JP4334446B2 - Semiconductor sealing material - Google Patents
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- JP4334446B2 JP4334446B2 JP2004274906A JP2004274906A JP4334446B2 JP 4334446 B2 JP4334446 B2 JP 4334446B2 JP 2004274906 A JP2004274906 A JP 2004274906A JP 2004274906 A JP2004274906 A JP 2004274906A JP 4334446 B2 JP4334446 B2 JP 4334446B2
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本発明は新規な特に流動性、硬化性、耐熱性、耐水性のバランスに優れ、表面実装時の耐ハンダクラック性に優れた半導体封止材料に関する。 The present invention relates to a novel semiconductor sealing material that is particularly excellent in the balance of fluidity, curability, heat resistance, and water resistance and excellent in solder crack resistance during surface mounting.
エポキシ樹脂は、種々の硬化剤で硬化させることにより、一般的に機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などの優れた硬化物となり、接着剤、塗料、積層板、成形材料、注形材料等、幅広い分野に使用されている。 Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, Used in a wide range of fields such as molding materials and casting materials.
また、特に半導体封止材料用途においては、近年、従来のピン挿入方式から表面実装方式に実装方法が急速に移行しつつあり、優れた耐ハンダクラック性を有する半導体封止材料が求められている。さらには高実装密度化に対応するため半導体のパッケージが薄型化する傾向にあり、厚さが１ｍｍ以下のＴＳＯＰ型パッケージも使用される様になった。従ってこれらに対応するため、耐ハンダクラック性に加え、低溶融粘度で流動性の高い材料が求められている。 Further, particularly in the application of semiconductor sealing materials, in recent years, the mounting method is rapidly shifting from the conventional pin insertion method to the surface mounting method, and a semiconductor sealing material having excellent solder crack resistance is required. . Furthermore, semiconductor packages tend to be thinner in order to cope with higher mounting density, and TSOP type packages having a thickness of 1 mm or less have also been used. Therefore, in order to cope with these problems, a material having low melt viscosity and high fluidity in addition to solder crack resistance is required.
従来より、半導体封止材料用途には、オルソクレゾールノボラック型エポキシ樹脂（以下「ＥＣＮ」という）が広く使用されているが、当該樹脂は耐熱性には優れるものの、流動性と耐ハンダクラック性に劣るという欠陥を有していた。 Conventionally, ortho-cresol novolac type epoxy resin (hereinafter referred to as “ECN”) has been widely used for semiconductor sealing materials. However, although the resin is excellent in heat resistance, it has excellent fluidity and solder crack resistance. It had the defect of being inferior.
そこで流動性に優れる高性能半導体封止材料としてジシクロペンタジエン型エポキシ樹脂を用いた封止材が、例えば下記公報に記載されている。
しかし、上記の何れのエポキシ樹脂組成物も半導体を封止する際の成形時の流動性は良好であるものの、封止硬化後の耐熱性が十分でないという課題を有していた。 However, although any of the above epoxy resin compositions has good fluidity during molding when sealing a semiconductor, it has a problem that heat resistance after sealing and curing is not sufficient.
本発明が解決しようとする課題は、流動性が良好で半導体を封止する際の成形に優れる上に、更に封止硬化後の耐熱性に優れる半導体封止材料を提供することにある。 An object of the present invention is to provide, on the fluidity excellent molding when sealing the good semiconductor, further to provide a semiconductor encapsulating material Ru excellent heat resistance after sealing curing.
本発明者等は鋭意検討した結果、エポキシ樹脂として不飽和脂環式化合物とフェノール類の重付加反応物とエピハロヒドリンを反応させて得られるエポキシ樹脂であって、ＧＰＣでのポリスチレン換算数平均分子量が１００〜２２０の範囲内に検出される、フェノール類１分子と不飽和脂環式化合物１分子が結合した置換フェノール類のモノグリシジルエーテルを主たる成分とする低分子量物質を０．１〜２．０重量％の範囲で含有するものであるエポキシ樹脂を用いることにより硬化物の耐熱性を低下させることなく、流動性を向上させて成形性を改善できることを見いだし本発明を完成するに至った。 The present inventors have a result of intensive studies, an unsaturated alicyclic compound and a phenol polyaddition reaction with epihalohydrin is reacted to give al is Ru epoxy resin as an epoxy resin, a polystyrene-reduced number average by GPC A low molecular weight substance having a molecular weight of 100 to 220 and having a monoglycidyl ether of a substituted phenol in which one molecule of phenol and one molecule of unsaturated alicyclic compound are bonded as a main component is 0.1 to 2 It was found that by using an epoxy resin contained in the range of 0.0% by weight, the fluidity can be improved and the moldability can be improved without reducing the heat resistance of the cured product, and the present invention has been completed. .
即ち、本発明はエポキシ樹脂（Ａ）と、硬化剤（Ｂ）と、無機充填剤（Ｃ）を必須成分とする半導体封止材料において、エポキシ樹脂（Ａ）が、不飽和脂環式化合物とフェノール類との重付加反応した構造を有する化合物とエピハロヒドリンとの反応物であって、かつ、エポキシ樹脂（Ａ）がＧＰＣでのポリスチレン換算数平均分子量１００〜２２０の範囲内に検出される、フェノール類１分子と不飽和脂環式化合物１分子が結合した置換フェノール類のモノグリシジルエーテルを主たる成分とする低分子量物質を０．１〜２．０重量％の範囲で含有するものであることを特徴とする半導体封止材料に関する。 That is, the present invention relates to a semiconductor sealing material having an epoxy resin (A), a curing agent (B), and an inorganic filler (C) as essential components, and the epoxy resin (A) is an unsaturated alicyclic compound. a reaction of the compound and epihalohydrin with a polyaddition reaction structure of a phenol and an epoxy resin (a) is detected within a polystyrene reduced number average molecular weight 100 to 220 of by GPC, and phenol A low-molecular-weight substance containing a monoglycidyl ether of a substituted phenol in which one molecule and one unsaturated alicyclic compound are bonded in a range of 0.1 to 2.0% by weight. The present invention relates to a characteristic semiconductor sealing material.
本発明によれば、流動性が良好で半導体を封止する際の成形に優れる上に、更に封止硬化後の耐熱性に優れるエポキシ樹脂組成物及び半導体封止材料を提供できる。 According to the present invention, it is possible to provide an epoxy resin composition and a semiconductor sealing material that are excellent in fluidity and excellent in molding at the time of sealing a semiconductor, and further excellent in heat resistance after sealing and curing.
