [1] to [12], further comprising a flux activator (C). [14] The resin composition according to [13], wherein the flux activator (C) contains a rosin-based resin. [15] The resin composition described in any one of [1] to [14], further comprising a curing catalyst (E). [16] The resin composition according to [15], wherein the curing catalyst (E) contains one or more species selected from the group consisting of organic peroxides and imidazole compounds. [17] The resin composition according to any one of [1] to [16], wherein the content of the amino tris-methanol novolac resin (A) is greater than that of the amino tris-methanol novolac resin (A) It is 1-60 mass parts with 100 mass parts of total with the said compound (B). [18] The resin composition according to any one of [1] to [17], wherein the content of the aforementioned compound (B) is equal to that of the aforementioned aminotrisalpine novolak resin (A) and the aforementioned compound (B) The total of 100 parts by mass is 40 to 85 parts by mass. [19] The resin composition described in any one of [1] to [18], which is used for an underfill material. [20] A laminate comprising: a support substrate, and a resin composition layer laminated on the support substrate and containing the resin composition described in any one of [1] to [19]. [21] The laminate according to [20], wherein the thickness of the resin composition layer is in the range of 5 to 500 μm. [22] A semiconductor wafer provided with a resin composition layer, comprising: a semiconductor wafer, and a layer laminated on the aforementioned semiconductor wafer using the resin composition described in any one of [1] to [19] . [23] A substrate for mounting a semiconductor chip provided with a layer of a resin composition, comprising: a substrate for mounting a semiconductor chip; A layer formed of the resin composition described. [24] A semiconductor device comprising: a semiconductor wafer provided with a resin composition layer as described in [22]. [25] A semiconductor device comprising: the substrate for mounting a semiconductor chip provided with a resin composition layer as described in [23]. [Effect of Invention]

根據本發明,可提供低空隙性及晶片黏接性優良的樹脂組成物、疊層體、設有樹脂組成物層之半導體晶片、設有樹脂組成物層之半導體晶片搭載用基板、及半導體裝置。According to the present invention, it is possible to provide a resin composition, a laminate, a semiconductor wafer provided with a resin composition layer, a substrate for mounting a semiconductor wafer provided with a resin composition layer, and a semiconductor device having low voids and excellent wafer adhesion. .

以下,針對用以實施本發明之形態(以下簡稱「本實施形態」)進行說明。另外,下列本實施形態係用以說明本發明之例示,本發明不限於僅本實施形態。Hereinafter, an embodiment for implementing the present invention (hereinafter referred to as "the present embodiment") will be described. In addition, the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to the present embodiment.

另外,本實施形態中,「(甲基)丙烯醯氧基」意指「丙烯醯氧基」及與其相對應之「甲基丙烯醯氧基」之兩者,「(甲基)丙烯腈」意指「丙烯腈」及與其相對應之「甲基丙烯腈」之兩者,「(甲基)丙烯酸」意指「丙烯酸」及與其相對應之「甲基丙烯酸」之兩者,「(甲基)丙烯酸酯」意指「丙烯酸酯」及與其相對應之「甲基丙烯酸酯」之兩者,「(甲基)烯丙基」意指「烯丙基」及與其相對應之「甲基烯丙基」之兩者。 又,本說明書中的「~」若無特別說明時,意指包含其兩端之數值作為上限值及下限值,且該上限值及下限值設定為單位相同。 In addition, in this embodiment, "(meth)acryloxy" means both "acryloxy" and its corresponding "methacryloxy", and "(meth)acrylonitrile" Means both "acrylonitrile" and its corresponding "methacrylonitrile", "(meth)acrylic acid" means both "acrylic acid" and its corresponding "methacrylic acid", "(meth)acrylic acid" "Acrylic acid ester" means both "acrylate" and its corresponding "methacrylate", "(meth)allyl" means "allyl" and its corresponding "methyl" Allyl" both. In addition, unless otherwise specified, "~" in this specification means that the values at both ends are the upper limit and the lower limit, and the upper limit and the lower limit are set in the same unit.

又,本實施形態中,「樹脂固體成分」或「樹脂組成物中之樹脂固體成分」除非特別說明,否則係指樹脂組成物中排除無機填充材(D)、硬化觸媒(E)、及溶劑後之成分,「樹脂固體成分100質量份」係指樹脂組成物中排除無機填充材(D)、硬化觸媒(E)、及溶劑後之成分之合計為100質量份。In addition, in this embodiment, "resin solid content" or "resin solid content in the resin composition" means that the resin composition excludes the inorganic filler (D), curing catalyst (E), and The components after the solvent, "100 parts by mass of the resin solid content" means that the total of the components in the resin composition excluding the inorganic filler (D), the curing catalyst (E), and the solvent is 100 parts by mass.

[樹脂組成物] 本實施形態之樹脂組成物含有:胺基三𠯤酚醛清漆樹脂(A)(以下也簡稱「樹脂(A)」)、選自由馬來醯亞胺化合物(BA)(以下也簡稱「化合物(BA)」)及檸康醯亞胺化合物(BB)(以下也簡稱「化合物(BB)」)構成之群組中之1種以上之化合物(B)、及無機填充材(D),前述無機填充材(D)包含具有含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上之官能基(d)之無機填充材(D1),前述化合物(B)包含化合物(B1)及化合物(B2),前述化合物(B1)為選自由重量平均分子量為3,000以上且9,500以下之馬來醯亞胺化合物(BA-1)及重量平均分子量為3,000以上且9,500以下之檸康醯亞胺化合物(BB-1)構成之群組中之1種以上,前述化合物(B2)為選自由重量平均分子量為300以上且未達3,000之馬來醯亞胺化合物(BA-2)及重量平均分子量為300以上且未達3,000之檸康醯亞胺化合物(BB-2)構成之群組中之1種以上,各前述重量平均分子量為利用凝膠滲透層析法求得之以標準聚苯乙烯換算之值。本實施形態之樹脂組成物由於如此地構成,因而成為低空隙性及晶片黏接性優良者。本實施形態之樹脂組成物由於具有如此的性能,故可理想地使用作為覆晶安裝所使用的底部填充材。 [Resin composition] The resin composition of the present embodiment contains: amino trisporine novolac resin (A) (hereinafter also referred to as "resin (A)"), maleimide compound (BA) (hereinafter also referred to as "compound (BA)") )”) and citraconimide compound (BB) (hereinafter also referred to as "compound (BB)") consisting of one or more compounds (B), and an inorganic filler (D), the aforementioned inorganic filler The material (D) includes an inorganic filler (D1) having at least one functional group (d) selected from the group consisting of (meth)acrylic group, vinyl group, styryl group, and phenyl group. The compound (B) includes a compound (B1) and a compound (B2), wherein the compound (B1) is selected from maleimide compounds (BA-1) having a weight average molecular weight of 3,000 to 9,500 and a weight average molecular weight of 3,000 One or more of the group consisting of citraconamide compounds (BB-1) having a weight average molecular weight of 300 or more and less than 3,000, wherein the compound (B2) is selected from maleimides having a weight average molecular weight of 300 or more and less than 3,000 One or more of the group consisting of the compound (BA-2) and the citraconamide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000, each of which has a weight average molecular weight obtained by using the gel permeation layer The value converted to standard polystyrene obtained by the analytical method. Since the resin composition of this embodiment is comprised in this way, it becomes what is excellent in low-void property and die adhesiveness. Since the resin composition of this embodiment has such performance, it can be used ideally as an underfill material used for flip-chip mounting.

本實施形態中,可獲得低空隙性及晶片黏接性優良的樹脂組成物之理由尚未闡明,惟本發明人們推斷如下。 通常,以馬來醯亞胺化合物及/或檸康醯亞胺化合物作為主成分之樹脂組成物並無法獲得充分的晶片黏接性,而不易抑制因半導體晶片安裝時或熱硬化時(後熟化時)的熱而產生的空隙、或從硬化後的晶片及基板剝離。 在此,胺基三𠯤酚醛清漆樹脂(A)由於具有三𠯤骨架,故可和馬來醯亞胺基及/或檸康醯亞胺基良好地反應。因此,樹脂(A)可理想地控制化合物(B)之自由基聚合反應的速度,含有樹脂(A)及化合物(B)之樹脂組成物可邊隨附於晶片及基板表面所存在的凹凸邊進行硬化。因此,該樹脂組成物可對於半導體晶片及基板具有優良的錨定效果,且對於半導體晶片及基板之低空隙性優良,可展現良好的晶片黏接性。又,樹脂(A)係於三𠯤骨架鍵結有酚醛清漆樹脂骨架,故即使在硬化後仍可大量含有羥基、胺基。因此,在硬化後,這些基和晶片表面之矽醇基之中仍會產生良好的化學鍵結,除了因前述錨定效果之外,更因如上述所生成的化學鍵結,而展現更進一步優良的晶片黏接性。如此的效果在無三𠯤骨架之酚醛清漆樹脂中,就實用性之觀點而言,並不足夠。 考慮上述觀點,含有樹脂(A)及化合物(B)之樹脂組成物具有優良的晶片黏接性,根據如此的樹脂組成物,即使因半導體晶片安裝時、熱硬化時(後熟化時)的熱,仍可理想地抑制空隙。而且,據認為即使在半導體晶片安裝後及後熟化後,仍可理想地抑制硬化物從晶片及基板剝離。 此外,本實施形態之樹脂組成物所含的無機填充材(D1)具有特定的官能基(d),且該官能基(d)和化合物(B)之反應性高,故據認為因半導體晶片安裝後及後熟化時的熱而會在化合物(B)與無機填充材(D1)之間形成牢固的化學鍵結。據認為其結果可抑制半導體晶片安裝後及後熟化時可能產生的空隙,而且即使在半導體晶片安裝後及後熟化後,仍可有效地抑制硬化物從晶片及基板剝離。 如上所述,據推測藉由樹脂(A)與化合物(B)之間的交互作用及化合物(B)與無機填充材(D1)之間的交互作用之協同作業,本實施形態之樹脂組成物會具有優良的晶片黏接性,並藉由使用如此的樹脂組成物,可理想地抑制通常因半導體晶片安裝時、熱硬化時(後熟化時)的熱而容易產生的空隙。又,考慮同樣的觀點,據推測即使在半導體晶片安裝後及後熟化後,仍可理想地抑制硬化物從晶片及基板剝離。 惟,理由並不限於此。 In the present embodiment, the reason why a resin composition with low voids and excellent wafer adhesion can be obtained has not been elucidated, but the present inventors infer as follows. In general, resin compositions mainly composed of maleimide compounds and/or citraconimide compounds cannot obtain sufficient chip adhesiveness, and it is difficult to suppress damage caused by semiconductor chip mounting or heat curing (post-curing). Voids generated by heat, or delamination from hardened wafers and substrates. Here, since the amino trisanthonium novolak resin (A) has a trisulphuric acid skeleton, it can react well with a maleimide group and/or a citraconyl imide group. Therefore, the resin (A) can ideally control the speed of the radical polymerization reaction of the compound (B), and the resin composition containing the resin (A) and the compound (B) can be attached to the surface of the chip and the surface of the substrate. Harden. Therefore, the resin composition can have an excellent anchoring effect on the semiconductor chip and the substrate, and has excellent low-void property on the semiconductor chip and the substrate, and can exhibit good chip adhesiveness. Also, since the resin (A) has a novolac resin skeleton bonded to the triad skeleton, it can still contain a large amount of hydroxyl groups and amino groups even after hardening. Therefore, after hardening, a good chemical bond will still be produced between these groups and the silanol groups on the wafer surface. In addition to the aforementioned anchoring effect, a further excellent chemical bond is exhibited due to the chemical bond generated as described above. Wafer adhesion. Such an effect is not sufficient from a practical point of view in a novolak resin without a three-skeleton. Considering the above point of view, the resin composition containing the resin (A) and the compound (B) has excellent chip adhesiveness. According to such a resin composition, even when the semiconductor chip is mounted or heat-cured (after-curing) due to heat , still ideally suppressing voids. Furthermore, it is considered that even after the semiconductor wafer is mounted and post-cured, peeling of the cured product from the wafer and the substrate can be suppressed ideally. In addition, the inorganic filler (D1) contained in the resin composition of this embodiment has a specific functional group (d), and the reactivity between the functional group (d) and the compound (B) is high, so it is considered that the semiconductor chip The heat after installation and post-curing forms a firm chemical bond between the compound (B) and the inorganic filler (D1). As a result, it is considered that voids that may be generated after semiconductor wafer mounting and post-curing can be suppressed, and even after semiconductor wafer mounting and post-curing, peeling of hardened products from the wafer and substrate can be effectively suppressed. As described above, it is presumed that the resin composition of this embodiment is due to the synergy between the interaction between the resin (A) and the compound (B) and the interaction between the compound (B) and the inorganic filler (D1). It has excellent die adhesion, and by using such a resin composition, it is possible to ideally suppress voids that are usually easily generated by heat during semiconductor chip mounting and thermosetting (post-curing). Also, considering the same point of view, it is presumed that peeling of the cured product from the wafer and the substrate can be preferably suppressed even after the semiconductor wafer is mounted and post-cured. However, the reason is not limited to this.

[胺基三𠯤酚醛清漆樹脂(A)] 本實施形態之樹脂組成物中,考慮可和化合物(B)獲得優良的反應性,且可獲得低空隙性及晶片黏接性優良的樹脂組成物之觀點,含有胺基三𠯤酚醛清漆樹脂(A)。胺基三𠯤酚醛清漆樹脂(A)若為分子內具有三𠯤環之苯酚甲醛樹脂(酚醛樹脂)即可,也可使用公知的樹脂。如此的胺基三𠯤酚醛清漆樹脂(A)可利用公知的方法製造,例如可藉由將酚醛樹脂以三聚氰胺等氮化合物進行改性而得。胺基三𠯤酚醛清漆樹脂(A)可單獨使用1種或適當混合2種以上來使用。 [Amino trisulfone novolak resin (A)] In the resin composition of this embodiment, in consideration of obtaining excellent reactivity with the compound (B), and obtaining a resin composition with low voids and excellent wafer adhesion, the amino trisanthene novolak resin ( A). The amino triserum novolac resin (A) may be a phenol-formaldehyde resin (phenolic resin) having a triserum ring in the molecule, and a known resin may be used. Such an amino trisanthene novolac resin (A) can be produced by a known method, for example, it can be obtained by modifying a phenolic resin with a nitrogen compound such as melamine. Amino trisanthene novolak resin (A) can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態之樹脂組成物中,胺基三𠯤酚醛清漆樹脂(A)的含量,考慮可和化合物(B)獲得優良的反應性,且可獲得更優良的低空隙性及晶片黏接性之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為1~60質量份。考慮可和化合物(B)獲得優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,胺基三𠯤酚醛清漆樹脂(A)的含量,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,為15~60質量份更佳,為15~50質量份再更佳,為17~45質量份又更佳,為20~40質量份再更理想。In the resin composition of the present embodiment, the content of the amino trisphenol-formaldehyde novolac resin (A) is considered to be able to obtain excellent reactivity with the compound (B), and to obtain better low-void property and chip adhesiveness. From a viewpoint, it is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the total of the aminotrisium novolak resin (A) and the compound (B). Considering that excellent reactivity with compound (B) can be obtained, and further excellent low-void property and chip adhesiveness can be obtained, the content of the amino trisanthene phenolic novolac resin (A) relative to the amino trisanthene The total of 100 parts by mass of the novolac resin (A) and the compound (B) is more preferably 15-60 parts by mass, more preferably 15-50 parts by mass, more preferably 17-45 parts by mass, and more preferably 20-40 parts by mass. The quality parts are even more ideal.

胺基三𠯤酚醛清漆樹脂(A),考慮可和化合物(B)獲得優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,其重量平均分子量宜為300~9,500,為500~5,000更佳。另外,本說明書中,重量平均分子量係利用GPC(凝膠滲透層析)法求得之以標準聚苯乙烯換算之值。Amino three phenolic novolac resin (A), considering that it can obtain excellent reactivity with compound (B), and can obtain further excellent low-void and chip adhesiveness, its weight average molecular weight is preferably 300~ 9,500, preferably 500~5,000. In addition, in this specification, a weight average molecular weight is the value calculated|required by the standard polystyrene conversion by the GPC (gel permeation chromatography) method.

胺基三𠯤酚醛清漆樹脂(A),考慮可和化合物(B)獲得優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,其氮含量在胺基三𠯤酚醛清漆樹脂100質量%中,宜為10~25質量%,為15~25質量%更佳。Aminotrisyl phenolic novolac resin (A), considering that it can obtain excellent reactivity with compound (B), and can obtain further excellent low-void property and chip adhesiveness, its nitrogen content is higher than that of aminotrisaltyl phenolic novolak resin (A). In 100% by mass of the novolak resin, it is preferably 10 to 25% by mass, more preferably 15 to 25% by mass.

胺基三𠯤酚醛清漆樹脂(A),考慮可和化合物(B)獲得優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,其羥基當量宜為80~200g/eq.,為100~180g/eq.更佳,考慮可獲得和化合物(B)之更進一步優良的反應性及更進一步優良的低空隙性,同時可獲得更進一步優良的晶片黏接性之觀點,為130~170g/eq.再更佳。另外,本實施形態中,羥基當量表示為了將胺基三𠯤酚醛清漆樹脂1g中所含的羥基予以乙醯化所需要的氫氧化鉀之mg數。具體而言,係依據JIS K 0070進行測定。Amino-based novolac resin (A), considering that it can obtain excellent reactivity with compound (B), and can obtain further excellent low-void property and chip adhesiveness, its hydroxyl equivalent should be 80~200g /eq., 100~180g/eq. is better, considering that it can obtain further excellent reactivity with compound (B) and further excellent low void property, and at the same time can obtain further excellent chip adhesion From a point of view, 130~170g/eq. is even better. In addition, in the present embodiment, the hydroxyl equivalent represents the number of mg of potassium hydroxide required to acetylate the hydroxyl group contained in 1 g of the aminotrisium novolac resin. Specifically, it measured based on JISK0070.

胺基三𠯤酚醛清漆樹脂(A),考慮可和化合物(B)獲得更優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,宜包含選自由下式(1)表示之化合物及下式(2)表示之化合物構成之群組中之1種以上。The amino trisporate novolac resin (A), considering that it can obtain better reactivity with the compound (B), and can obtain further excellent low-void and chip adhesiveness, preferably includes the following formula ( One or more of the group consisting of the compound represented by 1) and the compound represented by the following formula (2).

[化7] [chemical 7]

式(1)中,R 1各自獨立地表示氫原子、甲基、或乙基。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,R 1宜各自獨立地為氫原子或甲基。l、m、及n各自獨立地表示0~10之整數。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,l、m、及n宜各自獨立地為1~6之整數。(l+m+n)表示1~20之整數。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,(l+m+n)宜為3~18之整數。另外,式(1)表示之化合物也可為例如:包含式(1)中,R 1之基或其數值不同的化合物;l、m、及n之數值不同的化合物;(l+m+n)之數值不同的化合物等之混合物。 In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group. Considering that further excellent reactivity with compound (B) can be obtained, and further excellent low-void property and wafer adhesiveness can be obtained, R 1 is preferably each independently a hydrogen atom or a methyl group. l, m, and n each independently represent an integer of 0-10. In consideration of obtaining further excellent reactivity with the compound (B), and obtaining further excellent low-void property and wafer adhesiveness, l, m, and n are preferably each independently an integer of 1-6. (l+m+n) represents an integer from 1 to 20. In consideration of obtaining further excellent reactivity with compound (B), and obtaining further excellent low-void property and wafer adhesiveness, (l+m+n) is preferably an integer of 3-18. In addition, the compound represented by formula (1) may also be, for example: a compound comprising the radical of R in formula ( 1 ) or a different value thereof; a compound with different values of l, m, and n; (l+m+n ) is a mixture of compounds with different numerical values.

[化8] [chemical 8]

式(2)中,R 2各自獨立地表示氫原子、甲基、或乙基。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,R 2宜各自獨立地為氫原子、或甲基。o、p、q、r、及s各自獨立地表示0~10之整數。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,o、p、q、r、及s宜各自獨立地為1~4之整數。(o+p+q+r+s)表示1~20之整數。考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,(o+p+q+r+s)宜為5~20之整數。另外,式(2)表示之化合物也可為例如:包含式(2)中,R 2之基或其數值不同的化合物;o、p、q、r、及s之數值不同的化合物;(o+p+q+r+s)之數值不同的化合物等之混合物。 In formula (2), R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group. Considering that further excellent reactivity with compound (B) can be obtained, and further excellent low-void property and wafer adhesiveness can be obtained, R2 is preferably each independently a hydrogen atom or a methyl group. o, p, q, r, and s each independently represent an integer of 0 to 10. Considering the viewpoint that further excellent reactivity can be obtained with compound (B), and further excellent low-void property and wafer adhesiveness can be obtained, o, p, q, r, and s should each independently be 1~ Integer of 4. (o+p+q+r+s) represents an integer from 1 to 20. Considering that it can obtain further excellent reactivity with compound (B), and can obtain further excellent low-void property and chip adhesiveness, (o+p+q+r+s) should be between 5 and 20 integer. In addition, the compound represented by formula (2) may also be, for example: a compound comprising the base of R in formula ( 2 ) or a different value thereof; a compound with different values of o, p, q, r, and s; (o +p+q+r+s) is a mixture of compounds having different values.

