TW200906959A - Sealing epoxy resin compostion and eletronic component apparatus using the same - Google Patents

Abstract

The present invention provides a sealing epoxy resin composition comprising epoxy resin (A), curing agent (B) and a compound (C) having the unit represented by the following formula (I) and (II). A sealing epoxy resin composition which is flame retardant and also has excellent fluidity and low stress is provided. R1 represents alkylene group having 1 to 10 carbons. R2 and R3 represent alkyl group having 1 to 10 carbons, aryl group having 6 to 10 carbons, alkoxy group having 1 to 10 carbons, monovalence organic group having epoxy group with 1 to 10 carbons, monovalence organic group having carboxyl group with 1 to 10 carbons or poly(alkylene ether) having 3 to 500 carbons.

Description

200906959 九、發明說明： 本申請案主張於2007年5月10號向日本智慧財產局 提出申請之日本特願第2007-125526號的優先權，該專利 申請案所揭露之内容是完整結合於本說明書中。 【發明所屬之技術領域】 本發明是有關於一種密封用環氧樹脂組成物以及使用 該組成物的電子零件裝置。 【先前技術】200906959 IX. INSTRUCTIONS: This application claims the priority of Japanese Patent Application No. 2007-125526 filed on May 10, 2007, to the Japanese Intellectual Property Office, the disclosure of which is incorporated herein in its entirety. In the manual. [Technical Field of the Invention] The present invention relates to an epoxy resin composition for sealing and an electronic component device using the same. [Prior Art]

且以术，隹冤日日體寸电卞苓忏裒置的元件密封 領域，從生產率、成本等方面考慮樹脂密封成為主流，而 環氧樹脂成形材料被廣泛使用。這是由於環氧樹脂在電 性、耐濕性、耐熱性、機械特性、與嵌入物的黏合性等諸 特性上達到了平衡。近年來，由於f子零件的封裝型態朝 =小型化、㈣化等方向發展，故可實現多針孔(㈣化、 窄間距化之BGA職的可祕正在獻。預計今後會進 步向窄間距化方向發展。如此，在配線間產生大的電容， 使信號傳遞速度下降，因而可能會導致LSI的卫作速 遲。為了解決上述問題，在層間絕緣膜方面，人們正 發比介電常數低(Low.k)的絕緣材料。隨之，預計今^ 絕緣膜將多孔化’因而恐有相絕_強度降低之虞。曰3 因而’上述電子零件的封裝在冷熱循環時出穿 ^的問題’人們希望改善耐熱衝擊性。從上述技術：： ^ ，要求開發用以防止強度弱之層間絕、__^低 -力密封材料。作為改善環氧樹脂組成物的耐熱衝擊性，- 200906959 烷基醚基的矽嗣聚合物的技術(例如參照 曰本專利知·開平2-129220號公報）。 【發明内容】 β士 用含有聚亞烧基_基的梦酮聚合物作為可撓劑 ‘有變脂組成物的彈性率降低，但流動性和阻燃 趨勢。BGA封裝的密封方法中，將多個1C成 因的！^p成形增加’將其薄型且大面積成批密封， 求環氧树脂組成物的流動性要高。本發明 問題’提供—種特別是低應力化優異而又不損及流動性、 阻燃性等特性的密封用環氧樹脂組成物。 本發明關於以下内容。 有》1·種德、封用環氧樹脂組成物，其特徵在於：其中含 %氧樹脂(A)、硬化劑(B)以及含有下述結構式(I)以及(II) 斤示之單元的化合物 [化學式1] 〇 (i)In the field of component sealing, which is used for the day and the day, the resin sealing has become the mainstream in terms of productivity and cost, and epoxy resin molding materials are widely used. This is because the epoxy resin balances properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to the insert. In recent years, since the package type of the f-sub-components has been developed in the direction of miniaturization and (four), it is possible to realize the multi-pinhole ((4) and narrow-pitch BGA jobs. It is expected that the progress will be narrower in the future. In this way, a large capacitance is generated in the wiring, and the signal transmission speed is lowered, which may cause the LSI to be delayed. In order to solve the above problem, the dielectric constant is proportional to the interlayer insulating film. Low (Low.k) insulating material. As a result, it is expected that the insulating film will be porous, and thus there is a fear that the strength of the insulating film will decrease. 曰3 Thus, the package of the above electronic component is exposed during the hot and cold cycle. The problem 'People want to improve the thermal shock resistance. From the above technology:: ^, it is required to develop a layer to prevent the weak strength of the interlayer, __^ low-force sealing material. As a heat shock resistance to improve the epoxy resin composition, - 200906959 The technique of the oxime polymer of the ketone group (for example, refer to Japanese Patent Laid-Open No. Hei-2-292220). [Invention] The ketone polymer containing a polyalkylene group is used as a flexible agent. Variable fat The elastic modulus of the product is reduced, but the fluidity and the flame retardant tendency. In the sealing method of the BGA package, the formation of a plurality of 1C genes is increased by adding a thin and large-area batch seal to obtain an epoxy resin composition. The problem of the present invention is to provide a sealing epoxy resin composition which is excellent in low stress and which does not impair fluidity and flame retardancy, etc. The present invention relates to the following. A seed and epoxy resin composition characterized by comprising a % oxygen resin (A), a hardener (B), and a compound containing a unit of the following structural formula (I) and (II) [ Chemical formula 1] 〇(i)

β1 II R1^—〇- (R1表示碳原子數為1〜1〇的亞烷基。） [化學式2] 200906959 R211 II R1^—〇- (R1 represents an alkylene group having 1 to 1 ring of carbon atoms.) [Chemical Formula 2] 200906959 R2

II

(I I "Si—〇- 3(I I "Si-〇- 3

R :的Si表：1〜1()的烧基、碳原子數為6〜 的具有環氧基的-基、碳原子數為1〜 有羧基的1錢 子數為1〜10的具 鍵基。） 4以原子數為3〜的聚亞燒基 人jrtr/ 1所記叙料料氧樹驗錢，1中化 合物(c)6i數平均分子量施為2_〜20_底m 項1所賴之密封用環氧樹脂組成物，其中化 &物（）^數平均分子量Mn為5。。。〜觸。。。’、 成物Ι’ΐΠ1:3巾任1所記狀密封㈣氧樹腊組 單元與結構雜)所示之單元的 5.=項1〜4中任—項所記載之密封用環氧樹月 ίΓο重量:對於刚重量份環氧樹脂㈧，化合物(‘1 成物二二：：二封=樹㈣ 〜20重量份。 心魏樹MA)，化合物⑼為5 以/m1〜6中任—項所記載之密封用環氧樹脂紐 :=，c)為結構式(ι)部式⑼·結物;： 200906959 8.如$項7所記載之密封用環氧樹脂組成物，其中化 口物(C)為下述通式(3)所示之化合物。 [化學式3] R2 R2 〇R: Si table: a group having 1 to 1 (), a group having an epoxy group of 6 to 2, a group having 1 to 10 carbon atoms, and having 1 to 10 carbon atoms base. 4) The atomic number is 3~ polypyrylene Jrtr/ 1 is described as the material oxygen tree test, 1 compound (c) 6i number average molecular weight is applied as 2_~20_ bottom m item 1 The epoxy resin composition for sealing, wherein the average molecular weight Mn of the chemical compound is 5. . . ~touch. . . ', 成物Ι'ΐΠ1:3 towel any one of the sealed seals (4) Oxygen wax group unit and structure of the unit Month Γ 重量 weight: For the weight part of the epoxy resin (eight), the compound ('1 compound 22: two seal = tree (four) ~ 20 parts by weight. Heart Weishu MA), compound (9) is 5 / / m1 ~ 6 The epoxy resin for sealing described in the item: =, c) is a structural formula (1), (9), and the following: 8.06906959 8. The epoxy resin composition for sealing according to Item 7, wherein The oral substance (C) is a compound represented by the following formula (3). [Chemical Formula 3] R2 R2 〇

:—R1一〇>-H ~~R1一C-产0—R^-Si—Ο.卜 Si—R4—O’ -c- R3 R3:—R1一〇>-H ~~R1-C-Production 0—R^-Si—Ο. Bu Si—R4—O’ -c- R3 R3

V • (3) j、:構式(3)中，1為1〜200的整數，瓜1+叫為2〜400 , =數。R1表示碳原子數為丨〜⑺的亞烷基。R2及¥表; 子數為1〜1G的絲、碳原子數為6〜1G的芳基、^ 苴、婁t為1 1〇的烧氧基、碳原子數為1〜IQ的且有環肩 機基團、碳原子數為1〜1〇的具有細— 原子數為3〜_的聚亞絲·。R4W 反原子數為1〜1〇的二價烴基。） 1 種^子零件裝置，該電子零件I置具備以如前巧 導體元:所記載之密封用環氧樹脂組成物密細 易懂為和其他目的、特徵和優點能更_ 2下 例’並配合所附圖式，作詳細额 【實施方式】 及包ί於一種含有環氧樹脂(Α)、硬化劑⑻以 捕疋以之化合物(C)的密封用環氧樹脂紐成 200906959 物以及用該組成物密封的電子零件裝置。 本發明中使用的化合物(c)的特徵在於 結構3=1)的單元，化合物(C)發揮可挽劑的作用 式⑺的R只要是碳原子數為卜1()的 分散性的角度考慮，ri較佳的是亞丙基。式(^ 只要是碳原子數為wo的絲、碳原子數為6〜ι〇的芳 ΐ;碳=數，1〜10的院氧基、具有環氧基的碳原子數 為1〜10的-價有機基團、具有絲的碳原子數為卜1〇 的-價有機基_碳原子數為3〜的聚魏基鍵基即 可’彼此可以是相同的基團也可以是不同的基團。從彈性 率降低效果的角度考慮，R2、R3較佳的是燒基、芳基，特 別佳的是甲基。聚亞烧基_基可以列舉出：包括下述結構 式(5)的一價基團。 [化學式4] --CCH20---CHCH20--(5)V • (3) j, : In the construction (3), 1 is an integer from 1 to 200, and melon 1+ is called 2 to 400, = number. R1 represents an alkylene group having a carbon number of 丨~(7). R2 and ¥表; a filament having a number of 1 to 1 G, an aryl group having 6 to 1 G carbon atoms, an alkoxy group having a 娄t of 11 〇, a carbon atom number of 1 to IQ, and a ring The shoulder machine group, the poly-Asian wire having a fine number of atoms of 3 to _ having a carbon number of 1 to 1 Å. R4W A divalent hydrocarbon group having an anti-atom number of 1 to 1 Å. A type of sub-component device, the electronic component I is provided with a composition such as the former conductor element: the sealed epoxy resin composition is easy to understand and can be used for other purposes, features and advantages. And in conjunction with the drawings, a detailed amount of the [embodiment] and a sealing epoxy resin containing a resin (Α) and a hardener (8) to capture the compound (C) An electronic component device sealed with the composition. The compound (c) used in the present invention is characterized by a unit of the structure 3 = 1), and the compound (C) functions as a pliable agent. The R of the formula (7) is considered as long as the number of carbon atoms is di(1). Preferably, ri is a propylene group. Formula (^) is a filament having a carbon number of wo, and an aromatic fluorene having a carbon number of 6 to 〇; carbon = number, a laboxy group of 1 to 10, and a carbon atom having an epoxy group of 1 to 10; The valence organic group, the valence-containing organic group having a mercapile, and the poly-carbyl group having 3 to 30 carbon atoms may be the same group or different groups. From the viewpoint of the effect of lowering the modulus of elasticity, R2 and R3 are preferably an alkyl group or an aryl group, and particularly preferably a methyl group. The polyalkylene group can be exemplified by a monovalent structure including the following structural formula (5). [Chemical Formula 4] --CCH20---CHCH20--(5)