本発明で用いるエポキシ樹脂（Ａ）は、不飽和脂環式化合物とフェノール類との重付加反応した構造を有する化合物にエピハロヒドリンを反応させて得られる種々の構造のものが共存しており、また、様々な分子量の分子量分布を有するものであって、かつ、ＧＰＣでのポリスチレン換算数平均分子量が１００〜２２０の範囲内に検出される、フェノール類１分子と不飽和脂環式化合物１分子が結合した置換フェノール類のモノグリシジルエーテルを主たる成分とする低分子量物質を０．１〜２．０重量％の範囲で含有するものである。 The epoxy resin (A) used in the present invention coexists with various structures obtained by reacting an epihalohydrin with a compound having a structure obtained by polyaddition reaction of an unsaturated alicyclic compound and a phenol. One molecule of phenols and one molecule of unsaturated alicyclic compound having molecular weight distributions of various molecular weights and having a polystyrene-equivalent number average molecular weight in GPC of 100 to 220 are detected. It contains a low molecular weight substance having a monoglycidyl ether of a substituted substituted phenol as a main component in the range of 0.1 to 2.0% by weight.
本発明においてはこの様なエポキシ樹脂を用いることにより硬化物の耐熱性を低下させることなく、流動性を向上させて成形性を改善できる。 In the present invention, by using such an epoxy resin, the flowability can be improved and the moldability can be improved without reducing the heat resistance of the cured product.
本発明で使用されるエポキシ樹脂（Ａ）を誘導するフェノール類としては、フェノール、及びアルキル基、アルケニル基、アリル基、アリール基、アラルキル基或いはハロゲン基等が結合した置換フェノール類が挙げられる。具体的に例示すると、クレゾール、キシレノール、エチルフェノール、イソプロピルフェノール、ブチルフェノール、オクチルフェノール、ノニルフェノール、ビニルフェノール、イソプロペニルフェノール、アリルフェノール、フェニルフェノール、ベンジルフェノール、クロルフェノール、ブロムフェノール（各々ｏ、ｍ、ｐ−異性体を含む）、ビスフェノールＡ、ナフトール、ジヒドロキシナフタレン等が例示されるが、これらに限定されるものではない。またこれらの混合物を用いても構わない。これらの中でも流動性および硬化性が優れる点からフェノール、クレゾールが特に好ましい。 Examples of the phenols for deriving the epoxy resin (A) used in the present invention include substituted phenols to which phenol and an alkyl group, alkenyl group, allyl group, aryl group, aralkyl group, halogen group or the like are bonded. Specifically, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol (respectively o, m, p) -Including isomers), bisphenol A, naphthol, dihydroxynaphthalene and the like, but are not limited thereto. Moreover, you may use these mixtures. Among these, phenol and cresol are particularly preferable from the viewpoint of excellent fluidity and curability.
また不飽和脂環式化合物としては、１分子中に不飽和二重結合を２つ以上有する脂肪族環状炭化水素化合物であれば、特に限定されないが、例示するならばジシクロペンタジエン、テトラヒドロインデン、４−ビニルシクロヘキセン、５−ビニルノルボナ−２−エン、α−ピネン、β−ピネン、リモネン等が挙げられる。これらの中でも特性バランス、特に耐熱性、吸湿性の点からジシクロペンタジエンが好ましい。またジシクロペンタジエンは石油留分中に含まれることから、工業用ジシクロペンタジエンには他の脂肪族或いは芳香族性ジエン類等が不純物として含有されることがあるが、耐熱性、硬化性、成形性等を考慮すると、ジシクロペンタジエンの純度９０重量％以上の製品を用いることが望ましい。 Further, the unsaturated alicyclic compound is not particularly limited as long as it is an aliphatic cyclic hydrocarbon compound having two or more unsaturated double bonds in one molecule, but for example, dicyclopentadiene, tetrahydroindene, Examples include 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene. Among these, dicyclopentadiene is preferred from the viewpoint of property balance, particularly heat resistance and hygroscopicity. In addition, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, it is desirable to use a product having a purity of 90% by weight or more of dicyclopentadiene.
またここでいう２核体とは、不飽和脂環式化合物とフェノール類の反応物中の、脂環式化合物を結接基としたビスフェノール化合物のジグリシジルエーテル物を指す。この含有量は、ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）によって分析された重量割合で表される値である。 The dinuclear body here refers to a diglycidyl ether product of a bisphenol compound having an alicyclic compound as a linking group in a reaction product of an unsaturated alicyclic compound and a phenol. This content is a value represented by a weight ratio analyzed by gel permeation chromatography (GPC).
本発明で用いるエポキシ樹脂（Ａ）を得るには、特にその製造方法が限定されるものでなく、上述したフェノール類と不飽和脂環式化合物との重付加反応体である中間体（以下、この重付加反応体である中間体を単に「中間体」と略記する）とエピハロヒドヒンを反応させればよい。 In order to obtain the epoxy resin (A) used in the present invention, the production method is not particularly limited, and an intermediate (hereinafter, referred to as a polyaddition reactant of the above-described phenols and unsaturated alicyclic compound). The intermediate which is this polyaddition reactant is simply abbreviated as “intermediate”) and epihalohydrin may be reacted.
ここで、中間体は、特にその製造条件が限定されるものではないが、エポキシ樹脂（Ａ）の１５０℃での溶融粘度を１．０ポイズ以下にし、かつ２核体成分の含有量を４０〜７５重量％、より好ましくは４５〜６５重量％の範囲に設定するためには、反応時のフェノール類と不飽和脂環式化合物のモル比率を調整することが好ましく、不飽和脂環式化合物１モルに対してフェノール類を４モル以上使用することが好ましい。なかでもフェノール類／不飽和脂環式化合物＝２．５／１〜１５／１（モル比率）の範囲内で合成すると、目的のエポキシ樹脂を得るに好ましい中間体が得られる。 Here, the production conditions of the intermediate are not particularly limited, but the melt viscosity at 150 ° C. of the epoxy resin (A) is 1.0 poise or less, and the content of the binuclear component is 40. In order to set in the range of ˜75 wt% , more preferably 45 to 65 wt% , it is preferable to adjust the molar ratio of phenols and unsaturated alicyclic compound during the reaction. It is preferable to use 4 mol or more of phenols per 1 mol. Especially, when it synthesize | combines within the range of phenols / unsaturated alicyclic compound = 2.5 / 1-15/1 (molar ratio), a preferable intermediate body for obtaining the target epoxy resin will be obtained.
