TW200536921A - Adhesive composition circuit connection material, joint structure of circuit parts and semiconductor device - Google Patents
Adhesive composition circuit connection material, joint structure of circuit parts and semiconductor device Download PDFInfo
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- TW200536921A TW200536921A TW094106487A TW94106487A TW200536921A TW 200536921 A TW200536921 A TW 200536921A TW 094106487 A TW094106487 A TW 094106487A TW 94106487 A TW94106487 A TW 94106487A TW 200536921 A TW200536921 A TW 200536921A
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- circuit
- adhesive composition
- radical polymerization
- polymerization initiator
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H3/00—Toothed gearings for conveying rotary motion with variable gear ratio or for reversing rotary motion
- F16H3/44—Toothed gearings for conveying rotary motion with variable gear ratio or for reversing rotary motion using gears having orbital motion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H55/00—Elements with teeth or friction surfaces for conveying motion; Worms, pulleys or sheaves for gearing mechanisms
- F16H55/02—Toothed members; Worms
- F16H55/08—Profiling
- F16H55/0806—Involute profile
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H55/00—Elements with teeth or friction surfaces for conveying motion; Worms, pulleys or sheaves for gearing mechanisms
- F16H55/02—Toothed members; Worms
- F16H55/08—Profiling
- F16H2055/0866—Profiles for improving radial engagement of gears, e.g. chamfers on the tips of the teeth
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01079—Gold [Au]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/10251—Elemental semiconductors, i.e. Group IV
- H01L2924/10253—Silicon [Si]
Abstract
Description
200536921 (1) 九、發明說明 【發明所屬之技術領域】 本發明爲有關黏著劑組成物，電路連接材料，電路構 件之連接結構及半導體裝置。 【先前技術】 以往，半導體元件或液晶顯示元件用之黏著劑’多使 n用具有優良黏著性，特別是於高溫高濕條件下顯示優良黏 著性之環氧樹脂等之熱硬化性樹脂（參考例如特開平0 1 一 1 1 3 4 80號公報）。前述黏著劑，可於170至25 0°C之溫度 加熱1至3小時使其硬化而得黏著性。 近年來，隨著半導體元件之高集積化、液晶元件之高 精細化，元件間與電路間之間距已有狹窄化之傾向。前述 半導體元件等於使用上述黏著劑時，因硬化時加熱溫度較 局，或硬化速度較爲緩慢，而除黏著部位以外亦加熱至其 Φ 他週邊構件，而會有對週邊構件造成損害影響等傾向。又 ，因趨向低費用化，故有必須提高生產率之必要性，因此 極需求一種可於低溫（100至170°C )、短時間（1小時內 )，換言之，需具有「低溫速硬化」之黏著性。 又，近年來使用丙烯酸衍生物或甲基丙烯酸衍生物與 自由基聚合起始劑之過氧化物所得之自由基硬化型黏著劑 受到極大之注目。此黏著劑，爲利用具有優良反應性之反 應活性種之自由基聚合反應之硬化、黏著所得者，故可於 較短時間內硬化（參考例如2002 — 203 427號公報）。 200536921 (2) 但，因自由基硬化型黏著劑具有優良反應性，故進行 硬化處理時製程適應性會有狹窄化之傾向。例如，爲將半 導體元件或液晶顯示元件以電路連結而使用上述自由基硬 化型黏著劑時，製得該硬化物時之溫度或時間等製程條件 若有些許變動時，則會有不能安定的得到黏著強度、連接 電阻等特性之傾向。200536921 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to an adhesive composition, a circuit connection material, a connection structure of a circuit component, and a semiconductor device. [Prior art] In the past, adhesives for semiconductor devices or liquid crystal display devices have often used thermosetting resins such as epoxy resins that have excellent adhesion properties especially for high-temperature and high-humidity conditions. For example, Japanese Patent Application Laid-Open No. 0 1 to 1 1 3 4 80). The aforementioned adhesive can be cured by heating at a temperature of 170 to 250 ° C for 1 to 3 hours to obtain adhesiveness. In recent years, with the increasing integration of semiconductor devices and the higher definition of liquid crystal devices, the distance between devices and circuits has tended to become narrower. When the aforementioned semiconductor device is equal to the above-mentioned adhesive, the heating temperature is relatively local or the curing speed is slow during hardening, and besides the adhesive part, it is also heated to other peripheral members, which may cause damage to the peripheral members. . In addition, due to the trend toward lower costs, it is necessary to improve productivity. Therefore, there is a great need for a product that can be at low temperature (100 to 170 ° C) and short time (within 1 hour). In other words, it must have a "low temperature rapid hardening" Adhesiveness. In addition, radically curable adhesives obtained by using an acrylic acid derivative or a methacrylic acid derivative and a peroxide of a radical polymerization initiator have attracted much attention in recent years. This adhesive is obtained by the hardening and adhesion of the radical polymerization reaction of reactive species with excellent reactivity, so it can be hardened in a short time (refer to, for example, 2002-203 427). 200536921 (2) However, since the radical-curing adhesive has excellent reactivity, the process adaptability tends to be narrowed when curing is performed. For example, when the above radical-curable adhesive is used to connect a semiconductor element or a liquid crystal display element with a circuit, the process conditions such as temperature and time at which the cured product is obtained may vary in a stable manner. Trends in properties such as adhesive strength and connection resistance.
【發明內容】 本發明提供一種可進行低溫且極爲迅速之硬化處理， 硬化處理時具有更廣泛的製程適應性，具有極安定之黏著 強度或連接電阻之黏著劑組成物，電路連接材料，電路構 件之連接結構及半導體裝置之技術。 可解決以往問題之本發明黏著劑組成物，爲含有熱塑 性樹脂，與自由基聚合性化合物，與1分鐘半衰期溫度爲 90至145 °C之第1自由基聚合起始劑，與1分鐘半衰期溫 度爲150至175 °C之第2自由基聚合起始劑爲特徵。 其中所稱「1分鐘半衰期溫度」係指半衰期爲1分鐘 時之溫度，「半衰期」係指化合物之濃度減少至初期數値 一半時之時間。 本發明之黏著劑組成物，爲含有熱塑性樹脂，與自由 基聚合性化合物，與自由基聚合起始劑者，即自由基硬化 型黏著劑組成物。含有前述自由基聚合性化合物之黏著劑 組成物因具有優良之反應性，故即使於低溫下也可於極短 時間下硬化。又，自由基聚合起始劑使用1分鐘半衰期溫 -6 - 200536921 (3) 度爲相異之2種自由基聚合起始劑結果，於進行硬化處理 之際亦具有擴大製程適應性之效果。因此，前述由黏著劑 組成物所得之硬化物，於製得該硬化物之際，即使變動製 程溫度或時間時，也具有可以製得安定之黏著強度或連接 電阻等特性之效果。 又，大致上1分鐘半衰期溫度爲上述範圍內之自由基 硬化型黏著劑之活性能量較低，故儲存安定性會有降低之 n傾向。但，由本發明之黏著劑組成物所得之硬化物，與以 往物質相比較時，顯示出具有更優良之儲存安定性。推測 其應爲本發明之黏著劑組成物中，使用1分鐘半衰期溫度 顯著不同之2種自由基聚合起始劑所得之效果。 又，使用本發明之黏著劑組成物時，硬化處理可於短 時間內進行，且可擴大製程適應性等因素，故即使半導體 元件或液晶元件等元件間與電路間之間距狹窄化時，也可 防止除連接部以外而加熱至週邊構件，而對週邊構件造成 % 損害等影響，進而可提高生產率。 又，本發明之黏著劑組成物中，自由基聚合性化合物 以分子內具有2個以上（甲基）丙烯醯基者爲佳。使用前 述黏著劑組成物時，可於更短時間內進行硬化處理。其理 由推測應爲自由基聚合性化合物，具有2個以上高反應性 之自由反應性基所得者。 又’前述自由基聚合性化合物，因反應性基使用（甲 基）丙烯醯基，故無須選擇被黏著物之材質下，即可得到 強固之黏著性。因此，含有前述自由基聚合性化合物之本 200536921[Summary of the Invention] The present invention provides an adhesive composition capable of performing low-temperature and extremely rapid hardening treatment, which has wider process adaptability during hardening treatment, has extremely stable adhesive strength or connection resistance, circuit connection material, and circuit member. Connection structure and semiconductor device technology. The adhesive composition of the present invention that can solve the conventional problems is a thermoplastic resin, a radically polymerizable compound, a first radical polymerization initiator having a half-life temperature of 90 to 145 ° C, and a half-life temperature of one minute. It features a second radical polymerization initiator at 150 to 175 ° C. The "1 minute half-life temperature" refers to the temperature when the half-life is 1 minute, and the "half-life" refers to the time when the concentration of the compound decreases to half of the initial number. The adhesive composition of the present invention is a radical curing adhesive composition containing a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator. Since the adhesive composition containing the aforementioned radical polymerizable compound has excellent reactivity, it can be cured in a very short time even at low temperatures. In addition, the use of a radical polymerization initiator with a half-life temperature of 1 minute -6-200536921 (3) The two radical polymerization initiators with different degrees of results have the effect of expanding the process adaptability during hardening treatment. Therefore, when the hardened product obtained from the adhesive composition described above is obtained, even when the process temperature or time is changed, it has the effect of obtaining stable adhesive strength and connection resistance. In addition, since the active energy of the radical-curing adhesive having a half-life temperature of approximately 1 minute in the above range is low, the storage stability tends to decrease. However, the cured product obtained from the adhesive composition of the present invention exhibits more excellent storage stability when compared with conventional substances. It is presumed that this should be the effect obtained by using two kinds of radical polymerization initiators having significantly different half-life temperatures of 1 minute in the adhesive composition of the present invention. In addition, when the adhesive composition of the present invention is used, the hardening treatment can be performed in a short period of time, and factors such as process adaptability can be increased. Therefore, even when the distance between the element such as a semiconductor element, a liquid crystal element, and the circuit is narrowed, It can prevent the heating to the peripheral members other than the connection part, which can cause% damage to the peripheral members, and improve productivity. In the adhesive composition of the present invention, the radical polymerizable compound is preferably one having two or more (meth) acrylfluorenyl groups in the molecule. When the aforementioned adhesive composition is used, the hardening treatment can be performed in a shorter time. The reason is presumed to be a radically polymerizable compound having two or more highly reactive free-reactive groups. Furthermore, since the aforementioned radically polymerizable compound uses a (meth) acrylfluorenyl group as a reactive group, it is not necessary to select the material of the adherend to obtain strong adhesion. Therefore, the above-mentioned radical polymerizable compound is included.
發明黏著劑組成物，具有優良之泛用性，例如使用於半導 體元件或液晶顯示元件時也可得到更安定之黏著強度或連 接電阻等特性。 又，第1自由基聚合起始劑與第2自由基聚合起始劑 ，以皆使用分子量180至1 000之過氧化酯衍生物爲佳。The adhesive composition of the invention has excellent versatility. For example, when it is used for a semiconductor element or a liquid crystal display element, it can obtain more stable adhesive strength and connection resistance. Further, it is preferable that the first radical polymerization initiator and the second radical polymerization initiator both use a peroxy ester derivative having a molecular weight of 180 to 1,000.
