200911871 九、發明說明： 【發明所屬之技術領域】 本發明是有關於-種阻燃性及耐濕性優異的半 置、以及用於得到該半導體裝置的半導體密封用環裝 組成物。 a樹月旨 【先前技術】 近年來，隨著半導航件的高性能似及應 壤境的多樣化，在半導體封裝中對小型化、輕量化、^域· 化=狀的要求和對高溫或高濕條件下㈣久_要求型 盈提，。另外，由於最近對環境問題的意識有所提高，二 為性能之-，要求軟釺蟬的無织匕及封裝的無鹵素. 燃化。在日本專利第3349963號公報中記載著：環^ 和硬化劑均具有芳燒基祕(Phenol aralkyl)結構的環急: ，组成物的硬化物無鹵素、無私表現⑽紐，而 使用一裱戊二烯.苯酚聚合物的縮水甘油化物的環氧樹月1 或硬化劑的環氧樹脂組成物的硬化物的阻燃性非常差。曰 ^專利特開平2GG4·迎94號公報巾記㈣湘二環戊: 缔.苯驗聚合物的縣難和緣.聯苯練基魏樹脂Γ 用n芳燒基細旨作為硬化#丨的組合，而實施例 兄载著.雖然上述組合中無鹵素.無銻，但無機埴 ^ I V-0 a 2004；3^944 2载著··當相對於絲聯苯狄基環氧樹腊使用 =篁或等量以上的二環戍二稀.苯齡聚合物的環氧樹脂 、，硬化物的阻燃性下降。另外，在曰本專利第3349963 200911871 ::::: 量少的製品赫I户拉"，、法解決越疋咼價製品即上市絕對 2002-3別號公報P2的困境4日本專利特開平 齡聚合物的環氧‘在二環戍二稀·苯 化劑的組合纽細旨作為硬 實施例中還使的阻燃性優異，在其 【發明内容】氧樹s和二氧化録作為阻燃劑。 合物目供—種不使用_素化合物和娣化 成成物及使用該半導體密封用環氧樹脂- 濕性於上ϊ實況，謀求可得到具阻燃性及耐 組成物的半導體穿用環氧樹贿成物以及使用該 明。f㈣裝以進仃了深人研究，結果完成了本發 即，本發明之要旨構成如下。 環氧樹脂和無機填充劑，不的_樹脂、式⑺表示的 200911871[Technical Field] The present invention relates to a semiconductor device which is excellent in flame retardancy and moisture resistance, and a semiconductor sealing ring assembly for obtaining the semiconductor device. a tree month [previous technique] In recent years, with the high performance of semi-navigation parts and the diversification of the soil, the requirements for miniaturization, weight reduction, and field-likeness in the semiconductor package and the high temperature Or under high humidity conditions (four) long _ required type of profit,. In addition, due to the recent increase in awareness of environmental issues, and secondly, the performance of the soft-woven non-woven fabric and packaged halogen-free. Japanese Patent No. 3347936 describes that both the ring and the hardener have a Phenol aralkyl structure: the cured product of the composition is halogen-free and selfless (10), and a pentane is used. The flame retardancy of the cured product of the epoxy resin of the diethylene phenol polymer glycidyl ester 1 or the hardener is very poor.曰^ Patent special open flat 2GG4·Welcome 94th Announcement towel (4) Xiang Erhuan pentane: The benzene test polymer of the county difficulty and edge. Biphenyl base Wei resin Γ Use n aryl burnt base as the hardening #丨Combination, while the example brother is carried. Although the above combination is halogen-free, no sputum, but inorganic 埴 ^ I V-0 a 2004; 3 ^ 944 2 carrying · · when compared to lindenyl epoxy wax The use of an epoxy resin having a ruthenium or an equivalent amount of a bicyclic ruthenium diene or a benzoate polymer has a reduced flame retardancy. In addition, in this patent No. 3349963 200911871 ::::: A small amount of products, I I pull, ", the law to solve the more expensive products that are listed in the absolute 2002-3 slogan P2 dilemma 4 Japanese patent special Kaiping The epoxy resin of the aged polymer is excellent in flame retardancy as a combination of the bicyclononanthene and the benzoic agent, and is excellent in flame retardancy in the case of the invention. Burning agent. For the purpose of obtaining a semiconductor wearing epoxy having flame retardancy and composition resistance, the compound is not used, and the epoxy resin for semiconductor encapsulation is used without using the epoxy resin for sealing the semiconductor. Bribery and use of the Ming. f (4) was loaded with a deep research, and as a result, the present invention was completed, and the gist of the present invention is as follows. Epoxy resin and inorganic filler, not _resin, represented by formula (7) 200911871