また最終的に得られるエポキシ樹脂を、ＧＰＣでのポリスチレン換算数平均分子量が１００〜２２０の範囲内に検出される物質を０．１〜２．０重量％の範囲で含有するエポキシ樹脂（Ａ）に調整する方法として、（１）中間体を製造する際、重付加反応を行った後のフェノール類及び、未反応フェノール類１分子に不飽和脂環式化合物１分子が結合した置換フェノール類を主成分とした本発明のエポキシ樹脂（Ａ）に含有される低分子量物となり得る不純物を蒸留回収する方法、（２）中間体とエピハロヒドリンの反応によって得られたエポキシ樹脂から該低分子量物を蒸留回収する方法、或いは（３）得られた中間体或いはエポキシ樹脂を適当な溶剤を用いて再沈澱法により該低分子量物質を分離する方法等が挙げられるが、特にこれらの方法に限定されるものではない。中でも製造操作が簡便な点から（１）の方法が好ましい。 Moreover, the epoxy resin (A) which contains the substance detected in the range whose polystyrene conversion number average molecular weight in GPC is 100-220 weight in the range of 0.1-2.0 weight% in the epoxy resin finally obtained. (1) When producing an intermediate, phenols after polyaddition reaction and substituted phenols in which one molecule of unsaturated alicyclic compound is bonded to one molecule of unreacted phenols A method of distilling and recovering impurities that may be low molecular weight substances contained in the epoxy resin (A) of the present invention as a main component; (2) distilling the low molecular weight substances from an epoxy resin obtained by the reaction of an intermediate and an epihalohydrin. method for recovering, or (3) a method for separating the low molecular weight substances can be mentioned by reprecipitation using intermediate or epoxy resins suitable solvent obtained, in particular this It is not limited to the method. Among these, the method (1) is preferable from the viewpoint that the production operation is simple.
ここで上記中間体の製造法を詳述すれば、溶融或いは溶液にしたフェノール類に、重付加触媒を添加し、これに不飽和脂環式化合物を適下後、加熱攪拌し重付加反応を進行させ、その後に未反応フェノール類を蒸留回収し、重付加反応物を得る。ここで重付加触媒としては、塩酸、硫酸などの無機酸或いはパラトルエンスルホン酸等の有機酸或いはＡｌＣｌ3、ＢＦ3等のルイス酸等が挙げられる。この未反応フェノール類の蒸留回収する際、回収温度及び減圧度を適宜調整することにより、本発明のエポキシ樹脂（Ａ）を製造可能である。回収条件としては、温度を２００〜２８０℃、減圧度を０．５〜５Ｔｏｒｒに保つことにより、未反応フェノール類及び、フェノール類１分子に不飽和脂環式化合物１分子が結合した置換フェノール類を主成分とした本発明のエポキシ樹脂（Ａ）に含有される低分子量物の中間物質を蒸留回収できるが、反応器、攪拌機の能力等により、目的の低分子量物含有量が得られる様に調整すればよい。 Here, the method for producing the above intermediate will be described in detail. A polyaddition catalyst is added to the phenols that have been melted or made into a solution, and an unsaturated alicyclic compound is appropriately added thereto. Then, the unreacted phenols are recovered by distillation to obtain a polyaddition reaction product. Examples of the polyaddition catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as paratoluenesulfonic acid, and Lewis acids such as AlCl3 and BF3. When the unreacted phenols are recovered by distillation, the epoxy resin (A) of the present invention can be produced by appropriately adjusting the recovery temperature and the degree of vacuum. As recovery conditions, by maintaining the temperature at 200 to 280 ° C. and the degree of vacuum at 0.5 to 5 Torr, unreacted phenols and substituted phenols in which one molecule of unsaturated alicyclic compound is bonded to one molecule of phenol The low molecular weight intermediate substance contained in the epoxy resin (A) of the present invention containing as a main component can be recovered by distillation, but the target low molecular weight content can be obtained by the ability of the reactor, stirrer, etc. Adjust it.
次いで、この様にして得られた重付加反応物とエピハロヒドリンとを反応させることによって、目的とするエポキシ樹脂（Ａ）とすることができるが、この反応は公知の方法に従って良く、例えば次の反応が挙げられる。 Subsequently, the target epoxy resin (A) can be obtained by reacting the polyaddition reaction product thus obtained with epihalohydrin. This reaction may be carried out according to a known method, for example, the following reaction: Is mentioned.
先ず、中間体の水酸基に対して２〜１５当量、中でも溶融粘度の低減効果に優れる点から好ましくは３〜１０当量のエピハロヒドリンを添加して溶解し、その後、重付加反応物中の水酸基に対して０．８〜１．２当量の１０〜５０％ＮａＯＨ水溶液を５０〜８０℃の温度で３〜５時間要して適下する。適下後その温度で０．５〜２時間程度攪拌を続けて、静置後下層の食塩水を棄却する。次いで過剰のエピハロヒドリンを蒸留回収し祖樹脂を得る。これにトルエン、ＭＩＢＫ等の有機溶媒を加え、水洗−脱水−濾過−脱溶媒工程を経て、目的の樹脂を得ることができる。また不純物塩素量の低減等を目的に、反応の際ジオキサン、ＤＭＳＯ等の溶媒を併用しても良い。 First, 2 to 15 equivalents relative to the hydroxyl group of the intermediates, among them preferably from the viewpoint of excellent effect of reducing the melting viscosity and dissolved by adding 3 to 10 equivalents epihalohydrin, then the hydroxyl group of the polyaddition reaction product of On the other hand, 0.8 to 1.2 equivalents of 10 to 50% NaOH aqueous solution is suitably applied at a temperature of 50 to 80 ° C. for 3 to 5 hours. Stirring is continued for about 0.5 to 2 hours at that temperature after appropriate reduction, and the lower layer saline solution is discarded after standing. Then, excess epihalohydrin is recovered by distillation to obtain the resin. To this, an organic solvent such as toluene or MIBK is added, and a target resin can be obtained through a water washing-dehydration-filtration-desolvation step. For the purpose of reducing the amount of impurity chlorine, a solvent such as dioxane or DMSO may be used in the reaction.
ここで用いるエピハロヒドリンとしては、エピクロルヒドリンが最も一般的であるが、他にエピヨードヒドリン、エピブロムヒドリン、β−メチルエピクロルヒドリン等を用いてもよい。 As epihalohydrin used here, epichlorohydrin is the most common, but epiiodohydrin, epibromohydrin, β-methylepichlorohydrin, etc. may be used.
この様にして得られるエポキシ樹脂（Ａ）は、特にその構造が特定されるものではないが、その主たる成分として例えば下記一般式で示されるものが挙げられる。 The epoxy resin (A) thus obtained is not particularly specified in its structure, but examples of the main component include those represented by the following general formula.