無論第1自由基聚合起始劑與第2自由基聚合起始劑 ，爲同種之過氧化酯衍生物，且爲上述數値範圍內之分子 量時，其相互間可得到優良之相溶性，故所得之硬化物， 其全體可得到更安定之黏著強度或連接電阻等特性。 又，本發明之黏著劑組成物，相對於熱塑性樹脂1〇〇 質量份，以含有自由基聚合性化合物5 0至2 5 0質量份， 且第1自由基聚合起始劑與第2自由基聚合起始劑分別含 有〇 · 〇 5至3 0質量份爲佳。前述本發明之黏著劑組成物， 其結構材料之添加比例於上述範圍內時，可更顯著的發揮 本發明之效果。 又，此黏著劑組成物以再含有導電性粒子爲佳，其可 使前述黏著劑組成物具有導電性。如此，即可將此黏著劑 組成物於電路電極或半導體等電氣工業或電子工業之技術 領域中作爲導電性黏著劑使用。又，此時，因黏著劑組成 物具有導電性，故可使硬化後之連接電阻更爲減低。 又，此導電性粒子之添加比例，以對熱塑性樹脂100 質量份而言，導電性粒子以含有0 · 5至3 0質量份爲佳。 導電性粒子之添加比例於上述範圍內時，前述黏著劑組成 物’可使導電性粒子之效果更爲提升。例如，用於電路電 -8- 200536921 (5) 極之連接時，可防止相對向之電路電極間產生導電，或相 鄰接之電路電極間產生短路現象。又，添加有上述比例之 導電性粒子之黏著劑組成物，亦可顯現出電氣連接之異向 性，因而其可作爲異向性導電性黏著劑組成物使用。 又，本發明之電路連接材料，爲以電路方式連接相對 向之電路電極間之電路連接材料，且電路連接材料含有上 述黏著劑組成物爲特徵。Regardless of whether the first radical polymerization initiator and the second radical polymerization initiator are the same kind of peroxyester derivative and have a molecular weight within the above-mentioned range, they can obtain excellent compatibility with each other. The obtained hardened product can obtain more stable characteristics such as adhesive strength and connection resistance. In addition, the adhesive composition of the present invention contains 50 to 250 parts by mass of a radical polymerizable compound with respect to 100 parts by mass of the thermoplastic resin, and the first radical polymerization initiator and the second radical The polymerization initiator preferably contains from 0.05 to 30 parts by mass. When the addition ratio of the structural material of the aforementioned adhesive composition of the present invention is within the above range, the effect of the present invention can be more significantly exerted. The adhesive composition preferably further contains conductive particles, which can make the adhesive composition conductive. In this way, the adhesive composition can be used as a conductive adhesive in the technical fields of the electrical industry or the electronics industry such as circuit electrodes or semiconductors. At this time, since the adhesive composition has conductivity, the connection resistance after curing can be further reduced. In addition, the conductive particles are preferably added in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the thermoplastic resin. When the addition ratio of the conductive particles is within the above range, the effect of the conductive particles can be further enhanced by the aforementioned adhesive composition '. For example, when it is used for the connection of circuit electrodes (5), it can prevent conduction between the opposite circuit electrodes or short circuit between adjacent circuit electrodes. In addition, the adhesive composition containing the conductive particles in the above proportions also exhibits anisotropy in electrical connection, so it can be used as an anisotropic conductive adhesive composition. In addition, the circuit connecting material of the present invention is a circuit connecting material that connects the opposing circuit electrodes in a circuit manner, and the circuit connecting material contains the above-mentioned adhesive composition.
前述電路連接材料，即使於低溫下亦可於極短時間下 使相對向之電路電極間相互黏著，而可提升其製程之適應 性。又，由則述電路連接材料所得之硬化物，若改變製造 硬化物時之製程溫度或時間，亦可以得到具有安定化之黏 著強度或連接電阻等特性。又，此電路連接材料於含有上 述添加比例之導電性粒子時，可顯現出電氣連接之異向性 ，因而其可作爲電路電極用異向性導電性電路連接材料使 用。 又’上述黏著劑組成物或電路連接材料以形成爲薄膜 狀者爲佳。因作爲薄膜狀之黏著劑組成物或電路連接材料 具有優良之處理性，故可使生產率更向上提升。 又’本發明之電路連接結構爲，具有於第1電路基板 之主面上形成第1電路電極之第1電路構件，與於第2電 路基板之主面上形成第2電路電極之第2電路構件，與設 置於前述第1電路基板之主面與前述第2電路基板之主面 之間，使前述第1電路電極與前述第2電路形成對向配置 之狀態下以電路連接之電路連接構件之電路構件之連接結 -9- 200536921 (6) 構’且以前述電路連接構件，爲上述電路連接材料之硬化 物爲特徵。 前述電路構件之連接結構，可有效的利用於經電路連 接之電路電極。即，因使用可以電路連接第1電路電極與 第2電路電極之上述電路連接材料，故具有本發明連接構 造之電路構件，其品質不易分歧，而顯示出極安定之特性 。又，電路連接材料之硬化物含有導電性粒子時，可降低 % 連接電阻。經由添加此導電性粒子，可防止相對向之電路 電極間產生導電，或相鄰接之電路電極間產生短路現象。 又，添加有上述比例之導電性粒子時，可顯現出電氣連接 之異向性，而可作爲異向性電路連接材料。 又本發明之半導體裝置，其爲具有半導體元件，與搭 載半導體元件之基板，與設置於前述半導體元件與前述基 板間，以電路連接前述半導體元件與前述基板之半導體元 件連接構件之半導體裝置，其以半導體元件連接構件，爲 ^ 上述黏著劑組成物之硬化物或薄膜狀黏著劑爲特徵。 前述半導體裝置，因以電路連接半導體元件與基板之 黏著劑組成物之硬化物爲上述黏著劑組成物之硬化物，故 品質不易分歧，而可顯示出極爲安定之特性。又，黏著劑 組成物之硬化物含有導電性粒子時，可降低連接電阻。經 由添加此導電性粒子，可防止相對向之半導體元件與基板 間產生導電現象。又，添加有上述比例之導電性粒子時， 可顯現出電氣連接之異向性，而可作爲異向性半導體。 以下，必要時可參酌所附圖式，對本發明之較佳實施 -10- 200536921 (7) 形態作一說明。又，同一要件使用同一符號表示，而省略 重複之說明。又，以下說明中之（甲基）丙烯酸酯，係指 丙烯酸酯或其對應之甲基丙烯酸酯之意。 (黏著劑組成物） 本發明之黏著劑組成物，爲含有熱塑性樹脂、自由基 聚合性化合物、1分鐘半衰期溫度爲9 0至1 4 5。(：之第1自 • 由基聚合起始劑，與1分鐘半衰期溫度爲150至175。(：之 第2自由基聚合起始劑者。 其中，本發明之熱塑性樹脂，爲增強黏著之對象物（ 以下，簡稱爲「被黏著物」）相互間之黏著力者。 本發明所使用之熱塑性樹脂，並未有任何限制而可使 用公知物質。具體而言，例如可使用聚醯亞胺、聚醯胺、 苯氧基樹脂類、聚（甲基）丙烯酸酯類、聚醯亞胺類、聚 胺基甲酸酯類、聚酯類、聚乙烯基丁縮醛類等。其可單獨 % 使用或將2種以上混合使用皆可。又，前述樹脂於分子內 可具有矽氧烷鍵結或氟取代基。前述混合之樹脂間可完全 相溶，或產生微觀相分離之白濁狀態等亦可使用。 又，前述熱塑性樹脂之分子量越大時，越容易形成後 述之薄膜，又，也可以廣泛的設定可影響黏著劑流動性之 熔融黏度。可廣範圍的設定熔融黏度時，於該樹脂用於半 導體元件或液晶元件等之連接時，即使元件間與電路間之 間距狹窄化時，也可進一步防止黏著劑附著於週邊構件上 ，而可提局生產率。又此分子量之値超過1 5 0 0 0 0時，則 -11 - 200536921 (8) 與其他成份之相溶性將會有劣化之傾向，低於5 0 0時，於 作爲後述薄膜使用時，將會使薄膜之形成傾向不完全。因 此，此分子量之重量平均分子量以5000至150000爲佳， 又以1 0000至80000爲更佳。 又’本發明之自由基聚合性化合物，係指賦予能量時 即可產生自由基’且基於自由基連鎖反應產生聚合而形成 聚合物之化合物。此自由基聚合反應，一般相較於陽離子 % 聚合或陰離子聚合可更快速的進行反應。因此，使用自由 基聚合性化合物之本發明，可於較短時間內進行聚合。 本發明所使用之自由基聚合性化合物，只要分子內具 有（甲基）丙烯酸基、（甲基）丙烯醯基或乙烯基等烯烴 之化合物時，並未有任何限制而可使用公知之化合物。其 中’又以具有（甲基）丙烯醯基之自由基聚合性化合物爲 佳。 具體而言，具有（甲基）丙烯醯基之自由基聚合性化 % 合物’例如環氧基（甲基）丙烯酸酯低聚物、（甲基）丙 嫌酸尿烷酯低聚物、聚醚（甲基）丙烯酸酯低聚物、聚酯 (甲基）丙烯酸酯低聚物等低聚物，三羥甲基丙烷三（甲 基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚烷二醇 (甲基）丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、二環 戊烧氧乙基（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯 酸醋、二季戊四醇六（甲基）丙烯酸酯、異氰酸變性2官 能（甲基）丙烯酸酯、異氰酸變性3官能（甲基）丙烯酸 醋、2,2’ 一二（甲基）丙烯醯氧基二乙基磷酸酯、2一 （甲 -12- 200536921 Ο) 基）丙烯醯氧基乙基疊氮磷化物等多官能（甲基）丙烯酸 酯化合物等。前述化合物，必要時可單獨或將2種以上混 合使用。 使用反應性基之（甲基）丙烯醯基時，可無須選擇被 黏者物之材質下’即可得到強固之黏著性。此被黏著物， 例如由印刷電路板或聚醯亞胺等有機基材開始，至銅、銘 等金屬或 IT〇(Indium Tin Oxide)、氮化砂（SiN)、二 % 氧化矽（Si02 )等。 又，自由基聚合性化合物於分子內具有2個以上（甲 基）丙嫌酿基時’可使黏著所需加熱時間更短，黏著所需 加熱溫度更低等優點，故爲較佳。其推測應爲自由基聚合 性化合物之分子內具有許多自由反應性基之（甲基）丙烯 醯基所得之效果。 又，此自由基聚合性化合物之添加比例相對於熱塑性 樹脂1 〇 〇份以5 0至2 5 0質量份爲佳，以6 0至1 5 0質量份 ^ 爲更佳。自由基聚合性化合物之添加比例低於5 0質量份 時，黏著於被黏著物之黏著劑組成物之硬化物的耐熱性會 有降低之傾向，超過25 0質量份時，黏著劑組成物作爲後 述薄膜使用時，將會有不易形成薄膜之傾向。 又，本發明之黏著劑組成物含有自由基聚合起始劑。 自由基聚合性化合物，一旦開始自由基聚合反應後，則形 成連鎖反應，而形成強固之硬化狀態，但因欲產生最初自 由基爲相對上較爲困難者，故可再含有較容易生成自由基 之自由基聚合起始劑。 -13- 200536921 (10) 本發明中’自由基聚合起始劑爲倂用1分鐘半衰期溫 度爲90至145 °C之第1自由基聚合起始劑，與1分鐘半衰 期溫度爲150至175 °C之第2自由基聚合起始劑。 前述第1自由基聚合起始劑，於1分鐘半衰期溫度爲 9 〇至1 4 5 r之條件下，可使用公知化合物，第2自由基聚 合起始劑，於1分鐘半衰期溫度爲1 5 0至1 7 5 °C之條件下 ，亦可使用公知化合物。The aforementioned circuit connection material can adhere the opposing circuit electrodes to each other in a very short time even at a low temperature, thereby improving the process adaptability. In addition, if the hardened product obtained from the circuit connection material is changed in the process temperature or time when the hardened product is manufactured, it can also obtain stable adhesive strength and connection resistance. In addition, this circuit connecting material exhibits anisotropy of electrical connection when it contains conductive particles in the above-mentioned addition ratio, so it can be used as an anisotropic conductive circuit connecting material for circuit electrodes. It is preferable that the above-mentioned adhesive composition or circuit connection material is formed into a thin film. As a film-like adhesive composition or a circuit connection material, it has excellent local rationality, so that productivity can be further improved. The circuit connection structure of the present invention includes a first circuit member having a first circuit electrode formed on a main surface of a first circuit substrate, and a second circuit having a second circuit electrode formed on a main surface of the second circuit substrate. And a circuit connecting member which is provided between the main surface of the first circuit substrate and the main surface of the second circuit substrate so that the first circuit electrode and the second circuit face each other in an opposed arrangement. The connection structure of the circuit components-9-200536921 (6) The structure is characterized in that the aforementioned circuit connection component is a hardened material of the above-mentioned circuit connection material. The connection structure of the aforementioned circuit components can be effectively used for circuit electrodes connected through a circuit. That is, since the above-mentioned circuit connection material capable of circuit-connecting the first circuit electrode and the second circuit electrode is used, the circuit member having the connection structure of the present invention is unlikely to differ in quality and exhibits extremely stable characteristics. In addition, when the hardened material of the circuit connection material contains conductive particles, the% connection resistance can be reduced. By adding this conductive particle, it is possible to prevent conduction between opposing circuit electrodes or short circuit between adjacent circuit electrodes. In addition, when conductive particles are added in the above proportion, anisotropy of electrical connection can be exhibited, and it can be used as an anisotropic circuit connection material. The semiconductor device of the present invention is a semiconductor device having a semiconductor element, a substrate on which the semiconductor element is mounted, and a semiconductor element connection member provided between the semiconductor element and the substrate