考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,胺基三𠯤酚醛清漆樹脂(A)為式(1)表示之化合物與式(2)表示之化合物之混合物更佳。如此的混合物考慮可和化合物(B)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性及晶片黏接性之觀點,式(1)表示之化合物與式(2)表示之化合物之質量比(式(1)表示之化合物(質量份):式(2)表示之化合物(質量份))宜為50:50~90:10,為60:40~85:15更佳。Considering that it can obtain further excellent reactivity with the compound (B), and can obtain further excellent low-void property and chip adhesiveness, the amino trisulfone novolac resin (A) is represented by the formula (1) A mixture of the compound and the compound represented by formula (2) is more preferable. Considering that such a mixture can obtain further excellent reactivity with compound (B), and can obtain further excellent low-void property and wafer adhesiveness, the compound represented by formula (1) and the compound represented by formula (2) The mass ratio of the compounds (compound represented by formula (1) (parts by mass): compound represented by formula (2) (parts by mass)) is preferably 50:50~90:10, more preferably 60:40~85:15.

胺基三𠯤酚醛清漆樹脂(A)也可使用市售品,可列舉例如:DIC(股)製之LA-1356(商品名)、LA-3018-50P(商品名)、LA-7052(商品名)、LA-7054(商品名)、LA-7751(商品名)。Aminotrisalpine novolac resin (A) can also use commercially available products, for example: LA-1356 (trade name), LA-3018-50P (trade name), LA-7052 (trade name) manufactured by DIC Co., Ltd. name), LA-7054 (trade name), LA-7751 (trade name).

[化合物(B)] 本實施形態之樹脂組成物中,考慮低空隙性及優良的晶片黏接性之觀點,含有選自由馬來醯亞胺化合物(BA)及檸康醯亞胺化合物(BB)構成之群組中之1種以上之化合物(B)。化合物(B)若為分子內含有選自由馬來醯亞胺基及檸康醯亞胺基構成之群組中之1種以上者,則無特別限制。化合物(B)宜不和後述助熔劑活性劑(C)展現反應性。化合物(B)可單獨使用1種或混合使用2種以上。 [Compound (B)] In the resin composition of the present embodiment, considering the viewpoint of low void property and excellent chip adhesiveness, it contains a compound selected from the group consisting of maleimide compound (BA) and citraconamide compound (BB). One or more compounds (B). The compound (B) is not particularly limited as long as it contains one or more species selected from the group consisting of maleimide group and citraconimide group in the molecule. The compound (B) preferably does not exhibit reactivity with the flux activator (C) described later. Compound (B) can be used individually by 1 type or in mixture of 2 or more types.

本實施形態之化合物(B)中,考慮和胺基三𠯤酚醛清漆樹脂(A)具有更優良的反應性,且可獲得更優良的低空隙性及晶片黏接性之觀點,宜含有馬來醯亞胺化合物(BA)。又,馬來醯亞胺化合物(BA)比起環氧化合物,於保存時、或因加熱處理所致之和助熔劑活性劑的反應不易顯著地進行,不易發生助熔劑之活性劑的失活。In the compound (B) of the present embodiment, considering that it has better reactivity with the amino trisanthene phenolic novolak resin (A), and can obtain better low-void property and chip adhesiveness, it is preferable to contain maleic acid. Amide compound (BA). In addition, maleimide compound (BA) is less likely to remarkably react with the flux activator during storage or heat treatment than epoxy compounds, and the inactivation of the flux activator is less likely to occur. .

化合物(B)包含化合物(B1)及化合物(B2),化合物(B1)為選自由重量平均分子量為3,000以上且9,500以下之馬來醯亞胺化合物(BA-1)及重量平均分子量為3,000以上且9,500以下之檸康醯亞胺化合物(BB-1)構成之群組中之1種以上,化合物(B2)為選自由重量平均分子量為300以上且未達3,000之馬來醯亞胺化合物(BA-2)及重量平均分子量為300以上且未達3,000之檸康醯亞胺化合物(BB-2)構成之群組中之1種以上。The compound (B) includes a compound (B1) and a compound (B2), and the compound (B1) is selected from maleimide compounds (BA-1) having a weight average molecular weight of 3,000 to 9,500 and a weight average molecular weight of 3,000 or more In addition, one or more types of citraconimide compounds (BB-1) of 9,500 or less are selected from the group consisting of maleimide compounds (BB-1) having a weight average molecular weight of 300 or more and less than 3,000 ( One or more species of the group consisting of BA-2) and a citraconamide compound (BB-2) having a weight average molecular weight of 300 to less than 3,000.

本實施形態之樹脂組成物藉由含有化合物(B1)及(B2)作為化合物(B),會成為低空隙性及晶片黏接性更進一步優良者。其理由尚未闡明,惟本發明人們推斷如下。 亦即,據推測樹脂組成物藉由含有比較高分子量的化合物(B1),會緩和在半導體晶片安裝時或熱硬化時(後熟化時)之硬化收縮時所產生的應力。因此,會更進一步促進使用樹脂(A)所帶來的黏接性改善之效果。又,樹脂組成物也含有比較低分子量的化合物(B2)。因此,在半導體晶片安裝時或熱硬化時(後熟化時)可使交聯密度改善,且因為含有樹脂(A)及化合物(B1)所帶來的應力緩和,可進一步促進所展現的黏接性。惟,理由並不限於此。 The resin composition of this embodiment will become a thing with further excellent low-void property and die adhesiveness by containing compound (B1) and (B2) as compound (B). The reason for this has not been elucidated, but the present inventors infer as follows. That is, it is presumed that the resin composition contains the compound (B1) having a relatively high molecular weight, so that the stress generated during curing shrinkage during mounting of the semiconductor wafer or during thermal curing (post-curing) is expected to be relaxed. Therefore, the effect of improving the adhesiveness by using the resin (A) will be further promoted. In addition, the resin composition also contains a relatively low molecular weight compound (B2). Therefore, the crosslinking density can be improved during semiconductor wafer mounting or thermal curing (post-curing), and the stress relaxation caused by the inclusion of resin (A) and compound (B1) can further promote the developed adhesion. sex. However, the reason is not limited to this.

化合物(B1),考慮可獲得更進一步優良的低空隙性及晶片黏接性之觀點,宜包含馬來醯亞胺化合物(BA-1)。The compound (B1) preferably contains a maleimide compound (BA-1) from the viewpoint of obtaining further excellent low-void property and die adhesiveness.

化合物(B2),考慮可獲得更進一步優良的低空隙性及晶片黏接性之觀點,宜包含馬來醯亞胺化合物(BA-2)。The compound (B2) preferably contains a maleimide compound (BA-2) from the viewpoint of obtaining further excellent low-void property and die adhesiveness.

馬來醯亞胺化合物(BA-1),考慮可獲得又更進一步優良的低空隙性及晶片黏接性之觀點,其重量平均分子量宜為3,200以上且8,000以下,為3,300以上且6,000以下更佳。The maleimide compound (BA-1) has a weight average molecular weight of 3,200 to 8,000, more preferably 3,300 to 6,000, in view of obtaining further excellent low void property and wafer adhesiveness. good.

檸康醯亞胺化合物(BB-1),考慮可獲得又更進一步優良的低空隙性及晶片黏接性之觀點,其重量平均分子量宜為3,200以上且8,000以下,為3,300以上且6,000以下更佳。For the citraconamide compound (BB-1), the weight average molecular weight is preferably 3,200 to 8,000, more preferably 3,300 to 6,000, in view of obtaining further excellent low-void property and wafer adhesiveness. good.

馬來醯亞胺化合物(BA-2),考慮可獲得又更進一步優良的低空隙性及晶片黏接性之觀點,其重量平均分子量宜為350以上且2,800以下,為400以上且2,500以下更佳。The maleimide compound (BA-2) is preferably a weight average molecular weight of 350 to 2,800, more preferably 400 to 2,500, in view of obtaining further excellent low-void property and wafer adhesiveness. good.

檸康醯亞胺化合物(BB-2),考慮可獲得又更進一步優良的低空隙性及晶片黏接性之觀點,其重量平均分子量宜為350以上且2,800以下,為400以上且2,500以下更佳。For the citraconamide compound (BB-2), it is preferable to have a weight average molecular weight of not less than 350 and not more than 2,800, and more preferably not less than 400 and not more than 2,500, in view of obtaining further excellent low-void property and chip adhesiveness. good.

(馬來醯亞胺化合物(BA)) 馬來醯亞胺化合物(BA)若為分子中具有1個以上之馬來醯亞胺基之樹脂或化合物,則無特別限制。馬來醯亞胺化合物(BA)可使用1種或混合使用2種以上。 如此的馬來醯亞胺化合物(BA)可列舉例如:N-苯基馬來醯亞胺、N-羥苯基馬來醯亞胺、雙(4-馬來醯亞胺基苯基)甲烷、4,4-二苯基甲烷雙馬來醯亞胺、雙(3,5-二甲基-4-馬來醯亞胺基苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺基苯基)甲烷、苯基甲烷馬來醯亞胺、鄰苯雙馬來醯亞胺、間苯雙馬來醯亞胺、對苯雙馬來醯亞胺、2,2-雙(4-(4-馬來醯亞胺基苯氧基)-苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷、4,4-二苯基醚雙馬來醯亞胺、4,4-二苯基碸雙馬來醯亞胺、1,3-雙(3-馬來醯亞胺基苯氧基)苯、1,3-雙(4-馬來醯亞胺基苯氧基)苯、聚苯基甲烷馬來醯亞胺、酚醛清漆樹脂型馬來醯亞胺化合物、聯苯芳烷基型馬來醯亞胺化合物、2,2-雙(4-(4-馬來醯亞胺基苯氧基)苯基)丙烷、1,2-雙(馬來醯亞胺基)乙烷、1,4-雙(馬來醯亞胺基)丁烷、1,6-雙(馬來醯亞胺基)己烷、N,N’-1,3-伸苯基二馬來醯亞胺、N,N’-1,4-伸苯基二馬來醯亞胺、N-苯基馬來醯亞胺、下式(3)表示之馬來醯亞胺化合物、含有下式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物、下式(5)表示之馬來醯亞胺化合物、下式(6)表示之馬來醯亞胺化合物、及下式(7)表示之馬來醯亞胺化合物等。化合物(B)也能以將馬來醯亞胺化合物聚合而得的預聚物、及將馬來醯亞胺化合物和胺化合物等其它化合物聚合而得的預聚物等之形態含於本實施形態之樹脂組成物中。 (maleimide compound (BA)) The maleimide compound (BA) is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule. Maleimide compound (BA) can be used 1 type or in mixture of 2 or more types. Examples of such maleimide compounds (BA) include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleiminophenyl)methane , 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleiminophenyl)methane, bis(3-ethyl-5-methyl -4-maleiminophenyl)methane, bis(3,5-diethyl-4-maleiminophenyl)methane, phenylmethanemaleimide, o-phenylene bismale Phenyl imide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenylether bismaleimide, 4,4-diphenylbismaleimide Larimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethane Maleimide, novolac resin type maleimide compound, biphenylaralkyl type maleimide compound, 2,2-bis(4-(4-maleimidophenoxy) Phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido) Hexane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-phenylmaleimide , a maleimide compound represented by the following formula (3), a bismaleimide compound containing a structural unit represented by the following formula (4) and a maleimide group at both ends of the molecular chain, the following formula A maleimide compound represented by (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), and the like. The compound (B) can also be contained in the present embodiment in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing a maleimide compound and an amine compound, or the like. form of resin composition.

[化9] [chemical 9]

式(3)中,n3表示1~30之整數。In formula (3), n3 represents the integer of 1-30.

[化10] [chemical 10]

式(4)中,R 11表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基。R 12表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基。R 13各自獨立地表示氫原子、碳數1~16之直鏈狀或分支狀之烷基、或碳數2~16之直鏈狀或分支狀之烯基。n 5各自獨立地表示1以上且10以下之整數。 另外,式(4)表示之構成單元的詳細說明如後所述。 In formula (4), R 11 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons. R 12 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons. R 13 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbons, or a linear or branched alkenyl group having 2 to 16 carbons. n and 5 each independently represent an integer of 1 to 10. In addition, the detailed description of the structural unit represented by formula (4) is mentioned later.

[化11] [chemical 11]

式(5)中,R 8各自獨立地表示氫原子、甲基、或乙基。R 9各自獨立地表示氫原子或甲基。 In formula (5), R 8 each independently represent a hydrogen atom, a methyl group, or an ethyl group. R 9 each independently represent a hydrogen atom or a methyl group.

[化12] [chemical 12]

式(6)中,R 10各自獨立地表示氫原子、碳數1~5之烷基、或苯基。n4表示1~10之整數。R 10宜為氫原子。 In formula (6), R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. n4 represents an integer from 1 to 10. R 10 is preferably a hydrogen atom.

[化13] [chemical 13]

式(7)中,R 10各自獨立地表示氫原子或甲基,n2表示1以上之整數,宜表示1~10之整數。 In the formula (7), R 10 each independently represent a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more, preferably an integer of 1 to 10.

然後,針對含有式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物的結構進行說明。 雙馬來醯亞胺化合物也可具有多個式(4)表示之構成單元,此時,多個式(4)表示之構成單元中之R 11、R 12、及R 13可分別相同也可相異。又,雙馬來醯亞胺化合物也可為式(4)表示之構成單元中之R 11、R 12、及R 13、以及雙馬來醯亞胺化合物中之式(4)之構成單元的數值中之至少1個係為不同的化合物之混合物。 式(4)表示之構成單元中,R 11表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基。R 11考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有理想的黏度,且可理想地控制安裝時的熔融黏度之上昇的觀點,宜為直鏈狀或分支狀之伸烷基,為直鏈狀之伸烷基更佳。 Next, the structure of a bismaleimide compound containing a structural unit represented by formula (4) and maleimide groups at both ends of a molecular chain will be described. The bismaleimide compound may also have multiple structural units represented by formula (4). At this time, R 11 , R 12 , and R 13 in multiple structural units represented by formula (4) may be the same or may be different. In addition, the bismaleimide compound may be R 11 , R 12 , and R 13 in the structural unit represented by the formula (4), and the structural unit of the formula (4) in the bismaleimide compound. At least one of the numerical values is a mixture of different compounds. In the structural unit represented by formula (4), R 11 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons. R 11 Considering that the resin composition has an ideal viscosity when mounting the resin composition layer of the chip, and can ideally control the rise of the melt viscosity during mounting, it is preferably a linear or branched alkylene group , it is more preferably a linear alkylene group.

伸烷基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之伸烷基可列舉例如:亞甲基、伸乙基、伸丙基、2,2-二甲基伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸新戊基、二甲基伸丁基、甲基伸己基、乙基伸己基、二甲基伸己基、三甲基伸己基、甲基伸庚基、二甲基伸庚基、三甲基伸庚基、四甲基伸庚基、乙基伸庚基、甲基伸辛基、甲基伸壬基、甲基伸癸基、甲基伸十一烷基、甲基伸十二烷基、甲基伸十三烷基、甲基伸十四烷基、及甲基伸十五烷基。 The number of carbon atoms in the alkylene group is preferably 2 to 14, considering that the resin composition has a more ideal viscosity when mounting the resin composition layer on the chip, and can more ideally control the rise of the melt viscosity during mounting. , 4~12 is better. Linear or branched alkylene groups include, for example: methylene, ethylidene, propylidene, 2,2-dimethylpropylidene, butylene, pentyl, hexylene, heptyl Base, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Neopentyl, dimethylbutyl, methylhexyl, ethylhexyl, dimethylhexyl, trimethylhexyl, methylheptyl, dimethylheptyl, trimethylhexyl Heptyl, tetramethylheptyl, ethylheptyl, methyloctyl, methylnonyl, methyldecyl, methylundecyl, methyldodecyl, methyl Tridecyl, Methyltetradecyl, and Methylpentadecyl.

伸烯基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之伸烯基可列舉例如:伸乙烯基、1-甲基伸乙烯基、伸烯丙基、伸丙烯基、伸異丙烯基、伸1-丁烯基、伸2-丁烯基、伸1-戊烯基、伸2-戊烯基、伸異戊烯基、伸環戊烯基、伸環己烯基、及伸二環戊二烯基等。 The carbon number of the alkenylene group is preferably 2 to 14 in view of the fact that the resin composition has a more ideal viscosity when mounting the resin composition layer of the chip, and can more ideally control the rise of the melt viscosity during mounting. , 4~12 is better. Examples of linear or branched alkenylene groups include vinylene, 1-methylvinyl, allyl, propenyl, isopropenyl, 1-butenyl, and 2- Butenyl, 1-pentenyl, 2-pentenyl, isopentenyl, cyclopentenyl, cyclohexenyl, dicyclopentadienyl and the like.

式(4)表示之構成單元中,R 12表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基。R 12考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有理想的黏度,且可理想地控制安裝時的熔融黏度之上昇的觀點,宜為直鏈狀或分支狀之伸烷基,為直鏈狀之伸烷基更佳。 In the structural unit represented by the formula (4), R12 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons. R 12 Considering that the resin composition has an ideal viscosity when mounting the resin composition layer of the chip, and can ideally control the rise of the melt viscosity during mounting, it is preferably a linear or branched alkylene group , it is more preferably a linear alkylene group.

伸烷基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之伸烷基可參照前述R 11The number of carbon atoms in the alkylene group is preferably 2 to 14, considering that the resin composition has a more ideal viscosity when mounting the resin composition layer on the chip, and can more ideally control the rise of the melt viscosity during mounting. , 4~12 is better. For the linear or branched alkylene group, refer to the aforementioned R 11 .

伸烯基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之伸烯基可參照前述R 11The carbon number of the alkenylene group is preferably 2 to 14 in view of the fact that the resin composition has a more ideal viscosity when mounting the resin composition layer of the chip, and can more ideally control the rise of the melt viscosity during mounting. , 4~12 is better. For the linear or branched alkenylene group, refer to the aforementioned R 11 .

式(4)表示之構成單元中,R 11、及R 12可相同也可相異,考慮可更輕易合成雙馬來醯亞胺化合物之觀點,宜為相同。 In the structural unit represented by the formula (4), R 11 and R 12 may be the same or different, but they are preferably the same from the viewpoint of easier synthesis of the bismaleimide compound.

式(4)表示之構成單元中,R 13各自獨立地表示氫原子、碳數1~16之直鏈狀或分支狀之烷基、或碳數2~16之直鏈狀或分支狀之烯基。R 13考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有理想的黏度,且可理想地控制安裝時的熔融黏度之上昇的觀點,宜各自獨立地為氫原子、或碳數1~16之直鏈狀或分支狀之烷基,R 13之中,1~5個基(R 13)為碳數1~16之直鏈狀或分支狀之烷基,且剩餘的基(R 13)為氫原子更佳,R 13之中,1~3個基(R 13)為碳數1~16之直鏈狀或分支狀之烷基,且剩餘的基(R 13)為氫原子再更佳。 In the structural unit represented by formula (4), R 13 each independently represent a hydrogen atom, a linear or branched alkyl group with 1 to 16 carbons, or a linear or branched alkenes with 2 to 16 carbons base. R 13 Considering that the resin composition has an ideal viscosity when mounting the resin composition layer of the wafer, and can ideally control the rise of the melt viscosity during mounting, it is preferably each independently a hydrogen atom or a carbon number of 1 ~16 linear or branched alkyl groups, among R 13 , 1 to 5 groups (R 13 ) are linear or branched alkyl groups with 1 to 16 carbons, and the remaining groups (R 13 ) is more preferably a hydrogen atom, among R 13 , 1~3 groups (R 13 ) are linear or branched alkyl groups with 1~16 carbons, and the remaining groups (R 13 ) are hydrogen atoms Even better.

烷基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之烷基可列舉例如:甲基、乙基、正丙基、異丙基、1-乙基丙基、正丁基、2-丁基、異丁基、三級丁基、正戊基、2-戊基、三級戊基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、正己基、2-己基、3-己基、正庚基、正辛基、2-甲基戊基、3-甲基戊基、4-甲基戊基、2-甲基戊烷-3-基、及正壬基。 The carbon number of the alkyl group is preferably 2 to 14, considering that the resin composition has a more ideal viscosity when mounting the resin composition layer of the chip, and can more ideally control the rise of the melt viscosity during mounting. 4~12 is better. Linear or branched alkyl groups include, for example: methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl Base, n-pentyl, 2-pentyl, tertiary pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl , n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

烯基的碳數,考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為2~14,為4~12更佳。 直鏈狀或分支狀之烯基可列舉例如:乙烯基、烯丙基、4-戊烯基、異丙烯基、異戊烯基、2-庚烯基、2-辛烯基、及2-壬烯基。 The carbon number of the alkenyl group is preferably 2 to 14, considering that the resin composition has a more ideal viscosity when mounting the resin composition layer of the chip, and can more ideally control the rise of the melt viscosity during mounting. 4~12 is better. Examples of linear or branched alkenyl include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2- Nonenyl.

式(4)表示之構成單元中,n 5表示1~10之整數。 In the structural unit represented by formula (4), n5 represents the integer of 1-10.