この様なエポキシ樹脂（Ａ）は、既述の通り、ＧＰＣでのポリスチレン換算数平均分子量が１００〜２２０の範囲内に検出される物質（以下、「低分子量物質」と略記する）を０．１〜２．０重量％の範囲で含有するものである。 As described above, such an epoxy resin (A) represents a substance (hereinafter abbreviated as “low molecular weight substance”) having a polystyrene-reduced number average molecular weight in the range of 100 to 220 by GPC. It is contained in the range of 1 to 2.0% by weight.
ここで、ＧＰＣの測定法としては例えば、東ソー（株）製「ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）」（測定条件：流速＝１．０ml／分間，圧力＝９２Ｋｇ／ｃｍ２,カラム＝Ｇ４，３，２，２ＨＸＬ，検出器＝ＲＩ ３２×１０−６ＲＩＵＦＳ、溶離液＝テトラヒドロフラン）で行なう方法が挙げられる。 Here, as a measuring method of GPC, for example, “Gel Permeation Chromatography (GPC)” manufactured by Tosoh Corporation (measuring conditions: flow rate = 1.0 ml / min, pressure = 92 Kg / cm 2, column = G 4, 3 , 2, 2HXL, detector = RI 32 × 10 −6 RIUFS, eluent = tetrahydrofuran).
この様なエポキシ樹脂（Ａ）は、更に前記した低分子量物質を０．１〜２．０重量％の範囲で含有しており、更に、分子中の芳香核の核体数における２核体含有量が４０〜７５重量％、より好ましくは４５〜６５重量％とすることにより、更に組成物の流動性を向上させることができる。 Such an epoxy resin (A) further contains the above-mentioned low molecular weight substance in the range of 0.1 to 2.0% by weight, and further contains binuclear bodies in the number of aromatic nuclei in the molecule. When the amount is 40 to 75% by weight , more preferably 45 to 65% by weight , the fluidity of the composition can be further improved.
更に、１５０℃の溶融粘度が１．０ポイズ以下のものであることが無機充填剤の高充填化が可能となる点から好ましく、更に、エポキシ当量が好ましくは２３５〜２８０ｇ／ｅｑ、より好ましくは２３５〜２５５ｇ／ｅｑの範囲内にあるエポキシ樹脂が一層組成物の流動性が良好となり好ましい。 Further, it is preferable that the melt viscosity at 150 ° C. is 1.0 poise or less from the viewpoint that high filling of the inorganic filler is possible, and the epoxy equivalent is preferably 235 to 280 g / eq , more preferably An epoxy resin in the range of 235 to 255 g / eq is preferable because the fluidity of the composition is improved.
このような分子構造を有し、かつ上記条件を満足するエポキシ樹脂（Ａ）は、低分子量物質を適量含有しているため、非常に流動性が優れることから、封止の際の成形性が極めて良好となる他、無機充填材をより高充填化させることができ、より低吸水率とより低線膨張係数の耐ハンダクラック性が優れる硬化物を提供できる。一方ＥＣＮなどは、低分子量物質を上記範囲と同程度含有した場合は、硬化物中にボイドが発生したり、また耐熱性が大きく損なわれるが、本発明のエポキシ樹脂組成物の場合は、含有する低分子量物質は流動性の向上には効果を発揮するが、ボイドの発生や、耐熱性の低下は極めて小さくなる。ここで、低分子量物質の主たる成分としては、前記したとおり、フェノール類１分子と不飽和脂環式化合物１分子が結合した置換フェノール類のモノグリシジルエーテルが挙げられる。 Since the epoxy resin (A) having such a molecular structure and satisfying the above conditions contains an appropriate amount of a low molecular weight substance, it has excellent fluidity, and thus has a moldability at the time of sealing. In addition to being extremely good, the inorganic filler can be filled more highly, and a cured product having a low water absorption and a low coefficient of linear expansion and excellent solder crack resistance can be provided. On the other hand, when ECN and the like contain low molecular weight substances in the same range as above, voids are generated in the cured product, and heat resistance is greatly impaired, but in the case of the epoxy resin composition of the present invention, The low molecular weight substance is effective in improving the fluidity, but the generation of voids and the decrease in heat resistance are extremely small. Here, as described above , as a main component of the low molecular weight substance, monoglycidyl ether of a substituted phenol in which one molecule of phenol and one molecule of unsaturated alicyclic compound are bonded is mentioned.
また、上記記載の２核体含有量、溶融粘度、エポキシ当量の条件をも同時に満足するエポキシ樹脂は、低分子量でより優れた流動性を有しながら、官能基であるエポキシ基濃度が高いため、優れた硬化性と耐熱性を兼備できる。 In addition, the epoxy resin that satisfies the above-mentioned conditions for the binuclear content, the melt viscosity, and the epoxy equivalent simultaneously has a low molecular weight and excellent fluidity, and has a high epoxy group concentration as a functional group. Can have both excellent curability and heat resistance.
一方、上記条件を満足しない同様分子構造を有するエポキシ樹脂、つまりＧＰＣでのポリスチレン換算数平均分子量が１００〜２２０の範囲内に検出される、フェノール類１分子と不飽和脂環式化合物１分子が結合した置換フェノール類のモノグリシジルエーテルを主たる成分とする低分子量物質の含有量が０．１〜２．０重量％の範囲外であるものは、本発明のエポキシ樹脂と比較し、流動性或いは耐熱性、硬化性が劣る。つまり該低分子量物質の含有量は０．１重量％未満である場合は、本発明のエポキシ樹脂と比較し、流動性が低下する。一方、含有量が２．０重量％より多い場合は、本発明のエポキシ樹脂と比較し、流動性は向上するものの、耐熱性及び硬化性が低下する。
On the other hand, an epoxy resin having the same molecular structure that does not satisfy the above conditions, that is , one molecule of phenols and one molecule of unsaturated alicyclic compound , whose polystyrene-reduced number average molecular weight by GPC is detected in the range of 100 to 220, In the case where the content of the low molecular weight substance whose main component is monoglycidyl ether of bound substituted phenols is out of the range of 0.1 to 2.0% by weight, compared with the epoxy resin of the present invention, the flowability or Heat resistance and curability are inferior. That is, when the content of the low molecular weight substance is less than 0.1% by weight, the fluidity is lowered as compared with the epoxy resin of the present invention. On the other hand, when the content is more than 2.0% by weight, although the fluidity is improved as compared with the epoxy resin of the present invention, the heat resistance and curability are lowered.