mi I ch3 (式(5)中，1^及1¾較佳的是$20的範圍，其中任一個可 以為0。） 並且’化合物(C)較佳的是於兩末端含有結構式(1)之單 元的結構式(I)-結構式(II)-結構式⑴型的三嵌段共聚物，進 一步較佳的是於各單元間含有結合基。特別是上述通式(3) 的結構較佳。通式(3)的結構由與樹脂的相容性高的結構式 (I)之單元和包括結構式(II)的聚矽氧烷單元構成，上述結構 200906959 式(II)可降低彈性率。 敫奴通〇1(3)中’ 1為1〜200的整數，mi+m2為2〜400的 整數。R表示碳原子數為卜10的二價烴基。特別是從分 散5角度考慮’R4的碳原子數與在所有化合物(C)的分; 中是單一的相比’較佳的是在各分子間R4的碳原子數以上 述1〜10的範圍進行分佈。作為如上所述的化合物(C)，可 由Wacker社製商品名WAX OH 350D (開發品名 SLM446200 系列或 SLJ166卜 173卜 1732、1733=34) 獲取。具有環氧樹脂組成物的分散性越提高、含有結構式 (II)的梦酮結構域分散得越細’則環氧樹脂組成物的^生^ 越降低、應力越下降的優點。 從彈性率降低的角度考慮，上述化合物(C)的數平均分 子量Μη較佳的是2000〜20000，更佳的是3〇〇〇〜15〇〇〇， 特別，的是5000〜10000。化合物(c)的數平均分子量Μη 大於等於2000時，金屬剝離(peei)等對粘附體較佳。化合 物(C)的數平均分子量Μη小於等於20000時，可以抑制i 動性的降低。 本發明中使用的化合物(c)的數平均分子量Mn，利用 凝膠滲透層析法(GPC)，使用由標準聚苯乙烯得到的檢量 線進行測定而得到。在本發明中，上述Mn如下測定：採 用GPC法，其中泵使用（股)公司日立製作所製L_62〇〇型、 柱使用 TSKgel-G5000HXL 以及 TSKgel-G2000HXL (均由 TOSHO (股)公司製，商品名）、檢測器使用（股)公司日立製 作所製L-3300RI型，以四氫呋喃為溶離液，在溫度3〇。〇、 11 200906959 流量1.0 ml/分鐘的條件下進行測定。 1較佳的是20〜80的整數，進一步較佳的是％〜5〇 的整數。從製造方法的角度考慮，較佳的是，叫和瓜2為 大致相同的數值。將im+m2作為m時，m為2〜4〇〇的整 數，較佳的是10〜50的整數，進一步較佳的是〜如的 整數。 就上述化合物(C)的單元比而言，從彈性率降低、流動 性、黏合性之均衡的角度考慮，單元重量比以⑴/(11)計算 較佳的是3/7〜7/3’更佳的是4/6〜6/4，最佳的是5/5。在 3範圍大量存在，則流動性有大幅降低的 趨勢，右早70(H)大1存在，則黏合性趨於下降。 的是，單元比(1)/⑹相當於通式⑶的⑴/(mi+m2)。 〇 構成本發財使狀化合物(〇料(1 I:::，魏測定的來自各單元的質子的積分 相對於100 f量份環氧樹脂 5 20重量份。若上述化合物(C)的添加量小於的疋 則難以表現出作為可撓_效果上關， 量超過上述範圍，則流動性及阻燃性趨H物⑹的添加 體，在分子量相同而單元⑴大旦在况下為白色固 中使用_氧樹糊可以使用以往公知的環 12 200906959 3脂間:使:的環，]如有:將笨酴、甲驗、二甲 成α墓秘本?-、鄰笨一紛、雙齡A、雙齡F等苯_A/ ί二二、二經基萘等蔡_和曱趁、乙盤、丙 進^揚科具祕基的化合物在酸性催化劑下 、黍:聚：侍到的酚醛清漆相"旨環氧化的苯酚醛清 二祕清漆型環氧樹脂、具有三笨基甲 几条的衣氧樹脂等酚醛清漆型環氧樹脂； 雙酚A、雙酚f、雔酚s、 ’ 二縮水甘絲取代或未取代的伽等的 芪(stilbene)型環氧樹脂； 氫醌型環氧樹脂； 由鄰苯：曱酸、二聚酸等多元酸與環氧氣丙烷 (:P。她咖_反應得到的縮水甘油輕環氧樹脂； 庙jit苯基r、異氰尿酸等聚胺與環氧氯丙燒的反 應付到的縮水甘油胺型環氧樹脂； 一壤戊二_苯_貞的騎概崎氧化物； 含有萘環的環氧樹脂； 含有苯二甲基骨架、亞聯苯基骨架的祕韻基樹脂、蔡 盼.方烧基樹脂等蒡燒基型祕樹脂的環氧化物； 三羥曱基峨贿氧樹脂； 萜烯改性環氧樹脂； 將烯L鍵【X過乙酸等過酸氧化*得到的線狀脂肪族環氧 脂、脂環族環氧樹脂； 3 ”L原子的環氧樹脂等，上述樹脂可以單獨使用，也可以 13 200906959 是 兩種或兩種以上組合併用。 其中，從流動性及耐回流性的角度考慮，較 苯型壤氧樹腊、雙齡F型環氧樹脂、塞型環氧樹^以^ ==脂;從硬化性的角度考慮，‘“ 月漆氧樹月曰丨從低吸濕性的角度考慮，較佳 樹Γ;從耐熱性及低f曲性的角度考慮;二 =樹月1以及三苯基甲烧型環氧樹脂；從_ 基型環ΐϊΐ Hr是亞鮮基㈣氧触及萘齡.芳燒 ==提高高溫放置特性㈣度考慮，較佳=二 性良好的樹脂來實現無《化、無氣。 阻燃 氧樹型f氧樹月旨可以列舉如：下述通式(m)所示的環 曰，又酚F型環氧樹脂可以列舉如：下述通式αν、 =二下二 L化學式5] R^RZ Rs R6 〇-Y>-o-ch2-ch-ch2 (ni) R3 R4 R7 R8 ° R R4 R7 R8 (其中，R1〜R8選白& 未取代的-價M11原子以及碳原子數為1〜1G的取代或 全部不同。η /, ’可以是—部分或全部補，也可以是 χ 衣不0〜3的整數。） [化學式6] 200906959Mi I ch3 (In the formula (5), 1^ and 13⁄4 are preferably in the range of $20, any of which may be 0.) and 'the compound (C) preferably contains the structural formula (1) at both ends. The triblock copolymer of the structural formula (I) - structural formula (II) - structural formula (1) of the unit, further preferably contains a bonding group between the units. In particular, the structure of the above formula (3) is preferred. The structure of the formula (3) is composed of a unit of the structural formula (I) having high compatibility with a resin and a polyoxyalkylene unit comprising the formula (II), and the above structure 200906959 formula (II) can lower the modulus of elasticity. In 1(3), '1 is an integer from 1 to 200, and mi+m2 is an integer from 2 to 400. R represents a divalent hydrocarbon group having a carbon number of 10 . In particular, from the viewpoint of dispersion 5, the number of carbon atoms of 'R4 is compared with the fraction of all compounds (C); it is preferable that the number of carbon atoms of R4 in each molecule is in the range of 1 to 10 described above. Make distribution. The compound (C) as described above can be obtained from the trade name WAX OH 350D (developed product name SLM446200 series or SLJ166 173 rib 1732, 1733 = 34) manufactured by Wacker. The more the dispersibility of the epoxy resin composition is increased, and the smaller the mysterone domain of the structural formula (II) is dispersed, the more the epoxy resin composition is lowered and the stress is lowered. The number average molecular weight η of the above compound (C) is preferably from 2,000 to 20,000, more preferably from 3 to 15 Å, and particularly from 5,000 to 10,000, from the viewpoint of a decrease in the modulus of elasticity. When the number average molecular weight Μη of the compound (c) is 2,000 or more, metal pee or the like is preferable for the adherend. When the number average molecular weight Μη of the compound (C) is 20,000 or less, the decrease in the mobility can be suppressed. The number average molecular weight Mn of the compound (c) used in the present invention is obtained by gel permeation chromatography (GPC) using a calibration curve obtained from standard polystyrene. In the present invention, the above Mn is measured by the GPC method, in which the pump uses the L_62 type manufactured by Hitachi, Ltd., the column uses TSKgel-G5000HXL, and TSKgel-G2000HXL (both manufactured by TOSHO Co., Ltd., trade name). The detector was used in the L-3300RI type manufactured by Hitachi, Ltd., and the tetrahydrofuran was used as a dissolving solution at a temperature of 3 Torr. 〇, 11 200906959 The measurement was carried out under a flow rate of 1.0 ml/min. 1 is preferably an integer of 20 to 80, and further preferably an integer of from 5% to 5 。. From the viewpoint of the manufacturing method, it is preferable that the name and the melon 2 are substantially the same value. When im + m2 is taken as m, m is an integer of 2 to 4 Å, preferably an integer of 10 to 50, and further preferably an integer of 〜. With respect to the unit ratio of the above compound (C), from the viewpoint of the balance of the elastic modulus, the fluidity, and the adhesion, the unit weight ratio is preferably 3/7 to 7/3' calculated by (1)/(11). More preferably 4/6~6/4, the best is 5/5. When there is a large amount in the range of 3, the fluidity is greatly reduced. When 70 (H) is large, the adhesion tends to decrease. The unit ratio (1)/(6) corresponds to (1)/(mi+m2) of the general formula (3). 〇 constitutes the present futile compound (1 I:::, the integral of protons from each unit measured by Wei is 20 parts by weight relative to 100 f parts of epoxy resin. If the amount of the above compound (C) is added If the amount is less than 疋, it is difficult to express the additive which is more flexible than the above range, and the fluidity and flame retardancy tend to be H (6). The molecular weight is the same and the unit (1) is white in the case of large denier. Use _ oxygen tree paste can use the previously known ring 12 200906959 3 between the fat: make: the ring,] if there is: will be clumsy, a test, dimethyl into a tomb secret? -, neighboring stupid, double age A Benzene _A/ ί 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二Varnish phase " phenolic aldehyde-clearing varnish-type epoxy resin, phenolic varnish type epoxy resin such as oxy-resin resin with three stupid bases; bisphenol A, bisphenol f, phenol s, ' a stilbene type epoxy resin substituted or unsubstituted with dimethyl sulphate; a hydroquinone type epoxy resin; from o-benzene: citric acid, dimerization Polyacrylic acid such as acid and epoxidized gas propane (: P. Herba _ reaction to obtain glycidyl light epoxy resin; temple jit phenyl r, isocyanuric acid and other polyamines and glycidyl chloride reaction to the glycidol Amine type epoxy resin; a glutamic acid oxide of a pentylene benzene benzene; an epoxy resin containing a naphthalene ring; a syllabic resin containing a benzene dimethyl skeleton and a biphenylene skeleton, Cai Pan. An epoxide of a bismuth-based type resin such as a sinter-based resin; a trishydroxy hydrazine resin; a terpene-modified epoxy resin; a linear shape obtained by oxidizing an olefinic L bond [peric acid such as X-peracetic acid] Aliphatic epoxy resin, alicyclic epoxy resin; epoxy resin of 3" L atom, etc., the above resins may be used singly or in combination with each other, and may be used in combination with two or more types. From the point of view of reflowability, compared with benzene type oxidized tree wax, double age F type epoxy resin, plug type epoxy tree ^^==fat; from the viewpoint of hardenability, '“月漆氧树月曰丨From the viewpoint of low hygroscopicity, it is better for tree shrub; from the viewpoint of heat resistance and low f curvature; two = tree month 1 and triphenyl A fire-retardant epoxy resin; from the _ base ring ΐϊΐ Hr is a fresh base (4) oxygen touches the naphthalene age. aromatic burning == improve the high temperature placement characteristics (four) degree considerations, preferably = good secondary resin to achieve no The flame retardant oxygen tree type f oxygen tree may be exemplified by a ring enthalpy represented by the following formula (m), and a phenol F type epoxy resin may be exemplified by the following formula: αν, =2 2L Chemical Formula 5] R^RZ Rs R6 〇-Y>-o-ch2-ch-ch2 (ni) R3 R4 R7 R8 ° R R4 R7 R8 (wherein R1 to R8 are white & unsubstituted - valence M11 The atom and the substitution of the number of carbon atoms of 1 to 1 G are all different. η /, ' may be - partially or completely complemented, or may be an integer of 0 to 3. ) [Chemical Formula 6] 200906959

(其中，R1〜R8選自氫原子、碳原子數為1〜10的烷基、 碳原子數為1〜10的燒氧基、碳_原子數為6〜10的芳基以 及碳原子數為6〜10的芳烧基，可以是一部分或全部相 同，也可以是全部不同。η表示0〜3的整數。） [化學式7](wherein R1 to R8 are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number of The aryl group of 6 to 10 may be partially or entirely the same or may be all different. η represents an integer of 0 to 3.) [Chemical Formula 7]

〇-CH2-CH-CH2 (V) (其中’ R1〜R8選自氳原子以及碳原子數為1〜5的取代或 未取代的一價烴基’可以是一部分或全部相同，也可以是 全部不同。η表示0〜10的整數。） [化學式8]〇-CH2-CH-CH2 (V) (wherein 'R1 to R8 are selected from a halogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms' may be partially or wholly the same or may be all different η represents an integer of 0 to 10.) [Chemical Formula 8]

(其中，R1〜R8選自氫原子、取代或未取代的碳原子數為 1〜10的烷基以及取代或未取代的碳原子數為卜1〇的烷 也可以是全部不同。 氧基，可以是一部分或全部相同， 表示0〜3的整數。） 上述通式(III)所示的聯苯型環氧 4,4，雙(2,3-環〗 ' 丨旨可以列舉如：以 基)-3,3，，5,5’-四(wherein R1 to R8 are selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkyl group having 1 or less carbon atoms may be all different. It may be a part or all of the same, and represents an integer of 0 to 3.) The biphenyl type epoxy 4,4, bis(2,3-ring) represented by the above formula (III) can be exemplified by )-3,3,,5,5'-four

15 200906959 基)雙盼反應而得到 物可以由γχ_41 f為要成分的環氧樹脂。此種化合 等作為市售品而獲^(股)公司製商品名）15 200906959 Base) An epoxy resin having a desired composition of γχ_41 f as a desired component. Such a compound or the like is obtained as a commercial product and is obtained as a product name of the company.

Ri、所示的魏F型環氧樹脂例如可以由以Ri, the shown Wei F type epoxy resin can be, for example,

心二"為甲基、^〜及以氯原子- 公司為主要成分的YSLV_8GXY (東都化成(股） 1製商。口名）等作為市售品而獲取。 系絮3通Ϊ(ν)所示的E型;_脂可以藉由使原料篆 ] 員與絃氧氯丙烷在鹼性物質的存在下進行反應而得 此原料芪系苯酚類例如有：3_第三級丁基_4,4，_二羥基 ’5’5 _甲基篆、3_第三級丁基_4,4，_二經基_3, 5,卜二甲 基篆、4,4，-二經基-3,3，，5,5，_四甲紅、4,4，_二經基^3甲_ 一第三級丁基_5,5，·二曱基芪、4,4，_二羥基_3,3，-二第三級 :基_6,6’-二甲基芪等，其中較佳的是3_第三級丁基_4,4，_ 了'羥基_3’，5,5’-三曱基芪以及4,4，-二羥基_3,3，，5,5，_四甲基 芪。上述芪型苯酚類可以單獨使用，也可以是兩種或兩種 以上組合使用。 上述通式(VI)所示的含硫原子的環氧樹脂中，較佳的 是R2、R3、R6及R7為氫原子且R]、R4、以及r8為烷基 的環氧樹脂；更佳的是R2、R3、R6及R7為氫原子且尺〗及 R8為第三級丁基、R4及R5為甲基的環氧樹脂。此種化合 物可以由YSLV-120TE (東都化成(股)公司製商品名）等作 16 200906959 $市售品而齡。上述軌翻可叫獨 可LV J系你士工仏·、， ， r A ·· — ^ 可以是兩種或兩種以上組合使用 下述通式(VII)所示 齡醛清漆型環氧樹脂可以列舉如 的環氧樹脂等。 [化學式9] C^CH- ch2~9 / ci^-/Ch-ch2—ο R ’ ο 义R ch2---f□ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The ash 3 is ventilated by the type E (v); the _ lipid can be obtained by reacting a raw material with a string chloropropane in the presence of a basic substance to obtain a phenolic phenol such as: _ third-stage butyl _4,4,-dihydroxy '5'5 _methyl hydrazine, 3 _ tertiary butyl _4, 4, _ di-based _3, 5, bis-dimethyl hydrazine, 4,4,-di-diyl-3,3,,5,5,_tetramethyl red, 4,4,_di-diyl group ^3A_ a third-order butyl_5,5,·didecyl芪, 4, 4, _ dihydroxy _3, 3, - two third stage: yl-6,6'-dimethyl hydrazine, etc., of which 3_third butyl _4, 4 is preferred. _ 'Hydroxy-3', 5,5'-trimethylhydrazine and 4,4,-dihydroxy-3,3,5,5,-tetramethylguanidine. The above quinone type phenols may be used singly or in combination of two or more kinds. In the sulfur atom-containing epoxy resin represented by the above formula (VI), an epoxy resin in which R2, R3, R6 and R7 are a hydrogen atom and R], R4 and r8 are an alkyl group is preferred; An epoxy resin in which R2, R3, R6 and R7 are a hydrogen atom and R8 is a third-order butyl group, and R4 and R5 are a methyl group. Such a compound may be used as a commercial product by YSLV-120TE (trade name manufactured by Tohto Kasei Co., Ltd.) for 16 200906959. The above-mentioned rail-turning can be called LV J-series, your work, 、,,, r A ·· — ^ It is possible to use two or more combinations of the aldehyde-varnish type epoxy resin of the formula (VII) For example, an epoxy resin or the like can be cited. [Chemical Formula 9] C^CH-ch2~9 / ci^-/Ch-ch2-ο R ’ ο 义 R ch2---f

CI^CH—CH2- —ch2- u 中’ R選自氫原子以及碳原子 取代的-價烴基，n表示0〜10的整數。） 使严士，通式(VII)所示的酚醛清漆型環氧樹脂可·以藉由 衣氣氯峨與_清漆型祕樹脂反應_易得到。其 里通式(VII)中的反較佳的是：曱基、乙基、丙基、丁基、 氣式基、，丁基等碳原子數為1〜1G 基、甲氧基、乙 佳二θ ^氧基、、丁氡基等碳原子數為1〜10的烷氧基。更 (Viri疋氫原子或甲基。η較佳的是〇〜3的整數。上述通式 漆的，清漆型環氧樹脂中，較佳的是鄰甲驗酸清 (胳、，氡樹脂。此種化合物可以由E0CN-1G2G (日本化藥 商品名)等作為市售品而獲取。 所+ 一烯型環氧樹脂可以列舉如：下述通式(VI11) 斤不的環氧樹脂等。 [化學式10] 17 200906959In the case of CI^CH-CH2--ch2-u, 'R is selected from a hydrogen atom and a carbon-substituted-valent hydrocarbon group, and n represents an integer of 0 to 10. The phenol novolak type epoxy resin represented by the formula (VII) can be easily obtained by reacting the gas chloride with the varnish type secret resin. The anti-preferred in the general formula (VII) is: a mercapto group, an ethyl group, a propyl group, a butyl group, a gas group group, a butyl group, etc., having a carbon number of 1 to 1 G group, a methoxy group, and a bis group. An alkoxy group having 1 to 10 carbon atoms such as a di-theta-oxy group or a butyl group. Further, (Viri 疋 hydrogen atom or methyl group. η is preferably an integer of 〇 〜 3. In the varnish-type epoxy resin of the above general varnish, it is preferably an acid phthalate. Such a compound can be obtained as a commercial product by E0CN-1G2G (trade name of Nippon Chemical Co., Ltd.), etc. The mono-type epoxy resin can be exemplified by an epoxy resin having the following general formula (VI11). [Chemical Formula 10] 17 200906959

(八中R及R分別獨立地選自氫原子以及碳原子數為l 〜^的取代或未取代的—健基，η杨〇〜10的整數， m表示〇〜6的整數。） 上述式(VIII)中的Rl可以列舉如：氫原子、甲基、乙 二、=基、丁基、異丙基、第三級丁基等絲；乙稀基、 、丙土了烯基等烯基；鹵代烧基、氨基取代的炫基、疏 代的燒基等碳原子數為卜5的取代或未取代的一價 =。其中較佳的是甲基、乙基魏基以及氫原子，更佳 其疋甲基以及氫原子。R2可以列舉如：氫原子、甲基、乙 二、丙基、了基、異丙基、第三級T基魏基；乙稀基、 =丙基、T烯基等烯基；鹵代、氨基取代的烧基、疏 2代的絲#碳原子數為1〜5的取代或未取代的一價 、土其中車乂佳的疋氫原子。此種化合物可以由HP-7200 (大曰本油墨化學工業(股)公司製商品名）等作為市售品而 獲取。 萘型環氧樹脂可以列舉如：下述通式(Ιχ)所示的環氧 樹脂等；三苯基甲烷型環氧樹脂可以列舉如：下述通式(χ) 所示的環氧樹脂等。 [化學式11] 200906959 r ch-2ch-ch2 cl Ο II r^l—+CH2(Ethylene R and R are each independently selected from a hydrogen atom and a substituted or unsubstituted hexyl group having a carbon number of 1 to ^, an integer of η 〇 〇 10, and m represents an integer of 〇 〜6.) R1 in (VIII) may, for example, be a hydrogen atom, a methyl group, a ethane group, a decyl group, a butyl group, an isopropyl group or a third-order butyl group; or an ethyl group such as an ethylene group or a propyl group; The number of carbon atoms such as a halogenated group, an amino-substituted leuko group, and a halogenated group is a substituted or unsubstituted monovalent =. Preferred among them are a methyl group, an ethyl group and a hydrogen atom, more preferably a methyl group and a hydrogen atom. R2 may, for example, be a hydrogen atom, a methyl group, a ethanediyl group, a propyl group, a benzyl group, an isopropyl group, a third-order T-based wei group; an ethyl group such as an ethylene group, a propyl group or a T-alkenyl group; The amino-substituted alkyl group, the second-order silk ## has a substituted or unsubstituted monovalent carbon atom having a carbon number of 1 to 5, and a ruthenium hydrogen atom which is preferably a ruthenium. Such a compound can be obtained as a commercial product from HP-7200 (trade name, manufactured by Otsuka Ink Chemical Industry Co., Ltd.). Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following formula (Ιχ); and the triphenylmethane type epoxy resin may, for example, be an epoxy resin represented by the following formula (χ). . [Chemical Formula 11] 200906959 r ch-2ch-ch2 cl Ο II r^l-+CH2