(式中’ η為平均值’滿足ι<η$3的關係。） (式中，複數存在的R各自獨立表示氫原子或碳原 1〜4的絲^為平均值，滿足1如4的關係。）數4 〇cs2c^»2 該環氧樹脂組成物的特徵在於：上 點⑻（。〇滿足下述式(1)的關係、： 乳樹月曰之軟化 80SA+B 各 150 …（I)。 2.如上述1所記載之半導體 其特徵在於：上述式⑴矣_ AA、衣氣樹月曰組成物， 4〇t〜m：。 （)表不的祕_的軟化點(A)為 3. 如上述1或2所記载之 徵在於：上述式门彳本-^ »卜 用組成物，其特 6〇t：。 ）表不的裱氧樹脂的軟化點(B)為4CTC〜 4. 如上述1〜3由也 _ 榷m組成物，其特徵^一項所記載之半導體密封用環氧 重量百分比在於·上述無機填充劑的含量為75 ^ (Wt/°)〜85重量百分比(wt。/。）。 中任;置’該半導縣置是使縣上述1〜4 導體元件。 丁導體密封用環氧樹脂組成物來密封半 半導己載之半導體裝置，其特徵在於：上述 件搭栽在鋼系導線架0—)上。 200911871 合物樹脂組成物不使_化 下具有高可;，在錢 為讓本發明之上述和其他目的、特徵和優f 明如下。芈㈣貫_，魏合__，作.詳細說 【實施方式】 以下’詳細說明本發明。本發明之半 樹脂組成物的特徵在於：含有在封用環氧 式⑴衣不的酚醛樹脂之軟化點 明之半導體密封用環氧樹腊組成物能角提供阻燃性及低 有足2== 之碳化層之柔軟性，形成具 氣體向外部擴散的水準的交聯密 度而達成。另外’本發明之半導體密封用 高的上述式⑴表示的祕樹脂的縮水甘=】 了棱兩硬化物之阻燃性.，因此 =明之半導體密封用環氧樹脂的適當：二：上 述式（1)衣不的酚醛樹脂的縮水甘湳化物。 本發明之半㈣密_縣獅組絲含有上述式⑴ 不的祕齡。上述式⑴的祕細 酸性催化劑的存在下，使笨驗態代甲基聯 200911871 氧基曱基聯苯類等反應而得到。在式⑴中，R可 乳原子、甲基、乙基、丙基、丁基等碳原子數為】〜4的卜 基等’R各自可以相同也可以不同。n以平均值表干1 求其滿足Kng的關係。需要說明的是，式⑴中的η，(In the formula, 'η is the average value' satisfies the relationship of ι < η$3.) (In the formula, the R existing in the plural number independently represents the hydrogen atom or the filament of the carbonogen 1 to 4 is an average value, and satisfies the relationship of 1 such as 4 The number 4 〇cs2c^»2 The epoxy resin composition is characterized by: upper point (8) (. 〇 satisfies the relationship of the following formula (1),: softening of the milk tree 曰 80SA+B each 150 ... (I 2. The semiconductor according to the above 1, characterized in that the formula (1) 矣 _ AA, the sylvestre composition, 4 〇 t 〜 m: () the softening point of the secret _ (A) 3. The above-mentioned 1 or 2 is characterized by the above-mentioned formula: the composition of the composition of the above-mentioned formula, the special softening point (B) of the epoxy resin (4) is 4CTC. 〜4. The above-mentioned 1 to 3 is composed of a composition of _ 榷m, and the weight percentage of the epoxy for semiconductor sealing described in the above item is that the content of the inorganic filler is 75 ^ (Wt / °) to 85 by weight. Percentage (wt./.). In the middle of the position; the semi-conducting county is to make the county 1~4 conductor elements. A semiconductor device for sealing a semi-conductive self-contained epoxy resin composition is characterized in that the above-mentioned member is mounted on a steel lead frame 0-). The above-mentioned and other objects, features and advantages of the present invention are as follows.芈(四)贯_,魏合__,作作. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [Embodiment] Hereinafter, the present invention will be described in detail. The semi-resin composition of the present invention is characterized in that the epoxy resin composition for semiconductor sealing containing the softening point of the phenolic resin which is sealed with the epoxy type (1) is provided to provide flame retardancy and low enough 2== The flexibility of the carbonized layer is achieved by forming a crosslink density at a level at which the gas diffuses to the outside. Further, the shrinkage of the secret resin represented by the above formula (1) for the semiconductor sealing of the present invention is as follows: the flame retardancy of the ribbed two cured product. Therefore, the epoxy resin for sealing the semiconductor is suitable: 1) A shrinkage mannose of a phenolic resin. The half (four) dense _ county lion group silk of the present invention contains the secret age of the above formula (1). In the presence of the fine acid catalyst of the above formula (1), it is obtained by reacting a stupid methylation group 200911871 oxymercaptobiphenyl or the like. In the formula (1), the radicals such as R, such as a milk atom, a methyl group, an ethyl group, a propyl group and a butyl group, may be the same or different. n Find the relationship of Kng by the average value of 1 . It should be noted that η in the formula (1),
可以由祕翻旨的錢膠滲透層析G 聚苯乙烯換算之數平均分子量值而算出。疋而衣件的 上述式(1)表示的酚醛樹脂的软化點低，則環氧 成物的流動性及硬化物之阻燃性提高，但上述式⑴表= 驗=掠m的軟化點高則硬化物之耐熱性變高，因此從兩者 之均衡的肖度考慮’上述軟化_^桃〜⑽^ 、〜巧。這裏所說的軟化點是指按照依據‘ 、法測疋的值。上述式（1)表示的酚醛樹脂的軟化 =決於式⑴中的η值、即上述式⑴表示賴_脂的= 子：’匕酚醛樹脂的分子量低則其軟化點也變低 ;反之:齡· 的分子量高則軟化點也變高。因此，藉由控制上述 不崎轉脂的分子量，可以得到具所需軟化點的 I t °具體而言’為了得到軟化點低的齡藤樹脂，只 可.5苯?與雙鹵代甲基聯苯類反應時使用過剩的苯’ :了得到軟化點高的酚醛樹脂，只要在上述反應時減 少笨酚用量即可。 有上1 ΐ的疋本發明之半導體密封用環氧樹脂組成物含 / 表示的盼輕樹脂，使酚醛樹脂的羥基當量(χ) 氧樹脂的環氧當量⑺(咖.)的關係(χ/γ)為〇.s *的關。認為若上述關係(X/Y)偏離此範圍，則在硬 200911871 化物中過_環氧基或絲 構，因此吸濕性或耐熱性等諸牲欠應而形成殘留的交聯結 本發明之半導體密封用广^性差。 表示的環氧樹脂。上述式户樹脂組成物含有上述式(2) 月旨與環氧氯丙燒進行脫鹽氧樹脂例如藉由使祕樹 使苯紛與二環戊二稀^ =得到，上述祕樹脂是 平均值表示1要求其滿足】〈催^化劑進行聚合而得到。n以 式⑺中的η值可以、由 ^ f 3的關係。需要說明的是， 測定而求得的聚苯乙 、經凝轉透層析法(GPC) 上逑式⑺表示的^氣;^平均分子量值而算出。 成物之流動性及硬化物之點低，則環氧樹脂组 環氧樹月旨的軟化點高，列硬化、，兩;而上述式⑺表示的 者之均衡的角度考π匕物之辦熱性變高，因此從兩 佳的是4(TC〜6〇t i :化點通常為40°C〜80°C，較 咖4的方法測定的值。