雙馬來醯亞胺化合物在分子鏈之兩末端具有馬來醯亞胺基。兩末端意指在雙馬來醯亞胺化合物之分子鏈兩側之末端,例如式(4)表示之構成單元位在雙馬來醯亞胺化合物之分子鏈的末端時,意指在R 11之分子鏈的末端具有馬來醯亞胺基、或在馬來醯亞胺環之N原子的分子鏈之末端具有馬來醯亞胺基、或在兩側之末端具有馬來醯亞胺基。雙馬來醯亞胺化合物也可在分子鏈之兩末端以外具有馬來醯亞胺基。 馬來醯亞胺基係以式(8)表示,N原子鍵結於雙馬來醯亞胺化合物之分子鏈。又,鍵結於雙馬來醯亞胺化合物之馬來醯亞胺基可全部相同也可相異,惟分子鏈之兩末端的馬來醯亞胺基宜為相同。 The bismaleimide compound has maleimide groups at both ends of the molecular chain. Both ends mean the ends on both sides of the molecular chain of the bismaleimide compound. For example, when the constituent unit represented by formula (4) is at the end of the molecular chain of the bismaleimide compound, it means that at R 11 The end of the molecular chain has a maleimide group, or there is a maleimide group at the end of the molecular chain of the N atom of the maleimide ring, or there is a maleimide group at the end of both sides. . The bismaleimide compound may have maleimide groups other than both ends of the molecular chain. The maleimide group is represented by formula (8), and the N atom is bonded to the molecular chain of the bismaleimide compound. Also, the maleimide groups bonded to the bismaleimide compound may all be the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.

[化14] [chemical 14]

式(8)中,R 11各自獨立地表示氫原子、或碳數1~4之直鏈狀或分支狀之烷基。R 11考慮可更理想地和樹脂(A)反應之觀點,宜兩者皆為氫原子。 烷基的碳數,考慮可更理想地和樹脂(A)反應之觀點,宜為1~3,為1~2更佳。 直鏈狀或分支狀之烷基可參照前述R 13In formula (8), R 11 each independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbons. Considering that R 11 can more ideally react with the resin (A), both are preferably hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1-3, and more preferably 1-2, in view of being able to react with the resin (A) more ideally. As for the linear or branched alkyl group, refer to the aforementioned R 13 .

如此的雙馬來醯亞胺化合物可列舉例如式(9)表示之馬來醯亞胺化合物。它們可單獨使用1種或也可將式(9)中之a的重複數不同的2種以上之化合物適當地混合使用。As such a bismaleimide compound, the maleimide compound represented by formula (9) is mentioned, for example. These may be used alone or in combination of two or more compounds having different repeating numbers of a in formula (9) as appropriate.

[化15] [chemical 15]

式(9)中,a表示1~10之整數。a考慮在對於晶片之樹脂組成物層的安裝時,樹脂組成物具有更理想的黏度,且可更理想地控制安裝時的熔融黏度之上昇的觀點,宜為1~6之整數。式(9)表示之馬來醯亞胺化合物也可為a不同的化合物之混合物。In formula (9), a represents the integer of 1-10. a Considering that the resin composition has a more ideal viscosity when mounting the resin composition layer on the chip, and can more ideally control the rise of the melt viscosity during mounting, it is preferably an integer of 1 to 6. The maleimide compound represented by formula (9) may be a mixture of compounds with different a.

考慮可和樹脂(A)獲得更優良的反應性,且低空隙性及晶片黏接性更進一步優良,並可獲得溶劑溶解性優良的樹脂組成物之觀點,馬來醯亞胺化合物(BA)在上述之中,宜含有選自由2,2’-雙(4-(4-馬來醯亞胺基苯氧基)苯基)丙烷、1,2-雙(馬來醯亞胺基)乙烷、1,4-雙(馬來醯亞胺基)丁烷、1,6-雙(馬來醯亞胺基)己烷、N,N’-1,3-伸苯基二馬來醯亞胺、N,N’-1,4-伸苯基二馬來醯亞胺、N-苯基馬來醯亞胺、上述式(3)表示之馬來醯亞胺化合物、含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物、上述式(5)表示之馬來醯亞胺化合物、上述式(6)表示之馬來醯亞胺化合物、及上述式(7)表示之馬來醯亞胺化合物構成之群組中之1種以上,含有選自由2,2’-雙(4-(4-馬來醯亞胺基苯氧基)苯基)丙烷、上述式(3)表示之馬來醯亞胺化合物、含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物、上述式(5)表示之馬來醯亞胺化合物、上述式(6)表示之馬來醯亞胺化合物、及上述式(7)表示之馬來醯亞胺化合物構成之群組中之1種以上更佳。此外,馬來醯亞胺化合物(BA),考慮會有可和樹脂(A)獲得進一步優良的反應性,且可獲得進一步優良的低空隙性、晶片黏接性、及溶劑溶解性之傾向的觀點,含有選自由上述式(3)表示之馬來醯亞胺化合物、含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物、上述式(5)表示之馬來醯亞胺化合物、及上述式(6)表示之馬來醯亞胺化合物構成之群組中之1種以上再更佳。In view of obtaining a better reactivity with the resin (A), further improving the low-void property and wafer adhesion, and obtaining a resin composition with excellent solvent solubility, the maleimide compound (BA) Among the above, it is preferable to contain 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane Alkane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimaleyl imine, N,N'-1,4-phenylene dimaleimide, N-phenylmaleimide, a maleimide compound represented by the above formula (3), containing the above formula ( 4) The structural unit represented by and the bismaleimide compound containing maleimide groups at both ends of the molecular chain, the maleimide compound represented by the above formula (5), the bismaleimide compound represented by the above formula (6) One or more of the group consisting of maleimide compounds and maleimide compounds represented by the above formula (7), containing Aminophenoxy)phenyl)propane, a maleimide compound represented by the above formula (3), a compound containing a constituent unit represented by the above formula (4) and a maleimide group at both ends of the molecular chain Bismaleimide compound, maleimide compound represented by the above formula (5), maleimide compound represented by the above formula (6), and maleimide compound represented by the above formula (7) More than one kind in the group formed is more preferable. In addition, the maleimide compound (BA) is considered to have a tendency to obtain further excellent reactivity with the resin (A), and to obtain further excellent low-void property, wafer adhesiveness, and solvent solubility. From a viewpoint, a bismaleimide compound containing a maleimide compound represented by the above formula (3), a constituent unit represented by the above formula (4), and a maleimide group at both ends of the molecular chain More preferably, it is one or more selected from the group consisting of the compound, the maleimide compound represented by the above formula (5), and the maleimide compound represented by the above formula (6).

馬來醯亞胺化合物(BA-1),考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,宜含有選自由上述式(3)表示之馬來醯亞胺化合物及含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物構成之群組中之一種以上。The maleimide compound (BA-1) is considered to obtain further excellent reactivity with the resin (A), and to obtain further excellent low-void properties, wafer adhesiveness, and solvent solubility, It is preferable to contain a maleimide compound represented by the above formula (3) and a bismaleimide compound containing a structural unit represented by the above formula (4) and a maleimide group at both ends of the molecular chain More than one of the groups formed.

馬來醯亞胺化合物(BA-2),考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,宜含有選自由上述式(5)表示之馬來醯亞胺化合物及上述式(6)表示之馬來醯亞胺化合物構成之群組中之一種以上。The maleimide compound (BA-2) is considered to obtain further excellent reactivity with the resin (A), and to obtain further excellent low-void property, wafer adhesiveness, and solvent solubility, It is preferable to contain at least one kind selected from the group consisting of the maleimide compound represented by the above formula (5) and the maleimide compound represented by the above formula (6).

馬來醯亞胺化合物也可使用市售品,2,2’-雙(4-(4-馬來醯亞胺基苯氧基)苯基)丙烷可列舉例如:K・I化成(股)製BMI-80(商品名)。式(3)表示之馬來醯亞胺化合物可列舉例如:K・I化成(股)製BMI-1000P(商品名,式(3)中之n3=14(平均值),重量平均分子量:3,700)、K・I化成(股)製BMI-650P(商品名,式(3)中之n3=9(平均值))、K・I化成(股)製BMI-250P(商品名,式(3)中之n3=3~8(平均值))、K・I化成(股)製CUA-4(商品名,式(3)中之n3=1)等。含有式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物可列舉例如:日本化藥(股)製MIZ-001(商品名,含有式(9)表示之馬來醯亞胺化合物,且為式(9)中之a係1~6(整數)的混合物,重量平均分子量:3,900)。式(5)表示之馬來醯亞胺化合物可列舉例如:K・I化成(股)製BMI-70(商品名;雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷,重量平均分子量:550)。式(6)表示之馬來醯亞胺化合物可列舉例如:日本化藥(股)製MIR-3000-70MT(商品名,式(6)中之R 10全部為氫原子,且為n4係1~10之混合物,重量平均分子量:1,050)。式(7)表示之馬來醯亞胺化合物可列舉例如:大和化成工業(股)製BMI-2300(商品名)。 Commercially available maleimide compounds can also be used, and examples of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane include: K・I Chemical Co., Ltd. BMI-80 (trade name) manufactured. Examples of maleimide compounds represented by formula (3) include: BMI-1000P (trade name, n3=14 (average value) in formula (3) manufactured by K・I Chemical Co., Ltd., weight average molecular weight: 3,700 ), K・I Chemical Co., Ltd. BMI-650P (trade name, n3=9 (average value) in formula (3)), K・I Chemical Co., Ltd. BMI-250P (trade name, formula (3) ) in n3=3~8 (average value)), K・I Chemical Co., Ltd. CUA-4 (trade name, n3=1 in formula (3)), etc. Bismaleimide compounds containing a structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain include, for example: Nippon Kayaku Co., Ltd. MIZ-001 (trade name, containing A maleimide compound represented by formula (9), and a in formula (9) is a mixture of 1 to 6 (integer), weight average molecular weight: 3,900). The maleimide compound represented by formula (5) can be exemplified for example: BMI-70 (trade name; bis(3-ethyl-5-methyl-4-maleimide) manufactured by K.I Chemical Industry Co., Ltd. phenyl) methane, weight average molecular weight: 550). The maleimide compound represented by formula (6) can be enumerated for example: MIR-3000-70MT (trade name) manufactured by Nippon Kayaku Co., Ltd. (trade name, R in formula (6) 10 are all hydrogen atoms, and are n4 series 1 ~10 mixture, weight average molecular weight: 1,050). Examples of the maleimide compound represented by the formula (7) include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.

(檸康醯亞胺化合物(BB)) 檸康醯亞胺化合物(BB)並無特別限制,可列舉例如:鄰苯雙檸康醯亞胺、間苯雙檸康醯亞胺、對苯雙檸康醯亞胺、4,4-二苯基甲烷雙檸康醯亞胺、2,2-雙[4-(4-檸康醯亞胺基苯氧基)苯基]丙烷、雙(3,5-二甲基-4-檸康醯亞胺基苯基)甲烷、雙(3-乙基-5-甲基-4-檸康醯亞胺基苯基)甲烷、雙(3,5-二乙基-4-檸康醯亞胺基苯基)甲烷、1,3-伸二甲苯基雙(檸康醯亞胺)、N-[3-雙(三甲基矽基)胺基-1-丙基]檸康醯亞胺、N-[3-雙(三乙基矽基)胺基-1-丙基]檸康醯亞胺、N-[3-雙(三苯基矽基)胺基-1-丙基]檸康醯亞胺、N,N’-(間苯二亞甲基)二檸康醯亞胺、及N-[3-(亞甲基琥珀醯亞胺甲基)苄基檸康醯亞胺、下式(10)表示之檸康醯亞胺化合物、含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有檸康醯亞胺基之雙檸康醯亞胺化合物、下式(11)表示之檸康醯亞胺化合物、及下式(12)表示之檸康醯亞胺化合物。另外,雙檸康醯亞胺化合物可參照上述雙馬來醯亞胺化合物。針對式(4)表示之構成單元的詳細說明如上所述,關於檸康醯亞胺基,係於上述式(8)中,R 11中至少1個基為甲基,除此之外,可參照式(8)之結構。檸康醯亞胺化合物(BB)可使用1種或混合使用2種以上。 (Citraconamide Compound (BB)) The citraconamide compound (BB) is not particularly limited, and examples include o-phthalic biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, Citraconimide, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconiminophenoxy)phenyl]propane, bis(3 ,5-Dimethyl-4-citraconiminophenyl)methane, bis(3-ethyl-5-methyl-4-citraconiminophenyl)methane, bis(3,5 -Diethyl-4-citraconimidophenyl)methane, 1,3-xylylenebis(citraconimide), N-[3-bis(trimethylsilyl)amino- 1-Propyl]citraconimide, N-[3-bis(triethylsilyl)amino-1-propyl]citraconimide, N-[3-bis(triphenylsilyl) )amino-1-propyl]citraconimide, N,N'-(m-xylylene)dicitraconimide, and N-[3-(methylenesuccinimide) base) benzyl citraconimide, a citraconamide compound represented by the following formula (10), a bismuth containing a structural unit represented by the above formula (4) and a citraconamide group at both ends of the molecular chain A citraconamide compound, a citraconamide compound represented by the following formula (11), and a citraconamide compound represented by the following formula (12). In addition, the biscitraconimide compound can refer to the above-mentioned bismaleimide compound. The detailed description of the constituent units represented by the formula (4) is as described above. Regarding the citraconimide group, in the above formula (8), at least one of the R groups is a methyl group. In addition, it can be Refer to the structure of formula (8). The citraconimide compound (BB) can be used alone or in combination of two or more.

考慮可和樹脂(A)獲得更優良的反應性,且低空隙性及晶片黏接性更進一步優良,並可獲得溶劑溶解性優良的樹脂組成物之觀點,檸康醯亞胺化合物(BB)在上述之中,宜含有選自由下式(10)表示之檸康醯亞胺化合物、含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有檸康醯亞胺基之雙檸康醯亞胺化合物、下式(11)表示之檸康醯亞胺化合物、及下式(12)表示之檸康醯亞胺化合物構成之群組中之1種以上。In view of obtaining a better reactivity with the resin (A), further improving the low-void property and wafer adhesion, and obtaining a resin composition with excellent solvent solubility, the citraconamide compound (BB) Among the above, it is preferable to contain a compound selected from a citraconyl imide compound represented by the following formula (10), a biscitric acid containing a structural unit represented by the above formula (4) and a citraconyl imide group at both ends of the molecular chain. One or more of the group consisting of a citraconimide compound, a citraconamide compound represented by the following formula (11), and a citraconamide compound represented by the following formula (12).

檸康醯亞胺化合物(BB-1),考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,宜為下式(10)表示之檸康醯亞胺化合物及/或含有上述式(4)表示之構成單元以及在分子鏈之兩末端含有檸康醯亞胺基之雙檸康醯亞胺化合物。The citraconamide compound (BB-1) is considered to be able to obtain further excellent reactivity with the resin (A), and to obtain further excellent low-void properties, wafer adhesiveness, and solvent solubility, It is preferably a citraconamide compound represented by the following formula (10) and/or a biscitraconamide compound containing a structural unit represented by the above formula (4) and a citraconamide group at both ends of the molecular chain .

[化16] [chemical 16]

式(10)中,n 6表示1~30之整數。 In the formula (10), n 6 represents an integer of 1 to 30.

檸康醯亞胺化合物(BB-2),考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,宜為下式(11)表示之檸康醯亞胺化合物及/或下式(12)表示之檸康醯亞胺化合物。The citraconamide compound (BB-2) is considered to be able to obtain further excellent reactivity with the resin (A), and to obtain further excellent low-void properties, wafer adhesiveness, and solvent solubility, It is preferably a citraconimide compound represented by the following formula (11) and/or a citraconimide compound represented by the following formula (12).

[化17] [chemical 17]

式(11)中,R 8各自獨立地表示氫原子、甲基、或乙基。R 9各自獨立地表示氫原子或甲基。 In formula (11), R 8 each independently represent a hydrogen atom, a methyl group, or an ethyl group. R 9 each independently represent a hydrogen atom or a methyl group.

[化18] [chemical 18]

式(12)中,R 10各自獨立地表示氫原子或甲基,n4表示1以上之整數,宜表示1~10之整數。R 10宜為氫原子。 In the formula (12), R 10 each independently represent a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more, preferably an integer of 1 to 10. R 10 is preferably a hydrogen atom.

本實施形態之樹脂組成物中,化合物(B)的含量並無特別限制,考慮可獲得更進一步優良的低空隙性及晶片黏接性之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為40~85質量份,為50~85質量份更佳,為55~83質量份再更佳,為60~80質量份又更佳。In the resin composition of the present embodiment, the content of the compound (B) is not particularly limited. Considering that it can obtain further excellent low-void property and chip adhesiveness, the content of the compound (B) is higher than that of the amino trisulfone novolac resin (A) It is preferably 40-85 parts by mass, more preferably 50-85 parts by mass, even more preferably 55-83 parts by mass, and still more preferably 60-80 parts by mass, based on 100 parts by mass of the compound (B).

本實施形態之樹脂組成物中,考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,化合物(B1)的含量,相對於化合物(B1)與化合物(B2)之合計100質量份,宜為45質量份以上且90質量份以下,為45質量份以上且85質量份以下更佳,為45質量份以上且78質量份以下再更佳。又,化合物(B2)的含量,相對於化合物(B1)與化合物(B2)之合計100質量份,宜為10質量份以上且55質量份以下,為15質量份以上且55質量份以下更佳,為22質量份以上且55質量份以下再更佳。In the resin composition of the present embodiment, the compound (B1 The content of ) is preferably 45 parts by mass to 90 parts by mass, more preferably 45 parts by mass to 85 parts by mass, and 45 parts by mass relative to the total of 100 parts by mass of compound (B1) and compound (B2). It is more preferably more than or equal to 78 parts by mass or less. Also, the content of the compound (B2) is preferably 10 parts by mass to 55 parts by mass, more preferably 15 parts by mass to 55 parts by mass, based on 100 parts by mass of the total of the compound (B1) and the compound (B2). , more preferably 22 parts by mass or more and 55 parts by mass or less.

本實施形態之樹脂組成物中,考慮可和樹脂(A)獲得更進一步優良的反應性,且可獲得更進一步優良的低空隙性、晶片黏接性、及溶劑溶解性的觀點,馬來醯亞胺化合物(BA-1)的含量,相對於化合物(BA-1)與化合物(BA-2)之合計100質量份,宜為45~90質量份,為45~85質量份更佳,為45~78質量份再更佳。又,馬來醯亞胺化合物(BA-2)的含量,相對於化合物(BA-1)與化合物(BA-2)之合計100質量份,宜為10~55質量份,為15~55質量份更佳,為22~55質量份再更佳。In the resin composition of the present embodiment, in view of obtaining further excellent reactivity with the resin (A), and obtaining further excellent low-void property, chip adhesiveness, and solvent solubility, maleic acid The content of the imine compound (BA-1) is preferably 45 to 90 parts by mass, more preferably 45 to 85 parts by mass, with respect to 100 parts by mass of the total of the compound (BA-1) and the compound (BA-2). 45-78 parts by mass is even better. Also, the content of the maleimide compound (BA-2) is preferably 10 to 55 parts by mass, 15 to 55 parts by mass relative to the total of 100 parts by mass of the compound (BA-1) and the compound (BA-2). Parts are better, more preferably 22 to 55 parts by mass.

本實施形態之樹脂組成物中,考慮可獲得更進一步優良的低空隙性及晶片黏接性之觀點,檸康醯亞胺化合物(BB-1)的含量,相對於化合物(BB-1)與化合物(BB-2)之合計100質量份,宜為45~90質量份,為45質量份~85質量份更佳,為45~78質量份再更佳。又,檸康醯亞胺化合物(BB-2)的含量,相對於化合物(BB-1)與化合物(BB-2)之合計100質量份,宜為10~55質量份,為15~55質量份更佳,為22~55質量份再更佳。In the resin composition of the present embodiment, considering that further excellent low-void property and chip adhesiveness can be obtained, the content of the citraconamide compound (BB-1) is higher than that of the compound (BB-1) and The total of 100 parts by mass of the compound (BB-2) is preferably 45 to 90 parts by mass, more preferably 45 to 85 parts by mass, more preferably 45 to 78 parts by mass. Also, the content of the citraconamide compound (BB-2) is preferably 10 to 55 parts by mass, 15 to 55 parts by mass relative to 100 parts by mass of the total of the compound (BB-1) and the compound (BB-2). Parts are better, more preferably 22 to 55 parts by mass.

本實施形態之樹脂組成物中,考慮可獲得更優良的低空隙性及晶片黏接性之觀點,樹脂(A)及化合物(B)的含量(總量),相對於樹脂固體成分100質量份,宜為30質量份以上,為50質量份以上更佳,為70質量份以上再更佳,也可為80質量份以上。樹脂(A)及化合物(B)的含量(總量)之上限值,相對於樹脂固體成分100質量份,也可為100質量份以下,亦可為95質量份以下。In the resin composition of the present embodiment, the content (total amount) of the resin (A) and the compound (B) is based on 100 parts by mass of the solid content of the resin in consideration of obtaining better low-void property and die adhesiveness. , should be more than 30 parts by mass, more preferably more than 50 parts by mass, more preferably more than 70 parts by mass, and can also be more than 80 parts by mass. The upper limit of the content (total amount) of the resin (A) and the compound (B) may be 100 parts by mass or less or 95 parts by mass or less with respect to 100 parts by mass of resin solid content.

[助熔劑活性劑(C)] 本實施形態之樹脂組成物中,為了在覆晶安裝中使助熔劑活性展現,宜更含有助熔劑活性劑(C)。助熔劑活性劑(C)若為分子中具有1個以上之酸性部位的有機化合物,則無特別限制。酸性部位宜為例如:磷酸基、酚性羥基、羧基、及磺酸基,考慮在使用本實施形態之樹脂組成物作為底部填充材的半導體裝置中,會更有效地防止構成接合部之焊料、銅等金屬之遷移及腐蝕的觀點,為酚性羥基或羧基更佳。助熔劑活性劑(C)可單獨使用1種或適當混合2種以上來使用。 [Flux Activator (C)] In the resin composition of this embodiment, it is preferable to further contain a flux activator (C) in order to exhibit flux activity during flip-chip mounting. The flux activator (C) is not particularly limited as long as it is an organic compound having one or more acidic sites in the molecule. The acidic sites are preferably, for example, phosphoric acid groups, phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups. It is considered that in a semiconductor device using the resin composition of this embodiment as an underfill material, it will be more effective in preventing solder, From the viewpoint of migration and corrosion of metals such as copper, phenolic hydroxyl groups or carboxyl groups are more preferable. The flux activator (C) can be used individually by 1 type or in mixture of 2 or more types suitably.