(R )j (R2)k a2C -chchj, o 〇 -〇-ch2-CR3)i c»2ch^h： ό 〇 .(Rr)j (R2)k- f2C 'CH^h21 (R3)i (K) O-p) (其中，R1〜R3選自氫原子以及取代或未取代的碳原子數 為1^12的一價烴基，各自可以是一部分或全部相同，也 可以是全部不同。P為1或〇;卜rn分別為〇〜U的整數， I擇1 m p 4使(i+m)為1〜η的整數且(i+p)為1〜I〕 的整數。i為G〜3的整數；j為〇〜2的整數；k為〇〜 整數。） 上述通式(IX)所示的萘型環氧樹脂可以列舉如：.隨機 含有1個構成單元及爪個構成單元的無規共聚物；交替含 有1個構成單元及m個構成單元的交替共聚物；規則含有 1個構成單元及m個構成單元的共聚物；嵌段狀含有1個 構成單元及m個構成單元的嵌段共聚物。可以單獨使用其 ^任一種’也可以是兩種或兩種以上組合使用。r1、R2為 氫原子且R3為甲基的上述化合物可以 由NC-7000 (日本化 藥(股)公司製商品名）等作為市售品而獲取。 [化學式12] O-CH—CftCH2 0-CH-2CH-CH2Si-、人0(R )j (R2)k a2C -chchj, o 〇-〇-ch2-CR3)ic»2ch^h: ό 〇.(Rr)j (R2)k- f2C 'CH^h21 (R3)i (K Op) (wherein R1 to R3 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, each of which may be partially or wholly the same or may be all different. P is 1 or 〇 Bu rn is an integer of 〇~U, and I selects 1 mp 4 such that (i+m) is an integer of 1 to η and (i+p) is an integer of 1 to I]. i is an integer of G~3; j is an integer of 〇~2; k is 〇~ integer.) The naphthalene type epoxy resin represented by the above formula (IX) may, for example, be a random copolymer containing one constituent unit and a claw constituent unit at random. An alternating copolymer containing one constituent unit and m constituent units alternately; a copolymer containing one constituent unit and m constituent units; a block copolymer containing one constituent unit and m constituent units in a block form; . They may be used singly or in combination of two or more kinds. The above compound in which r1 and R2 are a hydrogen atom and R3 is a methyl group can be obtained as a commercial item from NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.). [Chemical Formula 12] O-CH-CftCH2 0-CH-2CH-CH2Si-, human 0

RR

RR

(X) Λ 〇-ci^ch-ch2 (其中，R選自氫原子以及碳原子數為1〜10的取代或未 取代的一價煙基，n表示1〜1〇的整數。） 19 200906959 為氫原子的上述化合物可以由(japan Epoxy Resin (股)公司製商品名)等作為市售品而獲取。 亞聯苯基型每氧樹脂可以.列舉如：下述通式(XI)所示 的環氧樹脂等；萘㈣絲型環氧樹脂可以列舉如：下述 通式(XII)所示的環氧樹脂等。 [化學式13](X) Λ 〇-ci^ch-ch2 (wherein R is selected from a hydrogen atom and a substituted or unsubstituted monovalent nicotine group having 1 to 10 carbon atoms, and n represents an integer of 1 to 1 。.) 19 200906959 The above-mentioned compound which is a hydrogen atom can be obtained as a commercial item (trade name, manufactured by japan Epoxy Resin Co., Ltd.). Examples of the biphenylene type peroxy resin include an epoxy resin represented by the following formula (XI); and a naphthalene (tetra) silk type epoxy resin: a ring represented by the following formula (XII) Oxygen resin, etc. [Chemical Formula 13]

(上式中，R1〜；R9可以是一部分或全部相同，也可以是全 部不同’R1〜R9選自氫原子、曱基、乙基、丙基、丁基、 異丙基、異丁基等碳原子數為1〜10的烧基；甲氧基、乙 氧基、丙氧基、丁氧基等碳原子數為丨〜忉的烷氧基；苯 基、甲苯基、二甲苯基等碳原子數為ό〜10的芳基；以及 苄基、笨乙基等碳原子數為6〜1〇的芳燒基，其中較值的 是氫原子和甲基。η表示0〜10的整數。） [化學式14](In the above formula, R1~; R9 may be partially or wholly the same, or may be all different 'R1 to R9 are selected from a hydrogen atom, a decyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, etc. a group having 1 to 10 carbon atoms; an alkoxy group having a carbon number of 丨~忉 such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a carbon such as a phenyl group, a tolyl group or a xylyl group; An aryl group having an atomic number of ό10; and an aryl group having a carbon number of 6 to 1 Å such as a benzyl group or a phenanthyl group, wherein a comparative value is a hydrogen atom and a methyl group. η represents an integer of 0 to 10. [Chemical Formula 14]

(其中，R]〜R2選自氳原子以及取代或未取代的碳原子數 為1〜12的一價烴基，各自可以是一部分或全部相同，也 20 200906959 可以是全部不同。η表示丨〜ι〇的整數。） 亞聯苯基型環氧樹脂可以由NC-3000 (日本化藥(股) 公司製商品名）作為市售品而獲取。萘酚·芳烷基型環氧樹 脂可以由ESN-175等（東都化成(股)公司製商品名）作為市 售品而獲取。上述環氧樹脂可以單獨使用任一種，也可以 是兩種組合使用。 環氧樹脂(Α)還可以使用下述結構式(XIII)所示的環氧 樹脂。 [化學式15](wherein R) to R2 are selected from the group consisting of a halogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, each of which may be partially or wholly the same, and 20 200906959 may be all different. η represents 丨~ι An integer of 〇.) The biphenylene type epoxy resin can be obtained as a commercial item from NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.). The naphthol aralkyl type epoxy resin can be obtained as a commercial product by ESN-175 (trade name, manufactured by Tohto Kasei Co., Ltd.). The above epoxy resins may be used singly or in combination of two or more. As the epoxy resin, an epoxy resin represented by the following structural formula (XIII) can also be used. [Chemical Formula 15]

(通式(XIII)中，R1選自取代或未取代的碳原子數為卜12 的烴基以及取代或未取代的碳原子數為丨〜12的蝝氧基， 可以是-部分或全部相同，也可叹全部不同。^為〇〜4 的整數。R2選自取代或未取代的碳原子數為的煙基 以及取代或未取代的碳原子數為！〜12的烷氧基，町以相 同也可以不同。m為0〜2的整數。） 土 上述通式(XIII)所示的縣_旨可㈣ 述通式 (XIV)〜(XXXII)所示的環氧樹脂等。 .(In the formula (XIII), R1 is selected from a substituted or unsubstituted hydrocarbon group having a carbon number of 12 and a substituted or unsubstituted fluorenyloxy group having a carbon number of from 丨12 to 12, which may be -partial or all the same. It is also possible to sigh all the different. ^ is an integer of 〇~4. R2 is selected from a substituted or unsubstituted carbon atom and a substituted or unsubstituted alkoxy group having a carbon number of ～12, the same m may be an integer of 0 to 2.) The soil represented by the above formula (XIII) is an epoxy resin represented by the above formula (XIV) to (XXXII). .

[化學式16] (XV) 200906959[Chemical Formula 16] (XV) 200906959

[化學式π][chemical formula π]

(XVI) 〇CH2CHCH2 och3 I ο(XVI) 〇CH2CHCH2 och3 I ο

〇CH2CHCH2 ο (ΧνΠ) [化學式18]〇CH2CHCH2 ο (ΧνΠ) [Chemical Formula 18]

(XVIII)(XVIII)

(XIX) [化學式19] 22 (XXI) 200906959(XIX) [Chemical Formula 19] 22 (XXI) 200906959

(XX)(XX)

[化學式20][Chemical Formula 20]

(XXII)(XXII)

(ΧΧΠΙ) [化學式21] \(ΧΧΠΙ) [Chemical Formula 21]

(XXV) [化學式22] 23 200906959 OCH,CHCH,(XXV) [Chemical Formula 22] 23 200906959 OCH, CHCH,

(XXVI)(XXVI)

CC

[化學式23][Chemical Formula 23]

(XXIX) [化學式24](XXIX) [Chemical Formula 24]

ί [化學式25]ί [Chemical Formula 25]

其中，從阻燃性、成形性的角度考慮，較佳的是上述 通式(XIV)所示的環氧樹脂。此種化合物可以由YX-8800 (Japan Epoxy Resin社製商品名）等獲取。 24 200906959 環氧樹脂(A)還可以使用下述通式(χχχιΙΙ)所示的化 合物。 [化學式26]Among them, the epoxy resin represented by the above formula (XIV) is preferred from the viewpoint of flame retardancy and moldability. Such a compound can be obtained from YX-8800 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) or the like. 24 200906959 The epoxy resin (A) can also be used as a compound represented by the following formula (χχχιΙΙ). [Chemical Formula 26]

(通式(xxxm)中，選自氫原子、經基、碳原子數為ι 〜8的烷基、碳原子數為丨〜6的烷氧基，可以是一部分或 全部相同，也可以是全部不同。R2及R3選自氫原子、碳 原子數為1〜6的烷基，可以是一部分或全部相同，也可以 是全部不同。η為1〜20的整數，m為1〜3的整數。） 從阻燃性、硬化性的角度考慮，通式(χχχιΙΙ)中的茁 較佳的是1〜2。η較佳的是卜5。通式(χχχιπ)所示的化 合物可以藉由使吲哚類和交聯劑在酸催化劑的存在下進行 反應’之後再與環氧鹵丙烧化合物反應而得到。 吲哚類的取代基R1可以列舉出：氫原子、甲氧基、乙 氧基、乙烯醚基、異丙氧基、烯丙氧基、丙炔醚基、丁氧 基、本乳基、甲基、乙基、乙烯基、乙炔基、正丙基、異 丙基、烯丙基、丙炔基、丁基、正戊基、第二級戊基、第 二級戊基、環己基、笨基'苄基等。較佳的是氫原子、碳 原子數為1〜3的烧基’更佳的是氫原子。 作為使交聯劑反應而得到的下述通式⑻的交聯基 團，可以列舉出：對苯二甲基、間苯二甲基、I;二亞乙 25 200906959 基本基、1,3-—亞乙基亞本基、1，4-二異亞丙基亞苯基、1 3 一異亞丙基亞本基、4,4 -一亞曱基聯苯基、3,4，__亞甲美 聯本基、3,3 -—亞曱基聯苯基、4,4’-二亞乙基聯笨基、3 4, 一亞乙基聯本基、3,3 -一亞乙基聯苯基、4,4’·-異亞丙其^ 聯苯基、3,4’-二異亞丙基聯苯基、3,3，-二異亞丙基聯苯基^ 可以將甲醛、乙醛、丙醛、丁醛、戊醛、苯甲醛、丙^等 醛類、酮類結合使用作為交聯劑。酸催化劑可以列舉如· 鹽酸、硫酸、磷酸、甲酸、草酸、三氟乙酸、對曱苯磺酸、 二甲基硫酸、二乙基硫酸、氯化辞、氯化銘、氯化鐵j二 氟化硼酸、離子交換樹脂、活性白土、二氧化石夕、氧化銘·; 沸石等。 [化學式27](In the formula (xxxm), an alkyl group selected from a hydrogen atom, a transradical group, a carbon number of 1 to 8 and an alkoxy group having a carbon number of 丨6 may be partially or wholly the same or all R2 and R3 are selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and may be partially or wholly the same, or may be all different. η is an integer of 1 to 20, and m is an integer of 1 to 3. The enthalpy in the formula (χχχιΙΙ) is preferably from 1 to 2 from the viewpoint of flame retardancy and hardenability. Preferably, η is Bu 5. The compound represented by the formula (?ιπ) can be obtained by reacting an anthracene and a crosslinking agent in the presence of an acid catalyst, followed by reaction with an epoxyhalide compound. Examples of the substituent R1 of the anthracene include a hydrogen atom, a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, an allyloxy group, a propynyl ether group, a butoxy group, a present dairy group, and a Base, ethyl, vinyl, ethynyl, n-propyl, isopropyl, allyl, propynyl, butyl, n-pentyl, second pentyl, second pentyl, cyclohexyl, stupid Base 'benzyl and the like. Preferably, a hydrogen atom or a burnt group having 1 to 3 carbon atoms is more preferably a hydrogen atom. Examples of the crosslinking group of the following formula (8) obtained by reacting a crosslinking agent include p-terephthale, m-xylylene, I; diethylene 25 200906959 basic group, 1,3- - ethylene subunit, 1,4-diisopropylidene phenylene, 13 isopropylidene subunit, 4,4-merylene phenyl, 3,4, __ Methylene group, Benzo, 3,3 --fluorenylbiphenyl, 4,4'-diethylidene, 3 4, ethylidene, 3,3-A Base phenyl, 4,4'-isopropylene, biphenyl, 3,4'-diisopropylidenebiphenyl, 3,3,-diisopropylidene biphenyl Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde, and ketone are used in combination as a crosslinking agent. The acid catalyst may, for example, be hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfonic acid, chlorinated, chlorinated, ferric chloride, j-difluorocarbon. Boric acid, ion exchange resin, activated clay, silica dioxide, oxidation, zeolite, etc. [Chemical Formula 27]

(通式(a)中，R2、R3選自氫原子、碳原子數為}〜6的烷 基，可以是一部分或全部相同，也可以是全部不同。瓜為 1〜3的整數。） 通式(XXXIII)所示的化合物可以由ENp_8〇 (東都化成 (股)公司製）等獲取。通式(ΧΧΧΙΠ)所示的化合物的軟化點 較佳的是40〜200°C，更佳的是50〜160〇C，進一步較佳的 是60〜120°C。上述軟化點小於40¾時，·硬化性降低；上 述軟化點超過200t時，流動性趨於降低。其中軟化點是 指根據JIS-K-69〗1的環球法測定的軟化點。 26 200906959 為了使上述各環氧樹脂在 揮各種性能，相對於環氧樹脂㈧總量種量上能發 量較佳的是大於等於3〇重量百分減_的添加 等於50 Wt%’進一步較佳的是。’二佳的是大於 劑為= 知的心(In the formula (a), R2 and R3 are selected from a hydrogen atom and an alkyl group having a carbon number of 1-6, which may be partially or wholly the same or may be all different. The melon is an integer of 1 to 3. The compound represented by the formula (XXXIII) can be obtained from ENp_8 (manufactured by Tohto Kasei Co., Ltd.) or the like. The softening point of the compound represented by the formula (ΧΧΧΙΠ) is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, still more preferably 60 to 120 ° C. When the softening point is less than 403⁄4, the hardenability is lowered. When the softening point exceeds 200t, the fluidity tends to decrease. The softening point thereof refers to the softening point measured according to the ring and ball method of JIS-K-69. 26 200906959 In order to make the above various epoxy resins perform various performances, the amount of energy generated relative to the total amount of epoxy resin (eight) is preferably greater than or equal to 3 〇 weight percent minus _ the addition is equal to 50 Wt%' further The good one is. 'Two best is greater than the agent = know the heart

Π雔it使苯紛、甲盼、間苯二紛、鄰苯二齡、 二二-=、胺基苯晴_“萘 13不酕一經基萘等萘酚類與曱醛、苯甲醛、水揚酿 等具祕基的化合物在雜雜劑下進行縮合或縮聚而得 到的酚醛清漆型酚醛樹脂； 、 由苯酚類及/或萘酚類與二甲氧基對二曱苯或雙（甲氧基甲 基)聯苯合成的苯酚.芳烷基樹脂、含有亞聯苯基骨架的苯 酚·芳烷基樹脂、萘酚.芳烷基樹脂等芳烷基型酚醛樹脂； 由苯酚類及/或萘酚類與二環戊二烯共聚而合成的二^戊 二烯型苯酚醛清漆樹脂、二環戊二烯型萘酚醛清漆樹脂等 一戍·一細型紛酸樹脂； 三苯基甲院型紛搭樹脂； 萜稀改性紛酸樹脂； 對苯二甲基及/或間苯二甲基改性酚醛樹脂； 蜜胺改性酚醛樹脂； 環戊二烯改性酚醛樹脂； 將上述樹脂中的兩種或兩種以上共聚而得到的酚駿樹脂 等。上述樹脂可以單獨使用，也可以是兩種或兩種以上組 27 200906959 合使用。 其中，從阻燃性、成形性的角度考慮，較佳的是下述 通式(XXXIV)所示的笨紛.芳烷基樹脂。 [化學式28]Π雔it makes benzene, 甲, 苯二二, 苯二二,二二-=, amino phenyl _ _ "naphthalene 13 is not a naphthol such as naphthalene and furfural, benzaldehyde, water a novolak-type phenolic resin obtained by condensation or polycondensation of a compound having a secret group such as a wine; a phenolic and/or naphthol and a dimethoxy-p-nonylbenzene or a bis(methoxy) Phenyl. aralkyl resin synthesized by bimethyl)biphenyl, phenolic aralkyl resin containing a biphenylene skeleton, aralkyl type phenol resin such as naphthol. aralkyl resin; by phenol and/or a dipentadiene type novolac resin synthesized by copolymerization of naphthol and dicyclopentadiene, a dicyclopentadiene type naphthol varnish resin, etc.; a fine-type acid resin; a resin; a dilute modified acid resin; a p-xylylene and/or m-xylylene modified phenolic resin; a melamine modified phenolic resin; a cyclopentadiene modified phenolic resin; a phenol resin obtained by copolymerization of two or more kinds, etc. The above resins may be used singly or in combination of two or two. Group 27200906959 used in combination. Among them, flame retardancy, moldability viewpoint, preferred is divergent stupid. Aralkyl resin represented by general formula (XXXIV) [Chemical Formula 28]