and electrically connecting the semiconductor element and the substrate with a circuit. It is characterized in that the semiconductor element connection member is a hardened product of the above-mentioned adhesive composition or a film-shaped adhesive. In the aforementioned semiconductor device, since the hardened material of the adhesive composition that connects the semiconductor element and the substrate with a circuit is the hardened material of the above-mentioned adhesive composition, the quality is not easily divergent, and it can exhibit extremely stable characteristics. In addition, when the hardened material of the adhesive composition contains conductive particles, the connection resistance can be reduced. By adding this conductive particle, it is possible to prevent a conductive phenomenon between the opposing semiconductor element and the substrate. In addition, when the conductive particles are added in the above proportion, anisotropy of electrical connection can be exhibited, and it can be used as an anisotropic semiconductor. In the following, when necessary, referring to the attached drawings, a description will be given of a preferred embodiment of the present invention -10- 200536921 (7). It should be noted that the same elements are represented by the same symbols, and redundant descriptions are omitted. The (meth) acrylate in the following description means acrylate or a corresponding methacrylate. (Adhesive composition) The adhesive composition of the present invention contains a thermoplastic resin, a radical polymerizable compound, and has a half-life temperature of 90 to 145 in 1 minute. (: The first self-based polymerization initiator and a one-minute half-life temperature of 150 to 175. (: The second free radical polymerization initiator. Among them, the thermoplastic resin of the present invention is an object for enhancing adhesion (Hereinafter referred to as "adhered object"). The thermoplastic resin used in the present invention can be a known substance without any limitation. Specifically, for example, polyimide, Polyamines, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes, polyesters, polyvinyl butyral, etc. It can be used alone% It is also possible to use a mixture of two or more kinds. In addition, the resin may have a siloxane bond or a fluorine substituent in the molecule. The mixed resins may be completely compatible with each other, or a white turbid state in which micro-phase separation occurs may be used. The larger the molecular weight of the thermoplastic resin, the easier it is to form a film described later, and the melt viscosity that can affect the fluidity of the adhesive can be set widely. When the melt viscosity can be set in a wide range, it is used for this resin. to When connecting a conductive element or a liquid crystal element, even when the distance between the element and the circuit is narrowed, it is possible to further prevent the adhesive from adhering to the peripheral member, which can improve local productivity. Moreover, the molecular weight is more than 1 5 0 0 When it is 0, -11-200536921 (8) The compatibility with other components tends to deteriorate. When it is lower than 500, when it is used as a film to be described later, the film formation tendency is incomplete. Therefore The weight-average molecular weight of this molecular weight is preferably 5,000 to 150,000, and more preferably 10,000 to 80,000. Also, the "radical polymerizable compound of the present invention means that radicals can be generated when energy is given" and is based on free radicals A chain reaction produces a compound that polymerizes to form a polymer. This radical polymerization reaction generally proceeds faster than cationic% polymerization or anionic polymerization. Therefore, the present invention using a radical polymerizable compound can be made shorter. Polymerization takes place within a time. As long as the radically polymerizable compound used in the present invention has a (meth) acrylic acid group and a (meth) acrylfluorene group in the molecule In the case of olefin compounds such as vinyl, known compounds can be used without any restrictions. Among them, a radically polymerizable compound having a (meth) acrylfluorenyl group is preferred. Specifically, it has (meth) % Free radical polymerizable compounds of propylene groups such as epoxy (meth) acrylate oligomers, (meth) propane urethane oligomers, and polyether (meth) acrylates are low Polymers, oligomers such as polyester (meth) acrylate oligomers, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol (formaldehyde Base) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (methyl) Acrylate, isocyanate modified 2-functional (meth) acrylate, isocyanate modified tri-functional (meth) acrylic acid vinegar, 2,2'-di (meth) acryloxydiethyl phosphate, 2 Mono (methyl-12- 200536921 〇) polyacryloxyethyl azide phosphide and other officials Capable of (meth) acrylate compounds, etc. The aforementioned compounds may be used alone or as a mixture of two or more of them as necessary. When using a (meth) acrylfluorenyl group having a reactive group, it is possible to obtain strong adhesion without selecting the material of the adherend. The adherend, for example, starts from an organic substrate such as a printed circuit board or polyimide, to metals such as copper and metal, or IT0 (Indium Tin Oxide), nitrided sand (SiN), and two percent silicon oxide (Si02). Wait. In addition, when the radically polymerizable compound has two or more (methyl) acryloyl groups in the molecule, it is preferable because it can shorten the heating time required for adhesion and lower the heating temperature required for adhesion. It is presumed to be an effect obtained by a (meth) acrylfluorenyl group having many freely reactive groups in the molecule of the radically polymerizable compound. The addition ratio of the radical polymerizable compound is preferably 50 to 250 parts by mass relative to 1,000 parts of the thermoplastic resin, and more preferably 60 to 150 parts by mass. When the addition ratio of the radical polymerizable compound is less than 50 parts by mass, the heat resistance of the hardened material of the adhesive composition adhered to the adherend tends to decrease. When it exceeds 250 parts by mass, the adhesive composition serves as When the film described later is used, it tends to be difficult to form a film. The adhesive composition of the present invention contains a radical polymerization initiator. A radical polymerizable compound, once the radical polymerization reaction starts, forms a chain reaction and forms a strong hardened state. However, since it is relatively difficult to generate the initial free radicals, it may be contained more easily to generate free radicals. Free radical polymerization initiator. -13- 200536921 (10) In the present invention, the 'radical polymerization initiator is the first radical polymerization initiator with a half-life temperature of 90 to 145 ° C for 1 minute, and a 1-minute half-life temperature of 150 to 175 ° C is the second radical polymerization initiator. The aforementioned first radical polymerization initiator can use a known compound under the condition that the 1-minute half-life temperature is 90 to 145 r, and the second radical polymerization initiator has a half-life temperature of 1 50 at 1 minute. It is also possible to use well-known compounds at temperatures up to 175 ° C.
其中又以第1自由基聚合起始劑與第2自由基聚合起 始劑同時爲過氧化酯衍生物爲佳。但只要其中之一爲過氧 化酯衍生物時，因其相互間具有優良之相溶性，故所得之 硬化物，可得到更安定之黏著強度或連接電阻等特性。 第1自由基聚合起始劑，具體而言例如異丙苯基過氧 化新癸酸酯、1，1, 3，3 —四甲基丁基過氧化新癸酸酯、1 一 環己基一 1 一甲基己基過氧化新癸酸酯、t -己基過氧化新 癸酸酯、t一丁基過氧化新癸酸酯、t一丁基過氧化三甲基 乙酸酯、1,1，3,3 —四甲基丁基過氧基一 2 —乙基己酸酯、 2,5 —二甲基一2,5 —二（2—乙基己醯基過氧基）己烷、t —己基過氧基一 2 —乙基己酸酯、t一丁基過氧基一 2 —乙 基己酸酯、t一丁基過氧基新庚酸酯、t一戊基過氧酯- 2 — 乙基己酸酯、二一 t 一丁基過氧基六氫對苯二甲酸酯、t-戊基過氧基—3, 5,5—三甲基己酸酯、3 —羥基一1，1—二甲 基丁基過氧化新癸酸酯、1，1,3，3 -四甲基丁基過氧基一 2 一乙基己酸酯、t-戊基過氧基新癸酸酯、t-戊基過氧基 新癸酸酯、t一戊基過氧基一 2 -乙基己酸酯、2,2’ 一偶氮 -14- 200536921 (11) 雙一2.4-二甲基戊腈、1，1’一偶氮雙—（1一乙醯氧基—1 一苯基乙烷）、2,2，一偶氮雙異丁腈、2,2’一偶氣雙（2 — 甲基丁腈）、二甲基一 2，2，—偶氮雙異丁腈、4,4’ 一偶氮 雙（4 一氰基戊酸）、1，1，一偶氮雙（〗一環己烷鎖腈）等 〇 第2自由基聚合起始劑，具體而言例如t一己基過氧 異丙基單碳酸酯、t-丁基過氧化馬來酸、t-丁基過氧基 • 一 3，5,5 —三甲基己醇酯、t一丁基過氧月桂酯、2,5 —二甲 基一 2,5 一二（3 —甲基苯醯過氧基）己烷、t一丁基過氧基 —2 —乙基己基單碳酸酯、t一己基過氧化苯甲酸酯、2,5 — 二甲基一 2，5 —二（苯醯過氧基）己烷、t一丁基過氧基苯 甲酸酯、二丁基過氧化三甲基己二酸酯、t -戊基過氧基 正辛酸酯、t-戊基過氧化異壬酸酯、t-戊基過氧化苯甲 酸酯等。 又，本發明之黏著劑組成物只要倂用第1自由基聚合 ^ 起始劑與第2自由基聚合起始劑即可，第1自由基聚合起 始劑亦可使用2種以上，第2自由基聚合起始劑也可使用 2種以上。 第1自由基聚合起始劑與第2自由基聚合起始劑之分 子量，以重量平均分子量爲180至1000者爲佳。第1自 由基聚合起始劑與第2自由基聚合起始劑中任一者爲上述 述値範圍內之分子量時，因具有優良相溶性，故所得之硬 化物’可顯示出更爲安定之黏著強度或連接電阻等特性。 第〗自由基聚合起始劑與第2自由基聚合起始劑添加 -15- • 05 200536921 (12) 質 份 劑 白 聚 會 有 本 相 下 並 如 域 接 焊 塑 可 量，以相對於熱塑性樹脂1 00份’其各自之量爲使用0 至30質量份爲佳，又以各自之量同時使用0.05至30 量份爲更佳。又，以各自之量同時使用ο·1至20質量 爲最佳。第1自由基聚合起始劑與第2自由基聚合起始 各自之添加量低於0.0 5質量份時，會有未能充分進行 由基聚合之現象，第1自由基聚合起始劑與第2自由基 合起始劑各自之添加量高於3 0質量份時，儲存安定性 Φ 有降低之傾向。 又，本發明中，所賦予之能量形態並未有特別限定 一般例如熱、電子線、r射線、紫外線、紅外線等。 目前仍未明瞭使用本發明之黏著劑組成物可得到具 充分安定之黏著強度或連接電阻之硬化物的原因，但， 發明者們推測其原因之一，應爲使用1分鐘半衰期溫度 異之2種自由基聚合起始劑所得，故即使不同製程條件 ，亦可得到較安定之自由基聚合反應速度。但，其原因 % 不僅限定於此。 本發明之黏者劑組成物以含有導線性粒子而爲較佳 含有導電性粒子結果，可賦予該黏著劑組成物導電性。 此’於電路電極或半導體等電氣工業或電子工業技術領 中可作爲導電性黏著性使用。 本發明所使用之導電性粒子，只要具有可以電路連 之導電性時則無特別限制，例如可使用Ag、Ni、Cu、 料等金屬或碳等。