助熔劑活性劑(C)並無特別限制,為了充分實施接合部之氧化膜的去除,酸解離常數pKa宜為3.8以上且15.0以下,考慮兼顧清漆之保存安定性與具備樹脂組成物之層的疊層體(設有支持基材之底部填充材)之保存安定性與助熔劑活性之觀點,為4.0以上且14.0以下更佳。The flux activator (C) is not particularly limited. In order to fully remove the oxide film at the junction, the acid dissociation constant pKa is preferably not less than 3.8 and not more than 15.0, considering the preservation stability of the varnish and the layer having a resin composition. From the standpoint of storage stability and flux activity of the laminate (the underfill provided with the supporting base material), it is more preferably 4.0 or more and 14.0 or less.

本實施形態之樹脂組成物中的助熔劑活性劑(C)的重量平均分子量或分子量並無特別限制,考慮防止在覆晶安裝中,助熔劑活性在展現前即已揮發,亦即在去除接合部的氧化膜前助熔劑活性劑(C)即已揮發之觀點,重量平均分子量或分子量宜為200以上,為250以上更佳。為了具有作為助熔劑活性劑之運動性並獲得充分的助熔劑活性,助熔劑活性劑(C)的重量平均分子量或分子量宜為8000以下,為1000以下更佳,為600以下再更佳。The weight-average molecular weight or molecular weight of the flux activator (C) in the resin composition of the present embodiment is not particularly limited, and it is considered to prevent the flux activity from volatilizing before the display in flip-chip mounting, that is, after removing the bond From the point of view that the pre-oxidized flux activator (C) in the part has volatilized, the weight average molecular weight or molecular weight is preferably 200 or more, more preferably 250 or more. In order to have mobility as a flux activator and obtain sufficient flux activity, the weight average molecular weight or molecular weight of the flux activator (C) is preferably 8000 or less, more preferably 1000 or less, and more preferably 600 or less.

助熔劑活性劑(C)並無特別限制可列舉例如:松脂酸、新松脂酸(neoabietic acid)、去氫松脂酸(dehydroabietic acid)、海松脂酸(pimaric acid)、異海松脂酸(pimaric acid)、長葉松脂酸(palustric acid)、雙酚酸、二氫松脂酸(dihydroabietic acid)、四氫松脂酸、氫化松香酯、及松香改性馬來酸樹脂等松香系樹脂;N,N’-雙(亞柳基)-1,2-丙烷二胺、及N,N’-雙(亞柳基)-1,3-丙烷二胺等二胺系;2-[雙(4-羥基苯基)甲基]苯甲酸。這些助熔劑活性劑(C)考慮對溶劑之溶解性、清漆之保存安定性與設有支持基材之底部填充材之保存安定性優良的觀點較為理想,助熔劑活性劑(C)包含松香系樹脂更佳。The flux agent active agent (C) is not particularly limited and may include, for example: rosinic acid, neoabietic acid, dehydroabietic acid, pimaric acid, and pimaric acid ), long leaf rosin acid (palustric acid), bisphenolic acid, dihydroabietic acid (dihydroabietic acid), tetrahydrorosinic acid, hydrogenated rosin ester, and rosin-modified maleic acid resin and other rosin-based resins; N,N' -Diamines such as bis(sulphonylene)-1,2-propanediamine and N,N'-bis(sulphonylene)-1,3-propanediamine; 2-[bis(4-hydroxybenzene base) methyl] benzoic acid. These flux activators (C) are ideal in view of their solubility in solvents, storage stability of varnishes, and storage stability of underfill materials provided with support substrates. Flux activators (C) include rosin-based Resin is better.

它們之中,考慮防止化合物(B)所導致之失活的觀點,助熔劑活性劑(C)包含選自由去氫松脂酸、雙酚酸、二氫松脂酸、四氫松脂酸、氫化松香酯、松香改性馬來酸樹脂、N,N’-雙(亞柳基)-1,2-丙烷二胺、及N,N’-雙(亞柳基)-1,3-丙烷二胺構成之群組中之1種以上更佳。又,這些助熔劑活性劑考慮反應性較低的觀點,並考慮幾乎不會引起和樹脂(A)及化合物(B)之反應,並維持去除氧化膜所必須之充足的助熔劑活性之觀點,更為理想。此外,考慮可獲得更進一步優良的助熔劑活性之觀點,助熔劑活性劑(C)為氫化松香酯的話,又更理想。Among them, from the viewpoint of preventing deactivation by the compound (B), the flux activator (C) contains a compound selected from the group consisting of dehydrorosinic acid, bisphenolic acid, dihydrorosinic acid, tetrahydrorosinic acid, and hydrogenated rosin esters. , rosin-modified maleic acid resin, N,N'-bis(willowylene)-1,2-propanediamine, and N,N'-bis(willowylene)-1,3-propanediamine More than one kind in the group is more preferable. Also, these flux activators are considered to be low in reactivity, and are considered to hardly cause a reaction with the resin (A) and the compound (B), and to maintain sufficient flux activity necessary to remove the oxide film, more ideal. In addition, it is more preferable that the flux activator (C) is a hydrogenated rosin ester from the viewpoint of obtaining further excellent flux activity.

助熔劑活性劑(C)可使用市售品。松香系樹脂可列舉例如:PINECRYSTAL(註冊商標,以下皆同)系列之KR-85(商品名,以下皆同)、KR-612、KR-614、KE-100、KE-311、PE-590、KE-359、KE-604、KR-120、KR-140、KR-614、D-6011、及KR-50M;MALKYD No32(以上為荒川化學工業股份有限公司製)等。A commercial item can be used for a flux activator (C). Examples of rosin-based resins include KR-85 (trade name, the same below), KR-612, KR-614, KE-100, KE-311, PE-590, KE-359, KE-604, KR-120, KR-140, KR-614, D-6011, and KR-50M; MALKYD No32 (manufactured by Arakawa Chemical Industry Co., Ltd.).

本實施形態之樹脂組成物中,助熔劑活性劑(C)的含量並無特別限制,考慮絕緣可靠性及安裝時確保充分的助熔劑活性之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為5~70質量份,為10~50質量份更佳,為15~40質量份再更佳。In the resin composition of this embodiment, the content of the flux activator (C) is not particularly limited. Considering the insulation reliability and the viewpoint of ensuring sufficient flux activity during installation, the content of the flux activator (C) should ) and compound (B) in total of 100 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass.

[無機填充材(D)] 本實施形態之樹脂組成物中,為了耐燃性之改善、熱傳導率之改善、及熱膨脹率之減少,而更含有無機填充材(D)。藉由使用無機填充材(D),可改善使用本實施形態之樹脂組成物而形成的薄膜等硬化物之耐燃性及熱傳導率,且可減少熱膨脹率。此外,可理想地控制樹脂組成物的最低熔融黏度。考慮適合用於底部填充材之觀點,樹脂組成物的最低熔融黏度宜為200Pa・s以上且30,000Pa・s以下。尤其,本實施形態之樹脂組成物中,由於含有如後詳述之無機填充材(D1)作為無機填充材(D),故會改善低空隙性及晶片黏接性。 [Inorganic filler (D)] The resin composition of this embodiment further contains an inorganic filler (D) for the purpose of improving flame resistance, improving thermal conductivity, and reducing thermal expansion coefficient. By using the inorganic filler (D), the flame resistance and thermal conductivity of cured products such as films formed using the resin composition of this embodiment can be improved, and the thermal expansion coefficient can be reduced. In addition, the minimum melt viscosity of the resin composition can be ideally controlled. In consideration of suitability for use as an underfill material, the minimum melt viscosity of the resin composition is preferably 200 Pa・s or more and 30,000 Pa・s or less. In particular, since the resin composition of this embodiment contains the inorganic filler (D1) which will be described in detail later as the inorganic filler (D), low-void property and die adhesiveness are improved.

無機填充材(D)並無特別限制,例如可包含各種公知的無機化合物,該無機化合物並不限於如下,可列舉例如:天然二氧化矽、熔融二氧化矽、非晶態二氧化矽、及中空二氧化矽等二氧化矽;軟水鋁石、氫氧化鋁、氧化鋁、及氮化鋁等鋁化合物;氧化鎂、及氫氧化鎂等鎂化合物;碳酸鈣、及硫酸鈣等鈣化合物;氧化鉬、及鉬酸鋅等鉬化合物;氮化硼;硫酸鋇;天然滑石、及煅燒滑石等滑石(talc);雲母;短纖維狀玻璃、球狀玻璃、及微粉末玻璃(例如E玻璃、T玻璃、D玻璃)等玻璃。又,欲對本實施形態之樹脂組成物賦予導電性或各向異性導電性時,無機填充材(D)也可使用例如:金、銀、鎳、銅、錫合金、鈀等金屬粒子。 它們之中,考慮樹脂組成物之耐燃性的改善及熱膨脹率之減少的觀點,無機填充材(D)宜包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上,包含選自由二氧化矽、氧化鋁、及氮化硼構成之群組中之1種以上更佳,其中,為二氧化矽再更佳。 這些無機填充材(D)可單獨使用1種或適當混合2種以上來使用。 The inorganic filler (D) is not particularly limited. For example, it may contain various known inorganic compounds. The inorganic compound is not limited to the following, for example: natural silica, fused silica, amorphous silica, and Silica such as hollow silica; Aluminum compounds such as boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride; Magnesium compounds such as magnesium oxide and magnesium hydroxide; Calcium compounds such as calcium carbonate and calcium sulfate; Molybdenum, and molybdenum compounds such as zinc molybdate; boron nitride; barium sulfate; natural talc, calcined talc and other talc (talc); mica; short fiber glass, spherical glass, and fine powder glass (such as E glass, T glass, D glass) and other glass. Also, when it is desired to impart electrical conductivity or anisotropic electrical conductivity to the resin composition of this embodiment, metal particles such as gold, silver, nickel, copper, tin alloy, and palladium can also be used as the inorganic filler (D). Among them, the inorganic filler (D) preferably contains a material selected from silicon dioxide, aluminum hydroxide, alumina, boehmite, boron nitride, One or more types selected from the group consisting of aluminum nitride, magnesium oxide, and magnesium hydroxide, more preferably including one or more types selected from the group consisting of silicon dioxide, aluminum oxide, and boron nitride, wherein, is Silica is even more preferred. These inorganic fillers (D) can be used individually by 1 type or in mixture of 2 or more types suitably.

無機填充材(D)之中,上述具體例之無機化合物本身的表面本來並不存在(甲基)丙烯酸基、乙烯基、苯乙烯基、或苯基等官能基。另一方面,本實施形態中的無機填充材(D)包含具有含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上之官能基(d)之無機填充材(D1)。另外,本實施形態中,「苯基」(「-C 6H 5」)意指直接鍵結於矽原子或碳原子者,其和例如直接鍵結於氮原子之苯基(胺基苯基)等視為不同而予以區別。如此的無機填充材(D1)中的官能基(d)和化合物(B)之反應性高,故據認為因半導體晶片安裝後及後熟化時的熱而會在化合物(B)與無機填充材(D1)之間形成牢固的化學鍵結。據認為其結果可抑制半導體晶片安裝後及後熟化時可能產生的空隙,而且即使在半導體晶片安裝後及後熟化後,仍可理想地抑制硬化物從晶片及基板剝離。 Among the inorganic fillers (D), functional groups such as (meth)acrylic, vinyl, styryl, or phenyl do not exist on the surface of the inorganic compound itself of the above specific example. On the other hand, the inorganic filler (D) in this embodiment contains a functional group containing at least one kind selected from the group consisting of (meth)acrylic, vinyl, styryl, and phenyl groups ( d) Inorganic filler (D1). In addition, in the present embodiment, "phenyl"("-C 6 H 5 ") means one directly bonded to a silicon atom or a carbon atom, and for example, a phenyl group directly bonded to a nitrogen atom (aminophenyl ) etc. shall be distinguished as different. The functional group (d) in such an inorganic filler (D1) has a high reactivity with the compound (B), so it is considered that the reaction between the compound (B) and the inorganic filler occurs due to the heat after the semiconductor wafer is mounted and post-cured. (D1) to form a strong chemical bond. As a result, it is considered that voids that may be generated after semiconductor wafer mounting and post-curing can be suppressed, and even after semiconductor wafer mounting and post-curing, peeling of hardened products from the wafer and substrate can be preferably suppressed.

本實施形態中的官能基(d)只要包含選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之至少1種,則無特別限制,考慮低空隙性及晶片黏接性的觀點,宜更包含矽原子,該矽原子和含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上的基直接鍵結的話較為理想。如此的矽原子和含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上的基直接鍵結之官能基(d),宜為含有選自由(甲基)丙烯醯氧基烷基矽基、乙烯基矽基、苯乙烯基矽基、及苯基矽基構成之群組中之1種以上的基,為含有選自由(甲基)丙烯醯氧基烷基矽基及乙烯基矽基構成之群組中之1種以上的基更佳。(甲基)丙烯醯氧基烷基矽基中的烷基部分之碳數宜為1~6,為1~3更佳。The functional group (d) in this embodiment is not particularly limited as long as it contains at least one selected from the group consisting of (meth)acrylic group, vinyl group, styryl group, and phenyl group, considering low porosity From the viewpoint of wafer adhesiveness, it is preferable to further contain a silicon atom that is directly connected to a group containing one or more kinds selected from the group consisting of (meth)acrylic group, vinyl group, styryl group, and phenyl group. Bonding would be ideal. Such a silicon atom and a functional group (d) containing one or more groups selected from the group consisting of (meth)acrylic group, vinyl group, styryl group, and phenyl group and directly bonded to each other are preferably those containing the selected One or more groups selected from the group consisting of (meth)acryloxyalkylsilyl, vinylsilyl, styrylsilyl, and phenylsilyl, containing a group selected from (methyl) One or more groups selected from the group consisting of an acryloxyalkylsilyl group and a vinylsilyl group are more preferable. The carbon number of the alkyl moiety in the (meth)acryloxyalkylsilyl group is preferably 1-6, more preferably 1-3.

本實施形態中的無機填充材(D1),考慮低空隙性及晶片黏接性的觀點,宜包含具有官能基(d)之化合物(d1)與不具有該官能基(d)之無機填充材(d2)的反應產物。 化合物(d1)若為可對於無機填充材(d2)的表面導入預定的官能基者,則無特別限制,可列舉例如:含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之至少1種的矽烷偶聯劑。如此的矽烷偶聯劑可適當採用通常無機物之表面處理所使用的矽烷偶聯劑。其具體例並不限於如下,可列舉:乙烯基三甲氧基矽烷及γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷等乙烯基矽烷系矽烷偶聯劑(具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物);三甲氧基苯基矽烷等苯基矽烷系矽烷偶聯劑(具有苯基之矽烷化合物);苯乙烯三甲氧基矽烷等苯乙烯矽烷系矽烷偶聯劑(具有苯乙烯基之矽烷化合物)等。這些矽烷偶聯劑可單獨使用1種或適當混合2種以上來使用。上述之中,考慮低空隙性及晶片黏接性的觀點,化合物(d1)宜包含選自由乙烯基矽烷系矽烷偶聯劑(具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物)、以及苯乙烯矽烷系矽烷偶聯劑(具有苯乙烯基之矽烷化合物)構成之群組中之1種以上,包含乙烯基矽烷系矽烷偶聯劑更佳,包含選自由乙烯基三烷氧基矽烷及γ-(甲基)丙烯醯氧基丙基三烷氧基矽烷構成之群組中之1種以上再更佳,包含選自由乙烯基三甲氧基矽烷及γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷構成之群組中之1種以上又更佳。 無機填充材(d2)並無特別限制,就可包含作為無機填充材(D)之無機化合物而言,可使用前述具體例,考慮低空隙性及晶片黏接性的觀點,宜包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上,包含二氧化矽更佳。 上述反應產物之製備方法並無特別限制,利用矽烷偶聯劑所為之處理可適當採用各種公知的方法。例如,無機填充材(d2)為二氧化矽時,上述處理也可於氣相實施,亦可於液相實施。 另外,無機填充材(D1)中的官能基(d)的含量並無特別限制,無機填充材(d2)為二氧化矽時,相對於二氧化矽100質量份,官能基(d)的含量也可為1~10質量份。 The inorganic filler (D1) in the present embodiment preferably includes a compound (d1) having a functional group (d) and an inorganic filler not having the functional group (d) in consideration of low porosity and wafer adhesion. The reaction product of (d2). The compound (d1) is not particularly limited as long as it can introduce a predetermined functional group to the surface of the inorganic filler (d2), and examples include: At least one silane coupling agent of the group consisting of phenyl groups. As such a silane coupling agent, a silane coupling agent commonly used for surface treatment of inorganic substances can be suitably used. Its specific examples are not limited to the following, but include vinyl silane-based silane coupling agents (with (meth)acrylic acid) such as vinyltrimethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane. base and/or vinyl silane compounds); phenylsilane-based silane coupling agents such as trimethoxyphenylsilane (silane compounds with phenyl groups); styrene-based silane-based silane coupling agents such as styrene trimethoxysilane (silane compound with styryl group), etc. These silane coupling agents can be used individually by 1 type or in mixture of 2 or more types suitably. Among the above, in view of low voids and wafer adhesiveness, the compound (d1) preferably includes a vinyl silane-based silane coupling agent (silane compound having a (meth)acrylic group and/or vinyl group), And one or more of the group consisting of styrene silane-based silane coupling agents (silane compounds with styrene groups), preferably including vinyl silane-based silane coupling agents, including vinyl trialkoxy silane And more preferably at least one of the group consisting of γ-(meth)acryloxypropyltrialkoxysilane, including vinyltrimethoxysilane and γ-(meth)acryloxysilane More preferably one or more of the group consisting of propyltrimethoxysilane. The inorganic filler (d2) is not particularly limited. As for the inorganic compound that can be included as the inorganic filler (D), the above-mentioned specific examples can be used. Considering the viewpoint of low porosity and chip adhesion, it is preferable to include a compound selected from two At least one selected from the group consisting of silicon oxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, preferably including silicon dioxide. The preparation method of the above-mentioned reaction product is not particularly limited, and various known methods can be appropriately adopted for the treatment with a silane coupling agent. For example, when the inorganic filler (d2) is silica, the above treatment may be performed in a gas phase or in a liquid phase. In addition, the content of the functional group (d) in the inorganic filler (D1) is not particularly limited, and when the inorganic filler (d2) is silica, the content of the functional group (d) relative to 100 parts by mass of silica 1 to 10 parts by mass may also be used.

另外,無機填充材(d2)為二氧化矽時,上述反應產物之具體例並不限於如下,可列舉:Admatechs(股)製之經乙烯基三甲氧基矽烷予以表面處理之0.3μmSV-EM1(商品名)、經乙烯基三甲氧基矽烷予以表面處理之SC1050-MLQ(商品名)、經乙烯基三甲氧基矽烷予以表面處理之SC2050-MNU(商品名)、經3-甲基丙烯醯氧基丙基三甲氧基矽烷予以表面處理之YA050C-MJE(商品名)、經乙烯基三甲氧基矽烷予以表面處理之Y50SV-AM1(商品名)、經苯基三甲氧基矽烷予以表面處理之Y50SP-AM1(商品名)等。上述之中,考慮低空隙性及晶片黏接性的觀點,上述反應產物之市售品宜包含選自由YA050C-MJE(商品名)、Y50SV-AM1(商品名)、及Y50SP-AM1(商品名)構成之群組中之1種以上,包含選自由YA050C-MJE(商品名)及Y50SV-AM1(商品名)構成之群組中之1種以上更佳。In addition, when the inorganic filler (d2) is silica, specific examples of the above-mentioned reaction product are not limited to the following, and examples include: 0.3 μm SV-EM1 ( trade name), SC1050-MLQ (trade name) with vinyltrimethoxysilane surface treatment, SC2050-MNU (trade name) with vinyltrimethoxysilane surface treatment, 3-methacryloxy YA050C-MJE (trade name) surface-treated with propyltrimethoxysilane, Y50SV-AM1 (trade name) surface-treated with vinyltrimethoxysilane, Y50SP surface-treated with phenyltrimethoxysilane - AM1 (trade name), etc. Among the above, considering the viewpoints of low porosity and wafer adhesion, the commercial products of the above-mentioned reaction products preferably include YA050C-MJE (trade name), Y50SV-AM1 (trade name), and Y50SP-AM1 (trade name). ), more preferably including one or more selected from the group consisting of YA050C-MJE (trade name) and Y50SV-AM1 (trade name).