OHOH

OHOH

RR

\ OHcHr〇~cH2O / n R\ OHcHr〇~cH2O / n R

(其中，R選自風原子以及碳原子數為1〜l〇的取代或未取 代的一價烴基’ η表示〇〜10的整數。） 更佳的是上述通式(XXXIV)中的R為氫原子、η的平 均值為0〜8的苯酚.芳烷基樹脂。具體例子有：對笨二甲 ，型苯酚.芳烷基樹脂、間笨二甲基型苯酚.芳烷基樹脂 ，。此種化合物可以由XLC (三井化學(股)公司製商品名） 等作為市售品而獲取。使用上述芳烷基型酚醛樹脂時，為 了發揮其性能，相對於硬化劑總量，上述芳烷基型酚醛樹 脂的添加量較佳的是大於等於30 wt%，更佳的是大於等於 50 wt%。 ' 奈紛.芳烷基樹脂可以列舉如：下述通式(χχχν)所示 的酚醛樹脂等。 [化學式29](wherein, R is selected from the group consisting of a wind atom and a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 10 ', and η represents an integer of 〇 10 10). More preferably, R in the above formula (XXXIV) is A phenol. aralkyl resin having a hydrogen atom and an average value of η of 0 to 8. Specific examples are: dioxin, phenol, aralkyl resin, m-dimethyl phenol, aralkyl resin. Such a compound can be obtained as a commercial product by XLC (trade name, manufactured by Mitsui Chemicals Co., Ltd.). When the above aralkyl type phenol resin is used, the amount of the above aralkyl type phenol resin to be added is preferably 30% by weight or more, and more preferably 50% or more, based on the total amount of the hardener. %. The arsenic resin may, for example, be a phenol resin represented by the following formula (χχχν). [Chemical Formula 29]

上述通式(XXXV)所示的萘酚.芳烷基樹脂可以列舉 如R、R均為氫的化合物等’此種化合物可以由SN-170 28 200906959 (新曰纖，公司製商品名)作為市售品· (χχχνι)所示的祕樹脂等。了乂列舉如.下速通式 [化學式30]The naphthol. aralkyl resin represented by the above formula (XXXV) may, for example, be a compound in which R and R are both hydrogen. The compound may be used as a compound of SN-170 28 200906959 (trade name, manufactured by Shinsei Fiber Co., Ltd.). Commercial product · The secret resin shown by (χχχνι).乂 如 如 . 下 下 下 [ [ [ [ [

(XXXVI) 分觸立地選自A原子以及碳肝數為1 =的取代或未取代的—價烴基；n表示Μ的整數； m表不〇〜6的整數。） 化學二=。(新…油 ± t攸減丈，曲的觀點考慮，較佳的是三苯基甲烧型酚駿 树月曰一笨基甲烧型紛酸·樹脂可以列舉如：下述通式 (XXXVII)所示的酚醛樹脂等。 [化學式31](XXXVI) is a substituted or unsubstituted valence hydrocarbon group selected from the group consisting of A atoms and having a carbon number of 1 =; n is an integer of Μ; m is an integer of ～6. ) Chemistry II =. (New ... oil ± t 攸 丈 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ) a phenol resin or the like as shown. [Chemical Formula 31]

(XXXVII) (其中，R選自氫原子以及碳原子數為卜1〇的取代或^ 取代的一價煙基’ η表示1〜1〇的整數。） R為氫原子的上述化合物可以由ΜΕΗ_75〇〇 (明和 成(股)公司製商品名）等作為市售品而獲取。 相對於硬化劑(Β)的總量，三苯基甲烷型酚醛樹脂的每 29 200906959 加量較佳的是10〜50wt%’進—步較佳的是15〜3〇对〇/。。 三苯基甲烷型酚醛樹脂的添加量大於等於1〇wt%時，減少 彎曲的效果良好；其添加量小於等於5〇 wt%時，阻燃性^ 酚醛清漆型酚醛樹脂例如有：苯酚醛清漆樹脂、甲酚 醛清漆樹脂、萘酚醛清漆樹脂等。其中較佳的是笨酚醛1 漆樹脂。 θ(XXXVII) (wherein, R is selected from a hydrogen atom and a substituted or substituted monovalent nicotine group 'n having a carbon number of 〇1〇 represents an integer of 1 to 1 。.) The above compound wherein R is a hydrogen atom may be represented by ΜΕΗ_75 〇〇 (Minghecheng Co., Ltd. product name) and the like are obtained as commercial products. The amount of the triphenylmethane type phenol resin per 30 200906959 is preferably 10 to 50% by weight relative to the total amount of the hardener (Β), and preferably 15 to 3 〇 〇 /. . When the addition amount of the triphenylmethane type phenol resin is 1% by weight or more, the effect of reducing the bending is good; when the amount is not less than 5 Å by weight, the flame retardant phenol novolak type phenol resin is, for example, a novolac varnish. Resin, cresol novolak resin, naphthol novolak resin, and the like. Among them, a phenol novolac 1 lacquer resin is preferred. θ

含有亞聯苯基骨架的苯酚·芳烧基樹脂可以列舉如： 述通式(XXXVIII)所示的盼路樹脂等。 [化學式32]The phenol-aryl-burning resin containing a biphenylene skeleton may, for example, be a desired resin represented by the above formula (XXXVIII). [Chemical Formula 32]

J R! R2 R5 R6 R1 R2 R5 R6 OH (xxxvni) V R3 R4 R^R8 V R广V 坑8 、Μ 上式(XXXVIII)中，Ri〜R9可以是一部分或全部 同，也可以是全部不同，R1〜R9選自：氫原子；曱美σ、目 基、丙基、丁基、異丙基、異丁基等碳原子數為 烷基；曱氧基、乙氧基、丙氧基、丁氧基等碳原子數為^ 〜10的烷氧基；苯基、甲苯基、二甲苯基等碳原子數為6 〜10的芳基；以及苄基、苯乙基等碳原子數為6〜10的— 燒基。其中較佳的是氫原子和甲基。n表示〇〜1〇的整數^ 上述通式(XXX VIII)所示的含有亞聯笨基骨架的笨°. 芳烷基樹脂可以列舉如：R1〜R9均為氫的化合物等。中 從熔融黏度的觀點考慮，縮合物的混合物較佳的是含^ 於等於50 wt%的n大於等於1的縮合物。此種化$物可= 由ΜΕΗ-7851 (明和化成(股)公司製商品名）作為;售二以 30 200906959 獲取。 ^上述苯酚.芳烷基樹脂、萘酚·芳烷基樹脂、二環戊二 烯51齡駿础g、三苯基細旨、清漆型盼搭 樹脂、含有亞聯苯基骨架的苯紛·芳絲樹脂可以單獨使用 任種’也可以是兩種或兩種以上組合使用。JR! R2 R5 R6 R1 R2 R5 R6 OH (xxxvni) V R3 R4 R^R8 VR wide V pit 8 , 上 In the above formula (XXXVIII), Ri~R9 may be part or all of the same, or all different, R1 〜R9 is selected from the group consisting of: a hydrogen atom; the σ, 目, propyl, butyl, isopropyl, isobutyl and the like have an alkyl group; an anthracene group, an ethoxy group, a propoxy group, a butoxy group. An alkoxy group having a carbon number of from 0 to 10; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; and a carbon atom having 6 to 10 such as a benzyl group or a phenethyl group; - burning base. Among them, preferred are a hydrogen atom and a methyl group. n represents an integer of 〇~1〇. The aralkyl resin containing a fluorene skeleton represented by the above formula (XXX VIII) may, for example, be a compound in which all of R1 to R9 are hydrogen. From the viewpoint of melt viscosity, it is preferred that the mixture of the condensate contains a condensate having an n of 1 or more and 50 or more. This kind of material can be = as ΜΕΗ-7851 (Minghe Chemical Co., Ltd. product name) as the product; Sale 2 to 30 200906959. ^The above phenol. aralkyl resin, naphthol aralkyl resin, dicyclopentadiene 51-year-old base g, triphenyl fine-grain, varnish-type resin, phenylene containing a biphenylene skeleton The aramid resin may be used singly or in combination of two or more kinds.

結合使用的上述硬化劑中，從硬化性的觀點考慮，特 別是酚醛清漆型酚醛樹脂較佳；從流動性、耐回流性的角 度考慮，較佳的是芳烷基型酚醛樹脂。 在本發明中，硬化劑（B)中還可以包括 (XXXIX)所示的化合物。 [化學式33]Among the above-mentioned hardeners to be used in combination, a novolac type phenol resin is preferable from the viewpoint of curability, and an aralkyl type phenol resin is preferred from the viewpoint of fluidity and reflow resistance. In the present invention, the compound represented by (XXXIX) may also be included in the hardener (B). [Chemical Formula 33]

(通式(XXXIX)中’R〗選自氫原子以及碳原子數為丨〜仞 的取代或未取代的一價烴基；R2選自氫原子以及碳原子數 為1〜10的取代或未取代的一價烴基；n表示〇〜1〇'的整 數，m表示〇〜1〇的整數，且n+mg i。） 上述通式(XXXIX)所示的化合物可以列舉如：隨機含 有η個構成單元及m個構成單元的無規共聚物；交替含有 η個構成單元及m個構成單元的交替共聚物；規則含有n 個構成單元及m個構成單元的共聚物；嵌段狀含有η個構 成單元及m個構成單元的嵌段共聚物。可以單獨使用其中 200906959 任一種，也可以是兩種或兩種以上組合使用。需要說明的 是，較佳的是η及m大於等於1。 上述通式(XXXIX)所示的化合物藉由使苯酚化合物和 芳香族醛以及亞聯苯基化合物在酸催化劑的存在下進行反 應而得到。苯酚化合物使用苯酚、甲酚、乙基苯酚、丁基 苯酚等取代的苯酚類。芳香族醛為具有一個結合在芳香^ 上的搭基的芳香族化合物。芳香族酸·例如有：苯甲酸、甲 基苯甲醛、乙基苯甲醛、第三級丁基苯甲醛等。亞聯苯基 化合物可以列舉出：亞聯苯二醇、亞聯苯二醇二曱醚、= 聯笨二醇二***、亞聯苯二醇二乙醯氧基酯、亞聯苯二醇 二丙氧基酯、亞聯苯二醇單甲醚、亞聯苯二醇單乙醯氧基 酯等。特別佳的是亞聯苯二醇、亞聯苯二醇二甲醚。還可 以使用下述通式(a)所示的亞聯苯基化合物。 [化學式34] α一 cH2_0~〇-ch2-ci ⑷ 上述通式(XXXIX)所示的化合物可以由HE_61〇c、 HE-62〇C (AIR WATER (股)公司製）等而獲取。 相對於硬化劑(B)的總量，通式(XXXIX)所示的化合物 的添加量通常為50〜90 wt%，較佳的是70〜85 wt%。通 式(XXXIX)所不的化合物的添加量大於等於5〇wt%時，阻 燃性良好，其添加量小於等於9〇wt%時，彎曲減少效果良 好0 本發明之密封用環氧樹脂組成物中，從提高阻燃性的 角度考慮可以含有危烯(acenaphthylene)。危烯可以由苊 32 200906959 (mpr)脫氫轉到，也可以制市售品。還可以作 危烯與其他芳香族烯烴的共聚物來使 的聚合物或危烯與其他芳香族烯烴的共 聚物的方法’可以列舉出：自由基聚合、陽離 3=聚Γ可以使用以往習知_劑，也可: m 用熱來進行聚合。此時，聚合溫度較 物j^i6Gc，更佳的是9()〜i5(rc。所得麟的聚合 t料麵_的絲物的軟健較佳的是 转〜：! 70〜130t。上述軟化點低於6代 ，二物：其成形性趨於下降。上述軟化 …?時/、與树脂的相容性趨於降低。 作為與料共㈣其他芳钱斯！，可 ?、:甲基苯乙H苯並麵、苯射喃、Ϊ‘ 基聯苯或它們的院基取代物等。除上述芳香族$ =1，還可以在不影響本發果的範_結合使用月旨 肪族烯烴可以列舉出:(甲基)丙烯酸及其酿、 ί康酸酐、富馬酸及其酿等。相對於聚合單體 族__量較麵是小於等於20職， 更佳的疋小於等於9 wt〇/Q。 並且’危烯可以和除危稀以外的一部 (】)預混。可以使料_部分或全部硬化娜)和、^ c以及危稀與其他芳香族埽烴的共聚物中的； :叮、二上(以下也稱作苊烯成分)預混而得到的物質。預 此可以按町料騎，即：輝)私从料成分分= 33 200906959 粉碎至微細，直接以固體狀態用混合機等混合的方法；將 (B)成分及苊烯成分均勻溶解於溶解兩者的溶劑中，之後除 去溶劑的m及在大於等棒)成分及烯成分^ 軟化點的溫度下將兩者熔融，之後將其混合 人(In the formula (XXXIX), 'R' is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 丨~仞; R2 is selected from a hydrogen atom and a substituted or unsubstituted carbon number of 1 to 10. a monovalent hydrocarbon group; n represents an integer of 〇~1〇', m represents an integer of 〇~1〇, and n+mg i.) The compound represented by the above formula (XXXIX) can be exemplified by: a random copolymer of a unit and m constituent units; an alternating copolymer containing n constituent units and m constituent units alternately; a copolymer containing n constituent units and m constituent units; and a block shape containing n constituents A block copolymer of units and m constituent units. Any of the 200906959 may be used alone or in combination of two or more. It should be noted that it is preferable that η and m are equal to or greater than 1. The compound represented by the above formula (XXXIX) can be obtained by reacting a phenol compound with an aromatic aldehyde and a biphenylene compound in the presence of an acid catalyst. The phenol compound is a phenol substituted with phenol, cresol, ethylphenol, butylphenol or the like. The aromatic aldehyde is an aromatic compound having a chelating group bonded to an aromatic group. Examples of the aromatic acid include benzoic acid, methyl benzaldehyde, ethyl benzaldehyde, and tertiary butyl benzaldehyde. The biphenylene compound may, for example, be a biphenylene glycol, a biphenylene glycol dioxime ether, a dimethicone diethyl ether, a biphenylene glycol diethoxylate or a biphenylene glycol. Propyloxy ester, biphenylene glycol monomethyl ether, bisylene glycol monoethoxycarbonyl ester, and the like. Particularly preferred are biphenylene glycol and biphenylene glycol dimethyl ether. A biphenylene compound represented by the following formula (a) can also be used. α-cH2_0~〇-ch2-ci (4) The compound represented by the above formula (XXXIX) can be obtained by HE_61〇c, HE-62〇C (manufactured by AIR WATER Co., Ltd.) or the like. The compound represented by the formula (XXXIX) is usually added in an amount of 50 to 90% by weight, preferably 70 to 85% by weight based on the total amount of the hardener (B). When the amount of the compound which is not represented by the formula (XXXIX) is 5% by weight or more, the flame retardancy is good, and when the amount is not less than 9 Å by weight, the effect of bending reduction is good. The substance may contain acenaphthylene from the viewpoint of improving flame retardancy. The olefin can be dehydrogenated by 苊 32 200906959 (mpr), and a commercial product can also be produced. A method in which a copolymer of a olefin and another aromatic olefin can be used as a copolymer of a polymer or a olefin and another aromatic olefin can be exemplified as: free radical polymerization, cation 3 = poly fluorene can be used. Knowing the agent, you can also: m Use heat to carry out the polymerization. At this time, the polymerization temperature is better than the material j^i6Gc, and more preferably 9()~i5(rc. The softness of the filament of the polymerized t-material of the obtained lining is preferably 〜~! 70~130t. The softening point is lower than 6 generations, and the second material: its formability tends to decrease. The above softening...?/, and the compatibility with the resin tends to decrease. As a total of (4) other Fang Qiansi!, can?, : A Benzophenone H benzohedral, benzoin, Ϊ' phenyl or their substituents, etc. In addition to the above aromatic $ =1, it can also be used in the form of a drug that does not affect the hair. The olefins may be exemplified by (meth)acrylic acid, its brewing, yaconic anhydride, fumaric acid, and its brewing, etc. The amount of the merging of the monomeric group is less than or equal to 20, and more preferably less than or equal to 9 wt〇/Q. And 'nutrients can be premixed with a part other than the rare ones. It can make the material _ part or all hardened Na) and ^ c and the copolymerization of the rare and other aromatic terpene hydrocarbons. In the product; : 叮, 二上 (hereinafter also referred to as terpene component) premixed. In the meantime, it can be used as a raw material, ie: Hui) private material component = 33 200906959 pulverized to fine, directly mixed with a mixer in a solid state; the component (B) and the terpene component are uniformly dissolved in the two dissolved In the solvent of the person, after removing the solvent m and melting at a temperature greater than the bar component and the softening point of the olefin component, the two are mixed.