又，可使用非導電性之玻璃、陶瓷、 膠等作爲核，並於該核上被覆前述金屬或碳黑所得者亦 -16- 200536921 (13) 。其中，金屬本身爲熱熔融性金屬時，或使用塑膠作爲核 而被覆金屬或碳黑所得者爲佳。此情形中，更容易將黏著 劑組成物之硬化物以加熱或加壓使其變形，而於電極間以 電路連接時，可增加電極與黏著劑組成物之接觸面積，而 提高電極間之導電性。Among them, it is preferable that the first radical polymerization initiator and the second radical polymerization initiator are both peroxide ester derivatives. However, as long as one of them is a peroxy ester derivative, since it has excellent compatibility with each other, the obtained hardened product can obtain more stable characteristics such as adhesive strength and connection resistance. The first radical polymerization initiator, for example, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxydecanoate, 1 cyclohexyl-1 1 Methylhexylperoxyneodecanate, t-hexylperoxynedecanoate, t-butylperoxynedecanoate, t-butylperoxytrimethylacetate, 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexylperoxy) hexane, t-hexyl Peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneheptanoate, t-pentylperoxy ester-2 — Ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-pentylperoxy-3, 5,5-trimethylhexanoate, 3-hydroxy-1 1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2 monoethylhexanoate, t-pentylperoxyneodecanoate Ester, t-pentylperoxy neodecanoate, t-pentylperoxy- 2-ethylhexanoate, 2,2'-azo-14- 200536921 (11) bis 2.4-dimethylvaleronitrile, 1,1'-azobis- (1-ethylacetoxy-1-phenylphenylethane), 2,2, -azobisisobutyronitrile, 2,2'- Azobis (2-methylbutyronitrile), dimethyl-1,2,2-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1,1 2nd radical polymerization initiators, such as azobis (〗-cyclohexane lock nitrile), specifically, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t- Butylperoxy • 3,5,5-trimethylhexanol ester, t-butylperoxylauryl ester, 2,5-dimethyl-2,5-di ((3-methylphenylhydrazone) Oxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (phenylhydrazone) (Oxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyl adipate, t-pentylperoxyn-octanoate, t-pentylperoxyisopropyl Nonanoate, t-pentyl benzoate and the like. In addition, the adhesive composition of the present invention only needs to use the first radical polymerization initiator and the second radical polymerization initiator. The first radical polymerization initiator may also use two or more kinds. The second Two or more radical polymerization initiators may be used. The molecular weight of the first radical polymerization initiator and the second radical polymerization initiator is preferably a weight average molecular weight of 180 to 1,000. When any of the first radical polymerization initiator and the second radical polymerization initiator has a molecular weight within the above-mentioned range, the obtained hardened product can be more stable because it has excellent compatibility. Adhesive strength or connection resistance. The first free radical polymerization initiator and the second free radical polymerization initiator are added -15- • 05 200536921 (12) The quality agent has the same phase and can be measured in the same manner as the domain welding, so that it can be compared with the thermoplastic resin. The amount of 100 parts is preferably from 0 to 30 parts by mass, and more preferably from 0.05 to 30 parts by weight. In addition, it is best to use ο · 1 to 20 in the respective amounts simultaneously. When the amount of each of the first radical polymerization initiator and the second radical polymerization initiator is less than 0.05 parts by mass, the radical polymerization may not be sufficiently performed. The first radical polymerization initiator and the first When the amount of each of the 2 radical initiators added is higher than 30 parts by mass, the storage stability Φ tends to decrease. In the present invention, the form of energy to be imparted is not particularly limited. In general, for example, heat, electron beams, r rays, ultraviolet rays, infrared rays, and the like. The reason why the adhesive composition of the present invention can be used to obtain a hardened product with sufficiently stable adhesive strength or connection resistance is still unknown, but the inventors have speculated that one of the reasons is that the 1-minute half-life temperature difference is 2 This kind of free radical polymerization initiator is obtained, so even under different process conditions, a more stable free radical polymerization reaction speed can be obtained. However, the reason% is not limited to this. The adhesive composition of the present invention preferably contains conductive particles and preferably contains conductive particles. As a result, the adhesive composition can be made conductive. It can be used as a conductive adhesive in the technical fields of the electrical industry or the electronics industry, such as circuit electrodes or semiconductors. The conductive particles used in the present invention are not particularly limited as long as they have electrical conductivity capable of being connected to a circuit. For example, metals such as Ag, Ni, Cu, and carbon, or carbon can be used. In addition, non-conductive glass, ceramics, glue, etc. can be used as the core, and the core or the carbon black obtained by coating the core is also -16- 200536921 (13). Among them, when the metal itself is a hot-melt metal, or a metal or carbon black is coated with plastic as a core, it is preferable. In this case, it is easier to deform the hardened material of the adhesive composition by heating or pressing, and when the circuit is connected between the electrodes, the contact area between the electrode and the adhesive composition can be increased to improve the conductivity between the electrodes. Sex.
又，此導電性粒子之表面，可再使用高分子樹脂被覆 所得之層狀粒子。於層狀粒子之狀態下，將導電性粒子添 加於黏著劑組成物中時，於增加導電性粒子之添加量時， 因被覆有樹脂，故可防止使導電性粒子間因接觸而產生短 路之情形，因而可提高電極電路間之絕緣性。又，前述導 電性粒子或層狀粒子可單獨或將2種以上混合使用亦可。 導電性粒子之平均粒徑，就分散性、導電性等觀點而 言，以1至1 8 // m爲佳。導電性粒子之添加比例，相對於 黏著劑組成物100體積％以0.1至30體積％爲佳，又以 〇.1至10體積％爲更佳。此數値低於0·1體積％時，則有 未能充分得到導電性之傾向，超過3 0體積％時，會有容 易引起電路短路之傾向。又，導電性粒子之添加比例（體 積％ )依23 t時黏著劑組成物硬化前各成份之體積爲基準 而決定，各成份之體積可由利用比重由重量計算體積之方 法，或該成份於不使其溶解膨潤下，將該成份投入放置有 適當溶劑（水、醇等）之量筒等容器中，由增加之體積予 以計算之方法等。 又，本發明之黏著劑組成物，以添加烷氧矽烷衍生物 或矽雜烷衍生物爲代表之偶合劑或黏著增強劑、平滑劑等 •17- 200536921 (14) 黏著輔助劑爲佳。添加前述物質時，可更發揮出本發明之 效果，又可賦予良好之密著性或處理性。具體而言，例如 以添加下述式（1 )所示化合物爲佳。 R1 OR4The surface of this conductive particle may be further coated with a layered particle obtained by coating with a polymer resin. When the conductive particles are added to the adhesive composition in the state of layered particles, when the amount of the conductive particles is increased, the resin is coated, so that the short circuit between the conductive particles due to contact can be prevented. In this case, the insulation between the electrode circuits can be improved. The conductive particles or layered particles may be used alone or in combination of two or more. The average particle diameter of the conductive particles is preferably from 1 to 1 8 // m from the viewpoints of dispersibility and conductivity. The addition ratio of the conductive particles is preferably 0.1 to 30% by volume relative to 100% by volume of the adhesive composition, and more preferably 0.1 to 10% by volume. When the number is less than 0.1% by volume, the conductivity may not be sufficiently obtained, and when it exceeds 30% by volume, the circuit tends to be short-circuited easily. In addition, the addition ratio (volume%) of conductive particles is determined based on the volume of each component of the adhesive composition before curing at 23 t. The volume of each component can be calculated by using the specific gravity to calculate the volume by weight, or the component can After dissolving and swelling, the ingredients are put into a container such as a graduated cylinder in which a suitable solvent (water, alcohol, etc.) is placed, and the method of calculating from the increased volume, etc. In addition, the adhesive composition of the present invention is preferably a coupling agent, an adhesion enhancer, a smoothing agent or the like represented by the addition of an alkoxysilane derivative or a silane derivative. 17-200536921 (14) An adhesion auxiliary agent is preferred. When the aforementioned substances are added, the effects of the present invention can be further exerted, and good adhesion or handling properties can be imparted. Specifically, for example, it is preferable to add a compound represented by the following formula (1). R1 OR4
R3 ^-〇—C—C=CH2 ⑴ 其中，式中，R^R2與R3各自獨立爲氫、碳數1至 ® 5之烷基、碳數1至5之烷氧基、碳數1至5之烷氧羰基 、或芳基；R4爲氫、或甲基；11爲丨至10之整數。 又’於式（1)中，R1爲碳數1至5之烷基或芳基； R2與R3各自獨立爲碳數2至3之烷氧基，η爲2至4時 ’可得到具有更優良之黏著性，與連接電阻而爲較佳。又 ’式（1 )所示化合物單獨使用1種或將2種以上混合使 用亦可。R3 ^ -〇-C-C = CH2 ⑴ Wherein, R ^ R2 and R3 are each independently hydrogen, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, and 1 to 5 carbons An alkoxycarbonyl group or an aryl group of 5; R4 is hydrogen or a methyl group; 11 is an integer from 1 to 10. Also, in the formula (1), R1 is an alkyl group or an aryl group having 1 to 5 carbon atoms; R2 and R3 are each independently an alkoxy group having 2 to 3 carbon atoms; Excellent adhesion, and better connection resistance. The compound represented by the formula (1) may be used alone or in combination of two or more.