無機填充材(D)的平均粒徑並無特別限制,考慮在使用本實施形態之樹脂組成物作為底部填充材時,因應排列於晶片之電極的窄節距化、電極間之窄間隙化的觀點,宜為3μm以下,為1μm以下更佳,也可為0.1μm以下。其平均粒徑的下限值並無特別限制,例如為10nm。另外,本實施形態中,無機填充材(D)的「平均粒徑」意指無機填充材(D)的中值粒徑。在此中值粒徑意指,以某粒徑作為基準將粉體之粒度分佈分成2群時,使粒徑較大側的粒子之體積和粒徑較小側的粒子之體積成為分別佔全部粉體之50%的粒徑。無機填充材(D)的平均粒徑(中值粒徑)係利用濕式雷射繞射-散射法進行測定。The average particle diameter of the inorganic filler (D) is not particularly limited. When using the resin composition of this embodiment as the underfill material, it is considered that the pitch of the electrodes arranged on the wafer is narrowed and the gap between the electrodes is narrowed. From a viewpoint, it is preferably 3 μm or less, more preferably 1 μm or less, and may be 0.1 μm or less. The lower limit of the average particle diameter is not particularly limited, and is, for example, 10 nm. In addition, in the present embodiment, the "average particle diameter" of the inorganic filler (D) means the median diameter of the inorganic filler (D). Here, the median particle size means that when the particle size distribution of the powder is divided into two groups based on a certain particle size, the volume of the particles on the larger particle size side and the volume of the particles on the smaller particle size side account for the total volume respectively. 50% of the particle size of the powder. The average particle size (median particle size) of the inorganic filler (D) was measured by a wet laser diffraction-scattering method.

本實施形態之樹脂組成物中,無機填充材(D)的含量並無特別限制,考慮絕緣可靠性及安裝時確保充分的助熔劑活性之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為20~500質量份,為50~400質量份更佳,為70~300質量份再更佳。無機填充材(D)的含量之上限也可為250質量份。又,考慮低空隙性及晶片黏接性的觀點,無機填充材(D1)的含量,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為20~500質量份,為50~400質量份更佳,為70~300質量份再更佳。無機填充材(D1)的含量之上限也可為250質量份。In the resin composition of the present embodiment, the content of the inorganic filler (D) is not particularly limited. Considering insulation reliability and ensuring sufficient flux activity during installation, the content of the inorganic filler (D) should It is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass, and even more preferably 70 to 300 parts by mass, with the total of 100 parts by mass of the compound (B). The upper limit of content of an inorganic filler (D) may be 250 mass parts. Also, from the viewpoint of low porosity and wafer adhesiveness, the content of the inorganic filler (D1) is preferably 20 to 100 parts by mass of the total of the aminotrisalpine novolak resin (A) and the compound (B). 500 parts by mass, more preferably 50 to 400 parts by mass, more preferably 70 to 300 parts by mass. The upper limit of content of an inorganic filler (D1) may be 250 mass parts.

[硬化觸媒(E)] 本實施形態之樹脂組成物宜更含有硬化觸媒(E)。樹脂組成物含有硬化觸媒(E)時,會有可更理想地控制樹脂(A)與化合物(B)之反應速度及化合物(B)之聚合速度,而且可獲得具有適當的成形性之樹脂組成物的傾向。硬化觸媒(E)若為可促進樹脂(A)與化合物(B)之反應及化合物(B)之聚合反應的化合物,則無特別限制。硬化觸媒(E)可單獨使用1種或混合使用2種以上。 [Hardening Catalyst (E)] The resin composition of this embodiment preferably further contains a hardening catalyst (E). When the resin composition contains the hardening catalyst (E), the reaction rate between the resin (A) and the compound (B) and the polymerization rate of the compound (B) can be more ideally controlled, and a resin with appropriate moldability can be obtained. compositional tendencies. The curing catalyst (E) is not particularly limited as long as it is a compound that can accelerate the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B). The hardening catalyst (E) can be used individually by 1 type or in mixture of 2 or more types.

本實施形態中的硬化觸媒(E)並無特別限制,可列舉例如:有機過氧化物、咪唑化合物、偶氮化合物、以及三乙胺及三丁胺以及它們的衍生物等三級胺。它們之中,考慮可獲得良好的反應速度及聚合速度,且可獲得良好的硬化速度之觀點,硬化觸媒(E)宜包含選自由有機過氧化物及咪唑化合物構成之群組中之1種以上,包含有機過氧化物及咪唑化合物之兩者更佳。The curing catalyst (E) in this embodiment is not particularly limited, and examples thereof include tertiary amines such as organic peroxides, imidazole compounds, azo compounds, and triethylamine, tributylamine, and derivatives thereof. Among them, the curing catalyst (E) preferably contains one selected from the group consisting of organic peroxides and imidazole compounds in view of obtaining a good reaction rate and polymerization rate, and obtaining a good curing rate. Of the above, it is more preferable to include both the organic peroxide and the imidazole compound.

本實施形態中,硬化觸媒(E)的含量並無特別限制,考慮可獲得良好的硬化速度之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為0.05~10質量份,為0.05~8質量份更佳。In the present embodiment, the content of the curing catalyst (E) is not particularly limited, but in view of obtaining a good curing rate, it is 100 parts by mass relative to the total of the aminotrisalpine novolak resin (A) and the compound (B). , preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass.

(有機過氧化物) 本實施形態中的有機過氧化物若為因熱而會釋放出可促進樹脂(A)與化合物(B)之反應及化合物(B)之聚合反應的活性物質(自由基)之化合物,則無特別限制,可使用公知的有機過氧化物。有機過氧化物可單獨使用1種或混合使用2種以上。 (organic peroxide) If the organic peroxide in this embodiment is a compound that releases an active substance (free radical) that can accelerate the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B) due to heat, there is no Particularly limited, known organic peroxides can be used. An organic peroxide can be used individually by 1 type or in mixture of 2 or more types.

本實施形態中,有機過氧化物的10小時半衰期溫度並無特別限制,宜為100℃以上,考慮製造性之觀點,為110℃以上更佳。為了可達成製造時之溶劑去除步驟的高溫化,有機過氧化物宜符合前述範圍的10小時半衰期溫度。In this embodiment, the 10-hour half-life temperature of the organic peroxide is not particularly limited, but it is preferably 100° C. or higher, and more preferably 110° C. or higher from the viewpoint of manufacturability. In order to increase the temperature of the solvent removal step during production, the organic peroxide should preferably meet the 10-hour half-life temperature in the aforementioned range.

有機過氧化物可列舉例如:過氧化二異丙苯、二(2-三級丁基過氧化異丙基)苯、1,1,3,3-四甲基丁基過氧化氫、2,5-二甲基-2,5-雙(過氧化三級丁基)己炔-3、過氧化苯甲醯、二(三級丁基)過氧化物、過氧化甲乙酮、及環己酮過氧化物等酮過氧化物;1,1-二(過氧化三級丁基)環己烷,及2,2-二(4,4-二(過氧化三級丁基)環己基)丙烷等過氧化縮酮;三級丁基過氧化氫、對薄荷烷(menthane)過氧化氫、二異丙苯過氧化氫、異丙苯過氧化氫、及三級丁基過氧化氫等過氧化氫;二(2-三級丁基過氧化異丙基)苯、2,5-二甲基-2,5-二(過氧化三級丁基)己烷、三級丁基過氧化異丙苯、二(三級己基)過氧化物、2,5-二甲基-2,5-二(過氧化三級丁基)己炔-3、α,α’-二(過氧化三級丁基)二異丙苯、及二(三級丁基)過氧化物等二烷基過氧化物;二過氧化苯甲醯、及二(4-甲基苯甲醯基)過氧化物等二醯基過氧化物;過氧化二碳酸二正丙酯、及過氧化二碳酸二異丙酯等過氧化二碳酸酯;2,5-二甲基-2,5-二(過氧化苯甲醯基)己烷、過氧化苯甲酸三級己酯、過氧化苯甲酸三級丁酯、及過氧化-2-乙基己酸三級丁酯等過氧化酯等。考慮可獲得更良好的反應速度及硬化速度之觀點,宜為選自由過氧化二異丙苯、二(2-三級丁基過氧化異丙基)苯、1,1,3,3-四甲基丁基過氧化氫、2,5-二甲基-2,5-雙(過氧化三級丁基)己炔-3、α,α’-二(三級丁基過氧化)二異丙苯、及三級丁基過氧化氫構成之群組中之1種以上。Examples of organic peroxides include dicumyl peroxide, bis(2-tertiary butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2, 5-Dimethyl-2,5-bis(tertiary butyl peroxide)hexyne-3, benzoyl peroxide, di(tertiary butyl) peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide Oxides and other ketone peroxides; 1,1-bis(tertiary butyl peroxide)cyclohexane, and 2,2-bis(4,4-bis(tertiary butyl peroxide)cyclohexyl)propane, etc. Peroxyketal; tertiary butyl hydroperoxide, p-menthane (menthane) hydroperoxide, dicumyl hydroperoxide, cumene hydroperoxide, and tertiary butyl hydroperoxide, etc. ; Bis(2-tertiary butyl peroxide cumene)benzene, 2,5-dimethyl-2,5-di(tertiary butyl peroxide)hexane, tertiary butyl peroxide cumene , Di(tertiary hexyl) peroxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide)hexyne-3, α,α'-bis(tertiary butyl peroxide ) dicumyl, and di(tertiary butyl) peroxide and other dialkyl peroxides; diperoxybenzoyl, and bis(4-methylbenzoyl) peroxide and other diacyl peroxides peroxydicarbonate such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate; 2,5-dimethyl-2,5-bis(benzoyl peroxide ) hexane, peroxyesters such as tertiary hexyl peroxybenzoate, tertiary butyl peroxybenzoate, and tertiary butyl peroxy-2-ethylhexanoate, etc. Considering that a better reaction speed and hardening speed can be obtained, it is preferably selected from dicumyl peroxide, bis(2-tertiary butylperoxyisopropyl)benzene, 1,1,3,3-tetrafluoroethylene Methylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexyne-3, α,α'-bis(tertiary butylperoxy)diiso One or more species from the group consisting of propylbenzene and tertiary butyl hydroperoxide.

本實施形態之樹脂組成物中,有機過氧化物的含量並無特別限制,考慮可獲得更進一步良好的反應速度及硬化速度之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜含有0.05質量份~10質量份,含有0.05質量份~8質量份更佳。In the resin composition of the present embodiment, the content of the organic peroxide is not particularly limited. Considering that a better reaction rate and curing rate can be obtained, compared with the amino trisanthene novolac resin (A) and the compound ( The total of 100 parts by mass of B) is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass.

(咪唑化合物) 咪唑化合物只要可促進樹脂(A)與化合物(B)之反應及化合物(B)之聚合反應,則無特別限制,可使用公知的咪唑化合物。咪唑化合物可使用1種或混合使用2種以上。 (imidazole compound) The imidazole compound is not particularly limited as long as it can accelerate the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known imidazole compounds can be used. The imidazole compound can be used 1 type or in mixture of 2 or more types.

咪唑化合物可列舉例如:2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、2,4,5-三苯基咪唑等。其中,考慮反應速度及硬化速度之調整更容易之觀點,宜為2-乙基-4-甲基咪唑。Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole, etc. . Among them, 2-ethyl-4-methylimidazole is preferable from the viewpoint of easier adjustment of the reaction rate and curing rate.

本實施形態之樹脂組成物中,咪唑化合物的含量並無特別限制,考慮反應速度及硬化速度之調整更為容易之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜為0.05質量份~10質量份,為0.05質量份~8質量份更佳。In the resin composition of the present embodiment, the content of the imidazole compound is not particularly limited. Considering that the adjustment of the reaction speed and the curing speed is easier, the ratio of the amino trisanthene novolak resin (A) and the compound (B) A total of 100 parts by mass is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 8 parts by mass.

(偶氮化合物) 偶氮化合物只要可促進樹脂(A)與化合物(B)之反應及化合物(B)之聚合反應,則無特別限制,可使用公知的偶氮化合物。偶氮化合物可使用1種或混合使用2種以上。 偶氮化合物可列舉例如:2,2’-偶氮雙丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)、及2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等。 (azo compounds) The azo compound is not particularly limited as long as it can accelerate the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known azo compounds can be used. An azo compound can be used 1 type or in mixture of 2 or more types. Azo compounds include, for example: 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4- Methoxy-2,4-dimethylvaleronitrile), etc.

本實施形態之樹脂組成物中,偶氮化合物的含量並無特別限制,考慮可獲得更進一步良好的反應速度及硬化速度之觀點,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,宜含有0.05~10質量份,含有0.05~8質量份更佳。In the resin composition of the present embodiment, the content of the azo compound is not particularly limited. Considering that a better reaction rate and curing rate can be obtained, the ratio of the amino tris phenolic novolak resin (A) and the compound (B ) to a total of 100 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass.

[其它成分] 本實施形態之樹脂組成物中,除了含有胺基三𠯤酚醛清漆樹脂(A)、化合物(B)、無機填充材(D)之外,不僅還可含有上述助熔劑活性劑(C)、硬化觸媒(E),亦可含有單獨1種或2種以上之其它成分。 [other ingredients] In the resin composition of the present embodiment, in addition to containing the amino trisanthene phenolic novolac resin (A), the compound (B), and the inorganic filler (D), not only the above-mentioned flux activator (C), hardener The catalyst (E) may contain one or more other components alone.

其它成分並無特別限制,可列舉例如:可撓性賦予成分。可撓性賦予成分若為可對於含有樹脂組成物之層賦予可撓性之類的成分,則無特別限制。如此的成分除了可列舉例如胺基三𠯤酚醛清漆樹脂(A)、化合物(B)、助熔劑活性劑(C)、無機填充材(D)、及硬化觸媒(E)之外,還可列舉:聚醯亞胺、聚醯胺醯亞胺、聚苯乙烯、聚烯烴、苯乙烯-丁二烯橡膠(SBR)、異戊二烯橡膠(IR)、丁二烯橡膠(BR)、(甲基)丙烯腈丁二烯橡膠(NBR)、聚胺甲酸酯、聚丙烯、(甲基)丙烯酸寡聚物、(甲基)丙烯酸聚合物、及聚矽氧樹脂等熱塑性高分子化合物。這些可撓性賦予成分可單獨使用1種或適當混合2種以上來使用。Other components are not particularly limited, and examples thereof include flexibility-imparting components. The flexibility imparting component is not particularly limited as long as it can impart flexibility to the layer containing the resin composition. In addition to such components, for example, amino trisanthene novolac resin (A), compound (B), flux activator (C), inorganic filler (D), and hardening catalyst (E) can be listed. List: polyimide, polyamideimide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), ( Thermoplastic polymer compounds such as meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer, and silicone resin. These flexibility imparting components can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態之樹脂組成物也可含有其它成分,亦即也可和無機填充材(D1)不同而另外含有矽烷偶聯劑。如此的矽烷偶聯劑可列舉已例示作為能於無機填充材(D1)之製備所使用者。矽烷偶聯劑的含量並無特別限制,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,可設為約0.05~20質量份。The resin composition of this embodiment may contain other components, that is, may contain a silane coupling agent separately from the inorganic filler (D1). Such silane coupling agents can be exemplified as those that can be used in the preparation of the inorganic filler (D1). The content of the silane coupling agent is not particularly limited, and may be about 0.05 to 20 parts by mass relative to 100 parts by mass of the total of the aminotrisium novolak resin (A) and the compound (B).

本實施形態之樹脂組成物中,為了疊層體之製造性進一步改善及填充材之進一步的分散性改善等,也可含有濕潤分散劑作為其它成分。濕潤分散劑若為通常塗料等所使用的濕潤分散劑,則無特別限制。可列舉例如:BYK(股)製之DISPERBYK(註冊商標)-110(商品名)、DISPERBYK-111(商品名)、DISPERBYK-180(商品名)、DISPERBYK-161(商品名)、BYK-W996(商品名)、BYK-W9010(商品名)、及BYK-W903(商品名)。這些濕潤分散劑可單獨使用1種或適當混合2種以上來使用。 使用濕潤分散劑時,其含量並無特別限制,考慮疊層體之製造性進一步改善的觀點,相對於無機填充材(D)100質量份,宜設為0.1~5質量份,設為0.5~3質量份更佳。另外,合併使用2種以上之濕潤分散劑時,它們的合計量宜符合前述比率。 In the resin composition of the present embodiment, a wetting and dispersing agent may be contained as another component for the purpose of further improving the manufacturability of the laminate, further improving the dispersibility of the filler, and the like. The wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent commonly used in paints and the like. Examples include DISPERBYK (registered trademark)-110 (trade name), DISPERBYK-111 (trade name), DISPERBYK-180 (trade name), DISPERBYK-161 (trade name), BYK-W996 ( (trade name), BYK-W9010 (trade name), and BYK-W903 (trade name). These wetting and dispersing agents can be used individually by 1 type or in mixture of 2 or more types suitably. When using a wetting and dispersing agent, its content is not particularly limited, but it is preferably 0.1 to 5 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the inorganic filler (D) from the viewpoint of further improving the manufacturability of the laminate. 3 parts by mass are better. In addition, when two or more types of wetting and dispersing agents are used in combination, their total amount should conform to the aforementioned ratio.

本實施形態之樹脂組成物也可含有和胺基三𠯤酚醛清漆樹脂(A)及化合物(B)不同的其它熱硬化性樹脂或化合物(以下也簡稱「其它熱硬化性樹脂」)作為其它成分。其它熱硬化性樹脂可列舉例如:氰酸酯化合物、苯并㗁𠯤化合物、芳香族一級胺化合物、環氧化合物、酚化合物、改性聚苯醚化合物、烯基取代納迪克醯亞胺化合物、氧雜環丁烷樹脂、及具有可聚合之不飽和基的化合物。這些其它熱硬化性樹脂可單獨使用1種或適當混合2種以上來使用。本實施形態中,考慮低空隙性及晶片黏接性的觀點,可包含上述之中選自由氰酸酯化合物、苯并㗁𠯤化合物、及芳香族一級胺化合物構成之群組中之1種以上之化合物(F)。化合物(F)的含量相對於胺基三𠯤酚醛清漆樹脂(A)、化合物(B)及化合物(F)之合計100質量份,可為1~50質量份,也可為3~35質量份,亦可為5~30質量份。The resin composition of this embodiment may also contain other thermosetting resins or compounds (hereinafter also referred to as "other thermosetting resins") different from the aminotrisalpine novolac resin (A) and the compound (B) as other components. . Other thermosetting resins include, for example, cyanate ester compounds, benzodiazepine compounds, aromatic primary amine compounds, epoxy compounds, phenol compounds, modified polyphenylene ether compounds, alkenyl-substituted nadicimide compounds, Oxetane resins, and compounds having polymerizable unsaturated groups. These other thermosetting resins can be used individually by 1 type or in mixture of 2 or more types suitably. In this embodiment, considering the viewpoints of low voids and wafer adhesion, one or more selected from the group consisting of cyanate ester compounds, benzodiazepine compounds, and aromatic primary amine compounds may be included. The compound (F). The content of the compound (F) may be 1 to 50 parts by mass or 3 to 35 parts by mass relative to 100 parts by mass of the total of the aminotrisalpine novolak resin (A), the compound (B) and the compound (F). , and may also be 5 to 30 parts by mass.

本實施形態之樹脂組成物中,在不損及期望之特性的範圍內,也可因各種目的而含有各種添加劑作為其它成分。添加劑可列舉例如:增黏劑、潤滑劑、消泡劑、整平劑、亮光劑、阻燃劑、及離子捕獲劑。這些添加劑可單獨使用1種或適當混合2種以上來使用。 本實施形態之樹脂組成物中,這些添加劑的含量並無特別限制,通常相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,分別為0.01~10質量份。 In the resin composition of the present embodiment, various additives may be contained as other components for various purposes within a range not impairing desired properties. Examples of additives include thickeners, lubricants, defoamers, leveling agents, brighteners, flame retardants, and ion trapping agents. These additives can be used individually by 1 type or in mixture of 2 or more types suitably. In the resin composition of this embodiment, the contents of these additives are not particularly limited, and are usually 0.01-10 parts by mass relative to 100 parts by mass of the total of the aminotrisalpine novolak resin (A) and the compound (B).

[樹脂組成物之理想的用途] 本實施形態之樹脂組成物之低空隙性及晶片黏接性優良。將本實施形態之樹脂組成物使用作為以疊層體的形態使用之底部填充材,宜為預塗型底部填充材時,其低空隙性及晶片黏接性優良,而且接合性及絕緣可靠性亦優良。本實施形態之樹脂組成物由於具有各種優良的特徵,故作為底部填充材係更為有用,作為預塗型底部填充材又更為有用。另外,關於疊層體係如後述。 [Ideal use of resin composition] The resin composition of this embodiment is excellent in low void property and chip adhesiveness. When the resin composition of this embodiment is used as an underfill material in the form of a laminate, preferably as a precoat type underfill material, it has excellent low-void property and chip adhesion, and it also has bonding properties and insulation reliability. Also excellent. Since the resin composition of this embodiment has various excellent characteristics, it is more useful as an underfill material, and it is more useful as a precoat type underfill material. In addition, the lamination system will be described later.

本實施形態之樹脂組成物作為底部填充材係為理想,且用於預塗型底部填充材更為理想,故使用樹脂組成物而得的片材及含有樹脂組成物之層(也簡稱「樹脂組成物層」)宜為半硬化狀態(B階)。另外,片材及樹脂組成物層的詳細說明如後所述。片材及樹脂組成物層藉由為半硬化狀態,可獲得更進一步優良的低空隙性及晶片黏接性。本實施形態中,半硬化狀態(B階)係指片材或樹脂組成物層中所含的各成分尚未積極地開始反應(硬化),惟片材或樹脂組成物層呈乾燥狀態,亦即加熱使溶劑揮發至無黏著性的程度為止之狀態,也包含不加熱且仍未硬化而僅使溶劑揮發之狀態。本實施形態中,半硬化狀態(B階)的最低熔融黏度通常為50,000Pa・s以下。最低熔融黏度的下限例如為10Pa・s以上。考慮適合用於底部填充材之觀點,半硬化狀態(B階)的最低熔融黏度宜為200Pa・s以上且30,000Pa・s以下。另外,本實施形態中,最低熔融黏度係以如下方法進行測定。亦即,使用層合機將樹脂組成物層疊層於支持基材等,藉此獲得厚度約0.4~0.6mm之樹脂片,使用該樹脂片作為樣本,利用流變儀(Thermo Fisher Scientific公司製HAAKE MARS60(商品名))測定熔融黏度。測定係使用平板徑8mm之一次性平行平板,於40℃~300℃之範圍,以昇溫速度10℃/分鐘、頻率10.0rad/秒、及應變0.1%之條件下測定樹脂片的熔融黏度。最低熔融黏度意指於40℃至300℃的範圍,黏度最低下時的黏度。The resin composition of this embodiment is ideal as an underfill material, and it is more ideal for a pre-coated underfill material. Therefore, the sheet obtained by using the resin composition and the layer containing the resin composition (also referred to as "resin composition") The composition layer") should be in a semi-hardened state (B stage). In addition, the details of the sheet and the resin composition layer will be described later. Since the sheet and the resin composition layer are in a semi-cured state, further excellent low-void property and die adhesiveness can be obtained. In this embodiment, the semi-hardened state (B stage) means that the components contained in the sheet or resin composition layer have not actively started to react (harden), but the sheet or resin composition layer is in a dry state, that is, The state in which the solvent is volatilized by heating to the extent that there is no stickiness also includes the state in which only the solvent is volatilized without heating and without hardening. In this embodiment, the minimum melt viscosity in the semi-hardened state (B stage) is usually 50,000 Pa・s or less. The lower limit of the lowest melt viscosity is, for example, 10 Pa・s or more. Considering the suitability for use as an underfill material, the minimum melt viscosity in the semi-hardened state (B stage) is preferably 200 Pa・s or more and 30,000 Pa・s or less. In addition, in this embodiment, the minimum melt viscosity is measured by the following method. That is, the resin composition is laminated on a support substrate or the like using a laminator to obtain a resin sheet with a thickness of about 0.4 to 0.6 mm, and the resin sheet is used as a sample, and a rheometer (HAAKE, manufactured by Thermo Fisher Scientific Co., Ltd.) MARS60 (trade name)) was used to measure the melt viscosity. The measurement uses a disposable parallel plate with a plate diameter of 8mm, and measures the melt viscosity of the resin sheet under the conditions of a heating rate of 10°C/min, a frequency of 10.0rad/s, and a strain of 0.1% in the range of 40°C to 300°C. The lowest melt viscosity refers to the viscosity at the lowest point in the range of 40°C to 300°C.

[樹脂組成物之製造方法] 本實施形態之樹脂組成物只要可獲得具有前述組成者,則製造方法並並無特別限制。樹脂組成物例如可藉由將胺基三𠯤酚醛清漆樹脂(A)、化合物(B)、無機填充材(D)、及因應需要之助熔劑活性劑(C)、硬化觸媒(E)、以及其它成分進行適當混合來製備。也可因應需要製成將這些成分溶解或分散於有機溶劑後的清漆之形態。清漆可理想地使用於製作疊層體時。具體的製造方法可參考後述疊層體之製造方法及實施例。 [Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment is not specifically limited as long as it can obtain the thing which has the said composition. The resin composition, for example, can be prepared by mixing amino tris-alcohol novolak resin (A), compound (B), inorganic filler (D), flux activator (C) as needed, hardening catalyst (E), and other ingredients are properly mixed to prepare. It can also take the form of a varnish obtained by dissolving or dispersing these components in an organic solvent as needed. Varnishes are ideally used when making laminates. For the specific manufacturing method, please refer to the manufacturing method and examples of the laminated body described later.

有機溶劑若為可各別理想地溶解或分散本實施形態之樹脂組成物中的各成分,且不損及本實施形態之樹脂組成物的效果者,則無特別限制。有機溶劑可列舉例如:甲醇、乙醇、及丙醇等醇類;丙酮、甲乙酮(以下有時省略稱「MEK」)、及甲基異丁基酮等酮類;二甲基乙醯胺、及二甲基甲醯胺等醯胺類;甲苯、及二甲苯等芳香族烴類。這些有機溶劑可單獨使用1種或適當混合2種以上來使用。The organic solvent is not particularly limited as long as it can dissolve or disperse each component in the resin composition of the present embodiment ideally and does not impair the effect of the resin composition of the present embodiment. Organic solvents include, for example, alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes referred to as "MEK" abbreviated as "MEK"), and methyl isobutyl ketone; dimethylacetamide, and Amides such as dimethylformamide; aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used individually by 1 type or in mixture of 2 or more types suitably.

[樹脂片] 樹脂片含有本實施形態之樹脂組成物。具體而言,樹脂片具有支持基材、及配置於支持基材的單面或雙面之樹脂層,且樹脂層含有本實施形態之樹脂組成物。該樹脂片亦稱為疊層樹脂片。樹脂片之樹脂層宜將未硬化狀態(A階)之樹脂組成物塗佈於支持基材後,使其成為半硬化狀態(B階)。如此的樹脂片之製造方法宜為通常製造B階化樹脂層及支持基材之複合體的方法。具體而言,可列舉藉由將未硬化狀態(A階)之樹脂組成物製成清漆的形態,再使用塗佈棒等公知的方法將該清漆塗佈於銅箔等支持基材後,於100~200℃之乾燥機中,加熱1~60分鐘之方法等來使其半硬化(B階化)並製造樹脂片之方法等。 另外,本實施形態中,未硬化狀態(A階)係指樹脂組成物幾乎未硬化而未凝膠化之狀態。塗佈於樹脂片之支持基材前的樹脂組成物,例如為樹脂組成物之構成成分的混合物(可含溶劑也可不含)、或將該混合物溶解或分散於溶劑後之清漆的形態,且為未硬化狀態(A階)。 [resin sheet] The resin sheet contains the resin composition of this embodiment. Specifically, the resin sheet has a support substrate, and a resin layer disposed on one or both sides of the support substrate, and the resin layer contains the resin composition of the present embodiment. This resin sheet is also called a laminated resin sheet. The resin layer of the resin sheet is preferably in a semi-cured state (B stage) after coating the resin composition in the uncured state (A stage) on the support substrate. The method for producing such a resin sheet is preferably a method for generally producing a composite of a B-staged resin layer and a support substrate. Specifically, it is possible to use a resin composition in an uncured state (A stage) in the form of a varnish, apply the varnish to a support substrate such as copper foil using a known method such as a coating bar, and then In a dryer at 100-200°C, heat for 1-60 minutes, etc. to make it semi-hardened (B-staged) and make a resin sheet, etc. In addition, in the present embodiment, the uncured state (A stage) refers to a state in which the resin composition is hardly cured and is not gelled. The resin composition coated in front of the support substrate of the resin sheet is, for example, a mixture of constituent components of the resin composition (which may or may not contain a solvent), or a varnish in which the mixture is dissolved or dispersed in a solvent, and It is in an unhardened state (stage A).

支持基材並無特別限制,可列舉例如:聚乙烯薄膜、聚丙烯薄膜、聚碳酸酯薄膜、聚對苯二甲酸乙二酯薄膜、及乙烯四氟乙烯共聚物薄膜、以及聚醯亞胺薄膜等有機系薄膜;於這些薄膜的表面塗佈有脫模劑之脫模薄膜;銅箔、及鋁箔等導體箔;玻璃板、SUS板、及FRP等板狀物。The supporting substrate is not particularly limited, and examples thereof include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, and polyimide films. Organic films such as these; release films coated with a release agent on the surface of these films; conductive foils such as copper foil and aluminum foil; plate-shaped objects such as glass plates, SUS plates, and FRP.

塗佈方法並無特別限制,可列舉例如:將樹脂組成物溶解於溶劑後的溶液利用塗佈棒、模塗機、刮刀、及貝克塗敷機(Baker applicator)等塗佈於支持基材上之方法。The coating method is not particularly limited, and examples include: coating a solution obtained by dissolving a resin composition in a solvent on a support substrate using a coating bar, a die coater, a doctor blade, and a Baker applicator. method.

樹脂片之中,單層樹脂片可將樹脂組成物成形成片狀而得。單層樹脂片之製造方法可依循常法來實施,並無特別限制。可列舉例如:在樹脂片之製法中,將樹脂組成物溶解於溶劑後之溶液塗佈於支持基材上並使其乾燥後,從樹脂片將支持基材剝離或進行蝕刻之方法。另外,也可藉由將樹脂組成物溶解於溶劑後之溶液供給於具有片狀之模槽的模具內並進行乾燥等來成形成片狀,而不使用支持基材來獲得單層樹脂片。Among the resin sheets, the single-layer resin sheet can be obtained by molding a resin composition into a sheet. The manufacturing method of the single-layer resin sheet can be implemented according to the usual method, and there is no special limitation. For example, in the manufacturing method of a resin sheet, the solution which melt|dissolved a resin composition in a solvent is apply|coated and dried on a support base material, and the method of peeling or etching a support base material from a resin sheet is mentioned. In addition, a single-layer resin sheet can also be obtained by supplying a solution obtained by dissolving a resin composition in a solvent into a mold having a sheet-shaped cavity and drying it to form a sheet without using a support base material.

在樹脂片或單層樹脂片之製作時,將溶劑去除時的乾燥條件並無特別限制,為低溫的話,溶劑容易殘留在樹脂組成物中,為高溫的話,樹脂組成物的硬化會進行,故宜為於20~170℃之溫度乾燥1~90分鐘。When making a resin sheet or a single-layer resin sheet, the drying conditions for removing the solvent are not particularly limited. If it is low temperature, the solvent will easily remain in the resin composition, and if it is high temperature, the hardening of the resin composition will proceed. It is suitable to dry at a temperature of 20~170°C for 1~90 minutes.

樹脂片或單層樹脂片之樹脂層的厚度,可利用樹脂組成物之溶液的濃度及塗佈的厚度來調整,並無特別限制,一般而言,塗佈的厚度較厚的話,乾燥時溶劑容易殘留,故宜為0.1~500μm。The thickness of the resin sheet or the resin layer of the single-layer resin sheet can be adjusted by the concentration of the solution of the resin composition and the thickness of the coating, and is not particularly limited. Generally speaking, if the thickness of the coating is thicker, the solvent will It is easy to remain, so it should be 0.1~500μm.

樹脂片或單層樹脂片例如可使用作為半導體晶圓及半導體晶片搭載用基板中的配線電路形成時的材料。The resin sheet or the single-layer resin sheet can be used, for example, as a material at the time of forming a wiring circuit in a semiconductor wafer or a substrate for mounting a semiconductor chip.

[疊層體] 藉由將本實施形態之樹脂組成物塗佈於支持基材上,可獲得低空隙性及晶片黏接性優良的具有含有樹脂組成物之層的疊層體。亦即,本實施形態之疊層體具備支持基材、及疊層於支持基材上之含有本實施形態之樹脂組成物之樹脂組成物層。如此的疊層體可藉由使本實施形態之樹脂組成物以層的形式成形於支持基材來獲得。支持基材並無特別限制,可使用高分子薄膜。高分子薄膜的材質可列舉例如:聚氯乙烯、聚偏二氯乙烯、聚乙烯、聚丙烯、聚丁烯、聚丁二烯、乙烯-丙烯共聚物、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物、及乙烯-乙烯醇共聚物等乙烯基系樹脂;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、及聚對苯二甲酸丁二酯等聚酯系樹脂;聚胺甲酸酯系樹脂;聚醯亞胺系樹脂;聚醯胺系樹脂等。支持基材可列舉:含有這些樹脂等之薄膜、以及於這些薄膜的表面塗佈有脫模劑之脫模薄膜。它們之中,宜為含有選自由聚酯系樹脂、聚醯亞胺系樹脂、及聚醯胺系樹脂構成之群組中之1種以上之樹脂的薄膜、以及於這些薄膜的表面塗佈有脫模劑之脫模薄膜,為含有係為聚酯系樹脂之一種的聚對苯二甲酸乙二酯之薄膜、或於含有聚對苯二甲酸乙二酯之薄膜的表面塗佈有脫模劑之脫模薄膜更佳。 [laminated body] By coating the resin composition of this embodiment on the support substrate, a laminate having a layer containing the resin composition excellent in low voids and die adhesiveness can be obtained. That is, the laminated body of this embodiment has a support base material, and the resin composition layer containing the resin composition of this embodiment laminated|stacked on a support base material. Such a laminate can be obtained by forming the resin composition of the present embodiment on a support substrate in a layer form. The support substrate is not particularly limited, and a polymer film can be used. Examples of polymer film materials include: polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polybutene, polybutadiene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate Vinyl resins such as ester copolymers and ethylene-vinyl alcohol copolymers; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; Urethane-based resins; polyimide-based resins; polyamide-based resins, etc. Examples of the supporting substrate include films containing these resins, and release films in which a release agent is coated on the surface of these films. Among them, films containing one or more resins selected from the group consisting of polyester-based resins, polyimide-based resins, and polyamide-based resins, and coating the surfaces of these films with The release film of the release agent is a film containing polyethylene terephthalate, which is a kind of polyester resin, or a film containing polyethylene terephthalate coated with a release film. The release film of the agent is better.

支持基材的厚度並無特別限制,考慮疊層體之製造更容易的觀點,例如將樹脂組成物塗佈於支持基材時的塗佈厚之更良好的安定性、及疊層體之更良好的搬運性之觀點,宜為10~100μm。支持基材的厚度的下限,考慮可更確保製造疊層體時的產量之觀點,為10μm以上更佳,為20μm以上再更佳,為25μm以上又更佳。支持基材的厚度的上限,考慮支持基材最終並不會以半導體裝置的構成構件形式存在,而會在步驟的途中剝離之觀點、以及考慮疊層體之製造成本的觀點,為80μm以下更佳,為50μm以下再更佳。The thickness of the support substrate is not particularly limited, and it is considered that the production of the laminate is easier, such as better stability of the coating thickness when the resin composition is applied to the support substrate, and better stability of the laminate. From the viewpoint of good portability, the thickness is preferably 10-100 μm. The lower limit of the thickness of the support base material is more preferably 10 μm or more, more preferably 20 μm or more, and more preferably 25 μm or more, from the viewpoint of ensuring a higher yield at the time of manufacturing the laminate. The upper limit of the thickness of the support base material is 80 μm or less in consideration of the viewpoint that the support base material does not exist in the form of a constituent member of the semiconductor device in the end, but will be peeled off in the middle of the process, and the production cost of the laminate. Better, more preferably less than 50 μm.

於支持基材上形成本實施形態之含有樹脂組成物之層,亦即形成樹脂組成物層來製造本實施形態之疊層體的方法並無特別限制。如此的製造方法可列舉例如:將本實施形態之樹脂組成物溶解或分散於有機溶劑後的清漆塗佈於支持基材的表面,進行加熱及/或於減壓下進行乾燥,去除溶劑來使本實施形態之樹脂組成物固化,並形成樹脂組成物層之方法。乾燥條件並無特別限制,有機溶劑相對於樹脂組成物層之含有比率,係以相對於樹脂組成物層之總量(100質量份)通常成為10質量份以下,宜成為5質量份以下的方式進行乾燥。達成該乾燥之條件取決於清漆中的有機溶劑之種類及摻合量而不同。例如,相對於胺基三𠯤酚醛清漆樹脂(A)與化合物(B)之合計100質量份,含有10~200質量份之甲乙酮的清漆時,於1氣壓下以90~160℃之加熱條件乾燥2~15分鐘係為大致的標準。本實施形態之疊層體中的樹脂組成物層的厚度並無特別限制,考慮樹脂組成物層在乾燥時更良好地去除較低分子量的揮發成分之觀點,以及考慮更有效且確實地發揮作為疊層體之功能的觀點,為5~500μm之範圍係理想,為10~100μm之範圍更佳。實施本實施形態之疊層體的製造後,也可為了保存等之目的,另外將保護薄膜疊層於和疊層體具有支持基材的面為相反側的面。The method of forming the resin composition-containing layer of the present embodiment on the support substrate, that is, forming the resin composition layer to produce the laminate of the present embodiment is not particularly limited. Such a production method includes, for example, applying a varnish obtained by dissolving or dispersing the resin composition of this embodiment in an organic solvent on the surface of a support substrate, heating and/or drying under reduced pressure, and removing the solvent to make The method of curing the resin composition of this embodiment to form a resin composition layer. Drying conditions are not particularly limited, and the content ratio of the organic solvent to the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less, based on the total amount of the resin composition layer (100 parts by mass). to dry. The conditions for achieving this drying vary depending on the type and blending amount of the organic solvent in the varnish. For example, in the case of a varnish containing 10 to 200 parts by mass of methyl ethyl ketone relative to 100 parts by mass of the total of the amino trisphenol novolac resin (A) and the compound (B), it is dried at 90 to 160°C under 1 atmosphere 2~15 minutes is the approximate standard. The thickness of the resin composition layer in the laminated body of this embodiment is not particularly limited, considering the point of view that the resin composition layer can better remove low molecular weight volatile components when drying, and consider that it can more effectively and reliably function as From the viewpoint of the function of the laminate, the range of 5 to 500 μm is ideal, and the range of 10 to 100 μm is more preferable. After the laminated body of this embodiment is manufactured, a protective film may be laminated separately on the surface of the laminated body opposite to the surface having the supporting base material for storage purposes.

[設有樹脂組成物層之半導體晶片及設有樹脂組成物層之半導體晶片搭載用基板] 本實施形態之設有樹脂組成物層之半導體晶片具備半導體晶片、及疊層於半導體晶片且係使用本實施形態之樹脂組成物而形成的層(樹脂組成物層)。 又,本實施形態之設有樹脂組成物層之半導體晶片搭載用基板具備半導體晶片搭載用基板、及疊層於半導體晶片搭載用基板且係使用本實施形態之樹脂組成物而形成的層(樹脂組成物層)。 另外,本實施形態之設有樹脂組成物層之半導體晶片也可特定為具備半導體晶片、及疊層於該半導體晶片之含有本實施形態之樹脂組成物之層(樹脂組成物層)者。又,本實施形態之設有樹脂組成物層之半導體晶片搭載用基板也可特定為具備半導體晶片搭載用基板、及疊層於該半導體晶片搭載用基板之含有本實施形態之樹脂組成物之層(樹脂組成物層)者。 [Semiconductor wafer provided with resin composition layer and substrate for mounting semiconductor wafer provided with resin composition layer] The semiconductor wafer provided with the resin composition layer of this embodiment includes a semiconductor wafer and a layer (resin composition layer) laminated on the semiconductor wafer and formed using the resin composition of this embodiment. Also, the substrate for mounting a semiconductor chip provided with the resin composition layer of this embodiment includes a substrate for mounting a semiconductor chip and a layer (resin composition layer). In addition, the semiconductor wafer provided with the resin composition layer of the present embodiment may also be specified as having a semiconductor wafer and a layer (resin composition layer) including the resin composition of the present embodiment laminated on the semiconductor wafer. In addition, the substrate for mounting a semiconductor chip provided with the resin composition layer of this embodiment may also be specified as having a substrate for mounting a semiconductor chip and a layer containing the resin composition of the present embodiment laminated on the substrate for mounting a semiconductor chip. (resin composition layer).

製作本實施形態之設有樹脂組成物層之半導體晶片的方法並無特別限制,例如於半導體晶圓之形成有電極的面亦即和基板實施接合的面,以面向本實施形態之疊層體的樹脂組成物層的方式進行貼合,並將疊層體中的支持基材剝離,其後實施利用切片鋸等所為之單片化,藉此可獲得設有樹脂組成物層之半導體晶片。又,製作本實施形態之設有樹脂組成物層之半導體晶片搭載用基板的方法並無特別限制,例如可藉由於半導體晶片搭載用基板之晶片搭載側的面,以面向本實施形態之疊層體之樹脂組成物層的方式進行貼合,並將疊層體中的支持基材剝離而獲得。The method of manufacturing the semiconductor wafer provided with the resin composition layer of this embodiment is not particularly limited. For example, the surface of the semiconductor wafer on which electrodes are formed, that is, the surface that is bonded to the substrate, faces the laminated body of this embodiment. A resin composition layer is bonded together, the support substrate in the laminate is peeled off, and then singulated with a dicing saw etc., whereby a semiconductor wafer provided with a resin composition layer can be obtained. Also, the method of manufacturing the semiconductor chip mounting substrate provided with the resin composition layer of this embodiment is not particularly limited. It is obtained by laminating the resin composition layers of the laminate and peeling off the support substrate in the laminate.

將本實施形態之疊層體貼合於半導體晶圓或半導體晶片搭載用基板之方法並無特別限制,可理想地使用真空加壓式層合機。此時,宜為藉由橡膠等彈性體對於本實施形態之疊層體進行加壓並貼合之方法。層合條件若為發明所屬技術領域中具有通常知識者通常使用的條件,則無特別限制,例如於50~140℃之溫度、1~11kgf/cm 2之範圍的接觸壓力、以及20hPa以下之環境減壓下實施。層合步驟之後也可利用金屬板所為之熱壓製來實施已貼合之疊層體的平滑化。層合步驟及平滑化步驟可利用市售的真空加壓式層合機連續地實施。貼附於半導體晶圓或半導體搭晶片載用基板之疊層體,於任一情況皆會在晶片之覆晶安裝前實施支持基材的去除。 The method of bonding the laminated body of this embodiment to the semiconductor wafer or the semiconductor wafer mounting substrate is not particularly limited, and a vacuum pressure laminator can be preferably used. In this case, a method of pressing and laminating the laminated body of the present embodiment with an elastic body such as rubber is suitable. Lamination conditions are not particularly limited as long as they are conditions commonly used by persons with ordinary knowledge in the technical field to which the invention belongs, for example, a temperature of 50~140°C, a contact pressure in the range of 1~11kgf/ cm2 , and an environment below 20hPa Implement under reduced pressure. Smoothing of the bonded laminate may also be carried out after the lamination step by means of hot pressing of the metal sheets. The lamination step and the smoothing step can be continuously implemented using a commercially available vacuum pressure laminator. For laminates attached to semiconductor wafers or substrates for mounting semiconductor chips, in either case, the supporting base material will be removed before flip-chip mounting of the chips.

[半導體裝置] 本實施形態之半導體裝置具備本實施形態之設有樹脂組成物層之半導體晶片及/或本實施形態之設有樹脂組成物層之半導體晶片搭載用基板。製造本實施形態之半導體裝置之方法並無特別限制,可列舉例如:將本實施形態之設有樹脂組成物層之半導體晶片搭載於半導體晶片搭載用基板之方法。又,也可於本實施形態之設有樹脂組成物層之半導體晶片搭載用基板搭載半導體晶片。將設有樹脂組成物層之半導體晶片搭載於半導體晶片搭載用基板之方法、及將半導體晶片搭載於設有樹脂組成物層之半導體晶片搭載用基板之方法,可理想地使用對應於熱壓接工法之覆晶接合器。又,本實施形態中,係簡單說明將半導體晶片覆晶安裝於半導體晶片搭載用基板的情況,惟也可令將半導體晶片予以覆晶安裝同時使用本實施形態之樹脂組成物的對象為半導體晶片搭載用基板以外。例如,本實施形態之樹脂組成物也可使用於在將半導體晶片搭載到半導體晶圓上時的半導體晶圓與半導體晶片之接合部、或經由TSV(Through Silicon Via)等來實施半導體晶片間連接之晶片疊層體中的各半導體晶片間之接合部,任一情況皆可獲得本實施形態之效果。 [實施例] [semiconductor device] The semiconductor device of the present embodiment includes the semiconductor wafer provided with the resin composition layer of the present embodiment and/or the semiconductor chip mounting substrate provided with the resin composition layer of the present embodiment. The method of manufacturing the semiconductor device of the present embodiment is not particularly limited, and examples thereof include a method of mounting the semiconductor wafer provided with the resin composition layer of the present embodiment on a substrate for mounting a semiconductor chip. Moreover, you may mount a semiconductor chip on the board|substrate for semiconductor chip mounting which provided the resin composition layer of this embodiment. The method of mounting a semiconductor chip provided with a resin composition layer on a substrate for mounting a semiconductor chip, and the method of mounting a semiconductor chip on a substrate for mounting a semiconductor chip provided with a layer of a resin composition can ideally use a method corresponding to thermocompression bonding. Flip-chip bonder of construction method. Also, in this embodiment, the case where the semiconductor chip is flip-chip mounted on the substrate for mounting the semiconductor chip is briefly described, but the object of flip-chip mounting the semiconductor chip and using the resin composition of the present embodiment may be the semiconductor chip. Except for mounting boards. For example, the resin composition of this embodiment can also be used in the junction between a semiconductor wafer and a semiconductor chip when mounting a semiconductor chip on a semiconductor wafer, or to implement connection between semiconductor chips via TSV (Through Silicon Via) or the like. The effect of this embodiment can be obtained in any case of the bonding portion between the semiconductor chips in the chip laminated body. [Example]

以下,使用實施例及比較例更具體地說明本實施形態。本實施形態不受下列實施例任何限定。 各質量份數係以胺基三𠯤酚醛清漆樹脂(A)及化合物(B)之總量100質量份作為基準之數值。 Hereinafter, this embodiment is demonstrated more concretely using an Example and a comparative example. This embodiment is not limited in any way by the following examples. Each part by mass is a numerical value based on 100 parts by mass of the total amount of the aminotrisalpine novolac resin (A) and the compound (B).

[樹脂組成物及疊層體之製作] (實施例1) 將作為胺基三𠯤酚醛清漆樹脂(A)之PHENOLITE(註冊商標)LA-1356(商品名,DIC(股),重量平均分子量:1,500,氮含量:19質量%,羥基當量:146g/eq.,非揮發成分:60質量%)45質量份(以非揮發成分換算為27質量份)、 作為第1化合物(B)之式(3)表示之馬來醯亞胺化合物(BMI-1000P(商品名),K・I化成(股),式(3)中,n3=14(平均值),重量平均分子量:3,700)40.5質量份、 作為第2化合物(B)之雙-(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷(BMI-70(商品名),K・I化成(股),重量平均分子量550)22.5質量份、 作為第3化合物(B)之式(6)表示之馬來醯亞胺化合物(MIR-3000-70MT(商品名),日本化藥(股),非揮發成分70質量%,重量平均分子量:1050)14.3質量份(以非揮發成分換算為10質量份)、 作為助熔劑活性劑(C)之氫化松香酯(PINECRYSTAL(註冊商標)KR-140(商品名),荒川化學工業(股),酸解離常數pKa:4.7,重量平均分子量:521)25質量份、 作為無機填充材(D)之漿體二氧化矽(YA050C-MJE(商品名),Admatechs(股),甲基丙烯酸矽烷表面處理二氧化矽,固體成分50質量%,分散介質:MEK,平均粒徑:50nm)400質量份(以非揮發成分換算為200質量份)、 作為第1硬化觸媒(E)之係為咪唑化合物之2-乙基-4-甲基咪唑(2E4MZ,四國化成工業(股),非揮發成分50質量%)2質量份(以非揮發成分換算為1質量份)、及 作為第2硬化觸媒(E)之係為有機過氧化物之α,α’-二(過氧化三級丁基)二異丙苯(PERBUTYL (註冊商標)P,日本油脂(股),10小時半衰期溫度:119.20℃)4質量份進行混合,並於60℃之熱水浴中使用高速攪拌裝置攪拌40分鐘,其後添加MEK,藉此獲得固體成分濃度為60質量%之清漆。將該清漆塗佈於表面有脫模劑塗層之厚度38μm之聚對苯二甲酸乙二酯薄膜(TR1-38(商品名,支持基材),UNITIKA(股)),於1大氣壓下,以100℃加熱乾燥5分鐘,獲得樹脂組成物層的厚度為30μm之疊層體。 另外,作為胺基三𠯤酚醛清漆樹脂(A)之LA-1356(商品名,DIC製),係式(1)表示之化合物(為式(1)表示之化合物的混合物,且該混合物中包含R 1各自獨立地為氫原子或甲基,l、m、n各自獨立地為1~6之整數,(l+m+n)為3~18之整數的化合物群)、及式(2)表示之化合物(為式(2)表示之化合物的混合物,且該混合物中包含R 2各自獨立地為氫原子或甲基,o、p、q、r、及s各自獨立地為1~4之整數,(o+p+q+r+s)為5~20之整數的化合物群)之混合物,且混合物中,式(1)表示之化合物(混合物)與式(2)表示之化合物(混合物)之質量比(式(1):式(2))為65(質量份):35(質量份)。 又,YA050C-MJE為二氧化矽與3-甲基丙烯醯氧基丙基三甲氧基矽烷的反應產物。亦即,YA050C-MJE,係以具有利用二氧化矽之表面之至少1個矽醇基與下式(13)中的至少1個甲氧基的反應而得之結構的官能基,作為二氧化矽表面所具有者來進行評價。 [Preparation of resin composition and laminate] (Example 1) PHENOLITE (registered trademark) LA-1356 (trade name, DIC (stock), weight average molecular weight: 1,500, nitrogen content: 19% by mass, hydroxyl equivalent: 146g/eq., non-volatile content: 60% by mass) 45 parts by mass (27 parts by mass in terms of non-volatile content), as the formula of the first compound (B) ( 3) The maleimide compound represented (BMI-1000P (trade name), K・I Chemical Co., Ltd., in formula (3), n3=14 (average value), weight average molecular weight: 3,700) 40.5 parts by mass , Bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K・I Chemical Co., Ltd.) as the second compound (B) , weight average molecular weight 550) 22.5 parts by mass, as the maleimide compound (MIR-3000-70MT (trade name), Nippon Kayaku (stock), non-volatile Component 70% by mass, weight average molecular weight: 1050) 14.3 parts by mass (10 parts by mass in terms of non-volatile components), hydrogenated rosin ester (PINECRYSTAL (registered trademark) KR-140 (trade name) as a flux activator (C) ), Arakawa Chemical Industry Co., Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) 25 parts by mass, silica (YA050C-MJE (trade name), Admatechs ( stock), methacrylic silane surface-treated silica, solid content 50% by mass, dispersion medium: MEK, average particle diameter: 50nm) 400 parts by mass (200 parts by mass in terms of non-volatile components), as the first hardening contact The medium (E) is 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Chemical Industry Co., Ltd., 50% by mass of non-volatile content) of imidazole compound (1 mass in terms of non-volatile content) parts), and as the second hardening catalyst (E) is α, α'-two (tertiary butyl peroxide) dicumyl (PERBUTYL (registered trademark) P) of organic peroxides, NOF ( stock), 10-hour half-life temperature: 119.20°C) 4 parts by mass were mixed, and stirred in a hot water bath at 60°C using a high-speed stirring device for 40 minutes, and then MEK was added to obtain a solid content concentration of 60% by mass varnish. This varnish is coated on the polyethylene terephthalate film (TR1-38 (trade name, support substrate), UNITIKA (stock)) of the thickness 38 μm of release agent coating on the surface, under 1 atmospheric pressure, It heat-dried at 100 degreeC for 5 minutes, and obtained the laminated body whose thickness of a resin composition layer was 30 micrometers. In addition, LA-1356 (trade name, manufactured by DIC) as the amino trisanthene novolak resin (A) is a compound represented by formula (1) (a mixture of compounds represented by formula (1), and the mixture contains R 1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l+m+n) is an integer of 3 to 18), and formula (2) The compound represented (is a mixture of compounds represented by formula (2), and the mixture includes R 2 each independently being a hydrogen atom or a methyl group, and o, p, q, r, and s each independently being one of 1 to 4 Integer, (o+p+q+r+s) is a mixture of compound groups of integers from 5 to 20), and in the mixture, the compound (mixture) represented by formula (1) and the compound (mixture) represented by formula (2) ) The mass ratio (formula (1): formula (2)) is 65 (parts by mass): 35 (parts by mass). Also, YA050C-MJE is a reaction product of silica and 3-methacryloxypropyltrimethoxysilane. That is to say, YA050C-MJE is a functional group having a structure obtained by reacting at least one silanol group on the surface of silicon dioxide with at least one methoxy group in the following formula (13). The owner of the silicon surface is evaluated.

[化19] [chemical 19]

(實施例2) 將作為無機填充材(D)之實施例1之YA050C-MJE替換成使用漿體二氧化矽(Y50SV-AM1(商品名),Admatechs(股),乙烯矽烷表面處理二氧化矽,固體成分50質量%,分散介質:MEK,平均粒徑:50nm)400質量份(以非揮發成分換算為200質量份),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 另外,Y50SV-AM1係二氧化矽與乙烯基三甲氧基矽烷的反應產物。亦即,YA050C-MJE,係以具有利用二氧化矽之表面之至少1個矽醇基與下式(14)中的至少1個甲氧基的反應而得之結構的官能基,作為二氧化矽表面所具有者來進行評價。 (Example 2) Replace the YA050C-MJE of Example 1 as the inorganic filler (D) with a slurry silica (Y50SV-AM1 (trade name), Admatechs (stock), vinyl silane surface-treated silica, solid content 50 mass %, dispersion medium: MEK, average particle diameter: 50 nm) 400 mass parts (200 mass parts in terms of non-volatile components), except that, it carried out similarly to Example 1, and obtained the varnish. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers. In addition, Y50SV-AM1 is the reaction product of silicon dioxide and vinyltrimethoxysilane. That is, YA050C-MJE is a functional group having a structure obtained by the reaction of at least one silanol group on the surface of silicon dioxide with at least one methoxy group in the following formula (14). The owner of the silicon surface is evaluated.

[化20] [chemical 20]

(實施例3) 將作為無機填充材(D)之實施例1之YA050C-MJE替換成使用漿體二氧化矽(Y50SP-AM1(商品名),Admatechs(股),苯基矽烷表面處理二氧化矽,固體成分50質量%,分散介質:MEK,平均粒徑:50nm)400質量份(以非揮發成分換算為200質量份),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 另外,Y50SP-AM1係二氧化矽與苯基三甲氧基矽烷的反應產物。亦即,YA050C-MJE,係以具有利用二氧化矽之表面之至少1個矽醇基與下式(15)中的至少1個甲氧基的反應而得之結構的官能基,作為二氧化矽表面所具有者來進行評價。 (Example 3) Replace the YA050C-MJE of Example 1 as the inorganic filler (D) with slurry silica (Y50SP-AM1 (trade name), Admatechs (stock), phenylsilane surface-treated silica, solid content 50 % by mass, dispersion medium: MEK, average particle diameter: 50 nm) and 400 parts by mass (200 parts by mass in terms of non-volatile components), and a varnish was obtained in the same manner as in Example 1. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers. In addition, Y50SP-AM1 is the reaction product of silicon dioxide and phenyltrimethoxysilane. That is, YA050C-MJE is a functional group having a structure obtained by reacting at least one silanol group on the surface of silicon dioxide with at least one methoxy group in the following formula (15). The owner of the silicon surface is evaluated.

[化21] [chem 21]

(實施例4) 將實施例1中的YA050C-MJE的使用量變更為200質量份(以非揮發成分換算為100質量份),且將LA-1356、BMI-70及MIR-3000-70MT的使用量分別變更為20質量份(非揮發成分換算)、27.3質量份(非揮發成分換算)及12.2質量份(非揮發成分換算),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 (Example 4) The amount of YA050C-MJE in Example 1 was changed to 200 parts by mass (100 parts by mass in terms of non-volatile components), and the amounts of LA-1356, BMI-70 and MIR-3000-70MT were changed to Except 20 mass parts (non-volatile matter conversion), 27.3 mass parts (non-volatile matter conversion), and 12.2 mass parts (non-volatile matter conversion), it carried out similarly to Example 1, and obtained the varnish. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers.

(比較例1) 將作為無機填充材(D)之實施例1之YA050C-MJE替換成使用漿體二氧化矽(YA050C-MJM(商品名),Admatechs(股),苯基胺基矽烷表面處理二氧化矽,固體成分50質量%,分散介質:MEK,平均粒徑:50nm)400質量份(以非揮發成分換算為200質量份),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 另外,YA050C-MJM係二氧化矽與苯基胺基丙基三甲氧基矽烷的反應產物。亦即,YA050C-MJM,係以具有利用二氧化矽之表面之至少1個矽醇基與下式(16)中的至少1個甲氧基的反應而得之結構的官能基,作為二氧化矽表面所具有者來進行評價。 (comparative example 1) Replace the YA050C-MJE in Example 1 as the inorganic filler (D) with slurry silica (YA050C-MJM (trade name), Admatechs (stock), phenylaminosilane surface-treated silica, solid A varnish was obtained in the same manner as in Example 1 except that the component was 50% by mass, dispersion medium: MEK, average particle diameter: 50 nm) and 400 parts by mass (200 parts by mass in terms of non-volatile components). Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers. In addition, YA050C-MJM is the reaction product of silicon dioxide and phenylaminopropyltrimethoxysilane. That is, YA050C-MJM is a functional group having a structure obtained by the reaction of at least one silanol group on the surface of silicon dioxide with at least one methoxy group in the following formula (16). The owner of the silicon surface is evaluated.

[化22] [chem 22]

(比較例2) 將實施例1中的YA050C-MJE之使用量變更為200質量份(以非揮發成分換算為100質量份),且不使用LA-1356,並且將BMI-70及MIR-3000-70MT的使用量分別變更為41.5質量份(非揮發成分換算)及18質量份(非揮發成分換算),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 (comparative example 2) The amount of YA050C-MJE in Example 1 was changed to 200 parts by mass (100 parts by mass in terms of non-volatile components), and LA-1356 was not used, and the amount of BMI-70 and MIR-3000-70MT was changed to Except having changed into 41.5 mass parts (non-volatile matter conversion) and 18 mass parts (non-volatile matter conversion), respectively, it carried out similarly to Example 1, and obtained the varnish. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers.

(比較例3) 不使用實施例1中之BMI-1000P,且將LA-1356、BMI-70、及MIR-3000-70MT的使用量分別變更為45質量份(非揮發成分換算)、38質量份(非揮發成分換算)、及17質量份(非揮發成分換算),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 (comparative example 3) BMI-1000P in Example 1 was not used, and the usage amounts of LA-1356, BMI-70, and MIR-3000-70MT were changed to 45 parts by mass (non-volatile content conversion), 38 parts by mass (non-volatile content Conversion) and 17 parts by mass (non-volatile matter conversion), and except that, it carried out similarly to Example 1, and obtained the varnish. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers.

(比較例4) 不使用實施例1中之BMI-70及MIR-3000-70MT,且將LA-1356及BMI-1000P的使用量分別變更為40質量份(非揮發成分換算)及60質量份(非揮發成分換算),除此之外,和實施例1同樣地進行並製得清漆。使用該清漆,和實施例1同樣地進行,獲得樹脂組成物層的厚度為30μm之疊層體。 (comparative example 4) Instead of using BMI-70 and MIR-3000-70MT in Example 1, the usage amounts of LA-1356 and BMI-1000P were changed to 40 parts by mass (in terms of non-volatile components) and 60 parts by mass (in terms of non-volatile components) respectively. ), except that, carry out and make varnish in the same manner as in Example 1. Using this varnish, it carried out similarly to Example 1, and obtained the laminated body whose resin composition layer thickness was 30 micrometers.

[疊層體之評價] 使用實施例1~4及比較例1~2得到的疊層體實施如下之評價。它們的結果如表1所示。 (1)半導體晶片安裝後的空隙之評價 將得到的疊層體裁切成8mm×8mm之正方形。裁切後的疊層體係對於半導體晶片搭載用基板(WALTS(股)製WALTS-KIT CC80(W)-0105JY(商品名))之焊墊(pad)部分中的15μm之銅電路面,以接觸裁切後的疊層體中之樹脂組成物層的方式進行疊層。其後,將疊層體中的聚對苯二甲酸乙二酯薄膜剝離。然後,使用覆晶接合器(LFB-2301(商品名),新川(股)),以台座溫度85℃、銲線壓頭(bond head)溫度120℃、荷重100N、及時間1秒之條件,於具有由銅及焊料構成的Cu柱作為電極之半導體晶片上,以接觸樹脂組成物層之剝離面的方式進行配置並予以熱壓接後,再以銲線壓頭溫度260℃、荷重50N、及時間4秒之條件進一步予以熱壓接來實施安裝。將安裝後的樣本(半導體晶片/樹脂組成物層/半導體晶片搭載用基板)使用超音波精密檢傷圖像處理裝置(μ-SDS(商品名),KJTD(股)製)來取得圖像資料,並由該圖像資料確認半導體晶片安裝部之範圍內的樹脂組成物層是否有空隙。 確認有空隙的部分所佔的面積之比例相對於半導體晶片安裝部之範圍內的樹脂組成物層所佔的面積之整體,未達10%時評價為A,為10%以上且未達20%時評價為B,為20%以上且未達30%時評價為C,為30%以上時評價為D。另外,確認有空隙之部分所佔的面積之比例愈小,則評價為愈可獲得絕緣可靠性高的疊層體,尤其確認有空隙的部分所佔的面積之比例未達10%的話,則評價為可獲得絕緣可靠性非常高的疊層體。 [Evaluation of laminated body] The following evaluation was implemented using the laminate obtained in Examples 1-4 and Comparative Examples 1-2. Their results are shown in Table 1. (1) Evaluation of voids after semiconductor wafer mounting The obtained laminate was cut into a square of 8 mm x 8 mm. For the laminated system after cutting, the copper circuit surface of 15 μm in the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by WALTS Co., Ltd.) The resin composition layer in the laminated body after cutting is laminated|stacked. Thereafter, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Xinchuan Co., Ltd.), under the conditions of pedestal temperature 85°C, bond head temperature 120°C, load 100N, and time 1 second, On a semiconductor wafer having a Cu pillar made of copper and solder as an electrode, arrange it in such a way as to contact the peeled surface of the resin composition layer and perform thermocompression bonding, and then use a wire bonding head temperature of 260°C and a load of 50N. And the condition of time 4 seconds is further carried out by thermocompression bonding to implement the installation. The mounted sample (semiconductor wafer/resin composition layer/semiconductor wafer mounting substrate) is imaged using an ultrasonic precision flaw inspection image processing device (μ-SDS (trade name), manufactured by KJTD Co., Ltd.) , and confirm whether there are voids in the resin composition layer within the range of the semiconductor chip mounting part from the image data. When the ratio of the area occupied by the portion where voids are confirmed to the total area occupied by the resin composition layer within the range of the semiconductor chip mounting portion is less than 10%, the evaluation is A, and it is more than 10% and less than 20%. When it is more than 20% and less than 30%, it is rated as C, and when it is more than 30%, it is rated as D. In addition, the smaller the proportion of the area occupied by the portion confirmed to have voids, the more reliable a laminate can be obtained. In particular, if the proportion of the area occupied by the portion confirmed to have voids is less than 10%, then the It was evaluated that a laminate with very high insulation reliability could be obtained.

(2)熱硬化後的空隙之評價 將得到的疊層體裁切成8mm×8mm之正方形。裁切後的疊層體係對於半導體晶片搭載用基板(WALTS(股)製WALTS-KIT CC80(W)-0105JY(商品名))之焊墊(pad)部分中的15μm之銅電路面,以接觸裁切後的疊層體中之樹脂組成物層的方式進行疊層。其後,將疊層體中的聚對苯二甲酸乙二酯薄膜剝離。然後,使用覆晶接合器(LFB-2301(商品名),新川(股)),以台座溫度85℃、銲線壓頭溫度120℃、荷重100N、及時間1秒之條件,於具有由銅及焊料構成的Cu柱作為電極之半導體晶片上,以接觸樹脂組成物層之剝離面的方式進行配置並予以熱壓接後,再以銲線壓頭溫度260℃、荷重50N、及時間4秒之條件進一步予以熱壓接來實施安裝。安裝後,使用防爆乾燥機(ESPEC製SPHH-201(商品名)),於溫度180℃進行2小時加熱處理並使其硬化後,將硬化後的樣本(半導體晶片/樹脂組成物層/半導體晶片搭載用基板)使用超音波精密檢傷圖像處理裝置(μ-SDS(商品名),KJTD(股)製)來取得圖像資料,並由該圖像資料確認半導體晶片安裝部之範圍內的樹脂組成物層是否有空隙。 確認有空隙的部分所佔的面積之比例相對於半導體晶片安裝部之範圍內的樹脂組成物層所佔的面積之整體,未達10%時評價為A,為10%以上且未達20%時評價為B,為20%以上且未達30%時評價為C,為30%以上時評價為D。另外,確認有空隙之部分所佔的面積之比例愈小,則評價為愈可獲得絕緣可靠性高的疊層體,尤其確認有空隙的部分所佔的面積之比例未達10%的話,則評價為可獲得絕緣可靠性非常高的疊層體。 (2) Evaluation of voids after thermal hardening The obtained laminate was cut into a square of 8 mm x 8 mm. For the laminated system after cutting, the copper circuit surface of 15 μm in the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by WALTS Co., Ltd.) The resin composition layer in the laminated body after cutting is laminated|stacked. Thereafter, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Xinchuan Co., Ltd.), under the conditions of pedestal temperature 85°C, wire bonding head temperature 120°C, load 100N, and time 1 second, the bonder made of copper On the semiconductor wafer with Cu pillars composed of solder and solder as electrodes, arrange them in such a way as to contact the peeled surface of the resin composition layer and perform thermocompression bonding. The conditions are further thermocompressed to implement the installation. After mounting, use an explosion-proof dryer (SPHH-201 (trade name) manufactured by ESPEC), heat treatment at a temperature of 180°C for 2 hours to harden, and then dry the hardened sample (semiconductor wafer/resin composition layer/semiconductor wafer) Mounting board) Use an ultrasonic precision inspection image processing device (μ-SDS (trade name), KJTD (KJTD) Co., Ltd.) to obtain image data, and use the image data to confirm the defects within the range of the semiconductor chip mounting part. Whether there are voids in the resin composition layer. When the ratio of the area occupied by the portion where voids are confirmed to the total area occupied by the resin composition layer within the range of the semiconductor chip mounting portion is less than 10%, the evaluation is A, and it is more than 10% and less than 20%. When it is more than 20% and less than 30%, it is rated as C, and when it is more than 30%, it is rated as D. In addition, the smaller the proportion of the area occupied by the portion confirmed to have voids, the more reliable a laminate can be obtained. In particular, if the proportion of the area occupied by the portion confirmed to have voids is less than 10%, then the It was evaluated that a laminate with very high insulation reliability could be obtained.

(3)熱硬化後的晶片黏接性之評價 將得到的疊層體裁切成8mm×8mm之正方形。裁切後的疊層體係對於半導體晶片搭載用基板(WALTS(股)製WALTS-KIT CC80(W)-0105JY(商品名))之焊墊(pad)部分中的15μm之銅電路面,以接觸裁切後的疊層體中之樹脂組成物層的方式進行疊層。其後,將疊層體中的聚對苯二甲酸乙二酯薄膜剝離。然後,使用覆晶接合器(LFB-2301(商品名),新川(股)),以台座溫度85℃、銲線壓頭溫度120℃、荷重100N、及時間1秒之條件,於具有由銅及焊料構成的Cu柱作為電極之半導體晶片上,以接觸樹脂組成物層之剝離面的方式進行配置並予以熱壓接後,再以銲線壓頭溫度260℃、荷重50N、及時間4秒之條件進一步予以熱壓接來實施安裝。安裝後,於防爆乾燥機(ESPEC製SPHH-201(商品名)),以溫度180℃進行2小時加熱處理並使其硬化。將硬化後的樣本(半導體晶片/樹脂組成物層/半導體晶片搭載用基板)使用旋轉式研磨裝置(裝置名:MetaServ(註冊商標)3000(商品名),BUEHLER公司製)僅將半導體晶片去除,獲得樹脂組成物層與半導體晶片搭載用基板之疊層體(A)。以目視觀察疊層體(A)中樹脂組成物層的表面,並以來自半導體晶片之配線層是否附著於該表面來確認剝離的狀況。 前述配線層全面地殘留在樹脂組成物層側時,視為未發生剝離,標記為A,前述配線層有一部分缺損時,視為有點發生剝離,標記為B,在半導體晶片去除作業中,半導體晶片脫落時,視為發生剝離,標記為C。另外,評價為A時,由於半導體晶片未從樹脂組成物層脫落,晶片黏接性非常優良,故評價為絕緣可靠性非常高的疊層體。評價為B時,在本晶片黏接性之評價中,係發生部分剝離,但作為半導體裝置仍可沒問題地運作,故評價為晶片黏接性良好、絕緣可靠性高的疊層體。 又,表1中,在半導體晶片安裝後,因為半導體晶片與樹脂組成物層之間空隙多,且半導體晶片與樹脂組成物層未黏接的部分多,而無法測定晶片黏接性時,記載為「E」。 (3) Evaluation of wafer adhesion after thermosetting The obtained laminate was cut into a square of 8 mm x 8 mm. For the laminated system after cutting, the copper circuit surface of 15 μm in the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by WALTS Co., Ltd.) The resin composition layer in the laminated body after cutting is laminated|stacked. Thereafter, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Xinchuan Co., Ltd.), under the conditions of pedestal temperature 85°C, wire bonding head temperature 120°C, load 100N, and time 1 second, the bonder made of copper On the semiconductor wafer with Cu pillars composed of solder and solder as electrodes, arrange them in such a way as to contact the peeled surface of the resin composition layer and perform thermocompression bonding. The conditions are further thermocompressed to implement the installation. After mounting, it heat-processed and hardened at the temperature of 180 degreeC for 2 hours in the explosion-proof dryer (SPHH-201 (trade name) manufactured by ESPEC). The hardened sample (semiconductor wafer/resin composition layer/substrate for semiconductor wafer mounting) was removed using a rotary polishing device (device name: MetaServ (registered trademark) 3000 (trade name), manufactured by BUEHLER Corporation) to remove only the semiconductor wafer, A laminate (A) of the resin composition layer and the substrate for mounting a semiconductor chip was obtained. The surface of the resin composition layer in the laminate (A) was observed visually, and the state of peeling was confirmed by whether or not the wiring layer derived from the semiconductor wafer was attached to the surface. When the aforementioned wiring layer remains entirely on the side of the resin composition layer, it is considered that no peeling has occurred, which is marked as A. When a part of the aforementioned wiring layer is missing, it is considered as a little peeling, which is marked as B. In the removal operation of the semiconductor wafer, the semiconductor When the wafer was peeled off, it was considered that peeling occurred, and it was marked as C. In addition, when the evaluation was A, since the semiconductor wafer did not come off from the resin composition layer and the wafer adhesiveness was very excellent, it was evaluated as a laminate with very high insulation reliability. When the evaluation is B, in this evaluation of wafer adhesiveness, partial peeling occurred, but it can still operate without any problem as a semiconductor device, so it was evaluated as a laminate with good wafer adhesiveness and high insulation reliability. In addition, in Table 1, after the semiconductor wafer is mounted, because there are many gaps between the semiconductor wafer and the resin composition layer, and there are many unbonded parts between the semiconductor wafer and the resin composition layer, and when the wafer adhesiveness cannot be measured, record to "E".

[表1]    實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 比較例4 半導體晶片安裝後的空隙 A A A A D C B B 熱硬化後的空隙 A A A A D C B B 熱硬化後的晶片黏接性 A A B A E C C C [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Void after semiconductor chip mounting A A A A D. C B B Void after heat hardening A A A A D. C B B Die Adhesion After Thermal Hardening A A B A E. C C C

本申請案係基於2021年10月15日提申之日本專利申請案(日本特願2021-169227號)及2022年2月24日提申之日本專利申請案(日本特願2022-026578號)者,並在此引用該等之內容作為參考。 [產業上利用性] This application is based on the Japanese patent application filed on October 15, 2021 (Japanese Patent Application No. 2021-169227) and the Japanese patent application filed on February 24, 2022 (Japanese Patent Application No. 2022-026578) , the contents of which are hereby incorporated by reference. [industrial availability]

本實施形態之樹脂組成物之低空隙性及晶片黏接性優良,故可理想地使用作為疊層體、設有樹脂組成物層之半導體晶片、設有樹脂組成物層之半導體晶片搭載用基板、及半導體裝置的材料。樹脂組成物作為底部填充材係為理想,作為預塗型底部填充材更為理想。The resin composition of this embodiment is excellent in low void property and chip adhesiveness, so it can be ideally used as a laminated body, a semiconductor chip provided with a resin composition layer, and a semiconductor chip mounting substrate provided with a resin composition layer , and materials for semiconductor devices. The resin composition is ideal as an underfill material, and is more ideal as a precoat type underfill material.

Claims (24)

一種樹脂組成物,含有: 胺基三𠯤酚醛清漆樹脂(A), 選自由馬來醯亞胺化合物(BA)及檸康醯亞胺化合物(BB)構成之群組中之1種以上之化合物(B),及 無機填充材(D); 該無機填充材(D)包含具有含有選自由(甲基)丙烯酸基、乙烯基、苯乙烯基、及苯基構成之群組中之1種以上之官能基(d)之無機填充材(D1), 該化合物(B)包含化合物(B1)及化合物(B2), 該化合物(B1)為選自由重量平均分子量為3,000以上且9,500以下之馬來醯亞胺化合物(BA-1)及重量平均分子量為3,000以上且9,500以下之檸康醯亞胺化合物(BB-1)構成之群組中之1種以上, 該化合物(B2)為選自由重量平均分子量為300以上且未達3,000之馬來醯亞胺化合物(BA-2)及重量平均分子量為300以上且未達3,000之檸康醯亞胺化合物(BB-2)構成之群組中之1種以上, 各該重量平均分子量為利用凝膠滲透層析法求得之以標準聚苯乙烯換算之值。 A resin composition comprising: Amino trisulfone novolac resin (A), One or more compounds (B) selected from the group consisting of maleimide compounds (BA) and citraconamide compounds (BB), and Inorganic filler (D); The inorganic filler (D) includes an inorganic filler (D1) having at least one functional group (d) selected from the group consisting of a (meth)acrylic group, a vinyl group, a styrene group, and a phenyl group. ), The compound (B) comprises compound (B1) and compound (B2), The compound (B1) is selected from maleimide compounds (BA-1) having a weight average molecular weight of 3,000 to 9,500 and citraconimide compounds (BB-1) having a weight average molecular weight of 3,000 to 9,500. ) of one or more of the groups formed, The compound (B2) is selected from a maleimide compound (BA-2) with a weight average molecular weight of 300 or more and less than 3,000, and a citraconimide compound (BB) with a weight average molecular weight of 300 or more and less than 3,000. -2) More than one of the groups formed, Each of these weight average molecular weights is a value in terms of standard polystyrene obtained by gel permeation chromatography. 如請求項1之樹脂組成物,其中,該官能基(d)更含有矽原子。The resin composition according to claim 1, wherein the functional group (d) further contains a silicon atom. 如請求項1或2之樹脂組成物,其中,該無機填充材(D1)包含具有該官能基(d)之化合物(d1)與不具有該官能基(d)之無機填充材(d2)之反應產物。The resin composition according to claim 1 or 2, wherein the inorganic filler (D1) comprises a compound (d1) having the functional group (d) and an inorganic filler (d2) not having the functional group (d) reaction product. 如請求項3之樹脂組成物,其中,該具有官能基(d)之化合物(d1)包含選自由具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物以及具有苯乙烯基之矽烷化合物構成之群組中之1種以上。The resin composition according to claim 3, wherein the compound (d1) having a functional group (d) is selected from a silane compound having a (meth)acrylic group and/or a vinyl group and a silane compound having a styryl group More than one species in the group. 如請求項3之樹脂組成物,其中,該無機填充材(d2)包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石(boehmite)、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上。The resin composition according to claim 3, wherein the inorganic filler (d2) comprises silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and one or more of the group consisting of magnesium hydroxide. 如請求項3之樹脂組成物,其中,該具有官能基(d)之化合物(d1)包含選自由具有(甲基)丙烯酸基及/或乙烯基之矽烷化合物以及具有苯乙烯基之矽烷化合物構成之群組中之1種以上,且該無機填充材(d2)包含選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之1種以上。The resin composition according to claim 3, wherein the compound (d1) having a functional group (d) is selected from a silane compound having a (meth)acrylic group and/or a vinyl group and a silane compound having a styryl group One or more of the group, and the inorganic filler (d2) contains silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide One or more of the groups formed. 如請求項1或2之樹脂組成物,其中,該無機填充材(D)的平均粒徑為3μm以下。The resin composition according to claim 1 or 2, wherein the average particle diameter of the inorganic filler (D) is 3 μm or less. 如請求項1或2之樹脂組成物,其中,該無機填充材(D)的含量相對於該胺基三𠯤酚醛清漆樹脂(A)與該化合物(B)之合計100質量份,為20~500質量份。Such as the resin composition of claim 1 or 2, wherein the content of the inorganic filler (D) is 20~ 500 parts by mass. 如請求項1之樹脂組成物,其中,該胺基三𠯤酚醛清漆樹脂(A)包含選自由下式(1)表示之化合物及下式(2)表示之化合物構成之群組中之1種以上; 式(1)中,R 1各自獨立地表示氫原子、甲基、或乙基,l、m、及n各自獨立地表示0~10之整數,(l+m+n)表示1~20之整數; 式(2)中,R 2各自獨立地表示氫原子、甲基、或乙基,o、p、q、r、及s各自獨立地表示0~10之整數,(o+p+q+r+s)表示1~20之整數。 The resin composition as claimed in claim 1, wherein the amino trismetherone novolak resin (A) contains one selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2) above; In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group, 1, m, and n each independently represent an integer of 0 to 10, and (l+m+n) represents an integer of 1 to 20 integer; In formula (2), R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, o, p, q, r, and s each independently represent an integer of 0 to 10, (o+p+q+r +s) means an integer from 1 to 20. 如請求項1或2之樹脂組成物,其中,該化合物(B1)的含量相對於該化合物(B1)與該化合物(B2)之合計100質量份,為45質量份以上且90質量份以下, 該化合物(B2)的含量相對於該化合物(B1)與該化合物(B2)之合計100質量份,為10質量份以上且55質量份以下。 The resin composition according to claim 1 or 2, wherein the content of the compound (B1) is not less than 45 parts by mass and not more than 90 parts by mass relative to 100 parts by mass of the total of the compound (B1) and the compound (B2), Content of this compound (B2) is 10 mass parts or more and 55 mass parts or less with respect to a total of 100 mass parts of this compound (B1) and this compound (B2). 如請求項1或2之樹脂組成物,其中,該馬來醯亞胺化合物(BA-1)包含選自由下式(3)表示之馬來醯亞胺化合物及含有下式(4)表示之構成單元以及在分子鏈之兩末端含有馬來醯亞胺基之雙馬來醯亞胺化合物構成之群組中之一種以上; 式中,n3表示1~30之整數; 式中,R 11表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基,R 12表示碳數1~16之直鏈狀或分支狀之伸烷基、或碳數2~16之直鏈狀或分支狀之伸烯基,R 13各自獨立地表示氫原子、碳數1~16之直鏈狀或分支狀之烷基、或碳數2~16之直鏈狀或分支狀之烯基,n 5表示1以上且10以下之整數。 The resin composition according to claim 1 or 2, wherein the maleimide compound (BA-1) comprises maleimide compounds represented by the following formula (3) and One or more of the group consisting of structural units and bismaleimide compounds containing maleimide groups at both ends of the molecular chain; In the formula, n3 represents an integer from 1 to 30; In the formula, R11 represents a linear or branched alkylene group with 1 to 16 carbons, or a linear or branched alkenylene group with 2 to 16 carbons, and R12 represents a linear or branched alkenyl group with 1 to 16 carbons. A linear or branched alkylene group, or a linear or branched alkenylene group with 2 to 16 carbons, R13 each independently represents a hydrogen atom, a straight or branched chain with 1 to 16 carbons An alkyl group, or a linear or branched alkenyl group with 2 to 16 carbons, n 5 represents an integer of 1 to 10. 如請求項1或2之樹脂組成物,其中,該馬來醯亞胺化合物(BA-2)包含選自由下式(5)表示之馬來醯亞胺化合物及下式(6)表示之馬來醯亞胺化合物構成之群組中之一種以上; 式中,R 8各自獨立地表示氫原子、甲基、或乙基,R 9各自獨立地表示氫原子或甲基; 式中,R 10各自獨立地表示氫原子、碳數1~5之烷基、或苯基,n4表示1~10之整數。 The resin composition according to claim 1 or 2, wherein the maleimide compound (BA-2) comprises a maleimide compound represented by the following formula (5) and a maleimide compound represented by the following formula (6). More than one of the group consisting of lymide compounds; In the formula, R 8 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R 9 each independently represent a hydrogen atom or a methyl group; In the formula, R 10 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, or a phenyl group, and n4 represents an integer of 1 to 10. 如請求項1或2之樹脂組成物,更含有助熔劑活性劑(C)。The resin composition according to claim 1 or 2 further contains a flux activator (C). 如請求項13之樹脂組成物,其中,該助熔劑活性劑(C)包含松香系樹脂。The resin composition according to claim 13, wherein the flux activating agent (C) comprises a rosin-based resin. 如請求項1或2之樹脂組成物,更含有硬化觸媒(E)。The resin composition according to claim 1 or 2 further contains a hardening catalyst (E). 如請求項15之樹脂組成物,其中,該硬化觸媒(E)包含選自由有機過氧化物及咪唑化合物構成之群組中之1種以上。The resin composition according to claim 15, wherein the hardening catalyst (E) contains at least one selected from the group consisting of organic peroxides and imidazole compounds. 如請求項1或2之樹脂組成物,其中,該胺基三𠯤酚醛清漆樹脂(A)的含量相對於該胺基三𠯤酚醛清漆樹脂(A)與該化合物(B)之合計100質量份,為1~60質量份。The resin composition according to claim 1 or 2, wherein, the content of the amino trisphenolic novolak resin (A) is 100 parts by mass of the total of the amino trisphenolic novolak resin (A) and the compound (B) , being 1 to 60 parts by mass. 如請求項1或2之樹脂組成物,其中,該化合物(B)的含量相對於該胺基三𠯤酚醛清漆樹脂(A)與該化合物(B)之合計100質量份,為40~85質量份。The resin composition according to claim 1 or 2, wherein the content of the compound (B) is 40 to 85 parts by mass relative to the total of 100 parts by mass of the aminotrisium novolak resin (A) and the compound (B) share. 如請求項1或2中任一項之樹脂組成物,其係用於底部填充材。The resin composition according to any one of claim 1 or 2, which is used as an underfill material. 一種疊層體,具備: 支持基材,及 疊層於該支持基材上且含有如請求項1至19中任一項之樹脂組成物之樹脂組成物層。 A laminate comprising: supporting substrate, and A resin composition layer laminated on the support substrate and containing the resin composition according to any one of claims 1 to 19. 如請求項20之疊層體,其中,該樹脂組成物層的厚度為5~500μm之範圍。The laminate according to claim 20, wherein the thickness of the resin composition layer is in the range of 5 to 500 μm. 一種設有樹脂組成物層之半導體晶片,具備: 半導體晶片,及 疊層於該半導體晶片且使用如請求項1至19中任一項之樹脂組成物而形成的層。 A semiconductor wafer provided with a resin composition layer, comprising: semiconductor wafers, and A layer laminated on the semiconductor wafer using the resin composition according to any one of claims 1 to 19. 一種設有樹脂組成物層之半導體晶片搭載用基板,具備: 半導體晶片搭載用基板,及 疊層於該半導體晶片搭載用基板且使用如請求項1至19中任一項之樹脂組成物而形成的層。 A substrate for mounting a semiconductor chip provided with a resin composition layer, comprising: A substrate for mounting a semiconductor chip, and A layer formed using the resin composition according to any one of claims 1 to 19, which is laminated on the substrate for mounting a semiconductor chip. 一種半導體裝置,具備: 如請求項22之設有樹脂組成物層之半導體晶片或如請求項23之設有樹脂組成物層之半導體晶片搭載用基板。 A semiconductor device having: A semiconductor wafer provided with a resin composition layer as in Claim 22 or a substrate for mounting a semiconductor chip provided with a resin composition layer as in Claim 23.
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