法等。其中較佳的是㈣混合法，該方法可得到均^混 合物，且雜質的混入少。熔融混合時的溫度沒有特別限定， 只要大於科(B)成分及/或⑽齡的軟化科可，較佳 的是100〜25CTC，更佳的是12〇〜綱。c。溶融混合的混^ 時間沒有特別限定，只要將兩者均勻混合即可，較佳的h 1小時〜20小時，更佳的是2小時〜15小時。土疋 將硬化劑(B)和危烯成分預混時，混合中危稀成分可以 聚合或與硬㈣⑼反應。本發明之密魏翻旨組成物 中，從提高由㈣成分的分散性產生的阻燃性的角卢考 慮’較佳的是，在硬化劑⑻的總量中含有大於等於9〇二％ 的上述預混物(苊稀改性硬化劑）。 危烯改性硬化劑中所含的上述輯成分的量較佳的是 5〜4〇wt%，更佳的是8〜25wt%。若上述危稀成分的量少 於5 Wt% ’則阻燃性趨於降低；若料成分的量多於4〇 wt%，則成形性趨於降低。從阻燃性和成形性的角度考慮， 本發明之環氧樹脂組成物巾所含的Μ烯結構的含有率較佳 的是0.1〜5 Wt%，更佳岐G.3〜3赠％。若㈣結構的含 有率少於0.1 Wt%，則阻燃性趨於變差；若苊烯結構的含 有率多於5 wt% ’則成形性趨於降低。 環氧樹脂(A)與硬化_)的當量比、即硬㈣中的經 34 200906959 基，量相對於環氣樹月旨 羥基數/環氧樹脂中 知的衣軋基數量之比(硬化劑中的 各自的未反應份，氣基數)沒有特別限定，為了減少 是〇.6〜U。為H、是設定為〇·5〜2的範圍，更佳的 氧樹脂組成物，進性及耐回流性優異的密封用環 1.2的範圍。 ’幸父佳的是將上述比例設定為0.8〜 (硬化劑中的縣數脂Λ的環氧基數量之比 定，為了減少各自的未反庫曰中的％乳基數)沒有特別限 為〜2的範圍，更佳的^6^述#量味佳的是設定 耐回流性優里的密封用产^ ·〜.3。為了得到成形性及 口二^、的在封用每乳樹脂組成物，進一 疋，上述當量比設定為〇.8〜12的範圍。 佳的 料，為了促進環氧樹 ⑹。硬滅進劑⑻沒有特別限定’只要是密 = 脂組成物中通常所使用的硬化促_即可，可=樹 U-二氮雜二環[5.4射-碳烯_7、】，5•二氮雜二=· 壬稀-5、5,6-二丁基胺基-】，8_二氮雜二環[5.蝴十操0J 等環脒化合物；以及 秦7 於上述化合物上加成馬來酸酐、1，‘笨藏、曱笨 萘醒、2,3-二甲基苯酿、2,6-二甲基苯醌、2’3_^其1，4- 甲基妙絲、2,3·二苯基从細 化合物以及重氮苯基找、祕樹料騎續的化合2 35 200906959 而形成的具有分子内極化的化合物； 苄基二甲胺、三乙醇胺、二曱胺基乙醇、三(二曱胺基甲基） 苯酚等三級胺類及其衍生物； 曱基σ米0坐、2·笨基〇米〇坐、2-苯基-4-甲基σ米〇坐、2-十七烧 基咪唑等咪唑類及其衍生物； 三丁基膦、曱基二苯基膦、三苯基膦、三(4-曱基苯基)膦、 二苯基膦、苯基膦等有機膦類；以及 於上述膦類上加成馬來酸針、上述I昆化合物、重氮苯基曱 烷、酚醛樹脂等具有π鍵的化合物而形成的具有分子内極 化的鱗化合物； 四苯基鐫硼酸四苯酯、四苯基鱗硼酸乙基三苯酯、四丁基 鱗爛酸四丁 S旨荨四取代鱗.四取代硼酸酉旨； 2-乙基_4_曱基咪唑·硼酸四苯酯、Ν_甲基嗎啉硼酸四苯酯 等四苯基硼鹽以及它們的衍生物等。 、上述硬化促進劑可以單獨使用，也可以是兩種或兩種 以上組合使用。 上述硬化促進劑中，從硬化性以及流動性的角度考 慮較佳的疋第二膦化合物與醌化合物的加成物，特別佳 的是二丁基膦與苯醌的加成物。從保存穩定性的角度考 慮二較佳的是環脒化合物與酚醛樹脂的加成物，更佳的是 重氮二環十一碳烯的酚醛清漆型酚醛樹脂鹽。相對於硬化 f進劑總量，上述較佳的硬化促進劑的添加量合計較佳的 &大於等於6Gwt% ’更佳岐大於等於8〇 wt%。 第二膦化合物與醌化合物的加成物中所使用的第三膦 36 200906959 化合物沒有特別限定，可以列舉如：二丁基苯基麟、丁基 =苯基膦、乙基：苯基膦、三苯基膦、三(4_f基苯基)麟土、 :(4-乙基苯基)膦、三(4_丙基苯基)膦、三(4_丁基苯基)麟、 ^(異丙基苯基)膦、三（第三級丁基苯基)膦、三(2,4_二曱基 ，基)膦、二(2,6-二甲基苯基)膦、三(2,4,6•三甲基苯基请、 三(2,6-二甲基斗乙氧基苯基)膦、三(4_甲氧基苯基)麟、三 (4-乙氧基苯基)膦等含技基、芳基的第三膦化合物，從 成形性的角度考慮，較佳的是三苯基膦。作為酿化合物， ^有特別限定，可以列舉如：鄰苯醒、對苯醌、二苯紛合 苯酉比、I，4-奈酿、惠等，從财濕性或保存穩定性的角度考 慮，較佳的是對苯醌。 硬化促進劑(E)的添加量沒有特別限定，只要是達到硬 化促進效果的量即可，相對於環氧樹脂 總量剛重量份，硬化促進_的添加量較佳的! ^重量f，更佳的是心5重量份。硬化促進‘_ 口f不足曰0.1重置份時，短時間的硬化性趨於變差；而超 .讀時’硬化速度太快，存在無法得到良好的成形 口口的趨勢。 如益之逸封用環氧樹脂組成物中，根據需要可以添 加無機填充劑(D)。 兴一本發月中，用的無機填充劑(D)沒有特別限定 ，可以列 =柄t氧切、結晶二氧化石夕、氧化紹、錯英石、 化錯等的粉末^氮化銘、氮化獨、氧化鈹、氧 禾次將匕們球形化而得到的珠粒；鈦酸鉀、碳 37 200906959 氮化矽、氧化鋁等的單晶纖維、玻璃纖維等。 1、阻燃效果的無機填充劑，更可以列舉出：氫氧化銘： ，氧化，、職鋅等。上述無機填充劑(D)可以單獨使用， /疋兩種或兩種以上結合使用。上述無機填充劑 ’ ^低線膨脹係數的角度考慮，較佳的是炫融二氧化 ，從同導熱性的角度考慮，較佳的是氧化鋁。從成形時 =流動性以及金屬模磨損性的肖度考慮，上述無機填充劑 (D)的形狀較佳的是球形或近似於球形。 從成形性、吸濕性、降低線膨脹係數以及提高強度的 角度考慮，相對於密封用環氧樹脂組成物，上述無機填充 劑(D)的添加量(含量)較佳的是65〜95 wt°/。，更佳的是'7〇 〜95 Wt:/0 ’進-步較佳的是75〜％加％。上糖機填充劑 的添加量小於65 wt%時，耐回流性趨於降低。 在使用無機填充劑(D)的情況下，為了提高樹脂成分與 填充劑的黏合性，較佳的是，在本發明之密封用環氧樹脂 組成物中更添加耦合劑(F)。耦合劑(F)為密封用環氧樹脂組 成物中通常所使用的耦合劑，沒有特別限定。可以列舉如： 含有一級及/或一級及/或二級胺基的♦院化合物、環氧笑 矽烷、毓基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等各 種石夕炫糸化合物；鈦系化合物、銘螯合物類、銘/錯系化合 物等。 例如有：乙烯基三氯矽烷、乙烯基三乙氧基矽院、乙 婦基二(P-甲氧基乙氧基)梦烧、γ-甲基丙烯醯氧丙基三甲氧 基矽烷、β-(3,4-環氧基環己基）乙基三甲氧基矽烷、γ_縮水 38 200906959 甘油氧丙基三曱氧基矽烷、γ·縮水甘油氧丙基甲基二曱氧 基石夕院、乙烯基三乙醯氧基石夕院、γ_疏基丙基三甲氧基石夕 烧γ-胺丙基二甲氧基梦烧、γ-胺丙基甲基二甲氧基梦烧、 γ-胺丙基三乙氧基矽烷、γ-胺丙基甲基二乙氧基矽烷、丫_ 苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、 γ-(Ν，Ν-二甲基)胺丙基三甲氧基矽烷、γ_(Ν，Ν_二乙基)胺丙 基二甲氧基梦院、γ-(Ν，Ν- — 丁基)胺丙基三甲氧基秒烧、 r 甲基)苯胺基丙基三甲氧基矽烷、γ-(Ν-乙基)笨胺基丙 基三甲氧基矽烷、γ-(Ν,Ν-二甲基)胺丙基三乙氧基石夕烧、 γ-(Ν，Ν-二乙基)胺丙基三乙氧基石夕烧、γ-(Ν，Ν-二丁基)胺丙 基二乙氧基碎烧、γ-(Ν-曱基)苯胺基丙基三乙氧基碎娱^、 γ-(Ν-乙基)苯胺基丙基三乙氧基矽烷、γ-(Ν，Ν-二甲基)胺丙 基曱基二甲氧基矽烷、γ-(Ν，Ν-二乙基)胺丙基曱基二甲氧基 矽烷、γ-(Ν，Ν-二丁基)胺丙基甲基二曱氧基矽烷、γ-(Ν-甲 基)苯胺基丙基甲基二甲氧基矽烷、γ-(Ν-乙基)苯胺基丙基 甲基二甲氧基矽烷、Ν-(三甲氧基甲矽烷基丙基)亞乙基二 „ 胺、Ν-(二曱氧基甲基甲矽烷基異丙基)亞乙基二胺、曱基 三曱氧基矽烷、二曱基二甲氧基矽烷、曱基三乙氧基矽烷、 γ-氯丙基三甲氧基矽烷、六曱基二矽烷、乙烯基三曱氧基 矽烷、γ-酼基丙基曱基二甲氧基矽烷等矽烷系耦合劑； 異丙基三異硬脂醯基鈦酸酯、異丙基三(二辛基焦磷酸酯） 鈦酸酯、異丙基三(Ν-胺乙基-胺乙基)鈦酸酯、四辛基二(雙 十三烷基亞磷酸醋)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基) 二(雙十三烷基)亞磷酸酯鈦酸醋、二(二辛基焦磷酸酯）氧基 39 200906959 乙酸酯鈦酸酯、二(二辛基焦鱗酸酯）亞乙基鈦酸酯、異丙 基三辛醯基鈦酸酯、異丙基二甲基丙婦酸異硬脂醯基鈦酸 酯、異丙基三（十二烷基)苯磺醯基鈦酸酯、異丙基異硬脂 醯基二丙烯酸鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、 異丙基二枯烯基苯基鈦酸酯、四異丙基雙(二辛基亞磷酸酯) 鈦酸s旨荨碳酸g旨系麵合劑等。上述轉合劑可以單獨使用一 種’也可以是兩種或兩種以上組合使用。 從流動性、金線變形降低、阻燃性的角度考慮，其中 車父佳的疋具有一級胺基結構的梦烧麵合劑。具有二級胺基 結構的矽烷耦合劑沒有特別限定，只要是分子内具有二級 胺基的矽烷化合物即可。例如有：γ_苯胺基丙基三甲氧基 矽烷、γ-苯胺基丙基三乙氧基矽烷、苯胺基丙基甲基二 甲氧基矽烷、γ-苯胺基丙基甲基二乙氧基矽烷、γ_苯胺基 丙基乙基一乙氧基石夕烧、γ_苯胺基丙基乙基二甲氧基石夕 烷、γ-苯胺基甲基三甲氧基矽烷、γ_苯胺基甲基三乙氧基 矽烷、γ-苯胺基曱基曱基二曱氧基矽烷、γ_苯胺基甲基甲 基二乙氧基矽烷、γ-苯胺基甲基乙基二乙氧基矽烷、γ_笨 胺基曱基乙基二甲氧基矽烷、Ν_(對甲氧基苯基)_γ_胺丙基 三甲氧基矽烷、Ν-(對甲氧基苯基)_γ_胺丙基三乙氧基矽 烷、Ν_(對甲氧基苯基)个胺丙基甲基二甲氧基矽烷、Ν_(對 甲氧基苯基)-γ-胺丙基甲基二乙氧基石夕烧、Ν_(對甲氧基苯 基)-γ-胺丙基乙基二乙氧基矽烷、Ν_(對甲氧基苯基)·γ_胺丙 基乙基二甲氧基矽烷、γ_(Ν_曱基)胺丙基三甲氧基矽烷、 ΗΝ-乙基)胺丙基三甲氧基矽烷、γ_(Ν•丁基)胺丙基三甲氧 200906959 fLaw and so on. Among them, a (4) mixing method is preferred, which results in a homogeneous mixture and less mixing of impurities. The temperature at the time of melt mixing is not particularly limited, and is preferably 100 to 25 CTC, more preferably 12 Å to 1 cm, as long as it is larger than the softening group of the component (B) and/or (10). c. The mixing time of the melt mixing is not particularly limited as long as the two are uniformly mixed, preferably from 1 hour to 20 hours, more preferably from 2 hours to 15 hours. Soil When the hardener (B) and the olefinic component are premixed, the mixed components may be polymerized or reacted with hard (4) (9). In the composition of the present invention, from the viewpoint of improving the flame retardancy of the dispersibility of the component (4), it is preferable that the total amount of the hardener (8) is 9% or more. The above premix (slipping modified hardener). The amount of the above-mentioned components contained in the oxyalkylene-modified hardener is preferably 5 to 4% by weight, more preferably 8 to 25% by weight. If the amount of the above-mentioned critical component is less than 5 Wt%', the flame retardancy tends to decrease; if the amount of the component is more than 4% by weight, the formability tends to decrease. The content of the terpene structure contained in the epoxy resin composition towel of the present invention is preferably 0.1 to 5 Wt%, more preferably 岐G.3 to 3% by weight, from the viewpoint of flame retardancy and moldability. If the content of the (iv) structure is less than 0.1 Wt%, the flame retardancy tends to be deteriorated; if the content of the terpene structure is more than 5 wt%, the formability tends to decrease. The equivalent ratio of epoxy resin (A) to hardening _), that is, the ratio of 34 200906959 base in hard (4), the amount of hydroxyl group relative to the number of hydroxyl groups in the epoxy resin / the number of coating bases in the epoxy resin (hardener) The respective unreacted parts and the number of gas bases in the middle are not particularly limited, and are reduced to 〇6 to U. H is a range of the sealing ring 1.2 which is set to have a range of 〇·5 to 2, a more preferable oxygen resin composition, and excellent reflowability and reflow resistance. 'Fortunately, it is better to set the above ratio to 0.8~ (the ratio of the number of epoxy groups in the hardener to the number of epoxy groups in the sputum, in order to reduce the number of the bases in the non-anti-storage) is not particularly limited to ~ The range of 2, the better ^6^说# The good taste is to set the sealing resistance to excellent sealing production ^ · ~.3. In order to obtain the moldability and the composition of each of the resin compositions for sealing, the above equivalent ratio is set to a range of 〇.8 to 12. Good material, in order to promote epoxy tree (6). The hard extruding agent (8) is not particularly limited as long as it is a hardening agent which is usually used in a fat composition, and can be used as a tree U-diazabicyclo[5.4-carbene-7,], 5• Diazabis=· 壬5,5,6-dibutylamino-],8-diazabicyclo[5. 十十操0J and other cyclic oxime compounds; and Qin 7 added to the above compounds Maleic anhydride, 1, 'stupid, 曱 萘 、, 2,3-dimethylbenzene, 2,6-dimethylphenyl hydrazine, 2'3 _ 1,4-methyl melamine, a compound having intramolecular polarization formed by a compound of 2,3·diphenyl from a fine compound and a diazo phenyl group, and a sapphire phenyl group; benzyl dimethylamine, triethanolamine, diamine Tertiary amines such as triethanol and tris(diamidomethyl) phenol and their derivatives; sulfhydryl σ m 0 sitting, 2 · stupid glutinous rice sitting, 2-phenyl-4-methyl σ m Imidazoles such as squat, 2-pyristyl imidazole and derivatives thereof; tributylphosphine, decyldiphenylphosphine, triphenylphosphine, tris(4-mercaptophenyl)phosphine, diphenylphosphine And an organic phosphine such as phenylphosphine; and a maleic acid needle added to the above phosphine, the above-mentioned I-Kun compound, a scaly compound having an intramolecular polarization formed by a compound having a π bond such as a nitrophenyl decane or a phenol resin; tetraphenyl phenyl tetraphenylphosphonate, ethyl triphenyl tetraphenyl sulfonate, and tetrabutyl fluorene Rotten acid tetrabutyl S is intended to be a tetra-substituted sulphate. Tetra-substituted boric acid; 2-ethyl-4-methyl-imidazole, tetraphenyl boron borate, tetraphenyl boronate such as tetramethyl phthalate Their derivatives and the like. These hardening accelerators may be used singly or in combination of two or more kinds. Among the above-mentioned hardening accelerators, an adduct of a ruthenium second phosphine compound and a ruthenium compound, which is preferable from the viewpoint of curability and fluidity, is particularly preferable as an adduct of dibutylphosphine and benzoquinone. From the viewpoint of storage stability, an adduct of a cyclic hydrazine compound and a phenol resin is preferable, and a novolac type phenol resin salt of diazodicycloundecene is more preferable. The total amount of the above-mentioned preferred hardening accelerator added is preferably > 6 Gwt% or more, more preferably 8% or more, based on the total amount of the hardening agent. The third phosphine used in the adduct of the second phosphine compound and the hydrazine compound 36 200906959 The compound is not particularly limited, and examples thereof include dibutylphenyl lin, butyl = phenylphosphine, and ethyl: phenyl phosphine. Triphenylphosphine, tris(4-fylphenyl) sulphate, :(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl) lin, ^( Isopropylphenyl)phosphine, tris(tertiary butylphenyl)phosphine, tris(2,4-diindenyl)phosphine, bis(2,6-dimethylphenyl)phosphine, tri 2,4,6•trimethylphenyl, tris(2,6-dimethylpipetoethoxyphenyl)phosphine, tris(4-methoxyphenyl)lin, tris(4-ethoxyl) The third phosphine compound containing a compound or an aryl group such as a phenyl)phosphine is preferably triphenylphosphine from the viewpoint of moldability. The brewing compound is particularly limited, and examples thereof include: o-benzene awake, For the benzoquinone, the diphenyl phthalocyanine ratio, the I, 4-nine, and the like, from the viewpoint of the wettability or the storage stability, the benzoquinone is preferred. The hardening accelerator (E) is added. The amount is not particularly limited as long as it is an amount that achieves a hardening promoting effect, and is relatively constant with respect to the total amount of the epoxy resin. The amount of addition, the amount of hardening promotion _ is preferably! ^ Weight f, more preferably 5 parts by weight of the heart. When the hardening promotes '_ mouth f is less than 0.1 part of the replacement part, the short-term hardening tends to be poor; In the case of ultra-reading, the hardening speed is too fast, and there is a tendency that a good forming mouth cannot be obtained. If the epoxy resin composition is used for the sealing of Yiyi, an inorganic filler (D) may be added as needed. In the middle of the month, the inorganic filler (D) used is not particularly limited, and it can be classified as a powder of oxygen, a crystalline cerium oxide, a oxidized smelting, a smectite, a chemical, or the like. Beads obtained by spheroidizing cerium oxide and oxygen oxalate; potassium titanate, carbon 37 200906959 Single crystal fiber such as tantalum nitride or alumina, glass fiber, etc. 1. Inorganic filler for flame retardant effect, Further, it can be exemplified by: Hydroxide: Oxidation, Zinc Oxide, etc. The above inorganic filler (D) may be used singly or in combination of two or more kinds. The above inorganic filler ' ^ low linear expansion coefficient From the perspective of consideration, it is better to smelt and dilute the oxidation, from the viewpoint of thermal conductivity. Alumina is preferred. The shape of the inorganic filler (D) is preferably spherical or approximately spherical in view of the degree of fluidity during formation and the degree of wear of the mold. From formability, hygroscopicity, The amount (content) of the inorganic filler (D) to be added is preferably 65 to 95 wt% per 100 parts by weight of the sealing epoxy resin composition, and more preferably '7〇~95 Wt:/0' is preferably 75~% plus %. When the addition amount of the sugar machine filler is less than 65 wt%, the reflow resistance tends to decrease. In the case of D), in order to improve the adhesion between the resin component and the filler, it is preferred to further add a coupling agent (F) to the epoxy resin composition for sealing of the present invention. The coupling agent (F) is a coupling agent generally used in the epoxy resin composition for sealing, and is not particularly limited. Examples thereof include: a compound compound containing a primary and/or primary and/or secondary amine group, a compound such as epoxy decane, decyl decane, alkyl decane, ureido decane, vinyl decane, and the like; Titanium compounds, chelates, and imprinted compounds. For example: vinyl trichloromethane, vinyl triethoxy oxime, ethyl geranyl (P-methoxyethoxy) dream burning, γ-methyl propylene oxypropyl trimethoxy decane, β -(3,4-Epoxycyclohexyl)ethyltrimethoxydecane, γ_shrinkage 38 200906959 Glyceroxypropyltrimethoxy decane, γ-glycidoxypropylmethyldimethoxy sulphate, Vinyl triethoxy oxime, γ-succinylpropyl trimethoxy sulphate γ-aminopropyl dimethoxy methoxy, γ-aminopropylmethyldimethoxy dream, γ-amine Propyltriethoxydecane, γ-aminopropylmethyldiethoxydecane, 丫-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, γ-(Ν,Ν - dimethyl)aminopropyltrimethoxydecane, γ-(Ν,Ν_diethyl)aminopropyldimethoxymethane, γ-(Ν,Ν-butyl)aminopropyltrimethoxy Second burn, r methyl)anilinopropyltrimethoxydecane, γ-(Ν-ethyl) amidopropyltrimethoxydecane, γ-(Ν,Ν-dimethyl)aminepropyltriethyl Oxygen stone, γ-(Ν,Ν-diethyl)amine propyl triethoxy zebra, γ-(Ν , Ν-dibutyl)amine propyl diethoxy pulverization, γ-(Ν-fluorenyl)anilinopropyl triethoxy cleavage, γ-(Ν-ethyl)anilinopropyl three Ethoxy decane, γ-(Ν, Ν-dimethyl)aminopropyl decyl dimethoxy decane, γ-(Ν, Ν-diethyl)aminopropyl decyl dimethoxy decane, γ -(Ν,Ν-dibutyl)aminopropylmethyldimethoxy decane, γ-(Ν-methyl)anilinopropylmethyldimethoxydecane, γ-(Ν-ethyl)aniline Propyl propyl dimethoxy decane, Ν-(trimethoxymethyl decyl propyl) ethylene bis amide, hydrazine - (dimethoxy methoxymethyl decyl isopropyl) ethylene Amine, mercaptotrimethoxydecane, dimercaptodimethoxydecane, mercaptotriethoxydecane, γ-chloropropyltrimethoxydecane, hexamethylene dioxane, vinyl tridecyloxydecane a decane-based coupling agent such as γ-mercaptopropyl decyl dimethoxy decane; isopropyl triisostearate titanate, isopropyl tris(dioctyl pyrophosphate) titanate, Propyltris(Ν-amineethyl-amineethyl) titanate, tetraoctyldi(ditridecylphosphite) titanate, tetrakis(2,2-diene) Oxymethyl-1-butyl) bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxy 39 200906959 Acetate titanate, di(dioctyl) Pyrophosphate)ethyl titanate, isopropyl tricapryl titanate, isopropyl dimethyl propyl acetoate isostearyl phthalate, isopropyl tris (dodecyl) benzene Sulfonyl titanate, isopropylisostearyl methacrylate titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl dicumyl phenyl titanate, four Isopropyl bis(dioctylphosphite) titanate s is intended to be a carbonated g. The above-mentioned conversion agent may be used singly or in combination of two or more kinds. From the viewpoints of fluidity, reduction of gold wire deformation, and flame retardancy, among them, the car's father's cockroach has a primary amine-based structure of the dream-burning dough mixture. The decane coupling agent having a secondary amino group structure is not particularly limited as long as it is a decane compound having a secondary amine group in the molecule. For example: γ-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, anilinopropylmethyldimethoxydecane, γ-anilinopropylmethyldiethoxy Decane, γ-anilinopropylethyl-ethoxy ethoxylate, γ-anilinopropylethyldimethoxycarbazide, γ-anilinomethyltrimethoxydecane, γ-anilinomethyl three Ethoxy decane, γ-anilinofluorenyl decyl decyloxy decane, γ-anilinomethylmethyldiethoxy decane, γ-anilinomethylethyldiethoxy decane, γ_stupid Aminomercaptoethyl dimethoxydecane, Ν-(p-methoxyphenyl)_γ-aminopropyltrimethoxydecane, Ν-(p-methoxyphenyl)_γ-aminopropyltriethoxy Decane, Ν_(p-methoxyphenyl)amine propylmethyldimethoxydecane, Ν-(p-methoxyphenyl)-γ-aminopropylmethyldiethoxylate, Ν_(pair Methoxyphenyl)-γ-aminopropylethyldiethoxydecane, Ν_(p-methoxyphenyl)·γ-aminopropyldimethoxydecane, γ_(Ν_曱yl) Aminopropyltrimethoxydecane, ΗΝ-ethyl)aminopropyltrimethoxydecane, _ (Ν • butyl) aminopropyl-trimethoxy 200906959 f