又’本發明之黏著劑組成物，可配合其他使用目的而 添加其他種材料。例如，可倂用提高黏著劑之交聯率之黏 著性增強劑。添加此物質時可更爲提升黏著強度。即，除 具有（甲基）丙烯醯基之自由基聚合性化合物以外，例如 可添加具有烯丙基、馬來醯亞胺基、乙烯基等可進行自由 基聚合之官能基的化合物。具體而言，例如Ν —乙烯基咪 唑、Ν —乙烯基吡啶、Ν —乙烯基吡咯烷酮、Ν —乙烯基甲 醛、Ν —乙烯基內酯、4,4’ —亞乙烯基雙（Ν，Ν—二甲基苯 胺）、Ν —乙烯基丙酮醯胺、Ν，Ν —二甲基丙烯醯胺、Ν — 異丙基丙烯醯胺、Ν，Ν -二乙基丙烯醯胺丙烯醯胺等。其 -18- 200536921 (15) 中’釗述黏著增強劑可單獨使用1種或將2種以上混合使 用亦可。 又’其可倂用單官能（甲基）丙烯酸酯等流動性提升 劑。添加後可提升流動性。具體而言，例如季戊四醇（甲 基）丙烯酸酯、2 —氰基乙基（甲基）丙烯酸酯、環己基 (甲基）丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、二環 戊烯氧乙基（甲基）丙烯酸酯、2一 （乙氧基乙氧基）乙 % 基（甲基）丙烯酸酯、2 -乙氧基乙基（甲基）丙烯酸酯 、2—乙基己基（甲基）丙烯酸酯、^ 一己基（甲基）丙烯 酸酯、2 —羥基乙基（甲基）丙烯酸酯、羥基丙基（甲基 )丙烯酸酯、異冰片基（甲基）丙烯酸酯、異癸基（甲基 )丙烯酸酯、異辛基（甲基）丙烯酸酯、η —月桂基（甲 基）丙儲酸酯、2-甲氧基乙基（甲基）丙綠酸酯、2-苯 氧基乙基（甲基）丙烯酸酯、四氫呋喃基（甲基）丙烯酸 酯、2—(甲基）丙烯醯氧乙基磷酸酯、ν，Ν—二甲基胺基 ¥ 乙基（甲基）丙烯酸酯、Ν，Ν—二甲基胺基乙基（甲基） 丙烯酸酯、Ν，Ν —二甲基胺基丙基（甲基）丙烯酸酯、Ν，Ν 一二甲基胺基丙基（甲基）丙烯酸酯、（甲基）丙烯烯基 嗎啉等。又，前述流動性提升劑可單獨使用1種，或將2 種以上混合使用亦可。 又，本發明可倂提升黏著性之橡膠系材料。添加此材 料時可緩和應力作用。具體而言，例如聚異戊二烯、聚丁 二烯、羧基末端聚丁二烯、羥基末端聚丁二烯、i，2 一聚 丁二烯、羧基末端1，2 -聚丁二烯、羥基末端1，2 -聚丁二 -19- 200536921 (16) 烯、丙烯酸橡膠 '苯乙烯一丁二烯橡膠、聚合物末端含有 羧基、羥基、（甲基）丙烯醯基或嗎啉基之丙烯腈-丁二 烯橡膠、羧基化腈橡膠、羥基末端聚（氧丙烯）、烷氧矽 烷基末端聚（氧丙烯）、聚（氧四伸甲基）二醇、聚烯二 醇、聚一 ε —內酯等。 又’橡膠系材料，就提升黏著性之觀點而言，以使用 支鏈或末端含有極性較高之官能基之氰基、羧基等之橡膠 Φ 系材料爲佳’又’就提高流動性之觀點而言，以使用液狀 者爲佳。具體而言，例如液狀丙烯腈一丁二烯橡膠、聚合 物末端含有羧基、羥基、（甲基）丙烯醯基或嗎啉基之液 狀丙嫌腈- 丁二烯橡膠、液狀羧基化腈橡膠等，極性基之 丙稀腈含量爲佔此橡膠材料系全體之1 〇至60質量％爲佳 。又前述橡膠材料可單獨使用1種，或將2種以上混合使 用亦可。 又’本發明可倂用t一丁基兒茶酚、t 一丁基酚、ρ — % 甲氧基酚等爲代表之聚合阻礙劑等添加劑。其可使儲存安 定性更爲提升。 本發明之黏著劑組成物，常溫下爲液狀之情形中可以 糊狀方式使用。常溫下爲固體時，可經由加熱使其糊化以 外，也可使用溶劑使其糊化。可使用之溶劑，只要不會與 黏著劑組成物反應，且可顯示出充分之溶解性之溶劑時， 則無特別限制，一般以於常壓下沸點爲5 0至1 5 0 °C者爲佳 。沸點低於5 0 °C時，因於室溫下具有容易揮發之傾向，故 必須於密閉環境下進行自由基聚合反應，使得使用上受到 -20- 200536921 (17) 限制。又，沸點超過1 5 0 °c時，因溶劑不易揮發，故黏著 後會有不易達到充分黏著強度之傾向。 又’本發明之黏著劑組成物可以薄膜狀形式使用。此 薄膜之製造方法’一般爲將溶劑加入黏著劑組成物所得之 混合液塗佈於氟樹脂薄膜、聚對苯二甲酸乙二醇酯薄膜、 離型紙等剝離性基材上，或將不織布等基材浸漬於混合液 後’放置於剝離基材上，隨後去除溶劑而製得薄膜。前述 | 黏著劑組成物形成薄膜狀時，則更容易進行處理。 又，本發明之黏著劑組成物添加導電性粒子而製作薄 膜時，可製得異向性導電性薄膜。此異向性導電性薄膜， 例如放置於基板上之對向電極間，經由加熱加壓使兩電極 連接以產生電氣上之連接。形成電極之基板，例如可使用 半導體、玻璃、陶瓷等無機質、聚醯亞胺、聚碳酸酯等有 機物、玻璃/環氧化物等或由其多數組合而成者。 又，本發明之黏著劑組成物可倂用加熱與加壓以進行 % 黏著。加熱溫度一般以5 0至1 9 0 °C爲佳。壓力則於不損傷 被黏著物之範圍內即可，一般以〇·1至lOMPa爲佳。其加 熱與加壓條件，一般爲於0 · 5至1 2 0秒之範圍內進行爲佳 〇 又，本發明之黏著劑組成物，因可於短時間內進行反 應，且具有優良儲存安定性，故極適合作爲電路連接材料 使用。例如於第1電路構件之電路電極與第2之電路構件 之電路電極以電路連接時，於前述電路構件成對向配置狀 態下，將本發明之黏著劑組成物濕於其中之一電極上，使 -21 - 200536921 (18) 另一電路電極以自由基聚合反應產生電路連接。前述黏著 劑組成物作爲電路連接材料使用時，可使電路於短時間產 生連接，而形成具有安定化之黏著強度或連接電阻等特性 之物。又’亦可抑制電路連接材料之硬化物的儲存性降低 等。又，含有導電性粒子之此電路連接材料，可顯示出異 向之電連接方式’故其可作爲電路電極用之異向導電性電 路連接材料使用。 Φ 又’此電路連接材料，可作爲熱膨脹係數相異之不同 種被黏著物之電路連接材料使用。具體而言，例如可使用 異向性導電性黏者劑、銀糊料、銀薄膜等爲代表之電路連 接材料、CSP用彈性體、CSP用底膜材料、log薄片等爲 代表之半導體兀件黏著材料。 (電路構件之連接材料） 其次’將對本發明之電路構件之連接結構中較佳實施 胃I 形態作一說明。圖1爲本發明電路構件之連接結構之一實 施形態槪略截面圖。如圖1所示般’本發明實施形態之電 路構件之連接結構1，爲具備有相互對向之第1電路構件 2 0與第2電路構件3 0，且於第1電路構件2 〇與第2電路 構件3 0之間，設有以電路連接前述構件之電路連接構件 1 〇，第1電路構件2 0爲具有第1電路基板2 1，與形成於 電路基板21之主面21a上之第1電路電極22。又，電路 基板2 1之主面2 1 a上’必要時可形成絕緣層（未標示於 圖式中）。 -22- 200536921 (19) 又，第2電路構件3 0爲具有第2電路基板3 1，與形 成於電路基板31之主面31a上之第2電路電極32。又， 電路基板3 1之主面3 1 a上，必要時可形成絕緣層（未標 示於圖式中）。In addition, the adhesive composition of the present invention can be added with other materials in accordance with other uses. For example, an adhesion-enhancing agent that increases the cross-linking rate of the adhesive may be used. Adding this substance can further improve the adhesive strength. That is, in addition to the radically polymerizable compound having a (meth) acrylfluorenyl group, for example, a compound having a functional group capable of radical polymerization such as an allyl group, a maleimide group, or a vinyl group can be added. Specifically, for example, N—vinylimidazole, N—vinylpyridine, N—vinylpyrrolidone, N—vinylformaldehyde, N—vinyllactone, 4,4′—vinylidenebis (N, N— Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, acrylamide, and the like. In its -18-200536921 (15), the "Zhaoshu adhesion enhancer" can be used singly or in combination of two or more kinds. It is also possible to use a fluidity-improving agent such as a monofunctional (meth) acrylate. After adding, it can improve fluidity. Specifically, for example, pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl Enoxyethyl (meth) acrylate, 2-mono (ethoxyethoxy) ethyl% (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, ^ hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isopropyl Decyl (meth) acrylate, isooctyl (meth) acrylate, η-lauryl (meth) propionate, 2-methoxyethyl (meth) propionate, 2- Phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, 2- (meth) acrylic acid oxyethyl phosphate, ν, N-dimethylamino group ethyl (methyl ) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (methyl) Acrylates, Ν, Ν-dimethylaminopropyl (meth) acrylates, (meth) propenylmorpholines, and the like. Moreover, the said fluidity improving agent may be used individually by 1 type, and may mix and use 2 or more types. In addition, the present invention can improve the adhesion of a rubber-based material. Adding this material reduces stress. Specifically, for example, polyisoprene, polybutadiene, carboxy-terminated polybutadiene, hydroxyl-terminated polybutadiene, i, 2-polybutadiene, carboxy-terminated 1,2-polybutadiene, Hydroxy-terminated 1,2-polybutadiene-19- 200536921 (16) olefin, acrylic rubber 'styrene-butadiene rubber, propylene containing carboxyl, hydroxyl, (meth) acryl fluorenyl or morpholinyl at the polymer terminal Nitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyene glycol, poly-ε -Lactones, etc. From the viewpoint of improving the adhesiveness, it is better to use a rubber Φ-based material such as a cyano group or a carboxyl group having a functional group with a higher polarity at the end of the chain, or from the viewpoint of improving fluidity. In terms of liquid, it is better to use liquid. Specifically, for example, a liquid acrylonitrile-butadiene rubber, a liquid acrylonitrile-butadiene rubber containing a carboxyl group, a hydroxyl group, a (meth) acryl fluorenyl group, or a morpholinyl group at the end of the polymer, a liquid carboxylation Nitrile rubber and the like, it is preferable that the content of acrylonitrile of the polar group is 10 to 60% by mass of the entire rubber material. The rubber material may be used singly or in combination of two or more kinds. In addition, the present invention can use additives such as polymerization inhibitors such as t-butylcatechol, t-butylphenol, and p-% methoxyphenol. It can improve storage stability. The adhesive composition of the present invention can be used in a paste form when it is liquid at normal temperature. When it is solid at normal temperature, it can be gelatinized by heating, or it can be gelatinized by using a solvent. The solvent that can be used is not particularly limited as long as it does not react with the adhesive composition and can exhibit sufficient solubility. Generally, those having a boiling point of 50 to 150 ° C at normal pressure are good. When the boiling point is lower than 50 ° C, it tends to volatilize at room temperature, so the radical polymerization must be performed in a closed environment, which limits its use to -20-200536921 (17). In addition, when the boiling point exceeds 150 ° C, the solvent is not easily volatile, so it is difficult to achieve sufficient adhesion strength after adhesion. In addition, the adhesive composition of the present invention can be used in the form of a film. The manufacturing method of this film is generally a method in which a mixed solution obtained by adding a solvent to an adhesive composition is coated on a detachable substrate such as a fluororesin film, a polyethylene terephthalate film, a release paper, or a non-woven fabric. After the substrate is immersed in the mixed solution, the substrate is placed on the release substrate, and then the solvent is removed to prepare a film. When the adhesive composition is formed into a thin film, it is easier to handle. In addition, when the adhesive composition of the present invention is added with conductive particles to produce a thin film, an anisotropic conductive film can be obtained. This anisotropic conductive film is, for example, placed between opposing electrodes on a substrate, and the two electrodes are connected by heating and pressure to generate an electrical connection. For the substrate forming the electrode, for example, inorganic materials such as semiconductors, glass, and ceramics, organic materials such as polyimide, polycarbonate, glass / epoxide, or the like can be used. In addition, the adhesive composition of the present invention can be subjected to heat and pressure for% adhesion. The heating temperature is generally 50 to 190 ° C. The pressure may be within a range that does not damage the adherend, and is generally preferably from 0.1 to 10 MPa. The heating and pressing conditions are generally performed within a range of 0.5 to 120 seconds. The adhesive composition of the present invention can react in a short period of time and has excellent storage stability. , So it is very suitable for use as a circuit connection material. For example, when the circuit electrode of the first circuit member and the circuit electrode of the second circuit member are connected in a circuit, the adhesive composition of the present invention is wetted on one of the electrodes in a state where the aforementioned circuit members are arranged in pairs. -21-200536921 (18) The other circuit electrode is connected by a radical polymerization reaction. When the aforementioned adhesive composition is used as a circuit connection material, the circuit can be connected in a short time, and a substance having stable adhesive strength or connection resistance can be formed. Also, it is also possible to suppress a decrease in the storage property of the hardened material of the circuit connection material. In addition, since this circuit connection material containing conductive particles can exhibit an anisotropic electrical connection method ', it can be used as an anisotropic conductive circuit connection material for circuit electrodes. Φ 'This circuit connection material can be used as a circuit connection material for different types of adherends with different thermal expansion coefficients. Specifically, for example, an anisotropic conductive adhesive, a silver paste, a silver thin film, and other circuit connecting materials, a CSP elastomer, a CSP base film material, and a log sheet can be used. Adhesive material. (Connection material of circuit member) Next, a description will be given of a preferable implementation of the stomach I shape in the connection structure of the circuit member of the present invention. FIG. 1 is a schematic cross-sectional view of an embodiment of a connection structure of a circuit component of the present invention. As shown in FIG. 1, a connection structure 1 of a circuit member according to an embodiment of the present invention includes a first circuit member 20 and a second circuit member 30 that are opposed to each other, and is provided in the first circuit member 20 and the first circuit member 20. Between the two circuit members 30, there is provided a circuit connection member 10 for connecting the aforementioned components with a circuit. The first circuit member 20 is a circuit board 21 having a first circuit board 21 and a first circuit board 21 formed on the main surface 21a of the circuit board 21. 1circuit electrode 22. In addition, an insulating layer (not shown in the drawings) may be formed on the main surface 2 1 a of the circuit substrate 21 if necessary. -22- 200536921 (19) The second circuit member 30 includes a second circuit substrate 31 and a second circuit electrode 32 formed on a main surface 31a of the circuit substrate 31. In addition, an insulating layer (not shown in the drawings) may be formed on the main surface 3 1 a of the circuit substrate 31 as necessary.