^^軟化點是指按照依據® 同，上述式(2)表示的環氧樹)^的_樹月旨的情形相 量，因此藉由將相射认氧樹的軟化點也取決於其分子 合的相對於二環戊二婦使用過剩的苯紛進行聚 化，可用量進行聚合的祕_進行環氧 了侍到軟化點高的環氧樹脂。 ㈣ 述式發I之半導體密封周環氧樹腊組成物中，要求上 翻旨之敗_)⑺與上述式⑺表示 的是U0。二C(c)的總計為8(rc〜15(rc，較佳 L。上迎軟化點總計小於8〇t：時，由於環 200911871 的魏點核，魏表面魏，在作 2 而上述軟化點的總計若超過150。(：，則; ==果=燒時生成的硬化物表面之- 劑。=二含== =、氧化銘、碳酸約、石夕酸舞、氫氧化鎂、氫氧化錯、碎 氧η、黏土、氧化鎂、氧化鋁、氧化鈹、氧化鐵： ϊ:ί、r二呂、氮切、氮化硼、雲母、玻璃、石英、 =專，^並不限於這些。上述無機填充劑中，較 -^化t靠性也良好的嫁融二氧化石夕或結晶二氧化石夕等 :=是=:是’上述無機填充劑可以單』 := 環氧樹脂組成物中’上述無機填充劑 為^ :〜90感的範圍，較佳的是75游〇〜85㈣的 二=無:t劑的含量太低，則有可能無法得到 丰二t 述無機填充劑的含量太高，則由於 ί 載的銅系導線架與_樹脂的線膨w不 不佳狀況有可I產生由熱衝擊(heat sh。峨熱應力引起的 誠ί外’在本發明之半導體密封賴氧樹齡成物中， 要可以使用硬化促進劑。可使關硬 二 :可以列舉出:2_甲基唯唑、2•乙綱、2•乙基= >圭尋㈣類；2仁甲胺基曱基)苯m氮雜二環 12 200911871 十-石炭參7等第3級胺類；三 重^ 用除ί= 表半導:密封用環氧樹赌組成物中’可以倂 劑。可併用的環氧樹脂用硬化劑可^^氣=用硬化 _系化合物、醯胺系化合物、:系:合物、 Γ 雙氰； 醯胺樹脂；齠贫-田綠r丞一妝合成的聚 來酸酐鄰 偏苯三酸野、苯均四酸酐、$ ΐ=Γ鄰苯二甲_、甲基四氣化鄰苯二甲酸軒 酸ί3 (me%i福化anhydride)'六氫化鄰苯二尹 其乐、Γ基六風化鄰苯二甲酸野；雙_;_(苯紛， ς =祕、芳香族取代苯酴H烧基取代萘紛、二 苯、絲取代二錄苯、二縣料)和各祕(甲駿、 駿、烧絲、苯㈣、燒基取代苯甲·、誠苯甲輕、 ^甲駿、戊二酸、鄰苯二甲駿、巴豆駿、肉桂搭等)的縮聚 g,酚類與各種二烯化合物(二環戊二烯、烯類、乙烯義It can be calculated from the number average molecular weight value of the G-polystyrene converted by the gelatin permeation chromatography. When the softening point of the phenol resin represented by the above formula (1) is low, the fluidity of the epoxy product and the flame retardancy of the cured product are improved, but the softening point of the above formula (1) = test = sweep m is high Then, the heat resistance of the cured product becomes high, so the above-mentioned softening _^ peach ~ (10) ^, 〜 巧 is considered from the balance of the two. The softening point mentioned here refers to the value measured according to the ‘ and method. The softening of the phenol resin represented by the above formula (1) = the value of η in the formula (1), that is, the formula (1) represents the y = lipid = sub-: 'the molecular weight of the phenolic phenol resin is low, and the softening point is also low; When the molecular weight of the age is high, the softening point also becomes high. Therefore, by controlling the molecular weight of the above-mentioned non-slip fat, it is possible to obtain I t ° having a desired softening point. Specifically, in order to obtain a rattan resin having a low softening point, only .5 benzene and a dihalomethyl group can be obtained. Excess benzene is used in the reaction of biphenyls: a phenolic resin having a high softening point is obtained, as long as the amount of stupid phenol is reduced in the above reaction.有 关系 有 有 有 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体γ) is the off of 〇.s *. It is considered that if the above relationship (X/Y) deviates from this range, the epoxy group or the silk structure is passed through the hard 200911871 compound, so that hygroscopicity or heat resistance and the like are formed to form a residual crosslinked junction. The sealing is poor. Indicated epoxy resin. The resin composition of the above formula contains the above formula (2) and is obtained by dehydrating an oxygen resin with epichlorohydrin, for example, by making a secret tree benzene and dicyclopentadiene, and the above-mentioned secret resin is represented by an average value. (1) It is required to satisfy the condition that the catalyst is obtained by polymerization. The value of n in the formula (7) may be a relationship of ^ f 3 . In addition, the polyphenylene obtained by the measurement and the average molecular weight value represented by the formula (7) on the coagulation-transfer chromatography (GPC) were calculated. When the fluidity of the product and the point of the hardened material are low, the softening point of the epoxy resin group is high, and the hardening point is high, and the equilibrium angle of the person represented by the above formula (7) is π. The heat is high, so the value from the two is 4 (TC ~ 6 〇 ti: the point is usually 40 ° C ~ 80 ° C, compared to the value measured by the method of the coffee 4 ^ ^ softening point is according to the basis of the same, The phasor of the epoxide tree of the epoxy tree) represented by the above formula (2), and therefore, the softening point of the oxygenated tree by the phase is also dependent on the molecular compounding relative to the use of the dicyclopentene The benzene is polymerized, and the amount of polymerization can be used to carry out the polymerization. The epoxy is applied to the epoxy resin having a high softening point. (4) In the composition of the semiconductor sealing week of the semiconductor wax of the above-mentioned type I, it is required to be defeated by the __(7) and the above formula (7) is U0. The total of two C(c) is 8 (rc~15 (rc, preferably L. The upper softening point is less than 8〇t: when, due to the Wei point core of the ring 200911871, the Wei surface Wei, the softening of the above 2 If the total of the points exceeds 150. (:, then; == fruit = the surface of the hardened material formed during the burning - the agent == two == =, oxidized, carbonic acid, stone, magnesium hydroxide, hydrogen Oxidation error, crushed oxygen η, clay, magnesia, alumina, yttria, iron oxide: ϊ: ί, r ru, nitrogen cut, boron nitride, mica, glass, quartz, = special, ^ is not limited to these Among the above inorganic fillers, the oxidized sulphur dioxide or the crystalline sulphur dioxide is also excellent in the above-mentioned inorganic fillers, etc.: = Yes =: is 'the above inorganic filler can be single': = epoxy resin composition The above inorganic filler is in the range of ～:90 sensation, preferably 75 〇 85 85 (4) bis=none: the content of the t agent is too low, and the inorganic filler may not be obtained. If the content is too high, it may be caused by thermal shock (heat sh caused by thermal stress) due to the unsatisfactory condition of the copper-based lead frame and the resin. In the semiconductor sealing oxidized tree age of the invention, a hardening accelerator can be used. The hardening can be used: 2 - methyl azole, 2 · ethyl, 2 · ethyl = >Class; 2, arylamino fluorenyl) benzene m azabicyclo 12 12 200911871 decene, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate It can be used as a tanning agent. The curing agent for epoxy resin can be used together with a hardening compound, a guanamine compound, a compound, a phthalocyanine, a guanamine resin, a plutonium-field green r丞A cosmetically synthesized poly(oric acid anhydride) o-trimellitic acid field, pyromellitic anhydride, ΐ = Γ phthalene _, methyl tetra gasified phthalic acid phthalic acid ί3 (me% i fuhua anhydride)' Hexahydrophthalic acid Yinqi, fluorenyl six weathering phthalic acid field; double _; _ (benzene, ς = secret, aromatic substituted benzoquinone H alkyl substituted naphthalene, diphenyl, silk substituted two recorded benzene, The second county material) and the secrets (Jinjun, Jun, burnt wire, benzene (four), burnt base replaced benzyl, benzene, light, ^ jun, glutaric acid, phthalic acid, croton, cinnamon Polycondensation g, phenols and various Chromene compound (dicyclopentadiene, vinyl, ethylene Yi
巧烯、降沐片二烯、乙稀基降冰片稀、θ氫茚、二乙J $，、一乙烯基聯苯、二異丙烯基聯苯、丁二烯、異戊二 ，等）的聚合物；酚類與酮類（丙酮、丁酮、甲基異丁基_、 苯乙_、二苯曱酉同等)的縮聚物；龄類與雙氯曱基苯的縮聚 13 200911871 物；雙酚類與各種醛的縮聚物；雙酚類以及它們的改性物; 、bf3«•胺錯合物、M衍生物等。f要制的是，上述 環氧樹墙用硬化劑可以單獨使用，也可以是兩種或兩種 上組合使用。 t述可併用的環氧樹脂用硬化劑只要是通常使用的環 氧樹脂用硬化劑即可，並不限於上述具體例子，但本發明 之目的在於不必使用鹵素化合物和銻化合物，而得到阻燃 性優異的環氧樹脂組成物，因此應極力避免使用含有南素、 二：,。另外’若上述可併用的環氧樹脂用硬化劑的添 加=夕，則有可能損及本發明之目的。因此，當本 ί:外:環氧樹脂含有除上述式⑴表示的酚_ 硬化劑在硬化劑時，上述可併用的環氧樹脂用 樹脂用硬化劑的總計中所占的比例較=:t用，氧 wt%，特難的是小於2Q wt%。 ^小於30 在本發明之半導體密封用環氧樹脂組 用除上述式(2)表示的環氧樹腊以外的氧樹 可以併 環氧獅的具體例子可以列舉出：軸可併用的 驗、芳麵取代苯齡、雜、燒基取燒基取代苯 ，取代，基苯、二幾基萘等)與各“（‘經基苯、 炫基駿、本甲搭、院基取代苯甲輕 -乙駿、 戊二駿、鄰苯二甲酸、巴豆•、肉桂心：駿、萘盤、 與各種二稀化合物（箱烯類、乙稀基、‘聚物；驗類 乙烯基降冰片稀、四氫節、二乙烯:、降冰片二烯、 Γ二烯、異戊二 14 200911871 婦等）的聚合物；_ 苯乙酮、二苯甲 ^_(丙酮、丁酉同、曱基異丁基酉同、 物；雙_與各種聚物；紛類與雙氯甲基苯的縮聚 水甘油峻系環氧播、丨1物，將醇類4縮水甘油化的縮 3,4-環氧基環己基曰甚烯基+環己烯二環氧化物或 的脂環式環氧樹^t 土]，4’-環氧基環己烷羧酸酯等為代表 (TGDDM)t四縮水甘油基二胺基二苯基甲燒 油胺系環氧翻旨；縮水n胺絲_為代表的縮水甘 是，上述環氧樹環，，。需要說明的 上組合使用。 钱彳d也可〜兩種或兩種以 可，要枝纽⑽環氧樹脂即 應極力避免使用^；從本發明之目姻角度考慮， 併用的環氧樹磨的。另外，若上述可 式⑺l 明之半導體密朗環氧雛含有除上述 氧樹月旨I上的環氧樹脂時’上述可併用的環 ==:占的比例較佳的是小—，特別二 ，本發明之半導體密封用環氧樹磨組成物中，為了在 I使與金屬模的離型變得良好，可以添加離型劑。作 二剎，可以使用以往習知的任一種物質，可以列舉如： 示櫚蠛、褐煤蝶等醋系蠟；硬脂酸、棕櫚酸等月旨肪酸 1及及些脂肪酸的金屬鹽、氧化聚乙婦、非氧化聚乙稀等 15 200911871 聚烯烴系蠟等。上述離型劑可以單獨使用，也可以是兩種 或兩種以上併用。相對於全部有機成分，上述離型=的添 加量較佳的是小於等於3 wt%。若離型劑的添加量太多， 則與導線架等的黏接變差。 在本發明之半導體密封用環氧樹脂組成物中，為了提 高樹脂成分與無機填充劑的黏接性，可以添加耦合劑。作 為耦合劑，可以使用以往習知的任一種物質，可以列舉如： 乙婦基燒氧基魏、基絲基魏、苯乙烯基院氧基 石夕燒、甲基丙觸氧纽氧基魏、丙_氧纽氧基石夕 _基_ 1基贱基魏、異氰酸醋燒氧基 石夕院τ各種絲基魏化合物；綠基錢合物、链整入 上^合以單獨使用，也可以是兩種或 =! 將預先以上_合劑進行表面處理的益機 混:可_合劑混合酬分 根據=可封=樹脂組成物中， 例子可以列舉忠：i 丁的可使用的添加劑的具體 的改性物、聚苯及f性物、丙稀猜共聚物 ==⑽氰酸_物、 只要ΐ習知的酞菁綠等著色劑等。可使⑽添加劑 於^=3=^#並不限於上述具體例子，但由 得到_性優異的環氧樹化合物或錄化合物，而 虱樹脂組成物，因此應極力避免添加 16 200911871 銻系阻燃劑。在本發明之 中，上述添加劑的添加量只 封用環氧樹脂組成物 密封半導體時的作業‘，及_性、且不妨礙 本發明之半導體 均勾分散混合各轉成分的以往習知日3物太可以採用可 ::丄:!明之半_密封用環氧樹脂組各 種成分全部粉碎並使用亨舍物藉由將各 倾合，__上述各種核二當= 卜1本發明之半導體裝置’可以藉由使用上述半導 旨組成物，利用傳遞成形等對搭載在導線 j的传體TL件進行樹絲封來製I本發明之半導 =裝1是用上述半導體密封用環氧樹脂組成物來密封半導 體兀件、，包括該半導體密封用環氧樹脂的硬化物。半導體 裝置可以列舉如··雙啦插式封裝(Dual In_line Package， DIP)、四方扁平封裝(Quad Flat Package，QFP)、球栅陣列 封裝(Ball Grid Array Package，BGA)、晶片級封裝(Chip Scale Package ’ CSP)、小尺寸封裝(Small Outline Package， S〇P)、薄型小尺寸封裳（Thin Small Outline Package， TSOP)、薄型四方扁平封裝(Thin Quad Flat pack，TQFp) 寸0 在本發明之半導體裝置中，從散熱性或高速電特性問 題的角度考慮，較佳的是，使用銅系導線架。銅系導線架 17 200911871 是指以銅合金為原料，實施了各種電鍍加卫的導線架。 «實施例》 、下利用5成例、實施例及比較例來具體說明本發 明。 x (合成例） 在8〇 C下，在2小時中邊加熱攪拌邊向2〜5莫耳的 苯射連續添加1莫耳的雙氯甲基聯苯。添加結束後，再 於80C下反應3小時’反應結束後在加誠Μ下除去過剩 的苯齡。向溶融狀態的樹脂中加人約3倍量的甲基異丁基 酮亚溶解，反覆進行水洗。之後，藉由在加熱減壓下館去 甲基異丁基酮，得到下述式⑶表示的化合物(m〜H3): 士 QB ___ (3) 藉由凝膠滲透層析法測定而求得的(Η1)〜(Η3)之式⑺中的 η如下0 (Η1) (Η2) (Η3) 1.5 η 与 2.0 η与23 如上所述’（HI)〜(Η3)中的η值的不同源於合成例中 使用的苯_莫耳數的不同。苯關莫耳數越大，η變得 越小，本紛的莫耳數越小，η變得越大。 (實施例及比較例） …按衣j所不配方（重量份)添加各種成分，用混合輕進 ’亚$成片劑’之後藉由傳遞成形來製備樹鹿成形 18 200911871 物，在160°C下硬化2小時、進一井 法測定硬化物的物性(吸咖續： (1) 吸濕率 在121°C及濕度1〇〇%下測定24小時後 率。需要說明的是，試驗片為直 ^的^加 盤形。 度4mm的圓 (2) 阻燃性Indomethacene, methicone, ethylene thinner, θ hydroquinone, diethylene J $, monovinyl biphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. Polymer; polycondensate of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl _, phenylethyl ketone, diphenyl hydrazine); polycondensation of ages and dichloro decyl benzene 13 200911871; Polycondensates of phenols and various aldehydes; bisphenols and their modifications; bf3«•amine complexes, M derivatives, and the like. It is to be noted that the above hardening agent for epoxy tree walls may be used singly or in combination of two or more. The curing agent for an epoxy resin which can be used in combination is not particularly limited to the above specific examples as long as it is a curing agent for an epoxy resin which is generally used, but the object of the present invention is to provide a flame retardant without using a halogen compound or a cerium compound. Excellent epoxy resin composition, so it should be avoided to use the inclusion of Nansu, II:,. Further, if the above-mentioned hardener for the epoxy resin which can be used in combination is added, the object of the present invention may be impaired. Therefore, when the epoxy resin contains a phenol_hardener represented by the above formula (1) in the curing agent, the ratio of the total amount of the hardener for the epoxy resin for the above-mentioned epoxy resin can be used as a ratio =: t With oxygen wt%, it is particularly difficult to be less than 2Q wt%. ^ Less than 30 In the epoxy resin group for semiconductor encapsulation of the present invention, an oxygen tree other than the epoxy resin wax represented by the above formula (2) can be used, and specific examples of the epoxy lion can be cited: Surface substitution of benzene, miscellaneous, pyrolyzed, substituted benzene, substituted, phenyl, di-heptyl, etc.) and each of the "(---- benzene, Hyun Jun, Ben Jia, the base-based replacement of benzene - B Jun, Wu Erjun, Phthalic Acid, Croton, Cinnamon Heart: Jun, naphthalene disk, and various dilute compounds (boxene, ethylene, 'polymer; test vinyl ice tablets, four Polymers of hydrogen hydride, diethylene: norbornadiene, decadiene, isoprene 14, 200911871, etc.; _ acetophenone, benzophenone _ (acetone, butyl hydrazine, decyl isobutyl hydrazine, ; double _ and various polymers; condensed condensed glycerin of dichloromethylbenzene, epoxide, hydrazine, glycidyl 3,4-epoxycyclohexyl hydrazide Alkenyl+cyclohexene diepoxide or alicyclic epoxy tree], 4'-epoxycyclohexane carboxylate, etc. (TGDDM)t tetraglycidyl Amino-based diphenyl-methyl oleylamine-based epoxy resin; shrinking n-amine wire _ is representative of the shrinking water, the above-mentioned epoxy tree ring, which needs to be used in combination. Or two kinds of epoxy resin should be avoided as much as possible; from the point of view of the present invention, the epoxy resin is used in combination. In addition, if the above semiconductor (6) When the epoxy resin in the above oxygen tree is used, the above-mentioned ring that can be used together ==: the proportion is preferably small, and particularly, in the epoxy resin composition for semiconductor sealing of the present invention. In order to improve the release of the metal mold from I, it is possible to add a release agent. For the second brake, any of the conventional materials may be used, and examples thereof include: vinegar wax such as palmetto or lignite butterfly; Stearic acid, palmitic acid, etc., such as fatty acid 1 and metal salts of some fatty acids, oxidized polyethylene, non-oxidized polyethylene, etc. 2009 200911 polyolefin wax, etc. The above release agent may be used alone or Two or more of them are used together. The above is relative to all organic components. The amount of addition of = is preferably 3 wt% or less. If the amount of the release agent added is too large, the adhesion to the lead frame or the like is deteriorated. In the epoxy resin composition for semiconductor encapsulation of the present invention, A coupling agent may be added to improve the adhesion between the resin component and the inorganic filler. As the coupling agent, any conventionally known one may be used, and examples thereof include: ethyl acetoin, keis, styrene, and styrene. Base oxylate oxime, methyl propyl oxy-oxygen, propionyl-oxy-oxyxanthene ketone ketone ketone ketone ketone ketone The base compound or the chain is used alone or in combination, or it may be two or =! The surface of the pre-existing _ mixture is mixed with the machine: the _ mixture can be mixed according to = sealable = resin composition In the examples, specific modifications of the usable additives, polyphenylene and f-forms, propylene-like copolymers == (10) cyanic acid, and as long as the known indocyanine greens, etc. Coloring agents, etc. The (10) additive may be not limited to the above specific examples, but an epoxy resin compound or a recording compound which is excellent in ytability is obtained, and a ruthenium resin composition is used, so that it is strongly avoided to add 16 200911871 lanthanide flame retardant. Agent. In the present invention, the amount of the above-mentioned additive is only encapsulated by the operation of sealing the semiconductor with the epoxy resin composition, and the prior art is not hindered by the semiconductor of the present invention. The material can be used as follows:: 丄:! 明半半_ Sealing epoxy resin group, all the components are pulverized, and each of the above-mentioned various cores is pulverized by using Henscher, __the above various cores are used = 1 semiconductor device of the invention 'The semi-conductor of the present invention can be manufactured by using a transfer molding or the like to bond a transfer TL member mounted on a wire j to the semiconductor package of the present invention. The composition encapsulates the semiconductor element and includes a cured product of the epoxy resin for semiconductor encapsulation. The semiconductor device may be, for example, a Dual In_line Package (DIP), a Quad Flat Package (QFP), a Ball Grid Array Package (BGA), or a Chip Level Package (Chip Scale). Package 'CSP), Small Outline Package (S〇P), Thin Small Outline Package (TSOP), Thin Quad Flat Pack (TQFp), 0 in the present invention In the semiconductor device, it is preferable to use a copper-based lead frame from the viewpoint of heat dissipation or high-speed electrical characteristics. Copper-based lead frame 17 200911871 refers to a lead frame that has been electroplated and reinforced with copper alloy as a raw material. «Examples>> The present invention will be specifically described using five examples, examples and comparative examples. x (Synthesis Example) 1 mol of bischloromethylbiphenyl was continuously added to 2 to 5 mol of benzene shot while heating and stirring for 2 hours at 8 ° C. After the end of the addition, the reaction was further carried out at 80 C for 3 hours. After the completion of the reaction, the excess benzene age was removed under the addition of sputum. To the molten resin, about three times the amount of methyl isobutyl ketone was dissolved, and washed with water. Thereafter, the compound (m to H3) represented by the following formula (3) is obtained by demethylation of methyl isobutyl ketone under heating and reduced pressure: 士QB___ (3) obtained by gel permeation chromatography. (Η1)~(Η3) The η in the formula (7) is as follows: 0 (Η1) (Η2) (Η3) 1.5 η and 2.0 η and 23 The difference in the value of η in '(HI)~(Η3) as described above is derived from The difference in the number of benzene-mole used in the synthesis example. The larger the benzene molar number, the smaller η becomes, and the smaller the molar number, the larger η becomes. (Examples and Comparative Examples) - Various ingredients were added according to the formula (parts by weight) of the garment j, and the tree deer was formed by transfer molding after mixing into a 'sub-$ tablet', at 160°. C-hardening for 2 hours, the physical properties of the cured product were measured by a well method (absorption continued: (1) The moisture absorption rate was measured at 121 ° C and humidity of 1% by weight after 24 hours. It should be noted that the test piece was Straight ^ ^ plus disc shape. Degree 4mm circle (2) flame retardancy
HUL94垂直試驗來物。其巾，以 mmx長150 mm、厚度分為〇 8 為見12.S 試驗。殘炎時間是指對5個為一;^。随^種來進行 ”足以下所有條件：（i)各試驗片 卜=是 於等於1G秒；⑼5個為—_㈣机广㈣场間均小 樣品下端305 mm的棉線時沒有滴夹^具處；㈣點燃題 “ “ 職下未完全燃燒的顆粒； (v)取去第2 -人的火焰後繼續燃燒的時 V-1是指滿^以下所有條件.m 為3G &以内。而 pe- . ,·.Γ ()各甙驗片點火後的殘炎時 i :時Η料二5個為—組的試樣點火10次後的 殘炎％間總S十小於專於250秒· t x 办，（U1)未燃燒至夾具處；（访） 點燃距一下鳊305 _的棉線 顆粒；W取去第2次的火焰後痒？下未儿王燃燒釣 妇设龜續燃燒的時間為00秒以 内。 19 200911871 知、» W · Wfc w 表1 實施例 1 食施例 2 實施例 3 女施例 I 4 實施例 5 實施例 6 比較例 1 比較例 2 比較例 3 環氣樹脂(E1) 8.8 1 11.6 8.6 8^ 環砂脂(E2) 8.7 **_ 8.6 112 環氣樹脂(E3) 9.1 8.7 硬化劑（H1) 73 9.5 71 - 硬化劑（H2) Ί5 7.5 硬化劑（H3) 7,7 77 10 7.5 硬化促進劑 03 03 03 03 02 0*2 οι η 02 0.1 添加劑 83 78 83 83 83 83 83 78 83 離型劑 0.3 03 03 03 03 0.3 〇3 03 03 耦合刺 吸濕率(％) 03 0.19 0.3 Q21 03 ~m~ 03 ~"02 _ 03 03 03 03 __ 03 〇Ξ~ 0.19 02 〇7^ 025 厚度0.8 mm 阻燃性 殘炎時間(秒） V-0 28 V-0 34 V-0 35 V-0 39 V-0 40 V-0 39 V-1 56 V-1 74 V-1 62 厚度1.6 mm 阻燃性 殘炎時間(秒） V-0 19 V-0 23 24 V-0 25 V-0 26 V-0 24 V-0 31 V-1 53 V-0 47一 (El) : XD-1000-2L· (曰本化藥製.，式(2)中的n与1.4，環氧 當量為241 g/eq. ’軟化點為57。〇。 (E2) : XD-1000-L (曰本化藥製，式(2)中的ngl 6，環氧當 量為245 g/eq. ’軟化點為66。〇。 (E3) : XD-1000 (曰本化藥製，式⑺中的n%1.8，環氧當量 為254 g/eq.，軟化點為74。〇。 (H1):合成例中得到的式⑺表示的酚醛樹脂（式(3)中的 η与1.5，羥基當量為199 g/eq·，軟化點為65。〇。 (H2):合成例中得到的式(3)表示的酚醛樹脂（式中的 H52.0，羥基當量為21〇 g/eq.，軟化點為77。〇)。 (H3) ·合成例中得到的式⑺表示的酚醛樹脂（式(3)中的 n=^2.3，羥基當量為219 g/eq.，軟化點為89〇C)。 硬化促進劑：三苯基膦(北興化學工業製）。 添加劑：MSR-2212(龍森製，熔融二氧化矽）。 離型劑：巴西棕櫊蠟1號(CERARICA野田製）。 20 200911871 耦合劑：ΚΒΜ-303 (信越化學工業製）。 由表1可知：使用了本發明之半導體密封用環氧樹月旨 組成物的實施例1〜6，即使不使用豳素或銻化合物，其阻 燃性也優異。特別是由實施例丨及實施例2的結果可知： 藉由將軟化點小於等於80°C的式（1)表示的酚醛樹脂和軟 化點小於等於6〇°C的式(2)表示的環氧樹脂組合，阻燃性進 一步提向。另外，由添加劑的添加量相同的實施例與比較 例的比較可知：與比較例相比，實施例之硬化物的吸濕率 低20°/。左右，可知：本發明之半導體密封用環氧樹脂組成 物之硬化物的耐濕性優異。 —雖然本發明已以較佳實施例揭露如上，然其並非用以 限=本發明，任何熟習此技藝者，在不脫離本發明之精神 =耗圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為准。 【圖式簡單說明】 益。 【主要元件符號說明】 無。 21HUL94 vertical test. The towel is shown in the 12.S test with a mmx length of 150 mm and a thickness of 〇8. Residual time means that 5 is one; ^. It is sufficient to carry out all the conditions: (i) each test piece = is equal to 1G seconds; (9) 5 is -_ (four) machine wide (four) between the field small sample at the lower end of the 305 mm cotton line without drop clips (4) igniting the title "" particles that are not completely burned under the occupation; (v) when the second person's flame is taken and continues to burn, V-1 means full ^ below all conditions. m is within 3G & - . ,·.Γ () After the smoldering of each test piece, the i: when the sputum is two, the sputum of the group is ignited for 10 times, and the total S is less than 250 seconds. Tx office, (U1) is not burned to the fixture; (visit) ignites the cotton granules from 鳊 305 _; W takes the second flame after itching? The time after the burning of the prince 19 200911871 知, » W · Wfc w Table 1 Example 1 Food Example 2 Example 3 Female Example I 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 环气树脂 (E1 ) 8.8 1 11.6 8.6 8^ Ring Grease (E2) 8.7 **_ 8.6 112 Ring Resin (E3) 9.1 8.7 Hardener (H1) 73 9.5 71 - Hardener (H2) Ί5 7.5 Hardener (H3) 7,7 77 10 7.5 Hardening accelerator 03 03 03 03 02 0*2 οι η 02 0.1 Additive 83 78 83 83 83 83 83 78 83 Release agent 0.3 03 03 03 03 0.3 〇3 03 03 Coupling Thorn moisture absorption rate (%) 03 0.19 0.3 Q21 03 ~m~ 03 ~"02 _ 03 03 03 03 __ 03 〇Ξ~ 0.19 02 〇7^ 025 Thickness 0.8 mm Flame retardant residual time (seconds) V- 0 28 V-0 34 V-0 35 V-0 39 V-0 40 V-0 39 V-1 56 V-1 74 V-1 62 Thickness 1.6 mm Flame retardant residual time (seconds) V-0 19 V-0 23 24 V-0 25 V-0 26 V-0 24 V-0 31 V-1 53 V-0 47 一(El) : XD-1000-2L· (曰本化制制.,式( 2) n and 1.4, epoxy equivalent is 241 g / eq. 'Softening point is 57. 〇. (E2) : XD-1000-L (made by 曰本化药, ngl 6, in formula (2) The epoxy equivalent was 245 g/eq. The softening point was 66. Hey. (E3) : XD-1000 (manufactured by Pharmacopoeia, n% 1.8 in the formula (7), epoxy equivalent of 254 g/eq., softening point of 74. 〇. (H1): Formula (7) obtained in the synthesis example The phenol resin (the η and 1.5 in the formula (3), the hydroxyl group equivalent of 199 g/eq·, and the softening point of 65. (H2): a phenol resin represented by the formula (3) obtained in the synthesis example (formula) In the case of H52.0, the hydroxyl group equivalent is 21 〇g/eq., and the softening point is 77. H). (H3) The phenol resin represented by the formula (7) obtained in the synthesis example (n=^2.3 in the formula (3) The hydroxyl equivalent is 219 g/eq., and the softening point is 89 〇C. Hardening accelerator: triphenylphosphine (manufactured by Behind Chemical Industry Co., Ltd.) Additive: MSR-2212 (manufactured by Ronsen, molten cerium oxide). Formulation: Brazilian brown wax No. 1 (CERARICA Noda). 20 200911871 Coupling agent: ΚΒΜ-303 (manufactured by Shin-Etsu Chemical Co., Ltd.) It can be seen from Table 1 that the epoxy resin composition for semiconductor sealing of the present invention is used. In Examples 1 to 6, the flame retardancy was excellent even without using a halogen or a ruthenium compound. In particular, from the results of Example 实施 and Example 2, it was found that the softening point was 80 ° C or less ( 1) The phenol resin and the epoxy resin combination represented by the formula (2) having a softening point of 6 〇 or less are further improved in flame retardancy, and the comparison between the examples in which the amounts of the additives are the same and the comparative examples shows that: Compared with the comparative example, the moisture absorption rate of the cured product of the example is as low as about 20°/., and it is understood that the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention is excellent in moisture resistance. The preferred embodiment is disclosed above, but it is not intended to limit the invention. Any person skilled in the art can make some modifications and retouchings without departing from the spirit of the invention. It shall be subject to the definition of the scope of the patent application attached. [Simple description of the diagram] Benefits. [Main component symbol description] None. 21