基矽烷、γ-(Ν-节基)胺丙基三曱氧基矽烧、γ-(Ν·曱基)胺丙 基三乙氧基矽烷、γ-(Ν-乙基)胺丙基三乙氧基矽烷、γ-(Ν-丁基)胺丙基三乙氧基石夕烧、基)胺丙基三乙氧基石夕 炫·、γ-(Ν-曱基)胺丙基曱基二曱氧基矽烷、γ-(Ν-乙基)胺丙 基曱基二甲氧基矽烷、γ_(Ν_丁基)胺丙基甲基二甲氧基矽 烧、γ-(Ν-节基)胺丙基曱基二甲氧基矽烷、Ν-β·(胺乙基)个 胺丙基三甲氧基矽烷、γ_(β_胺乙基)胺丙基三曱氧基矽烷、 Ν-β-(Ν-乙烯基苄基胺乙基胺丙基三曱氧基矽烷等。其 中’特別佳的是，含有下述通式(4)所示的胺基矽烷耦合劑。 [化學式35] R1 O^-NH-fcH2-)^-Si-(-〇R3) m (4) (其中，R1選自氫原子、碳原子數為1〜6的烷基以及碳 f子^為1〜2的烷氧基；R2選自碳原子數為1〜6的烷基 笨基’ R3表示甲基或乙基；η為1〜6的整數，瓜為i 〜3的整數。） 4目對於畨封用環氧樹脂組成物，耦合劑的總 ΪΪΓ；37〜W，更佳的是⑽5〜⑺碼，進-wt〇/。時，^: 〜2·5 Wt%。耦合劑的總添加量不足0.037 裝的成雜合輯於降低；若超過5.G，則封 加離型♦丨。組成物巾，根據需要可以添 _〜Γο重100重量份環氧樹脂(A)，較佳的是使用 垔77氧化型或非氧化型的聚烯烴作為離型劑， 41 200906959 2Π0.1〜5重量份。離型劑的添加量不足o.oi 〇番θ子在離型性不充分的趨勢；若離型劑的添加量 型^聚敎!，=則黏合性趨於降低。作為氧化型或非氧化 PED h丨i 〇以列舉出：H〇eChSt (股)公司製Η4或ΡΕ、 =量為·〜麵曝子量聚 ：：：；：：： 型劑的μ力^伤時，存在離型性不充分的趨勢；若離 ^添加錢過1G重量份，讎合性趨於降低。 製備，氧樹脂組成物可以採用任何方法來 法例如Ϊ 分散混合即可。一般的方 後，使用:日3定，t量的各種成分用混合器等充分混合 進行、擠出機等進行炫融混煉，然後 明之ί封°例如利用以下方法可以得到本發 nn 然後進仃冷卻、粉碎等方法。雹 錢：:於：組成物以符合成形條件的尺寸及重量製 本發月之電子零件裝置具備以本發明之密封用環氧樹 42 200906959 件。上述電子零件裝置有:於引線框架、 -、二、载體、配線板、玻璃、矽晶圓等支撐部件上 片雪電晶體、二極體、晶體間流器等主動元 件及、電阻 '線圈等被動元件等元件，並將必需 部分以本發明之密封用環氧樹脂組成物密封的電子零件裝 置等。Base decane, γ-(Ν-knot) aminopropyltrimethoxy oxime, γ-(indolyl)aminopropyltriethoxydecane, γ-(Ν-ethyl)aminepropyl Ethoxy decane, γ-(Ν-butyl)-amine propyl triethoxy sulphur, syl-propyl propyl triethoxy sulphate, γ-(indenyl-mercapto)aminopropyl fluorenyl曱oxydecane, γ-(Ν-ethyl)aminopropyl decyl dimethoxy decane, γ_(Ν-butyl)amine propylmethyldimethoxy oxime, γ-(Ν-] Aminopropyl decyl dimethoxy decane, Ν-β·(aminoethyl)aminopropyltrimethoxy decane, γ_(β-aminoethyl)aminopropyltrimethoxy decane, Ν-β - (Ν-vinylbenzylamine ethylamine propyl trimethoxy decane, etc., wherein 'excellently, it contains an amino decane coupling agent represented by the following formula (4). [Chemical Formula 35] R1 O^-NH-fcH2-)^-Si-(-〇R3) m (4) (wherein R1 is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon f group of 1 to 2) Alkoxy; R2 is selected from an alkyl group having 1 to 6 carbon atoms; R3 represents a methyl group or an ethyl group; η is an integer of 1 to 6, and melon is an integer of i to 3.) Using an epoxy resin composition, Total ΪΪΓ agent; 37~W, more preferably is ⑽5~⑺ code into -wt〇 /. When, ^: ~2·5 Wt%. The total addition amount of the couplant is less than 0.037, and the mixed mixture is reduced; if it exceeds 5.G, the release ♦ 丨 is added. The composition towel may be added with 100 parts by weight of the epoxy resin (A) as needed, preferably a 垔77 oxidized or non-oxidized polyolefin as a release agent, 41 200906959 2Π0.1~5 Parts by weight. The addition amount of the release agent is insufficient. o. oi θ θ is in a tendency to be insufficient in release property; if the addition amount of the release agent is 敎 敎 !, =, the adhesion tends to decrease. As oxidized or non-oxidized PED h丨i 〇 exemplified by: H〇eChSt (share) company made Η 4 or ΡΕ, = amount is ~ ~ face exposure amount of poly:::;::: type agent μ force ^ At the time of injury, there is a tendency that the release property is insufficient; if the weight is added by 1 G by weight, the affinity tends to decrease. The oxy resin composition can be prepared by any method such as hydrazine dispersion mixing. In general, use: Day 3, various components of t amount are thoroughly mixed with a mixer, etc., and the extruder or the like is subjected to smelting and kneading, and then the sealing method is used, for example, the following method can be used to obtain the present nn and then仃 Cooling, pulverization, etc.雹 Money::: The composition is made of the size and weight according to the molding conditions. The electronic component device of the present month is provided with the epoxy resin for sealing 42 200906959 of the present invention. The electronic component device includes: an active component such as a snow crystal, a diode, a crystal interposer, and a resistor 'coil on a lead frame, a second carrier, a carrier, a wiring board, a glass, a germanium wafer, and the like. An electronic component device or the like which is an element such as a passive component and which is required to be sealed with the epoxy resin composition for sealing of the present invention.

此種電子零件裝置可以列舉如：於引線框架上固定半 導體7G件’並將接合鋒Gnding pad)#元件的端子部分和 引線部分利用引線接合(wirebonding)或膠帶連接後，使用 本發明之密封用環氧樹脂組成物，藉由傳遞成形等進行密 封而形成的雙列直插式封裝(Dual Inline Package，DIP)、塑 膠導腳晶片承載器(Plastic Leaded Chip Carrier，PLCC)、方 塊形扁平封裝式(Quad Flat Package，QFP)、小外型封裝 (Small Outline Package ’ SOP)、小尺寸 j 形引腳封裝（Small Outline J-lead package，SOJ)、薄型小尺寸封裝(Thin Small Outline Package，TSOP)、薄型四方扁平封裝(Thin Quad Flat Package’ TQFP)等普通樹脂密封型iC;將以膠帶連接於帶 載上的半導體晶片以本發明之密封用環氧樹脂組成物進行 密封的帶載封裝(Tape Carrier Package，TCP);將利用引線 接合、晶片倒裝焊接、焊錫等連接在形成於配線板或玻璃 上的配線上的半導體晶片、電晶體、二極體、晶體閘流器 等主動元件及/或電容器、電阻、線圈等被動元件以本發明 之密封用環氧樹脂組成物進行密封的晶片直接貼裝(Chip On Board，COB)模組、混合積體電路、多片模組；於内面 43 200906959 形成有配雜連接用端子的有機基板的 利用膠帶或引線接合來連接元件和形成於有的， 線後，以本發明之密封用環氣榭月匕έ 土板上的配 ^•KBall 〇rid A,ay,Such an electronic component device may be, for example, a terminal for fixing a semiconductor 7G member and bonding a terminal Gnding pad to a lead frame by wire bonding or tape bonding, and using the sealing of the present invention. Epoxy resin composition, dual in-line package (DIP), plastic leaded chip carrier (PLCC), square-shaped flat package formed by transfer molding, etc. (Quad Flat Package, QFP), Small Outline Package 'SOP, Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP) Ordinary resin-sealed iC such as a thin quad flat package (TQFP); a tape-loaded package in which a semiconductor wafer to be taped on a tape is sealed with the epoxy resin composition for sealing of the present invention (Tape) Carrier Package, TCP); a semiconductor that is connected to wiring formed on a wiring board or glass by wire bonding, wafer flip-chip bonding, soldering, or the like Active components such as a chip, a transistor, a diode, a crystal thyristor, and/or a passive component such as a capacitor, a resistor, a coil, etc., are directly mounted on a chip by a sealing epoxy resin composition of the present invention (Chip On Board, COB) module, hybrid integrated circuit, multi-chip module; on the inner surface 43 200906959, an organic substrate having a terminal for mating connection is formed by tape or wire bonding to connect the element and formed thereon, and the present invention is The sealing ring is made of 环 榭 • 匕έ 匕έ 匕έ 匕έ 匕έ 匕έ • A A A A A A