第1電路構件20與第2電路構件3 0，只要爲可形成 連接電路之必要電極時，則無特別限制。具體而言，例如 可形成液晶顯示器所使用之ITO等電極之玻璃或塑膠基板 ，印刷電路板、陶瓷電路板、可撓性電路板、半導體矽晶 體等，又其必要時可組合使用。本實施形態中，由印刷電 路板或聚醯亞胺等有機物所得之材質開始，至銅、鋁等金 屬或 ITO( indium tin oxide)、氮化砂（SiNx)、二氧化 矽（Si02 )等無機材質等具有多種多樣表面狀態之電路構 件。 電路連接構件1 〇，爲含有絕緣性物質Π與導電性粒 子7。導電性粒子7，除相對向之第1電路電極22與第2 % 電路電極3 2之間以外，亦配置於主面2 1 a與3 1 a之間。 本實施形態之電路構件之連接結構1中，第1電路電極22 與第2電路電極3 2之間爲介由導電性粒子7以電路連接 。因此，可大幅降低第1電路電極22與第2電路電極32 間之連接電阻。因此，可使第1電路電極22與第2電路 電極3 2之間之電流極順利的流動，而可充分發揮電路所 具有之機能。又，此導電性粒子7於上述添加比例時，可 使電路連接產生異向性。 又，電路連接構件1 〇不含有導電性粒子7時，欲使 -23- 200536921 (20) 第1電路電極22與第2電路電極3 2之間流通一定量之電 流時，一般則必須直接接觸或於極接近之距離下方可產生 連接電路。 電路連接構件1 0，可使用含有上述黏著劑組成物之電 路連接材料之硬化物所構成，因對於第1電路構件20或 第2電路構件3 0而言，電路連接構件1 0之黏著強度極高 ，且可長時間持續於此狀態下。因此，第1電路電極22 φ 與第2電路電極3 2之間可確保電氣特性維持於極高之長 期信賴性。 (半導體裝置） 以下，將對本發明之半導體裝置之實施形態作一說明 。圖2爲本發明之半導體裝置之一實施形態槪略截面圖。 如圖2所示般’本發明實施形態之半導體裝置2，爲具備 有半導體元件50，與半導體支撐構件之基板6〇，半導體 ^ 元件5 0與基板6 0之間，設置有以電路連接之半導體連接 構件4 0。又，半導體元件連接構件4 0層合於基板6 〇之主 面60a上，半導體元件50再層合於該半導體元件連接構 件4 0之上。 基板60具備有電路圖型61，電路圖型61，爲於基板 60之主面60a上介由半導體連接構件40，或直接與半導 體元件5 0產生電路連接。又，其受封閉材料7 0所密封， 而形成半導體裝置2。 半導體5 0之材料並未有任何限制，例如可爲砂、鍺 -24- 200536921 (21) 等第四族之半導體元件，GaAs、InP、GaP、InGaAs、 InGaAsP 、 AlGaAs 、 I n A s 、 GalnP 、 AllnP 、 AkGalnP 、The first circuit member 20 and the second circuit member 30 are not particularly limited as long as they are necessary electrodes for forming a connection circuit. Specifically, for example, glass or plastic substrates that can form electrodes such as ITO used in liquid crystal displays, printed circuit boards, ceramic circuit boards, flexible circuit boards, and semiconductor silicon crystals can be used in combination when necessary. In this embodiment, starting from materials obtained from printed circuit boards or organic materials such as polyimide, to metals such as copper and aluminum, or inorganic materials such as ITO (indium tin oxide), nitrided sand (SiNx), and silicon dioxide (Si02). Circuit components with various surface conditions such as materials. The circuit connection member 10 is an insulating material Π and a conductive particle 7. The conductive particles 7 are disposed between the main circuit surfaces 2 1 a and 3 1 a in addition to the first circuit electrode 22 and the 2% circuit electrode 32 facing each other. In the connection structure 1 of the circuit member of this embodiment, the first circuit electrode 22 and the second circuit electrode 32 are connected to each other via a conductive particle 7 through a circuit. Therefore, the connection resistance between the first circuit electrode 22 and the second circuit electrode 32 can be significantly reduced. Therefore, the current between the first circuit electrode 22 and the second circuit electrode 32 can be extremely smoothly flowed, and the function of the circuit can be fully exerted. When the conductive particles 7 are added in the above-mentioned ratio, anisotropy can be generated in the circuit connection. In addition, when the circuit connection member 10 does not contain the conductive particles 7, in order to make -23- 200536921 (20) a certain amount of current flow between the first circuit electrode 22 and the second circuit electrode 32, it is generally necessary to directly contact Or a connection circuit can be generated below a very close distance. The circuit connection member 10 can be formed by using a hardened material of the circuit connection material containing the above-mentioned adhesive composition. For the first circuit member 20 or the second circuit member 30, the adhesion strength of the circuit connection member 10 is extremely high. High, and can continue in this state for a long time. Therefore, the long-term reliability of the electrical characteristics can be maintained between the first circuit electrode 22 φ and the second circuit electrode 32. (Semiconductor Device) Hereinafter, an embodiment of the semiconductor device of the present invention will be described. FIG. 2 is a schematic cross-sectional view of an embodiment of a semiconductor device according to the present invention. As shown in FIG. 2, a semiconductor device 2 according to an embodiment of the present invention is provided with a semiconductor element 50 and a substrate 60 of a semiconductor supporting member, and a semiconductor element 50 and a substrate 60 are provided with a circuit connection. Semiconductor connection member 40. The semiconductor element connection member 40 is laminated on the main surface 60a of the substrate 60, and the semiconductor element 50 is further laminated on the semiconductor element connection member 40. The substrate 60 is provided with a circuit pattern 61, which is a circuit connection between the main surface 60a of the substrate 60 via the semiconductor connection member 40 or the semiconductor element 50 directly. The semiconductor device 2 is sealed with a sealing material 70. There are no restrictions on the material of the semiconductor 50. For example, it can be a semiconductor device of the fourth group such as sand, germanium-24-200536921 (21), GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, I n As, GalnP. , AllnP, AkGalnP,
GaNAs、GaNP、GalnAs、GalnNP、GaSb、InSb、GaN、 AIN、InGaN、InNAsP等 111 — V族化合物半導體元件， HgTe、HgCdTe、CdMnTe、CdS、CdSe、MgSe、MgS、 ZnSe、ZeTe等II — VI族化合物半導體元件，與CuInSe ( CIS )等各種化合物皆可使用。GaNAs, GaNP, GalnAs, GalnNP, GaSb, InSb, GaN, AIN, InGaN, InNAsP, etc. 111-V compound semiconductor components, HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe, etc. II-VI Group VI Compound semiconductor devices and various compounds such as CuInSe (CIS) can be used.
半導體元件連接構件40，爲含有絕緣性物質1 1與導 電性粒子7。導電性粒子7，除半導體元件5 0與電路圖型 61之間以外，亦配置於半導體元件50與主面60a之間。 本實施形態之半導體裝置2中，半導體元件5 0與電路圖 型6 1之間爲介由導電性粒子7以電路連接。因此，可大 幅降低半導體元件5 0與電路圖型6 1間之連接電阻。因此 ，可使半導體元件5 0與電路圖型6 1之間之電流極順利的 流動，而可充分發揮半導體所具有之機能。又，此導電性 粒子7於上述添加比例時，可使電路連接產生異向性。 又，半導體元件連接構件40不含有導電性粒子7時 ，欲使半導體元件5 0與電路圖型6 1間流通一定量之電流 時，一般則必須直接接觸或於極接近之距離下方可產生連 接電路。 半導體元件連接構件40，可使用含有上述黏著劑組成 物之電路連接材料之硬化物所構成，因對於半導體元件50 與基板60而言，半導體連接構件40之黏著強度極高，且 可長時間持續於此狀態下。因此，半導體元件5 0與基板 -25- 200536921 (22) 60之間可確保電氣特性維持於極高之長期信賴性 【實施方式】 [實施例] 以下，將本發明以實施例爲基礎作具體之說明，但本 發明並不受以下實施例所限制。The semiconductor element connection member 40 includes an insulating substance 11 and conductive particles 7. The conductive particles 7 are arranged between the semiconductor element 50 and the main surface 60a in addition to the semiconductor element 50 and the circuit pattern 61. In the semiconductor device 2 according to this embodiment, the semiconductor element 50 and the circuit pattern 61 are connected to each other via a conductive particle 7 in a circuit. Therefore, the connection resistance between the semiconductor element 50 and the circuit pattern 61 can be greatly reduced. Therefore, the current between the semiconductor element 50 and the circuit pattern 61 can flow extremely smoothly, and the function of the semiconductor can be fully exerted. When the conductive particles 7 are added in the above-mentioned ratio, anisotropy can be generated in the circuit connection. In addition, when the semiconductor element connection member 40 does not contain the conductive particles 7, if a certain amount of current is to flow between the semiconductor element 50 and the circuit pattern 61, it is generally necessary to directly contact or connect the circuit below a close distance. . The semiconductor element connection member 40 can be formed by using a hardened product of a circuit connection material containing the above-mentioned adhesive composition. For the semiconductor element 50 and the substrate 60, the adhesion strength of the semiconductor connection member 40 is extremely high and can last for a long time. In this state. Therefore, the semiconductor element 50 and the substrate-25-200536921 (22) 60 can ensure long-term reliability in maintaining electrical characteristics. [Embodiments] [Examples] Hereinafter, the present invention will be specifically described based on examples. The description, but the present invention is not limited by the following examples.