また、本発明で用いる硬化剤（Ｂ）としては、通常エポキシ樹脂の硬化剤として常用されている化合物はすべて使用することができ、特に限定されるものではないが、例えばフェノールノボラック樹脂、オルソクレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ビスフェノールＦノボラック樹脂、フェノール類−ジシクロペンタジエン重付加型樹脂、ジヒドロキシナフタレンノボラック樹脂、キシリデン基を結接基とした多価フェノール類、フェノール−アラルキル樹脂、ナフトール類樹脂ジエチレントリアミン、トリエチレンテトラミンなどの脂肪族アミン類、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどの芳香族アミン類、ポリアミド樹脂およびこれらの変性物、無水マレイン酸、無水フタル酸、無水ヘキサヒドロフタル酸、無水ピロメリット酸などの酸無水物系硬化剤、ジシアンジアミド、イミダゾール、ＢＦ3 −アミン錯体、グアニジン誘導体等の潜在性硬化剤等が挙げられる。中でも半導体封止材用としては、上記フェノールノボラック樹脂等の芳香族炭化水素−ホルムアルデヒド樹脂が硬化性、成形性、耐熱性に優れること、またフェノール−アラルキル樹脂が硬化性、成形性、低吸水率に優れる点から好ましい。 In addition, as the curing agent (B) used in the present invention, any compound that is usually used as a curing agent for epoxy resins can be used, and is not particularly limited. For example, phenol novolac resin, orthocresol Novolak resin, bisphenol A novolak resin, bisphenol F novolak resin, phenols-dicyclopentadiene polyaddition type resin, dihydroxynaphthalene novolak resin, polyhydric phenols having a xylidene group as a linking group, phenol-aralkyl resin, naphthols resin Aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, polyamide resins and modified products thereof, maleic anhydride Phthalic anhydride, hexahydrophthalic anhydride, acid anhydride curing agents such as pyromellitic anhydride, dicyandiamide, imidazoles, BF3 - amine complex latent curing agent such as guanidine derivatives. Above all, for semiconductor encapsulants, aromatic hydrocarbon-formaldehyde resins such as phenol novolac resins are excellent in curability, moldability, and heat resistance, and phenol-aralkyl resins are curable, moldability, low water absorption. From the point which is excellent in it.
これらの硬化剤の使用量は、エポキシ樹脂を硬化せしめる量であれば何れでもよく、特に限定されないが、好ましくは用いるエポキシ樹脂の一分子中に含まれるエポキシ基の数と、硬化剤中の活性水素の数が当量付近となる量である。 The amount of these curing agents used is not particularly limited as long as it cures the epoxy resin, but preferably the number of epoxy groups contained in one molecule of the epoxy resin used and the activity in the curing agent. The amount of hydrogen is about equivalent.
上掲された如き各化合物を硬化剤として用いる際は、硬化促進剤を適宜使用することができる。 When each compound as listed above is used as a curing agent, a curing accelerator can be appropriately used.
硬化促進剤としては公知慣用のものがいずれも使用できるが、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩、等が挙げられ、これらは単独のみならず２種以上の併用も可能である。 As the curing accelerator, any known and conventional ones can be used. Examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. Two or more types can be used in combination.
また本発明のエポキシ樹脂組成物は、必須成分である上述したエポキシ樹脂（Ａ）に加え、さらにその他のエポキシ樹脂（Ｄ）を併用しても構わない。この際に用いられるエポキシ樹脂（Ｄ）としては、公知慣用のものが何れも使用でき、例えばビスフェノールＡジグリシジルエーテル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビフェニル型２官能エポキシ樹脂等が挙げられるが、これらに限定されるものではない。 The epoxy resin composition of the present invention may be used in combination with another epoxy resin (D) in addition to the above-described epoxy resin (A), which is an essential component. As the epoxy resin (D) used in this case, any known ones can be used. For example, bisphenol A diglycidyl ether type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type Examples thereof include, but are not limited to, epoxy resins, bisphenol F novolac type epoxy resins, brominated phenol novolac type epoxy resins, naphthol novolac type epoxy resins, biphenyl type bifunctional epoxy resins, and the like.
また必要に応じて、着色剤、難燃剤、離型剤、またはカップリング剤などの公知慣用の各種の添加剤成分も適宜配合せしめることができる。また、本発明のエポキシ樹脂組成物から成形材料を調製するには、エポキシ樹脂、硬化剤、硬化促進剤、その他の添加剤をミキサー等によって十分に均一に混合した後、更に熱ロールまたはニーダ−等で溶融混練し、射出あるいは冷却後粉砕するなどして得ることができる。 Further, if necessary, various known and commonly used additive components such as a colorant, a flame retardant, a release agent, or a coupling agent can be appropriately blended. Further, in order to prepare a molding material from the epoxy resin composition of the present invention, an epoxy resin, a curing agent, a curing accelerator and other additives are sufficiently uniformly mixed by a mixer or the like, and then further heated roll or kneader. For example, it can be obtained by melt-kneading, etc., or by pulverizing after injection or cooling.
この様にして得られる本発明のエポキシ樹脂組成物は、特にその用途が限定されるものではなく、例えば、半導体封止材料や、エポキシ樹脂の溶剤溶解性に優れるために電気積層板用途でのワニス等が挙げられる。また、本発明のエポキシ樹脂を臭素化多価フェノール類で変性を施したオリゴマー型エポキシ樹脂を積層板用途に用いることもできる。さらにはこれに多官能型エポキシ樹脂を配合或いは変性し耐熱性を付与させたシステムも使用できる。 The epoxy resin composition of the present invention obtained in this way is not particularly limited in its use. For example, it is excellent in semiconductor sealing materials and epoxy resin solvent solubility, so that it can be used in electrical laminates. A varnish etc. are mentioned. Moreover, the oligomer type epoxy resin which modified | denatured the epoxy resin of this invention with brominated polyhydric phenols can also be used for a laminated board use. Furthermore, a system in which a polyfunctional epoxy resin is blended or modified to impart heat resistance can also be used.
また高分子タイプエポキシ樹脂を得るために、２段法反応の原料樹脂として当該樹脂を使用することも可能である。 In order to obtain a polymer type epoxy resin, it is also possible to use the resin as a raw material resin for a two-step reaction.
これらの用途の中でも、特に耐ハンダクラック性に著しく優れる等の利点から半導体封止材料用途が極めて有用である。 Among these uses, a semiconductor encapsulating material application is extremely useful due to advantages such as remarkably excellent solder crack resistance.