Pack. CSP)等。 ）曰日片尺寸封裳細 環氧=:電路板中也可以有效使用本發明之密封用 /作為使用本發明之密封用環氧樹脂組成物來對元件進 仃搶封的方法，低壓傳遞成形法最常用， 成形法、壓縮成形法等。 用射出 (實施例） 、接下來，利用實施例來說明本發明，但本發明之範圍 並不受這些實施例的限制。 作為化合物(C)的可撓劑[1]〜[7]由Wacker社開發材 料開發σσ號碼SLJ1661-01〜03或SLJ1731〜1734而獲 取。可撓劑[1]〜[7]中’ R1均為五亞甲基_(Ch2)5_，R2及 R均為曱基。它們的數平均分子量Μη以及單元(I)與(π) 的重置比(Ι)/(Π)即(MPCL/MpDMS)如表1所示。 [表1] 可撓劑 Μη Mpcl/Mpdms 開發品號碼 可撓劑1 3878 5/5 SLJ1661-01 可撓劑2 6000 3/7 SLJ1731 可撓劑3 6000 4/6 SLJ1732 可撓劑4 6179 5/5 SLJ1661-02 可撓劑5 6000 6/4 SLJ1733 可撓劑6 6000 7/3 SLJ1734 可撓劑7 10968 5/5 SLJ1661-03 200906959 (1)/(11)即(MPCl/Mpdms)根據由]H-NMR測定的炎白A 單元的質子的積分值來計算。 上述使用的化合物(C)的數平均分子量Mn，可利用凝 膠滲透層析法(GPC)，使用由標準聚苯乙烯得到的檢量線 進行測定而得到。在本發明中，上述Mn如下測定：利用 GPC法，其中泵使用（股)公司日立製作所製L_62〇〇型，杈 使用 TSKgel-G5000HXL 以及 TSKgel-G2000HXL(均為 TOSHO(股)公司製商品名），檢測器使用（股)公司日立製作 所製L-3300RI型，以四氫咬喃為溶離液，在溫度、 流量1.0 ml/分鐘的條件下進行測定。 再由上述Μη、重量比(i)/(n)、各單元的分子量來估算 可撓劑[1]〜[7]的m]+m2以及卜如表2所示。 [表2] 可撓劑 1 2 3 4 5 6 7 各單元聚 聚己内酯 m=(m]+m2) 18 16 21 26 32 37 48 合度估算 聚二甲基;ε夕 氧烷 27 57 49 41 32 24 74 實施例1〜12、比較例1〜4 :密封用環氧樹脂組成物的製 作 準備以下材料： 環氧當量為196、熔點為106〇c的聯苯型環氧樹脂 (Japan Epoxy Resin (股)公司製，商品名 γχ_4〇〇〇Η)(環氧 樹脂1); 45Pack. CSP) and so on.曰 片 尺寸 尺寸 环氧 环氧 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The method is most commonly used, forming method, compression forming method, and the like. The invention is illustrated by the following examples, but the scope of the invention is not limited by the examples. The flexible agents [1] to [7] as the compound (C) were obtained from Wacker's development material development σσ numbers SLJ1661-01 to 03 or SLJ1731 to 1734. In the flexible agents [1] to [7], R1 is pentamethylene-(Ch2)5_, and R2 and R are both fluorenyl groups. Their number average molecular weight Μη and the reset ratio (Ι)/(Π) of the units (I) and (π), that is, (MPCL/MpDMS) are shown in Table 1. [Table 1] Flexible Agent Μ Mpcl/Mpdms Developer Number Resilience 1 3878 5/5 SLJ1661-01 Flexibility 2 6000 3/7 SLJ1731 Flexibility 3 6000 4/6 SLJ1732 Flexible Agent 4 6179 5/ 5 SLJ1661-02 flexible agent 5 6000 6/4 SLJ1733 flexible agent 6 6000 7/3 SLJ1734 flexible agent 7 10968 5/5 SLJ1661-03 200906959 (1) / (11) ie (MPCl / Mpdms) according to by] The integral value of the protons of the white A unit measured by H-NMR was calculated. The number average molecular weight Mn of the compound (C) used above can be measured by gel permeation chromatography (GPC) using a calibration curve obtained from standard polystyrene. In the present invention, the Mn is measured by the GPC method, in which the pump uses the L_62 type manufactured by Hitachi, Ltd., and the TSKgel-G5000HXL and TSKgel-G2000HXL (both are manufactured by TOSHO Co., Ltd.). The detector was used in the L-3300RI type manufactured by Hitachi, Ltd., and the tetrahydrogenate was used as a solution, and the measurement was carried out under the conditions of a temperature and a flow rate of 1.0 ml/min. Further, from the above Μη, the weight ratio (i)/(n), and the molecular weight of each unit, m]+m2 of the flexible agents [1] to [7] and the results are shown in Table 2. [Table 2] Flexible agent 1 2 3 4 5 6 7 Each unit of polycaprolactone m=(m]+m2) 18 16 21 26 32 37 48 Cohesion estimation polydimethyl; epsetene oxide 27 57 49 41 32 24 74 Examples 1 to 12 and Comparative Examples 1 to 4: Preparation of epoxy resin composition for sealing The following materials were prepared: a biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 〇c (Japan Epoxy) Resin (stock) company, trade name γχ_4〇〇〇Η) (epoxy resin 1); 45

N-苯基-γ-胺丙基三曱氧基矽烷(矽烷耦合劑）； 二正丁基膦與對苯醌的加成反應物(硬化促進劑丄）； 200906959 羥基當量為199、軟化點為89°C的含有亞聯苯基骨架 的苯酚·芳烷基樹脂（明和化成（股）公司製，商品名N-phenyl-γ-aminopropyltrimethoxy decane (decane coupling agent); addition reaction of di-n-butylphosphine with p-benzoquinone (hardening accelerator 丄); 200906959 hydroxyl equivalent of 199, softening point A phenolic aralkyl resin containing a biphenylene skeleton at 89 ° C (Mingwa Chemical Co., Ltd., trade name

MEH-7851)(硬化劑1);羥基當量為104、軟化點為83°C 的三苯基甲烷型酚醛樹脂（明和化成（股）公司製，商品名 MEH-7500-3S)(硬化劑 2); 可撓劑1〜10 :上述可撓劑[1]〜[7]以及用於比較的接 枝層包圍矽酮橡膠粒子的芯殼型可撓劑8 (三菱Ray〇n (股) 么司製’品號S2001) '芯殼型可挽劑9 (三菱Rayon (股) 公司製，品號S5535)、芯殼型可撓劑1〇 (三菱Rayon (股) 公司製，品號SRK200)。 "平均粒徑為21.7 μιη、比表面積為1.3 m2/g的球形熔融 二氧化矽（無機填充劑1);以及 、、其他添加成分：氧化聚乙烯、褐煤酸酯、炭黑。使用 上成分’按表3、表4所示進行添加，在混煉溫度為80 :^煉時間為15分賴條件下進行航煉，製作密 、裱氧樹脂組成物。需要說明的是，在表2、表3中， 除無機填細1财卜，添加3M均為重量份。 46 200906959 [表3] 成分 實施例 1 2 3 4 5 6 7 8 環氧樹脂1 100 100 100 100 100 100 100 100 硬化劑1 31 31 31 31 31 31 31 31 硬化劑2 37 37 37 37 37 37 37 37 可撓劑1 15 可撓劑2 15 可撓劑3 15 可撓劑4 15 5 可撓劑5 15 可撓劑6 15 可撓劑7 15 硬化促進劑1 5 5 5 5 5 5 5 5 氧化聚乙烯 3 3 3 3 3 3 3 3 褐煤酸酯 1 1 1 1 1 1 1 1 炭黑 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 矽烷耦合劑 5 5 5 5 5 5 5 5 無機填充劑1 (wt%) 89 89 89 89 89 89 89 89MEH-7851) (hardener 1); a triphenylmethane type phenolic resin having a hydroxyl equivalent of 104 and a softening point of 83 ° C (manufactured by Megumi Kasei Co., Ltd., trade name MEH-7500-3S) (hardener 2 ); flexible agent 1 to 10: the above flexible agents [1] to [7] and the core-shell type flexible agent 8 (Mitsubishi Ray〇n (share)) which is used to compare the graft layer to surround the fluorenone rubber particles. System 'Product No. S2001) 'Core-shell type pliable agent 9 (Mitsubishi Rayon Co., Ltd., product number S5535), core-shell type flexible agent 1〇 (Mitsubishi Rayon Co., Ltd., product number SRK200) . "Spherical molten cerium oxide (inorganic filler 1) having an average particle diameter of 21.7 μηη and a specific surface area of 1.3 m2/g; and other additive components: oxidized polyethylene, montanic acid ester, and carbon black. The above-mentioned components were added as shown in Tables 3 and 4, and air-sealing was carried out under the conditions of a kneading temperature of 80: a refining time of 15 minutes to prepare a dense and oxime resin composition. It should be noted that in Tables 2 and 3, in addition to the inorganic filling, the addition of 3M is a part by weight. 46 200906959 [Table 3] Ingredient Example 1 2 3 4 5 6 7 8 Epoxy Resin 1 100 100 100 100 100 100 100 100 Hardener 1 31 31 31 31 31 31 31 31 Hardener 2 37 37 37 37 37 37 37 37 Flexible Agent 1 15 Flexible Agent 2 15 Flexible Agent 3 15 Flexible Agent 4 15 5 Flexible Agent 5 15 Flexible Agent 6 15 Flexible Agent 7 15 Hardening Accelerator 1 5 5 5 5 5 5 5 5 Oxidation Polyethylene 3 3 3 3 3 3 3 3 Brown acid ester 1 1 1 1 1 1 1 1 Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 矽 耦合 coupling agent 5 5 5 5 5 5 5 5 Inorganic filler 1 (wt%) 89 89 89 89 89 89 89 89

47 200906959 [表4]47 200906959 [Table 4]

環氣gjfT 硬化劑 硬化劑2 可撓 可撓 可撓齊 55£Τ5 硬化j 氧化％ 褐煤酸酯 舰施例1〜12以及比較例1〜4製作的密封用環氧 ==:特性’藉由以下各種特性試驗⑴〜(9)來進行 5平價^價結果如表5及表6所示。 ί 紐日㈣是，齡㈣㈣環氧赫組餘的成形， 、（3)中是使用傳遞成形機，使密封用環氧樹脂 組成物在金屬模溫度為18此、成形壓力為6 9略、硬化 ^間為％秒的條件下成形。特性試驗(5)、⑹、⑼中是在 上述成形叙在175t下進行6小時的後硬化來進行成 形。在特性試驗⑺巾，將後硬化之前的試驗片作為AM、 將後硬化之後的試驗片作為AC。 (1)凝膠時間 使用JSR製Curelastometer，於溫度i80°C下測定3 g 48 以直至扭矩曲線上升 環氧樹脂組成物成形成直 成形後立即使用肖氏D硬环气gjfT hardener hardener 2 flexible and flexible, 55 Τ5 hardened, j, oxidized %, lignite ship, examples 1 to 12, and comparative examples 1 to 4, sealed epoxy ==: characteristics' The following various characteristic tests (1) to (9) were carried out to perform the five parity price results as shown in Tables 5 and 6. ί New Zealand (4) is the formation of the age (four) (four) Epoxy Hex, and (3) is the use of a transfer molding machine, so that the sealing epoxy resin composition at the mold temperature of 18, the forming pressure is 6 9 slightly, The hardening is formed under conditions of % seconds. In the characteristic tests (5), (6), and (9), it was formed by post-hardening for 6 hours at 175 ton. In the characteristic test (7) towel, the test piece before post-hardening was used as AM, and the test piece after post-hardening was used as AC. (1) Gel time Using a Curelastometer manufactured by JSR, 3 g 48 was measured at a temperature of i80 ° C until the torque curve rose. The epoxy resin composition was formed into a straight shape and immediately after the formation of Shore D hard.