(導電性粒子之調整） 於聚苯乙烯粒子之表面，設置厚度爲0.2// m之鎳層 ’再於此鎳層之外側，設置〇 · 2 // m之金層，而製得平均 粒徑4 // m、比重2 · 5之導電性粒子。 [實施例1] 將苯氧樹脂（平均分子量4 5 0 0 0，優你旺公司製，商 品名PKHC ) 50質量份，溶解於甲基乙基酮75質量份中 ’得固體成份40質量％之溶液。 隨後，於此溶液中，添加自由基聚合性化合物之異氰 酸EO改質二丙烯酸酯（東亞合成公司製，商品名：Μ — 2 1 5 ) 25質量份、丙烯酸尿烷酯（共榮社化學公司製，商 品名·· AT - 600 ) 20質量份、2 - （甲基）丙烯醯氧乙基 磷酸酯（共榮社化學公司製，商品名：賴特酯P — 2M ) 5 質量份，自由基聚合起始劑之t —己基過氧基一 2 -乙基己 酸酯（1分鐘半衰期溫度1 3 2.6 t，日本油脂公司製，商 品名：過己 Z ) 1 .5質量份、t 一己基過氧基苯甲酸酯（1 -26- 200536921 (23) 分鐘半衰期溫度1 6 0.3 °C，日本油脂公司製，餘^ 商品名：過 己Z ) 1 . 5質量份後，所得混合液中添加導窜 嚷丨主粒子使其 達1 · 5體積％後，得黏著劑組成物A。 其次，將所得黏著劑組成物A使用公知徐彳 &佈裝置塗佈 於一側面經表面處理所得之厚度8 0 // m之氟樹脂薄_上 經於70 °C、10分鐘熱風乾燥處理結果，得靥摩 15 # m之薄膜狀電路連接材料A。(Adjustment of conductive particles) On the surface of the polystyrene particles, a nickel layer having a thickness of 0.2 // m is provided, and then a gold layer of 0.2 m is provided outside the nickel layer to obtain an average particle. Conductive particles with diameter 4 // m and specific gravity 2 · 5. [Example 1] 50 parts by mass of a phenoxy resin (average molecular weight 4500, manufactured by Youniwang Corporation, trade name PKHC) was dissolved in 75 parts by mass of methyl ethyl ketone to obtain a solid content of 40% by mass. Its solution. Subsequently, to this solution, 25 parts by mass of urethane acrylate (Kyoeisha Co., Ltd.) was modified with isocyanate EO modified diacrylate (manufactured by Toa Kosei Co., Ltd., trade name: M — 2 1 5), which is a radically polymerizable compound. Manufactured by Chemical Industry Co., Ltd., AT-600) 20 parts by mass, 2-(meth) acrylic acid oxyethyl phosphate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Wright ester P — 2M) 5 parts by mass , T-hexylperoxy- 2-ethylhexanoate (1 minute half-life temperature 1 3 2.6 t, manufactured by Japan Oil Corporation, trade name: Koji Z) 1.5 parts by mass, t-hexylperoxybenzoate (1 -26- 200536921 (23) minute half-life temperature 1 6 0.3 ° C, manufactured by Nippon Oil & Fats Co., Ltd., ^ trade name: perhexano Z) 1.5 parts by mass After channeling main particles were added to the mixed solution to make it 1.5% by volume, an adhesive composition A was obtained. Next, the obtained adhesive composition A was coated on a side of a fluororesin with a thickness of 8 0 // m by using a well-known Xujing & cloth device and subjected to surface treatment, and then subjected to hot air drying treatment at 70 ° C for 10 minutes. As a result, a film-shaped circuit connection material A of 15 #m was obtained.
[實施例2] 除自由基聚合起始劑之t一己基過氧基 乙基己酸 酯之添加比例設定爲1質量份’ 1一己基過氧其#m；B： ’蒌本甲酸酯 之添加比例設定爲2質量份以外，其他皆依實施例i相胃 方法，製得薄膜狀電路連接材料B ° [比較例1 ][Example 2] The addition ratio of t-hexylperoxyethylhexanoate other than the radical polymerization initiator was set to 1 part by mass '1-hexylperoxy its #m; B:' 蒌 本 Formate The addition ratio was set to 2 parts by mass, and the film-like circuit connection material B was prepared according to the method of the stomach phase in Example i. [Comparative Example 1]
除自由基聚合起始劑之t一己基過氧基〜2^7 乙基已酸 酯之添加比例設定爲3質量份’且不使用t〜己基過氧其 苯甲酸酯以外，其他皆依實施例1相同方法，製得薄膜狀 電路連接材料C ° [比較例2] 除不使用自由基聚合起始劑之己基過氧基一 2-乙 基己酸酯，且t 一己基過氧基苯甲酸酯之添加比例設定爲 3質量份以外，其他皆依實施例1相同方法，製得薄膜狀 -27- 200536921 (24) 電路連接材料D。 [比較例3 ] 除自由基聚合起始劑之t -己基過氧基 Λ 之〜2 —乙基己酸 酯及t一己基過氧基苯甲酸酯以二丙基過氧 逐一碳酸酯（1 分鐘半哀期溫度爲88.3 °C，日本油脂公司製 〜口 ’商品名：派 羅爾IPP) 3質量份替代以外，其他皆依實施例1相同方 Φ 法，製得薄膜狀電路連接材料E。 (評估方法） [連接電阻之測定] 使用依上述方法所得之薄膜狀電路連接材料A至D， 於形成有5 0 0條線寬2 5 // ηι、間距5 0 // m、厚度丨8 # m之 銅電路配線之可撓性電路板（FPC )，與形成有〇·2 // m之 氧化銦（ITO )之薄層的玻璃（厚度1 · 1mm、表面電阻2〇 〇/□)以熱壓者裝置（加熱方式：接觸加熱型，東麗機 械公司製）進行寬度2mm之電路連接。此時加熱加壓之 條件，爲加熱溫度1 6 0 °C、1 7 0 °C、1 9 0 °C，加壓壓力爲 3 Μ P a、加熱加壓時間爲1 5秒。經由此電路連接之電路間 之電阻値，爲於連接後立即，及於85 °C、85% RH之高溫 高濕槽中保持1 20小時後使用測定器測定。電阻値爲以 1 5 0點相鄰接之電路間之電阻値之平均（X + 3 σ )表示。 所得之結果係如表1所示。 -28- 200536921 (25) (評估方法2 ) [黏著劑強度之測定] 將依上述至法所製得之薄膜狀電路連接材料A至D 之黏著強度依Π S — Z 0 2 3 7爲基準，以9 0度剝離法進行測 定評估。黏著強度之測定裝置爲使用單式龍（剝離速度 5 0mm/min、25、東洋保特公司製）。所得結果係如表2所 示。Except for the addition of t-hexylperoxy ~ 2 ^ 7 ethyl caproate, which is a radical polymerization initiator, to 3 parts by mass, and t ~ hexylperoxy and its benzoate are not used. In the same manner as in Example 1, a film-shaped circuit connection material C was obtained. [Comparative Example 2] Except for a hexylperoxy-2-ethylhexanoate without using a radical polymerization initiator, and t-hexylperoxy Except that the benzoate addition ratio was set to 3 parts by mass, the film-like material -27- 200536921 (24) circuit connection material D was prepared in the same manner as in Example 1 for the rest. [Comparative Example 3] t-hexylperoxy Λ, 2-ethylhexanoate and t-hexylperoxybenzoate, except for the radical polymerization initiator, were dipropylperoxy one by one carbonate ( The temperature of 1 minute and a half period is 88.3 ° C. The product name: Pyrol IPP (made by Japan Oils and Fats Co., Ltd.) is replaced by 3 parts by mass, and the film-like circuit connection material is prepared in the same manner as in Example 1 E. (Evaluation method) [Measurement of connection resistance] Using the film-shaped circuit connection materials A to D obtained according to the above method, 5 0 0 line widths 2 5 // η, pitch 5 0 // m, thickness 丨 8 Flexible circuit board (FPC) for copper circuit wiring of #m, and glass formed with a thin layer of indium oxide (ITO) of 0.2m / m (thickness 1.1mm, surface resistance 2000 / □) A hot press device (heating method: contact heating type, manufactured by Toray Machinery Co., Ltd.) was used to make a circuit connection with a width of 2 mm. The conditions for heating and pressing at this time are heating temperatures of 160 ° C, 170 ° C, and 180 ° C, the pressing pressure is 3 MPa, and the heating and pressing time is 15 seconds. The resistance 电路 between the circuits connected by this circuit is measured immediately after the connection and in a high-temperature and high-humidity tank at 85 ° C and 85% RH for 1 to 20 hours. Resistance 値 is represented by the average (X + 3 σ) of resistance 间 between adjacent circuits at 150 points. The results obtained are shown in Table 1. -28- 200536921 (25) (Evaluation Method 2) [Measurement of Adhesive Strength] The adhesive strength of the film-like circuit connection materials A to D prepared according to the above method is based on Π S — Z 0 2 3 7 The measurement and evaluation were performed by a 90 degree peel method. The measuring device for the adhesive strength was a single-type dragon (peeling speed 50 mm / min, 25, manufactured by Toyobo Co., Ltd.). The results obtained are shown in Table 2.
表1Table 1
項目 加熱 連接電距 1 (Ω ) 黏著強度（N/m) 溫度 黏著後立即 1 2 0 h 後 黏著後立即 12 Oh 後 實施例 1 60°C 2.3 2.5 1050 900 1 1 70°C 2. 1 2.5 980 930 1 90°C 2.4 2.8 1020 950 實施例 1 60°C 1.9 2.4 1100 1040 2 1 70°C 2. 1 2.7 1030 980 1 90°C 2.0 2.6 1060 980 比較例 1 60°C 2.3 3.3 870 600 1 1 70°C 3.6 8.6 730 550 1 90°C 10以上 10以上 240 1 30 比較例 1 60°C 4.6 10以上 530 400 2 1 70°C 3.8 10以上 740 475 1 90°C 1.9 3.4 900 560 -29- 200536921 (26) 實施例1、2之薄膜狀電路連接材料A與B，於加熱 溫度1 6 0至1 9 0 °C之間，得知於連接後立即’及於8 5 °C、 8 5% RH之高溫高濕槽中保持120小時後，亦顯示出良好 之連接電阻與黏著強度，得知其於廣域之加熱溫度下亦顯 示出良好之特性。相對於此，非本發明內容之比較例1之 薄膜狀電路連接材料C，於17(TC加熱時之85X：、85% RH 下保持120小時後，及，於190°C加熱時皆顯示出較高之 0 連接電阻，且黏著強度於連接後立即，及於8 5 t、8 5 % RH之高溫高濕槽中保持1 2 0小時後之數値，亦顯示出低 於實施例1、2之數値。又，比較例2之薄膜狀電路連接 材料D ’於160至170 °C加熱時顯示出較高之連接電阻， 且黏著強度顯示出較低値。 (評估方法3 ) 將實施例1與比較例3所得之薄膜狀電路連接材料a % 與E，放置於真空包裝材料中，並於40。(：下放置3日後。 將FPC與ITO以上述加熱壓著裝置於16〇。〇、3MPa、1〇 秒間之條件下進行加熱壓著。所得薄膜依評估方法丨與2 爲基準測定連接電阻與黏著強度。其結果如表2所示。 -30- 200536921 (27) 表2 項目 1接電阻（Ω ) 黏著強度（N/m) 放置前 40°C、放置3曰後 放置前 4〇°C、放置3日後 實施例1 2.3 2.1 1050 1080 比較例3 2.5 10以上 650 320 於表2中，實施例1之薄膜狀電路連接材料A，於放 9 置於40°C之前後中，皆顯示出良好之連接電阻與黏著強度 ’得知其具有優良之儲存安定性。相對於此，非本發明之 比較例3之薄膜狀電路連接連接材料E，於40 °C、放置3 曰後，其連接電阻會上升，且黏著強度減半，得知其安定 性並不佳。 依本發明內容，爲提供一種可進行低溫且極爲迅速之 硬化處理，硬化處理時具有更廣泛的製程適應性，具有極 安定之黏著強度或連接電阻之黏著劑組成物，電路連接材 % 料，電路構件之連接結構及半導體裝置。 【圖式簡單說明】 圖1 :本發明之電路構件之連接結構之一實施形態之 槪略截面圖。 圖2 :本發明之半導體裝置之一實施形態之槪略截面 圖。 【主要元件之符號說明】 -31 - 200536921 (28) 1 :連接結構 2 :半導體裝置 7 :導電性粒子 1 〇 :電路連接構件 11 :絕緣性物質 2 0、3 0 :電路構件 2 1、3 1 :電路基板Item Heating connection distance 1 (Ω) Adhesive strength (N / m) Temperature Immediately after adhesion 1 2 0 h Immediately after adhesion 12 Oh Immediate Example 1 60 ° C 2.3 2.5 1050 900 1 1 70 ° C 2. 1 2.5 980 930 1 90 ° C 2.4 2.8 1020 950 Example 1 60 ° C 1.9 2.4 1100 1040 2 1 70 ° C 2. 1 2.7 1030 980 1 90 ° C 2.0 2.6 1060 980 Comparative Example 1 60 ° C 2.3 3.3 870 600 1 1 70 ° C 3.6 8.6 730 550 1 90 ° C 10 or more 10 or more 240 1 30 Comparative Example 1 60 ° C 4.6 10 or more 530 400 2 1 70 ° C 3.8 10 or more 740 475 1 90 ° C 1.9 3.4 900 560 -29 -200536921 (26) The film-like circuit connection materials A and B of Examples 1 and 2 were heated at a temperature of 160 to 190 ° C. It was learned immediately after the connection, and at 8 5 ° C, 8 After holding it in a 5% RH high-temperature and high-humidity tank for 120 hours, it also showed good connection resistance and adhesion strength. It was learned that it also showed good characteristics at a wide range of heating temperature. In contrast, the film-shaped circuit connection material C of Comparative Example 1 which is not the content of the present invention, after being held at 17 ° C for 85X: and 85% RH for 120 hours, and when heated at 190 ° C The higher 0 connection resistance, and the adhesive strength immediately after the connection, and the number after 120 hours in a high temperature and high humidity tank of 85 t, 85% RH, also showed lower than Example 1, The number 2 is 2. The film-shaped circuit connection material D 'of Comparative Example 2 shows a high connection resistance and a low adhesive strength when heated at 160 to 170 ° C. (Evaluation method 3) Will be implemented The film-like circuit connection materials a% and E obtained in Example 1 and Comparative Example 3 were placed in a vacuum packaging material and placed at 40. (: placed underneath for 3 days. FPC and ITO were heated and pressed at 160 ° with the above heating and pressing device. 〇, 3MPa, 10 seconds under heating and pressing conditions. The obtained film was used to evaluate the connection resistance and adhesive strength according to the evaluation method 丨 and 2. The results are shown in Table 2. -30- 200536921 (27) Table 2 Items 1Resistance (Ω) Adhesive strength (N / m) 40 ° C before storage, 40 ° C before storage 3. Example 3 after being placed for 3 days 2.3 2.1 1050 1080 Comparative Example 3 2.5 10 or more 650 320 In Table 2, the film-like circuit connection material A of Example 1 was displayed before and after being placed 9 at 40 ° C. The good connection resistance and adhesion strength 'showed that it has excellent storage stability. In contrast, the film-shaped circuit connection connection material E, which is not the comparative example 3 of the present invention, was placed at 40 ° C for 3 months, and its connection The resistance will increase, and the adhesive strength will be reduced by half, and it is learned that its stability is not good. According to the present invention, in order to provide a low-temperature and extremely rapid hardening process, the hardening process has a wider process adaptability and is extremely stable. Adhesive composition with stable adhesive strength or connection resistance, circuit connection material, circuit member connection structure and semiconductor device. [Brief description of the drawings] Figure 1: One embodiment of the connection structure of the circuit member of the present invention Schematic cross-sectional view. Figure 2: Schematic cross-sectional view of one embodiment of a semiconductor device of the present invention. [Description of Symbols of Main Components] -31-200536921 (28) 1: Connection structure 2: Half Conductor device 7: Conductive particle 1 0: Circuit connection member 11: Insulating substance 2 0, 3 0: Circuit member 2 1, 3 1: Circuit board
2 2、3 2 :電路電極 5 0 :半導體元件 60 :基板 6 0 a :主面 6 1 :電路圖型 7 0 :密封材料2 2, 3 2: Circuit electrode 50: Semiconductor element 60: Substrate 60 0a: Main surface 6 1: Circuit pattern 7 0: Sealing material
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| JP2004140181A JP2005320455A (en) | 2004-05-10 | 2004-05-10 | Adhesive composition, material for connecting circuit, connecting structure of circuit member and semiconductor device |
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| TW095100333A TWI277642B (en) | 2004-05-10 | 2005-03-03 | Semiconductor devices containing adhesive composition |
| TW095141736A TW200718765A (en) | 2004-05-10 | 2005-03-03 | Adhesive composition, material for connecting circuit, connecting structure of circuit member and semiconductor device |
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| KR100727741B1 (en) | 2005-12-30 | 2007-06-13 | 제일모직주식회사 | Anisotropic conductive adhesive for hyper speed hardening, and anisotropic conductive film using the same |
| EP2251910B1 (en) * | 2006-04-26 | 2012-07-04 | Hitachi Chemical Company, Ltd. | Adhesive tape and solar cell module using the same |
| CN102942881B (en) * | 2006-05-09 | 2015-03-18 | 日立化成株式会社 | Adhesive sheet, and connecting structure for circuit member and semiconductor device which use the adhesive sheet |
| JP5137347B2 (en) * | 2006-07-12 | 2013-02-06 | 旭化成イーマテリアルズ株式会社 | Thermosetting coating composition |
| JP5018779B2 (en) * | 2006-08-22 | 2012-09-05 | 日立化成工業株式会社 | Circuit connection material, circuit member connection structure, and circuit member connection structure manufacturing method |
| CN101617267B (en) * | 2007-02-20 | 2012-08-15 | 三井化学株式会社 | Curable resin composition for sealing liquid crystal, and method for production of liquid crystal display panel using the same |
| US20080292801A1 (en) * | 2007-05-23 | 2008-11-27 | National Starch And Chemical Investment Holding Corporation | Corrosion-Preventive Adhesive Compositions |
| JP5292838B2 (en) * | 2007-08-30 | 2013-09-18 | 日立化成株式会社 | Adhesive and circuit member connection structure |
| CN101836266B (en) * | 2007-10-22 | 2012-02-15 | 日本化学工业株式会社 | Coated conductive powder and conductive adhesive using the same |
| JP5549103B2 (en) * | 2008-07-11 | 2014-07-16 | デクセリアルズ株式会社 | Anisotropic conductive film |
| TWI382225B (en) * | 2008-08-06 | 2013-01-11 | Au Optronics Corp | Liquid crystal display and packaging method thereof |
| JP5728803B2 (en) * | 2008-09-30 | 2015-06-03 | デクセリアルズ株式会社 | Anisotropic conductive adhesive and method for manufacturing connection structure using the same |
| KR101228780B1 (en) * | 2009-04-28 | 2013-01-31 | 히다치 가세고교 가부시끼가이샤 | Circuit connecting material, film-like circuit connecting material using the circuit connecting material, structure for connecting circuit member, and method for connecting circuit member |
| JP5621320B2 (en) * | 2010-05-19 | 2014-11-12 | デクセリアルズ株式会社 | Method for manufacturing connection structure |
| JP5293779B2 (en) * | 2010-07-20 | 2013-09-18 | 日立化成株式会社 | Adhesive composition, circuit connection structure, semiconductor device and solar cell module |
| CN105860910A (en) * | 2010-07-26 | 2016-08-17 | 日立化成株式会社 | Adhesive composition, connection structure, connection structure manufacturing method and application of adhesive composition |
| KR101293788B1 (en) * | 2010-11-24 | 2013-08-06 | 제일모직주식회사 | Composition For Anisotropic Conductive Film And Anisotropic Conductive Film Using the Same |
| KR20120076187A (en) * | 2010-12-29 | 2012-07-09 | 제일모직주식회사 | Anisotropic conductive film |
| WO2013035164A1 (en) * | 2011-09-06 | 2013-03-14 | 日立化成株式会社 | Adhesive composition and connection body |
| JP5844588B2 (en) * | 2011-09-21 | 2016-01-20 | デクセリアルズ株式会社 | Circuit connection material, connection method using the same, and connection structure |
| TWI591151B (en) | 2013-05-24 | 2017-07-11 | 明基材料股份有限公司 | Adhesive composition for conduction between electrical elements |
| CN103360956B (en) * | 2013-06-18 | 2015-06-03 | 明基材料有限公司 | Sticking agent for electrical property conduction between electronic components |
| JP6398570B2 (en) * | 2013-10-09 | 2018-10-03 | 日立化成株式会社 | Circuit connection material, circuit member connection structure, and method of manufacturing circuit member connection structure |
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| JP3749032B2 (en) * | 1999-01-14 | 2006-02-22 | 株式会社フジクラ | Method of switching connection between waveguide type optical device and optical fiber |
| KR100483565B1 (en) * | 1999-02-08 | 2005-04-15 | 히다치 가세고교 가부시끼가이샤 | Circuit adhesive |
| JP2001323246A (en) * | 2000-03-07 | 2001-11-22 | Sony Chem Corp | Adhesive for connecting electrode and bonding method using the adhesive |
| JP2001262078A (en) * | 2000-03-17 | 2001-09-26 | Sony Chem Corp | Connecting material |
| WO2001082363A1 (en) * | 2000-04-25 | 2001-11-01 | Hitachi Chemical Co., Ltd. | Adhesive for circuit connection, circuit connection method using the same, and circuit connection structure |
| JP4599666B2 (en) * | 2000-06-29 | 2010-12-15 | 日立化成工業株式会社 | Conductive resin paste composition and semiconductor device using the same |
| JP2002184487A (en) * | 2000-12-15 | 2002-06-28 | Sony Chem Corp | Anisotropic conductive adhesive |
| JP4590732B2 (en) * | 2000-12-28 | 2010-12-01 | 日立化成工業株式会社 | Circuit connection material, circuit board manufacturing method using the same, and circuit board |
| JP2002201456A (en) * | 2000-12-28 | 2002-07-19 | Hitachi Chem Co Ltd | Adhesive composition, connecting method of circuit terminal using the same, and connected structure of circuit terminal |
| TWI230191B (en) * | 2000-12-28 | 2005-04-01 | Hitachi Chemical Co Ltd | Circuit connecting adhesive with anisotropic conductivity connecting method of circuit board and circuit connecting construction by using the adhesive |
| JP3858740B2 (en) * | 2002-03-27 | 2006-12-20 | 日立化成工業株式会社 | Adhesive composition for circuit connection and circuit connection structure using the same |
| JP2004067908A (en) * | 2002-08-07 | 2004-03-04 | Sumitomo Bakelite Co Ltd | Anisotropically electroconductive adhesive |
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| KR100832625B1 (en) | 2008-05-27 |
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| TWI277642B (en) | 2007-04-01 |
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