以下に本発明の半導体封止材料について詳述すると、本発明の半導体封止材料は、上記したエポキシ樹脂（Ａ）並びに硬化剤（Ｂ）の他、更に無機充填剤（Ｃ）を必須の成分として含有するものである。 The semiconductor encapsulating material of the present invention will be described in detail below. The semiconductor encapsulating material of the present invention is an essential component of the inorganic filler (C) in addition to the epoxy resin (A) and the curing agent (B) described above. It is contained as
この様な本発明の半導体封止材料は、半導体を封止する際の成形時の流動性、硬化性、成形性や封止硬化後の耐熱性、さらにはプリント基板へ実装する際の耐ハンダクラック性等の全ての要求特性を満足するものである。 Such a semiconductor encapsulating material of the present invention has fluidity, curability, moldability, heat resistance after encapsulating and curing at the time of molding a semiconductor, and solder resistance when mounted on a printed circuit board. It satisfies all required characteristics such as cracking properties.
本発明で用いる無機充填剤（Ｃ）は、硬化物の機械強度、硬度を高めることのみならず、低吸水率、低線膨張係数を達成し、耐ハンダクラック性を高めるための必須成分である。 The inorganic filler (C) used in the present invention is an essential component not only for increasing the mechanical strength and hardness of the cured product, but also for achieving a low water absorption rate and a low linear expansion coefficient, and improving solder crack resistance. .
その配合量は、特に限定されるものではないが、組成物中７５〜９５重量％の範囲で用いることが、特にそれらの特性が際立つものとなり、特に半導体封止剤用途において耐ハンダクラック性が非常に優れる点から好ましい。 The blending amount is not particularly limited, but using in the range of 75 to 95% by weight in the composition makes the characteristics particularly prominent, and particularly has a solder crack resistance in semiconductor encapsulant applications. It is preferable from the point of being very excellent.
また、ここで特筆すべき点は、本発明において７５重量％以上無機充填剤を使用しても流動性、成形性を全く損なうことがないことである。。 In addition, the point to be noted here is that the flowability and moldability are not impaired at all even if an inorganic filler of 75% by weight or more is used in the present invention. .
この様な無機充填剤（Ｃ）としては、特に限定されないが溶融シリカ、結晶シリカ、アルミナ、タルク、クレー、ガラス繊維等が挙げられる。これらの中でも、特に半導体封止材料用途においては溶融シリカ、結晶シリカが一般的に用いられており、特に流動性に優れる点から溶融シリカが好ましい。また球状シリカ、粉砕シリカ等も使用できる。 Such inorganic filler (C) is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, clay, and glass fiber. Among these, fused silica and crystalline silica are generally used particularly for semiconductor sealing material applications, and fused silica is particularly preferred from the viewpoint of excellent fluidity. Spherical silica, pulverized silica and the like can also be used.
また上述した（Ａ）〜（Ｃ）の各成分の他にテトラブロモビスフェノールＡ型エポキシ樹脂、ブロム化フェノールノボラック型エポキシ樹脂等の臭素化エポキシ樹脂、三酸化アンチモン、ヘキサブロモベンゼン等の難燃剤、カ−ボンブラック、ベンガラ等の着色剤、天然ワックス、合成ワックス等の離型剤及びシリコンオイル、合成ゴム、シリコーンゴム等の低応力添加剤等の種々の添加剤を適宜配合してもよい。 In addition to the components (A) to (C) described above, brominated epoxy resins such as tetrabromobisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, flame retardants such as antimony trioxide and hexabromobenzene, Various additives such as a colorant such as carbon black and bengara, a release agent such as natural wax and synthetic wax, and a low stress additive such as silicone oil, synthetic rubber and silicone rubber may be appropriately blended.
また本発明の半導体封止材料は、必須成分である上述したエポキシ樹脂（Ａ）に加え、さらにその他のエポキシ樹脂（Ｄ）を併用しても構わない。この際に用いられるエポキシ樹脂（Ｄ）としては、公知慣用のものが何れも使用でき、例えばビスフェノールＡジグリシジルエーテル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビフェニル型２官能エポキシ樹脂等が挙げられるが、これらに限定されるものではない。これらの中でも、特に耐熱性に優れる点からオルソクレゾールノボラック型エポキシ樹脂が、また流動性に優れる点からビフェニル型２官能エポキシ樹脂が好ましい。 In addition to the above-described epoxy resin (A), which is an essential component, the semiconductor sealing material of the present invention may further use other epoxy resin (D). As the epoxy resin (D) used in this case, any known ones can be used. For example, bisphenol A diglycidyl ether type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type Examples thereof include, but are not limited to, epoxy resins, bisphenol F novolac type epoxy resins, brominated phenol novolac type epoxy resins, naphthol novolac type epoxy resins, biphenyl type bifunctional epoxy resins, and the like. Among these, an ortho-cresol novolak type epoxy resin is particularly preferable from the viewpoint of excellent heat resistance, and a biphenyl type bifunctional epoxy resin is preferable from the viewpoint of excellent fluidity.
また必要に応じて、着色剤、難燃剤、離型剤、またはカップリング剤などの公知慣用の各種の添加剤成分も適宜配合せしめることができる。また、本発明のエポキシ樹脂組成物から半導体封止材料を調製するには、上記各成分をミキサー等によって十分に均一に混合した後、更に熱ロールまたはニーダ−等で溶融混練し、冷却後粉砕し、タブレット化するなどして得ることができる。 Further, if necessary, various known and commonly used additive components such as a colorant, a flame retardant, a release agent, or a coupling agent can be appropriately blended. In addition, in order to prepare a semiconductor sealing material from the epoxy resin composition of the present invention, the above components are sufficiently uniformly mixed by a mixer or the like, then melt-kneaded with a hot roll or a kneader, and pulverized after cooling. And can be obtained by tableting.
次に本発明を製造例、実施例およびその比較例により具体的に説明する。尚、例中において部は特に断りのない限りすべて重量部である。 Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. In the examples, all parts are parts by weight unless otherwise specified.
尚、溶融粘度は５０ＨｚのもとにおいてＲｅｓｅａｃｈ ｅｑｕｉｐｍｅｎｔＬＴＤ．製「ＩＣＩ ＣＯＮＥ ＆ ＰＬＡＴＥ ＶＩＳＣＯＭＥＴＥＲ」で測定した。 The melt viscosity is 50% at Research Equipment LTD. It was measured by “ICI CONE & PLATE VISCOMTER” manufactured by the manufacturer.
軟化点は明峰社製作所(株)製「軟化点測定器」（加熱器：ＨＵ−ＭＫ，検出器ＡＳＰ−Ｍ２）測定した。また、低分子量物含有量並びに２核体成分含有量は、東ソー（株）製「ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）」（測定条件：流速＝１．０ml／分間，圧力＝９２Ｋｇ／ｃｍ２,カラム＝Ｇ４，３，２，２ＨＸＬ，検出器＝ＲＩ ３２×１０−６ＲＩＵＦＳ、溶離液＝テトラヒドロフラン）で測定した。 The softening point was measured by “Softening point measuring device” (heater: HU-MK, detector ASP-M2) manufactured by Meihosha Mfg. Co., Ltd. Further, the content of low molecular weight substances and the content of binuclear components are “Gel permeation chromatography (GPC)” manufactured by Tosoh Corporation (measurement conditions: flow rate = 1.0 ml / min, pressure = 92 Kg / cm 2, Column = G4, 3, 2, 2HXL, detector = RI 32 × 10 −6 RIUFS, eluent = tetrahydrofuran).
製造例１
攪拌機、温度計、４つ口フラスコにフェノール１２２２ｇ（１３モル）を、ＢＦ3・フェノール錯体１７ｇを添加し充分混合した。その後ジシクロペンタジエン１７７ｇ（１．３モル）を系内温度を１１０〜１２０℃に保ちながら４時間要して添加した。その後系内温度を１２０℃に保ち、３時間加熱攪拌し、得られた反応生成物溶液にマグネシウム化合物「KW-1000」（商品名；協和化学工業(株)社製）５２ｇを添加し、１時間攪拌して触媒を失活させた後、反応溶液を濾過した。得られた透明溶液を未反応フェノールを蒸留回収しながら２３０℃に昇温し、１Ｔｏｒｒの減圧下で４時間ホールドした。その結果褐色の固形樹脂３７９ｇを得た。この樹脂の軟化点は９２℃、水酸基当量は１７１g/eqであった。
Production Example 1
A stirrer, thermometer, and 4-necked flask were mixed with 1222 g (13 mol) of phenol and 17 g of BF3 / phenol complex and mixed well. Thereafter, 177 g (1.3 mol) of dicyclopentadiene was added over 4 hours while maintaining the system temperature at 110 to 120 ° C. Thereafter, the system temperature was kept at 120 ° C., and the mixture was heated and stirred for 3 hours. To the resulting reaction product solution, 52 g of a magnesium compound “KW-1000” (trade name; manufactured by Kyowa Chemical Industry Co., Ltd.) was added. After stirring for a period of time to deactivate the catalyst, the reaction solution was filtered. The obtained transparent solution was heated to 230 ° C. while distilling and recovering unreacted phenol, and held under a reduced pressure of 1 Torr for 4 hours. As a result, 379 g of a brown solid resin was obtained. The softening point of this resin was 92 ° C., and the hydroxyl equivalent was 171 g / eq.
この樹脂３４２ｇにエピクロルヒドリン７４０ｇ（８モル）を加え溶解する。それに８０℃で２０％ＮａＯＨ４４０ｇ（２．２モル）を８時間かけて攪拌しながら滴下し、さらに３０分間攪拌を続けてその後静置した。下層の食塩水を棄却し、エピクロルヒドリンを１５０℃で蒸留回収した後、粗樹脂にＭＩＢＫ７５０ｇを加え、さらに水２５０ｇを加え８０℃にて水洗した。そして下層の水洗水を棄却した後、脱水、濾過を経てＭＩＢＫを１５０℃で脱溶剤して目的のエポキシ樹脂（Ｉ）４１９ｇを得た。この樹脂は褐色固体で、低分子量物含有量０．４１重量％、軟化点６０℃、１５０℃での溶融粘度０．６ポイズ、２核体成分含有量５３重量％、エポキシ当量は２６１g/eqであった。 740 g (8 mol) of epichlorohydrin is added to 342 g of this resin and dissolved. To this, 440 g (2.2 mol) of 20% NaOH was added dropwise at 8O 0 C over 8 hours while stirring, and the mixture was further stirred for 30 minutes and then allowed to stand. The lower layer saline was discarded and epichlorohydrin was recovered by distillation at 150 ° C., and then 750 g of MIBK was added to the crude resin, and 250 g of water was further added and washed at 80 ° C. And after discarding the lower rinsing water, MIBK was removed at 150 ° C. through dehydration and filtration to obtain 419 g of the desired epoxy resin (I). This resin is a brown solid, low molecular weight content 0.41% by weight, softening point 60 ° C., melt viscosity 0.6 poise at 150 ° C., dinuclear component content 53% by weight, epoxy equivalent 261 g / eq Met.
製造例２
製造例１で得られた中間体を使用し、エピクロルヒドリンを１１１０ｇ（１２モル）に変更した以外は実施例１と同様にして、エポキシ樹脂（II）４０６ｇを得た。この樹脂は褐色固体で、低分子量物含有量０．３２重量％、軟化点５９℃、１５０℃での溶融粘度０．３ポイズ、２核体成分含有量５８重量％、エポキシ当量は２３９g/eqであった。
Production Example 2
406 g of epoxy resin (II) was obtained in the same manner as in Example 1 except that the intermediate obtained in Production Example 1 was used and epichlorohydrin was changed to 1110 g (12 mol). This resin is a brown solid with a low molecular weight content of 0.32% by weight, a softening point of 59 ° C., a melt viscosity of 0.3 poise at 150 ° C., a dinuclear component content of 58% by weight, and an epoxy equivalent of 239 g / eq. Met.
製造例３
中間体を製造する際の未反応フェノールの回収条件を、２５０℃、１Ｔｏｒｒに変更した以外は、製造例１と同様にして中間体を得た。これを原料に用い、実施例１と同様にして目的のエポキシ樹脂（III）４０４ｇを得た。この樹脂は褐色固体で、低分子量物含有量０．２１重量％、軟化点５４℃、１５０℃での溶融粘度０．４ポイズ、２核体成分含有量５４重量％、エポキシ当量は２４９g/eqであった。
Production Example 3
An intermediate was obtained in the same manner as in Production Example 1, except that the recovery condition of unreacted phenol when producing the intermediate was changed to 250 ° C. and 1 Torr. Using this as a raw material, 404 g of the target epoxy resin (III) was obtained in the same manner as in Example 1. This resin is a brown solid with a low molecular weight content of 0.21 wt%, a softening point of 54 ° C., a melt viscosity of 0.4 poise at 150 ° C., a dinuclear component content of 54 wt%, and an epoxy equivalent of 249 g / eq. Met.
製造例４
中間体を製造する際の未反応フェノールの回収条件を、２１０℃、１Ｔｏｒｒに変更した以外は、製造例１と同様にして中間体を得た。これを原料に用い、実施例１と同様にして目的のエポキシ樹脂（IV）４０９ｇを得た。
この樹脂は褐色固体で、低分子量物含有量１．２１重量％、軟化点５９℃、１５０℃での溶融粘度０．５ポイズ、２核体成分含有量５６重量％、エポキシ当量は２５９g/eqであった。
Production Example 4
An intermediate was obtained in the same manner as in Production Example 1 except that the conditions for recovering unreacted phenol during the production of the intermediate were changed to 210 ° C. and 1 Torr. Using this as a raw material, 409 g of the desired epoxy resin (IV) was obtained in the same manner as in Example 1.
This resin is a brown solid with a low molecular weight content of 1.21% by weight, a softening point of 59 ° C., a melt viscosity of 0.5 poise at 150 ° C., a dinuclear component content of 56% by weight, and an epoxy equivalent of 259 g / eq. Met.
製造比較例１
中間体を製造する際の未反応フェノールの回収条件を、２７０℃、１Ｔｏｒｒに変更し、窒素バブリングを施した以外は、製造例１と同様にして中間体を得た。これを原料に用い、実施例１と同様にして目的のエポキシ樹脂（Ｖ）４００ｇを得た。この樹脂は褐色固体で、低分子量物含有量０．０２重量％、軟化点６３℃、１５０℃での溶融粘度０．８ポイズ、２核体成分含有量５４重量％、エポキシ当量は２６３g/eqであった。
Production Comparative Example 1
An intermediate was obtained in the same manner as in Production Example 1, except that the unreacted phenol recovery conditions for producing the intermediate were changed to 270 ° C. and 1 Torr, and nitrogen bubbling was performed. Using this as a raw material, 400 g of the target epoxy resin (V) was obtained in the same manner as in Example 1. This resin is a brown solid with a low molecular weight content of 0.02% by weight, a softening point of 63 ° C., a melt viscosity of 0.8 poise at 150 ° C., a dinuclear component content of 54% by weight, and an epoxy equivalent of 263 g / eq. Met.
製造比較例２
中間体を製造する際の未反応フェノールの回収条件を、１７０℃、１Ｔｏｒｒに変更た以外は、製造例１と同様にして中間体を得た。これを原料に用い、実施例１と同様にして目的のエポキシ樹脂（VI）３９９ｇを得た。この樹脂は褐色固体で、低分子量物含有量２．３９重量％、軟化点５９℃、１５０℃での溶融粘度０．４ポイズ、２核体成分含有量５４重量％、エポキシ当量は２６２g/eqであった。
Production Comparative Example 2
An intermediate was obtained in the same manner as in Production Example 1 except that the conditions for recovering unreacted phenol during production of the intermediate were changed to 170 ° C. and 1 Torr. Using this as a raw material, 399 g of the desired epoxy resin (VI) was obtained in the same manner as in Example 1. This resin is a brown solid with a low molecular weight content of 2.39% by weight, a softening point of 59 ° C., a melt viscosity of 0.4 poise at 150 ° C., a dinuclear component content of 54% by weight, and an epoxy equivalent of 262 g / eq. Met.
実施例１〜８及び比較例１〜４
第１表で表される配合に従って調製した混合物を熱ロールにて１００℃・８分間混練りし、その後粉砕したものを１２００〜１４００Ｋｇ／ｃｍ２の圧力にてタブレットを作製し、それを用いてトランスファー成形機にてプランジャー圧力８０ｋｇ／ｃｍ2、金型温度１７５℃、成形時間１００秒の条件下にて封止し、厚さ２mmのフラットパッケージを評価用試験片として作成した。その後１７５℃で８時間の後硬化を施した。その際の流動性の 標として、試験用金型を用い、１７５℃／７０ｋｇ／ｃｍ2、 １２０秒の条件でスパイラルフローを測定した。
Examples 1-8 and Comparative Examples 1-4
A mixture prepared according to the formulation shown in Table 1 was kneaded with a hot roll at 100 ° C. for 8 minutes, and then pulverized to produce a tablet at a pressure of 1200 to 1400 Kg / cm 2 , and using it Sealing was performed with a transfer molding machine under the conditions of a plunger pressure of 80 kg / cm 2, a mold temperature of 175 ° C., and a molding time of 100 seconds, and a flat package having a thickness of 2 mm was prepared as a test specimen for evaluation. Thereafter, post-curing was performed at 175 ° C. for 8 hours. A spiral mold was measured under the conditions of 175 ° C./70 kg / cm 2 and 120 seconds using a test mold as a standard for fluidity at that time.
この評価用試験片を用い、８５℃・８５％ＲＨ条件下での吸水率、ＤＭＡによるガラス転移温度、及び２０個の試験片を８５℃・８５％ＲＨの雰囲気下中１６８時間放置し、吸湿処理を行った後、これを２６０℃のハンダ浴に１０秒浸せきた際の、クラック発生率を第１表に示す。Ｎ−６６５はオルソクレゾールノボラック型エポキシ樹脂（大日本インキ化学工業（株）製 商品名：ＥＰＩＣＬＯＮＮ−６６５、軟化点６８℃、エポキシ当量２０８g/eq、１５０℃の溶融粘度３．０ポイズ）、１５３はテトラブロモビスフェノールＡ型エポキシ樹脂（大日本インキ化学工業（株）製、商品名：ＥＰＩＣＬＯＮ １５３、軟化点７０℃、エポキシ当量４０１g/eq）、ＴＤ−２１３１はフェノールノボラック樹脂（大日本インキ化学工業（株）製 商品名：フェノライトＴＤ−２１３１、軟化点８０℃、水酸基当量１０４g/eq）を示す。 Using this test specimen for evaluation, the water absorption rate under 85 ° C./85% RH conditions, the glass transition temperature by DMA, and 20 test specimens were left in an atmosphere of 85 ° C./85% RH for 168 hours to absorb moisture. Table 1 shows the crack generation rate when this was immersed in a 260 ° C. solder bath for 10 seconds after the treatment. N-665 is an ortho-cresol novolak type epoxy resin (trade name: EPICLONN-665, manufactured by Dainippon Ink and Chemicals, Inc., softening point 68 ° C., epoxy equivalent 208 g / eq, melt viscosity 3.0 poise at 150 ° C.), 153 Is a tetrabromobisphenol A type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: EPICLON 153, softening point 70 ° C., epoxy equivalent 401 g / eq), TD-2131 is a phenol novolac resin (Dainippon Ink Chemical Co., Ltd.) Product name: Phenolite TD-2131, softening point 80 ° C., hydroxyl group equivalent 104 g / eq).
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