mm 200906959 密封用環氧樹脂組成物的凝膠時間 的時間作為凝膠時間(秒）。 (2)熱時硬度 在上述成形條件下將密封用 徑50 mmx厚度3 mm的圓盤， 度計進行測定。 ⑶螺旋流動度(spiral flow) 根據EMMM-66，使用旋流測定用金屬模，將密封 環氧樹脂組成物按上述條件進行成形，求出流 (cm )。 肝 (4)圓盤流動度 土， ’ 、”厂mm (U)x25 mm (H)的上 产:列mm (D) x 15 mm (H)的下模的圓板流 度測疋用千板金屬模，用域天平稱量5 g密封用環氧 脂組成物，放置在加熱至18Gt的下模的中心部 ^ 78N^,ba,fa1 9〇# =件下進灯壓％成形，以游標尺測定成形品 =徑(_’叫平均值(職)作為圓 (5)彎曲試驗 又 用尺寸為 7GmmXl〇mmx3 (6)線膨脹率測定 49 200906959 ，用理學電機製熱機械分析裝置(tas_igg)，在升溫速 二為C/分鐘的條件下測定19mmx3mmx3mm形狀的試 片的線膨脹曲線，由上述線膨脹曲線的彎曲點求出破璃 匕轉變溫度(以下簡稱為Tg)。另外，由小於等於Tg的斜 2以及大於祕Tg的斜率分财錄賴値(以下將前 者間記為αΐ、將後者簡記為心）。 (7) 黏合強度 μ於金屬模上鋪塾3〇 μηι厚的東海金屬製銘輪圈及銅 箔，使用成形尺寸為7〇mmxl〇mmx3 mm試驗片，製作 ，仃熱處理(AM)、進行了 17rc/6小時的熱處理(Ac)的樣 :。使用A&D社製Tensilon試驗機垂直剝離鋁輪圈及銅 vl，測定此時的力作為黏合強度(N/m)。 (8) UL燃燒試驗 +使，成形厚度為1/32英寸(〇 8 mm)的試驗片的金屬 模’將岔封用環氧樹脂組成物在金屬模溫度為18〇它、成 形壓力為6.9 MPa、硬化時間為9〇秒的成形條件下成形， 再於180 C下進行6小時的後硬化，按照UL-94試驗法坪 價阻燃性。 (9) 耐熱衝擊性 將外形尺寸為40 mmx40 mmx2 mm厚的球柵陣列 (Ball Grid Array, BGA)封裝密封，上述BGA封農上捭載 有9 mmx9 mmx〇.28 mm的使用了日立化成工業(股)&司 製HSG-255 (第二代Low_k對應層間絕緣膜；膜楊氏率為 10 GPa)的石夕酮晶片以及半徑為28醜、金屬厚度為〇 3 _ 50 200906959 的鍍鉻的銅製熱塗佈器。對8個封裝進行溫度循環試驗(_65 °C/15分鐘㈠+150°C/15分鐘）。利用日立建機製超聲波探測 映射裝置(HYE-FOCUS)觀測Low-k封裝内部的剝離狀 態。以相對於試驗封裝數(8個）的不良封裝數進行評價。 [表5] 担曰 實施例 1 2 3 4 5 6 7 8 凝膠時間（秒） 30 28 28 28 28 28 25 27 熱時硬度（一） 79 79 79 80 80 80 81 80 螺旋流動度(英寸） 52 42 43 43 38 33 37 45 圓盤流動度(mm) 89 86 87 87 74 69 78 90 彎曲彈性率 室溫(GPa) 260〇C (MPa) 25.1 22.3 22.5 23.8 25.3 25.4 24.9 25.5 448 492 544 510 581 519 535 653 線膨脹係數 αι 8.2 8.2 8.1 7.7 7.8 8.0 8.0 8.5 (PPm ) α2 30 34 32 31 32 31 36 33 玻璃化轉變溫度 137.2 145.8 143.6 142.8 135.6 132.4 140.2 148.7 Α1剝離(AM) 730 650 620 605 595 580 695 660 黏合強度 Α1剝離(AC) 810 725 635 650 630 625 785 715 (N/m) Cu剝離(AM) 205 300 275 295 255 240 285 300 Cu剝離(AC) 90 180 150 185 145 125 205 140 UL 阻燃性試驗 1/32英寸 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 500循環 3/8 4/8 3/8 0/8 0/8 0/8 0/8 0/8 耐熱衝擊性 1000循環 4/8 5/8 4/8 1/8 3/8 3/8 1/8 2/8 1500循環 5/8 7/8 6/8 2/8 4/8 4/8 3/8 3/8 2000循環 6/8 8/8 7/8 4/8 6/8 7/8 4/8 3/8 51 200906959 [表6] 項目 實施例 比較例 9 10 11 12 1 2 3 4 凝膠時間（秒） 28 28 28 29 28 24 24 24 熱時硬度（一） 80 79 75 74 83 83 83 83 螺旋流動度(英寸） 45 43 42 41 44 29 29 34 圓盤流動度(mm) 89 84 84 82 91 77 80 71 彎曲彈性率 室溫(GPa) 260°C (MPa) 24.6 23.5 22.5 21.8 26.5 25.7 26.0 25.8 562 379 303 296 894 737 755 649 線膨脹係數 (ppm ) α! α2 8.2 7.4 6.7 6.2 9.0 8.5 9.1 8.8 32 30 32 32 30 32 34 33 玻璃化轉變溫度 144.3 139.4 136.3 136.4 140.0 148.4 1513 144.5 黏合強度 (N/m) Α1剝離(AM) 620 540 455 400 500 560 665 650 Α1剝離(AC) 720 565 570 565 505 700 730 745 Cu剝離(AM) 320 260 235 240 220 285 305 295 Cu剝離(AC) 190 205 220 235 110 115 105 145 UL 阻燃性試驗 1/32英寸 V-0 V-0 V-0 V-0 V-0 V-1 V-1 V-1 耐熱衝擊性 500循環 0/8 0/8 1/8 Γ 3/8 5/8 0/8 1/8 0/8 1000循環 0/8 2/8 4/8 6/8 「7/8 4/8 3/8 3/8 1500循環 1/8 5/8 6/8 6/8 8/8 6/8 4/8 6/8 2000循環 2/8 5/8 8/8 7/8 6/8 7/8 Γ 8/8 7/8 由表5、表6可知：添加了 15重量份化合物(c)作為 可撓劑的實施例1〜7與比較例2〜4相比，前者在螺旋流 動度以及圓盤流動度的流紐方面與後者等同或更。 特別是化合物(Q的數平均分子量低的實施例丨中流動性 優異。另外’將實_ 2〜6進行比較時可知 之(1)與⑻的重量比(_)小於等於丨時流動性良好（) 由表5、表6可知:在室溫以及靴 效果方面，添加了 15重量份可繞劑 羊降低 例2〜4相比，前者較後者優異外只二:7與比較 量比(_)相等(5/5)的實施例卜卜將化'物(C)之重 數平均分子量Μη為約6000的實…=比較時可知： 最優異。再將實施例2〜6進 ^的彈性率降低效果 較日守可知：化合物(C)之 52 200906959 ⑴興⑷的h比(1)/⑼越小，彈性率降低效果越高。 再者，在線膨脹係數α1方面，將化 =_(5/5财施例Η。進行比㈣^ = :刀：：Μη為約6_的實施例4的線膨脹係數⑹最： 播。，將改變了實施例4中使用的可撓劑4之添加量的實 =4、8〜！2進行比較時可知：化合物(c)的添加量最多 的只％例12中線膨脹係數α1降低效果高。 夕 並且，實施例2〜12相對於比較例卜3而言，& j合力整體上有變強的趨勢。再將實施例卜4、7進行 提g時，藉由提高化合物(〇的分子量，其對&的黏合性 劑二二Tv;添:格了除化合物(C)以外的可撓 勺為V·1規格，相對於此，在實施例中 :物(C)的添加量增加至3G重量份的實施例12也 了 V-0規格，是阻燃性轉優賤_。 在耐熱衝擊4驗中，相對於未添加可撓劑的比較例1 生率古比，例2〜4均有少許改善’但與實施例相比不良發 的每^丨！實施例中，將化合物(C)之重f比晴1)相等(5/5) 約lorJ' 、4、7進行比較時可知：數平均分子量Mn為 10奮旦的μ她例4的耐熱衝擊性最優異。並且，使用了 螌實施例4中使用的可撓劑4的實施例9在耐熱衝 最i異。經過1000猶環未出現不良封裝，因此財熱衝擊性 產業上利用性 53 200906959 祕κ本發明之&氧樹脂組成物在轉障性的π转 性和低應力化優異，也可適用於且有第=的科，流動 緣膜的1C封裝。 U…有第一代L〇w-k層間絕 —雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 乾圍當視後附之申請專利範圍所界定者為準。 Γ 【圖式簡單說明】 鼓 【主要元件符號說明】Mm 200906959 The gel time of the epoxy resin composition for sealing is taken as the gel time (seconds). (2) Hardness at the time of heat Under the above-mentioned forming conditions, a disk having a diameter of 50 mmx and a thickness of 3 mm was measured and measured. (3) Spiral flow According to EMMM-66, a sealed metal mold was used, and the sealed epoxy resin composition was molded under the above conditions to obtain a flow (cm). Liver (4) disc fluidity soil, ',' factory mm (U) x 25 mm (H) upper production: column mm (D) x 15 mm (H) lower die circular flow measurement For the metal mold of the plate, weigh 5 g of the epoxy resin composition for sealing with a domain balance, and place it in the center of the lower mold heated to 18 Gt. ^78N^,ba,fa1 9〇#=Parts under the lamp pressure molding, Measuring ruler for the ruler = diameter (_' is called average (job) as a circle (5) bending test and size is 7GmmXl〇mmx3 (6) linear expansion rate determination 49 200906959, using the electromechanical mechanism thermomechanical analysis device (tas_igg The linear expansion curve of the test piece having a shape of 19 mm x 3 mm x 3 mm was measured under the condition that the heating rate was 2 C/min, and the glass transition temperature (hereinafter abbreviated as Tg) was determined from the bending point of the linear expansion curve. It is equal to the slope 2 of Tg and the slope of the secret Tg. The following is the record of the former as αΐ and the latter as the heart. (7) The adhesive strength μ is spread on the metal mold and the thickness of the East China Sea is 3〇μηι thick. Metal indenter ring and copper foil, fabricated using a test piece of 7〇mmxl〇mmx3 mm, 仃 heat treatment (AM), 17rc/6 hours Heat treatment (Ac): The aluminum rim and copper vl were vertically peeled off using a Tensilon tester manufactured by A&D, and the force at this time was measured as the adhesive strength (N/m). (8) UL burning test + making, forming The metal mold of the test piece having a thickness of 1/32 inch (〇8 mm) is formed by using an epoxy resin composition at a mold temperature of 18 Å, a forming pressure of 6.9 MPa, and a hardening time of 9 sec. Formed under conditions, and then post-cured at 180 C for 6 hours, according to UL-94 test method, flame resistance. (9) Thermal shock resistance Ball grid array with dimensions of 40 mm x 40 mm x 2 mm (Ball Grid) Array, BGA) package seal, the above BGA seal is loaded with 9 mmx9 mmx〇.28 mm using Hitachi Chemical Industry Co., Ltd. HSG-255 (second generation Low_k corresponding interlayer insulation film; A 10 gram lithopone wafer and a chrome-plated copper thermal coater with a radius of 28 ug and a metal thickness of 〇3 _ 50 200906959. Temperature cycling test for 8 packages (_65 °C / 15 minutes (1) +150 ° C / 15 minutes). Use the Hitachi built mechanism ultrasonic detection mapping device (HYE-FOCUS) to observe the inside of the Low-k package The peeling state was evaluated by the number of defective packages with respect to the number of test packages (8). [Table 5] Example 1 2 3 4 5 6 7 8 Gel time (seconds) 30 28 28 28 28 28 25 27 Thermal hardness (1) 79 79 79 80 80 80 81 80 Spiral fluidity (inches) 52 42 43 43 38 33 37 45 Disk fluidity (mm) 89 86 87 87 74 69 78 90 Bending elastic modulus room temperature (GPa 260〇C (MPa) 25.1 22.3 22.5 23.8 25.3 25.4 24.9 25.5 448 492 544 510 581 519 535 653 Linear expansion coefficient αι 8.2 8.2 8.1 7.7 7.8 8.0 8.0 8.5 (PPm ) α2 30 34 32 31 32 31 36 33 Glass transition Temperature 137.2 145.8 143.6 142.8 135.6 132.4 140.2 148.7 Α1 peeling (AM) 730 650 620 605 595 580 695 660 Bonding strength Α1 peeling (AC) 810 725 635 650 630 625 785 715 (N/m) Cu peeling (AM) 205 300 275 295 255 240 285 300 Cu stripping (AC) 90 180 150 185 145 125 205 140 UL flame retardancy test 1/32 inch V-0 V-0 V-0 V-0 V-0 V-0 V-0 V- 0 500 cycles 3/8 4/8 3/8 0/8 0/8 0/8 0/8 0/8 Thermal shock resistance 1000 cycles 4/8 5/8 4/8 1/8 3/8 3/8 1/8 2/8 1500 cycle 5/8 7/8 6/8 2/8 4/8 4/8 3/8 3/8 2000 cycle 6/8 8/8 7/8 4/8 6/8 7/8 4/8 3/8 51 200906959 [Table 6] Project example comparison example 9 10 11 12 1 2 3 4 Gel time (seconds) 28 28 28 29 28 24 24 24 Hardness on heat (1) 80 79 75 74 83 83 83 83 Spiral fluidity (inches) 45 43 42 41 44 29 29 34 Disk fluidity (mm) 89 84 84 82 91 77 80 71 Flexural Elasticity Room Temperature (GPa) 260°C (MPa) 24.6 23.5 22.5 21.8 26.5 25.7 26.0 25.8 562 379 303 296 894 737 755 649 Linear Expansion Coefficient (ppm) α! α2 8.2 7.4 6.7 6.2 9.0 8.5 9.1 8.8 32 30 32 32 30 32 34 33 Glass transition temperature 144.3 139.4 136.3 136.4 140.0 148.4 1513 144.5 Adhesive strength (N/m) Α1 peeling (AM) 620 540 455 400 500 560 665 650 Α1 peeling (AC) 720 565 570 565 505 700 730 745 Cu Stripping (AM) 320 260 235 240 220 285 305 295 Cu Stripping (AC) 190 205 220 235 110 115 105 145 UL Flame Retardancy Test 1/32" V-0 V -0 V-0 V-0 V-0 V-1 V-1 V-1 Thermal shock resistance 500 cycles 0/8 0/8 1/8 Γ 3/8 5/8 0/8 1/8 0/8 1000 cycles 0/8 2/8 4/8 6/8 "7/8 4/8 3/8 3/8 1500 cycle 1/8 5/8 6/8 6/8 8/8 6/ 8 4/8 6/8 2000 cycle 2/8 5/8 8/8 7/8 6/8 7/8 Γ 8/8 7/8 As shown in Table 5 and Table 6, 15 parts by weight of compound (c added) In Examples 1 to 7 which are flexible agents, the former is equivalent to or more in terms of the spiral flow degree and the flow of the disk fluidity than the comparative examples 2 to 4. In particular, the compound (Q has a low number average molecular weight and has excellent fluidity. In addition, when the actual ratio of (1) to (8) is less than or equal to 丨, the fluidity is good. () It can be seen from Tables 5 and 6 that in addition to the room temperature and the effect of the boot, 15 parts by weight of the retractable sheep are added, and the former is superior to the latter, and the former is only two: 7 and the comparative amount ratio (_ The equivalent (5/5) embodiment will convert the weight average molecular weight Μη of the substance (C) to about 6,000. = When comparing, it is known that: the most excellent. The elasticity of the examples 2 to 6 is further improved. The rate reduction effect is better than that of the Japanese Guardian: Compound (C) 52 200906959 (1) The smaller the h ratio (1)/(9) of Xing (4), the higher the elastic modulus reduction effect. Furthermore, the linear expansion coefficient α1 will be corrected =_( 5/5 Example Η. The coefficient of linear expansion (6) of Example 4, which is ratio (4)^ = : knife::Μη is about 6_, is the most: broadcast, and the flexible agent 4 used in the embodiment 4 is changed. When the actual amount of the addition amount was 4, 8 to 2, it was found that the addition amount of the compound (c) was the highest, and only the example 12 of the example 12 had a high effect of lowering the linear expansion coefficient α1. 12 Compared with the comparative example 3, the combined force of & j has a tendency to become stronger as a whole. When the examples 4 and 7 are carried out, the adhesion of the compound (the molecular weight of the oxime to the & The second agent T2; the addition: the flexible spoon other than the compound (C) is V·1 specification, and in the embodiment, the addition amount of the substance (C) is increased to 3G parts by weight. 12 also V-0 specification, is the flame retardant conversion 贱 _. In the thermal shock 4 test, compared to the comparative example 1 without the addition of flexible agent, the ratio of 2 to 4 has a little improvement 'but Compared with the examples, in the examples, the weight of the compound (C) is equal to that of the clear 1 (5/5). When comparing lorJ', 4, and 7, the number average molecular weight Mn is known. The thermal shock resistance of Example 4 was the most excellent, and Example 9 using the flexible agent 4 used in Example 4 was the most heat-resistant. Therefore, the utilization of the thermal shock industry 53 200906959 κ κ The oxy-resin composition of the present invention is excellent in the π-transformation and low-stress of the barrier property, and is also applicable to The first section, the 1C package of the flow film. U...the first generation of L〇wk interlayers - although the invention has been disclosed in the preferred embodiments as above, it is not intended to limit the invention, and anyone skilled in the art The invention may be modified and retouched without departing from the spirit and scope of the invention. Therefore, the protection of the present invention is defined by the scope of the patent application. Γ [Simple description] Drums [Main component symbol description]

Ml 54Ml 54

Claims (1)

200906959 十、申請專利範圍： 1.一種密封用環氧樹脂組成物，包栝： 一環氧樹脂(A); 一硬化劑(B);以及 一化合物(C)，該化合物(C)包括下述結構式⑴以及(II) 所示的軍元， (I )200906959 X. Patent application scope: 1. A sealing epoxy resin composition, comprising: an epoxy resin (A); a hardener (B); and a compound (C), the compound (C) including The military elements shown in structural formulas (1) and (II), (I) 式(I)中’ R1表示碳原子數為1〜10的亞烷基； R2 ' —-Si—Ο-_ (II) I R3 式(Π)中，R2及R3表示碳原子數為1〜1〇的烷基、碳 原子數為6〜10的芳基、碳原子數為卜1〇的烧氧基、碳 原子數為1〜10的包括環氧基的—财機顧、碳原子數 為1〜10的包括縣的-價有機基團或碳原子數為3〜· 的聚亞烧基_基。 2·如申請專利範㈣1項所述之密制環氧樹脂喊 物，其Λ該物(c)的數平均分子量Mn為2_至2〇_。 3·如申凊專纖圍第1項所述之密封用環氧樹脂組成 55 200906959 4如均分子量Mn為5_至10000。 4.如申印專利範圍第i :1〇〇〇〇 物，其中轉_所_單咖料樹脂組成 量比_1)為3/7至7/3。 …構式fft)所不的單元的重 封用專利範圍第1項至第4項中任—項所述之穷 1辰氧树脂组成物’其中相對於_重量份的二 月曰⑷，該化合物(〇為1至5〇重量份。的該壤㈣ 6.如申請專利範圍第i項至 封用環氧樹脂組成物，苴中相對於_貝：任顧述之飨 封用項所述之密 辆-結構式㈣^/:物伽結構输結構 物，請專利範圍第7項所述之密封用環氧樹脂組成 化合物(C)為下述通式(3)所示的化合物， rIn the formula (I), 'R1 represents an alkylene group having 1 to 10 carbon atoms; R2 '--Si-Ο-_ (II) I R3 In the formula (Π), R2 and R3 represent a carbon number of 1~ An alkyl group having 1 〇, an aryl group having 6 to 10 carbon atoms, an alkoxy group having a carbon number of 1 〇, an alkyl group having an epoxy group having 1 to 10 carbon atoms, and a carbon atom number It is a polyalkylene group containing 1 to 10 including a valence organic group or a carbon atom number of 3 to. 2. The secret epoxy resin shunt as described in claim 1 (4), wherein the number average molecular weight Mn of the substance (c) is 2 to 2 Å. 3. The sealing epoxy resin composition as described in Item 1 of Shenyu Special Fibers 55 200906959 4 If the average molecular weight Mn is 5_ to 10000. 4. For example, the scope of the patent application is i:1, which is 3/7 to 7/3 of the resin composition ratio _1). The re-encapsulation of the unit of the formula fft) is not limited to the 二 part by weight of the February 1st (4). Compound (〇1 to 5〇 parts by weight of the soil (4) 6. As claimed in the scope of claim i to the epoxy resin composition, in the case of 苴贝: The compact type-structure (4)^/: material structure transfer structure, the epoxy resin composition compound (C) for sealing according to item 7 of the patent range is a compound represented by the following formula (3), r R2 R2 O H’ 〇一Rl—c~，〇—R^-Si—0 »-Si—R4—O^-C—Ri一 R3 R3 .(3) 的敕Γ構式(3)中，1為1至200的整數；mi+m2為2至400 ^ t ，Rl表示碳原子數為1至10的亞烷基；R2及R3表 不妷原子數為1至1〇的烷基、碳原子數為6至10的芳基、 56 200906959 碳原子數為1至10的烷氧基、碳原子數為1至10的包括 環氧基的一價有機基團、碳原子數為1至10的包括羧基的 一價有機基團或碳原子數為3至500的聚亞烷基醚基；R4 表示碳原子數為1至10的二價烴基。 9.一種電子零件裝置，該電子零件裝置包括以如申請 專利範圍第1項至第4項中任一項所述之密封用環氧樹脂 組成物密封的半導體元件。 57 200906959 七、 指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 無 八、 本案若有化學式時，請揭示最能顯示發明特徵的化 學式： 無R2 R2 O H' 〇 R1—c~, 〇—R^-Si—0 »-Si—R4—O^-C—Ri—R3 R3 . (3) 敕Γ (3), 1 An integer of from 1 to 200; mi+m2 is from 2 to 400 ^ t, R1 represents an alkylene group having from 1 to 10 carbon atoms; and R2 and R3 represent an alkyl group having from 1 to 1 atom, a carbon atom An aryl group of 6 to 10, 56 200906959 an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms A monovalent organic group including a carboxyl group or a polyalkylene ether group having 3 to 500 carbon atoms; and R4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. An electronic component device comprising a semiconductor device sealed with the epoxy resin composition for sealing according to any one of claims 1 to 4. 57 200906959 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: