TWI412305B - A circuit connection material, a connection structure of a circuit component, and a connection method of a circuit component - Google Patents
A circuit connection material, a connection structure of a circuit component, and a connection method of a circuit component Download PDFInfo
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本發明係關於用以將具有電路電極的電路構件彼此間進行連接之電路連接材料、電路構件之連接構造及電路構件之連接方法。The present invention relates to a circuit connecting material for connecting circuit members having circuit electrodes, a connection structure of circuit members, and a method of connecting circuit members.
近年來，隨著精密電子機器領域中電路之高密度化進行，電極寬度、電極間隔變得極為狹窄，容易發生配線脫落、剝離或移位。為解決此問題，開發低溫速硬化性優異，而且，具有充分長之可使用時間之電氣．電子用電路連接材料(例如專利文獻1、2)。In recent years, as the density of circuits in the field of precision electronic devices has increased, the electrode width and the electrode interval have become extremely narrow, and wiring peeling, peeling, or displacement is likely to occur. In order to solve this problem, it is excellent in the development of low-temperature-speed hardening, and it has a long enough usable time. A circuit connecting material for electronics (for example, Patent Documents 1 and 2).
專利文獻1：國際公開98/44067號手冊Patent Document 1: International Publication No. 98/44067
專利文獻2：國際公開01/015505號手冊Patent Document 2: International Publication No. 01/015505
然而，上述傳統的電路連接材料係依構成連接電路構件之材料種類，而有黏合強度未必充分之問題。尤其，支持電路電極之基板係以聚對苯二甲酸乙二醇酯、聚醯亞胺樹脂、聚醚碸、丙烯酸樹脂或玻璃所形成之基板時，或於電路構件之表面，形成由矽酮樹脂、聚醯亞胺樹脂、丙烯酸樹脂等所成之層時，明顯地有黏合強度降低之問題。However, the above conventional circuit connecting material has a problem that the bonding strength is not necessarily sufficient depending on the kind of material constituting the connecting circuit member. In particular, when the substrate supporting the circuit electrode is a substrate formed of polyethylene terephthalate, polyimide resin, polyether fluorene, acrylic resin or glass, or on the surface of the circuit member, an fluorenone is formed. When a layer formed of a resin, a polyimide resin, an acrylic resin or the like is formed, there is a problem that the adhesive strength is lowered.
因此，本發明係以提供即使將具有以聚對苯二甲酸乙二醇酯、聚醯亞胺樹脂、聚醚碸、丙烯酸樹脂或玻璃所形 成之基板之電路構件、或於表面上形成由矽酮樹脂、聚醯亞胺樹脂、丙烯酸樹脂等所成之層之電路構件，進行連接時，可得到充分黏合強度之電路連接材料。Accordingly, the present invention is to provide a shape even in the form of polyethylene terephthalate, polyimine resin, polyether oxime, acrylic resin or glass. When a circuit member made of a substrate or a circuit member formed of a layer made of an fluorenone resin, a polyimide resin, an acrylic resin or the like is formed on the surface, a circuit connecting material having a sufficient adhesive strength can be obtained.
本發明之電路連接材料係含有藉由光或熱硬化之黏合劑組成物、與具有胺基甲酸酯基及酯基之有機化合物，用以將具有基板及形成於該基板的主面上之電路電極的電路構件彼此間進行連接之電路連接材料。The circuit connecting material of the present invention comprises a light or heat-hardened adhesive composition, and an organic compound having a urethane group and an ester group for using the substrate and the main surface formed on the substrate. A circuit connecting material in which circuit members of circuit electrodes are connected to each other.
本發明之電路連接材料係藉由併用黏合劑組成物、與具有胺基甲酸酯基及酯基之有機化合物，即使將具有以聚對苯二甲酸乙二醇酯、聚醯亞胺樹脂、聚醚碸、丙烯酸樹脂或玻璃所形成之基板之電路構件、或於表面上形成由矽酮樹脂、聚醯亞胺樹脂、丙烯酸樹脂等所成之層之電路構件，進行連接時，可得到充分的黏合強度。The circuit connecting material of the present invention is a combination of a binder composition and an organic compound having a urethane group and an ester group, even if it has a polyethylene terephthalate or a polyimide resin. A circuit member of a substrate formed of a polyether fluorene, an acrylic resin or glass, or a circuit member formed of a layer formed of an fluorenone resin, a polyimide resin, an acrylic resin or the like on a surface thereof can be sufficiently connected. Bond strength.
上述黏合劑組成物係以含有自由基聚合性化合物及藉由加熱或光產生自由基的自由基起始劑者為宜。此時，就更加提昇與金屬等之無機物表面之黏合強度之觀點，自由基聚合性化合物係以含有具有丙烯酸酯基或甲基丙烯酸酯基之磷酸酯化合物為宜。The above binder composition is preferably one containing a radical polymerizable compound and a radical initiator which generates a radical by heating or light. In this case, from the viewpoint of further enhancing the adhesion strength to the surface of the inorganic material such as metal, the radical polymerizable compound preferably contains a phosphate compound having an acrylate group or a methacrylate group.
上述有機化合物之玻璃轉移溫度係以50℃以上為宜。藉由有機化合物兼具有胺基甲酸酯基及酯基，而且，玻璃轉移溫度為50℃以上，可更加提高高溫高濕試驗後之黏合強度。有機化合物僅具有胺基甲酸酯基及酯基中之一者時，玻璃轉移溫度為50℃以上時，雖然可抑制於高 溫高濕環境時黏合強度的降低，但初期之黏合強度並不足。相對於此，若使用兼具有胺基甲酸酯基及酯基之有機化合物之電路連接材料，可充分高地維持初期之黏合強度，進而抑制於高溫高濕環境時黏合強度的降低。The glass transition temperature of the above organic compound is preferably 50 ° C or higher. Since the organic compound has both a urethane group and an ester group, and the glass transition temperature is 50 ° C or higher, the bonding strength after the high temperature and high humidity test can be further improved. When the organic compound has only one of a urethane group and an ester group, the glass transition temperature is 50° C. or more, although it can be suppressed to be high. The bond strength is lowered in a warm and humid environment, but the initial bond strength is insufficient. On the other hand, when a circuit connecting material having an organic compound having a urethane group and an ester group is used, the initial bonding strength can be sufficiently maintained, and the adhesion strength can be suppressed in a high-temperature and high-humidity environment.
另外，具有胺基甲酸酯基及酯基之上述有機化合物係以具有芳香族基及/或環狀脂肪族基為宜，重量平均分子量係以5000至100000為宜。Further, the above organic compound having a urethane group and an ester group is preferably an aromatic group and/or a cyclic aliphatic group, and the weight average molecular weight is preferably from 5,000 to 100,000.
本發明之電路連接材料係以含有導電性粒子為宜。藉此，可維持同一基板上之電路電極彼此間之絕緣狀態的同時，更安定地將電路構件彼此間電性連接。The circuit connecting material of the present invention preferably contains conductive particles. Thereby, the circuit members can be electrically connected to each other more stably while maintaining the insulation state between the circuit electrodes on the same substrate.
本發明之電路構件之連接構造係具有第1基板及於該第1基板的主面上所形成的第1電路電極之第1電路構件、與具有第2基板及於該第2基板的主面上所形成的第2電路電極之第2電路構件，藉由本發明之電路連接材料的硬化物所形成且設置於第1及第2電路構件之間的電路連接構件，該第1電路電極與該第2電路電極成對峙的同時，連接成電性連接者。The connection structure of the circuit member of the present invention includes a first substrate, a first circuit member of the first circuit electrode formed on the main surface of the first substrate, and a second substrate and a main surface of the second substrate a second circuit member of the second circuit electrode formed thereon, a circuit connecting member formed between the first and second circuit members by the cured material of the circuit connecting material of the present invention, the first circuit electrode and the second circuit member The second circuit electrode is connected to the electrical connector while being paired.
另外，本發明之電路構件之連接方法係藉由對將具有第1基板及於該第1基板的主面上所形成的第1電路電極之第1電路構件、與上述本發明之電路連接材料所成之層、與具有第2基板及於該第2基板的主面上所形成的第2電路電極之第2電路構件之順序層合第1電路電極與該第2電路電極成對峙之層合體進行加熱及加壓後，連接第1電路構件及第2電路構件而使第1電路電極與第2電路 電極成電性連接者。Further, the connection method of the circuit member of the present invention is based on the first circuit member having the first substrate and the first circuit electrode formed on the main surface of the first substrate, and the circuit connecting material of the present invention. The formed layer and the second circuit member having the second substrate and the second circuit electrode formed on the main surface of the second substrate are laminated in a layer in which the first circuit electrode and the second circuit electrode are opposed to each other After heating and pressurizing the body, the first circuit member and the second circuit member are connected to form the first circuit electrode and the second circuit The electrode is electrically connected.
本發明之電路構件之連接構造係藉由本發明之電路連接材料而使電路構件彼此間連接，電路構件彼此間之黏合強度高，於高溫高濕下之耐久性亦優異。另外，若依本發明之電路構件之連接方法，藉由本發明之電路連接材料而使電路構件彼此間連接，可得到電路構件彼此間之黏合強度高，於高溫高濕下之耐久性亦優異之電路構件之連接構造。In the connection structure of the circuit member of the present invention, the circuit members are connected to each other by the circuit connecting material of the present invention, and the bonding strength between the circuit members is high, and the durability is excellent under high temperature and high humidity. Further, according to the connection method of the circuit member of the present invention, the circuit members are connected to each other by the circuit connecting material of the present invention, whereby the bonding strength between the circuit members is high, and the durability is excellent under high temperature and high humidity. Connection structure of circuit components.
於上述之電路構件之連接構造及電路構件之連接方法中，第1及第2電路電極中至少一個之表面為含有至少1種選自金、銀、錫、鉑族之金屬及銦-錫氧化物所成群之材料所成為宜。In the connection structure of the circuit member and the connection method of the circuit member, at least one of the first and second circuit electrodes has at least one metal selected from the group consisting of gold, silver, tin, and platinum, and indium-tin oxide. The materials in which the objects are grouped are suitable.
於上述之電路構件之連接構造及電路構件之連接方法中，第1及第2基板中至少一個為含有至少1種選自聚對苯二甲酸乙二醇酯、聚醚碸、環氧樹脂、丙烯酸樹脂、聚醯亞胺樹脂及玻璃所成群之材料所形成的基板為宜。另外，第1及第2電路構件中至少一個與電路連接構件之間，形成含有至少1種選自矽酮樹脂、丙烯酸樹脂及聚醯亞胺樹脂所成群之層為宜。此等上述本發明之電路連接材料，硬化形成電路連接構件時，與以此等特定材料所構成之層之間，發生高黏著強度。In the connection structure of the circuit member and the connection method of the circuit member, at least one of the first and second substrates contains at least one selected from the group consisting of polyethylene terephthalate, polyether oxime, and epoxy resin. A substrate formed of a material composed of an acrylic resin, a polyimide resin, and a glass is preferable. Further, it is preferable that at least one of the first and second circuit members and the circuit connecting member are formed of a layer containing at least one selected from the group consisting of an anthrone resin, an acrylic resin, and a polyimide resin. When the circuit connecting material of the present invention described above is hardened to form a circuit connecting member, high adhesion strength occurs between layers formed of such specific materials.
由本發明提供即使將具有以聚對苯二甲酸乙二醇酯、聚醯亞胺樹脂、聚醚碸、丙烯酸樹脂或玻璃所形成之基板 之電路構件、或於表面上形成由矽酮樹脂、聚醯亞胺樹脂、丙烯酸樹脂等所成之層之電路構件，進行連接時，可得到黏合強度充分強之電路連接材料。另外，由本發明容易同時得到黏合強度及除此之外之要求特性(連接電阻、絕緣性等)。另外，由本發明，用以得到如上述效果之材料組成選擇之幅度比較大。The present invention provides a substrate formed even with polyethylene terephthalate, polyimine resin, polyether oxime, acrylic resin or glass. When the circuit member or the circuit member formed of a layer formed of an fluorenone resin, a polyimide resin, an acrylic resin or the like is formed on the surface, a circuit connecting material having a sufficiently strong bonding strength can be obtained. Further, according to the present invention, it is easy to simultaneously obtain the adhesive strength and other required characteristics (connection resistance, insulation, etc.). Further, according to the present invention, the material composition selection for obtaining the above effects is relatively large.
以下係關於本發明適合之實施形態，依情況參考圖式詳細地說明。但是，本發明並非侷限於下述之實施形態者。Hereinafter, embodiments suitable for the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the embodiments described below.
有關本實施形態之電路連接材料係含有藉由光或熱硬化之黏合劑組成物。此黏合劑組成物係以含有自由基聚合性化合物及藉由加熱或光產生自由基的自由基起始劑者為宜。The circuit connecting material according to this embodiment contains a binder composition which is cured by light or heat. The binder composition is preferably one containing a radical polymerizable compound and a radical initiator which generates a radical by heating or light.
自由基聚合性化合物係具有藉由活性自由基聚合之官能基。例如，適合使用丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺化合物。作為光自由基聚合性化合物，有聚合性單體及聚合性低聚物等。因為聚合性低聚物一般為高黏度，所以使用聚合性低聚物時，併用低黏度之聚合性多官能丙烯酸酯單體等之聚合性單體，調整黏度為宜。The radically polymerizable compound has a functional group polymerized by living radicals. For example, an acrylate compound, a methacrylate compound, or a maleimide compound is suitably used. Examples of the photoradical polymerizable compound include a polymerizable monomer and a polymerizable oligomer. Since the polymerizable oligomer is generally high in viscosity, when a polymerizable oligomer is used, it is preferred to use a polymerizable monomer such as a low-viscosity polymerizable multifunctional acrylate monomer to adjust the viscosity.
作為丙烯酸酯化合物或甲基丙烯酸酯化合物，可使用環氧(甲基)丙烯酸酯低聚物、胺基甲酸酯(甲基)丙烯酸酯低聚物、聚醚(甲基)丙烯酸酯低聚物、聚酯(甲基)丙烯酸酯低聚物等之聚合性低聚物、或丙烯酸酯、甲 基丙烯酸酯等之聚合性單體。As the acrylate compound or the methacrylate compound, an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, or a polyether (meth) acrylate oligomer can be used. Polymeric oligomer such as a polyester or a (meth) acrylate oligomer, or an acrylate or a A polymerizable monomer such as a acrylate.
作為丙烯酸酯，可舉例如三甲醇丙烷三丙烯酸酯、聚乙二醇二丙烯酸酯、聚伸烷基二醇二丙烯酸酯、季戊四醇丙烯酸酯、2-氰基乙基丙烯酸酯、環己基丙烯酸酯、二環戊烯基丙烯酸酯、二環戊烯氧基乙基丙烯酸酯、2-(2-乙氧基乙氧基)乙基丙烯酸酯、2-乙氧基乙基丙烯酸酯、2-乙基己基丙烯酸酯、正己基丙烯酸酯、2-羥乙基丙烯酸酯、羥丙基丙烯酸酯、異冰片基丙烯酸酯、異癸基丙烯酸酯、異辛基丙烯酸酯、正月桂基丙烯酸酯、2-甲氧基乙基丙烯酸酯、2-苯氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、新戊二醇二丙烯酸酯、二季戊四醇六丙烯酸酯、烯丙基丙烯酸酯等之單官能或多官能之丙烯酸酯單體。Examples of the acrylate include trimethylolpropane triacrylate, polyethylene glycol diacrylate, polyalkylene glycol diacrylate, pentaerythritol acrylate, 2-cyanoethyl acrylate, and cyclohexyl acrylate. Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-ethoxyethyl acrylate, 2-ethyl Hexyl acrylate, n-hexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isodecyl acrylate, isooctyl acrylate, n-lauryl acrylate, 2-methyl Monofunctional or polyfunctional such as oxyethyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate, allyl acrylate Acrylate monomer.
作為甲基丙烯酸酯，可使用將上述丙烯酸酯之丙烯醯基轉換成甲基丙烯醯基之化合物等。具體上，可舉例如叔丁基胺基乙基甲基丙烯酸酯、環己基甲基丙烯酸酯、二環戊烯氧基乙基甲基丙烯酸酯、2-羥乙基甲基丙烯酸酯、異冰片基甲基丙烯酸酯、異癸基甲基丙烯酸酯、正月桂基甲基丙烯酸酯、硬脂基甲基丙烯酸酯、十三烷基甲基丙烯酸酯、縮水甘油基甲基丙烯酸酯、烯丙基甲基丙烯酸酯等之單官能或多官能之甲基丙烯酸酯單體。As the methacrylate, a compound obtained by converting the acryl oxime group of the above acrylate to a methacryl oxime group can be used. Specific examples thereof include tert-butylaminoethyl methacrylate, cyclohexyl methacrylate, dicyclopentenyloxyethyl methacrylate, 2-hydroxyethyl methacrylate, and isobornyl. Methyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, glycidyl methacrylate, allyl A monofunctional or polyfunctional methacrylate monomer such as methacrylate.
作為丙烯酸酯或甲基丙烯酸酯，除了上述以外，適合使用具有丙烯酸酯基或甲基丙烯酸酯基、及磷酸酯基之磷酸酯化合物。作為此磷酸酯化合物，以下述一般式(1) 所表示之化合物為宜。式(1)中，n係表示1至3之整數，R表示氫原子或甲基。作為式(1)中所表示之磷酸酯化合物之具體例，可舉例如單(2-甲基丙烯醯氧乙基)酸式磷酸酯、二(2-甲基丙烯醯氧乙基)酸式磷酸酯。如相關業者所理解，此磷酸酯化合物係可由例如磷酸酐與2-羥乙基丙烯酸酯反應而合成。As the acrylate or methacrylate, in addition to the above, a phosphate compound having an acrylate group, a methacrylate group, and a phosphate group is suitably used. As this phosphate compound, the following general formula (1) The compounds indicated are suitable. In the formula (1), n represents an integer of 1 to 3, and R represents a hydrogen atom or a methyl group. Specific examples of the phosphate compound represented by the formula (1) include mono(2-methylpropenyloxyethyl) acid phosphate and bis(2-methylpropoxy oxyethyl) acid. Phosphate ester. As understood by those skilled in the relevant art, this phosphate compound can be synthesized, for example, by reacting phosphoric anhydride with 2-hydroxyethyl acrylate.
作為馬來醯亞胺化合物係以具有至少2個以上之馬來醯亞胺基者為宜。作為具有2個以上之馬來醯亞胺基之馬來醯亞胺化合物，可舉例如1-甲基-2,4-雙馬來醯亞胺苯、N,N’-間伸苯基雙馬來醯亞胺、N,N’-對伸苯基雙馬來醯亞胺、N,N’-間甲基伸苯基雙馬來醯亞胺、N,N’-4,4-伸聯苯基雙馬來醯亞胺(biphenylenebismaleimide)、N,N’-4,4’-(3,3’-二甲基伸聯苯基)雙馬來醯亞胺、N,N’-4,4’-(3,3’-二甲基二苯基甲烷)雙馬來醯亞胺、N,N’-4,4’-(3,3’-二乙基二苯基甲烷)雙馬來醯亞胺、N,N’-4,4’-二苯基甲烷雙馬來醯亞胺、N,N’-4,4’-二苯基丙烷雙馬來醯亞胺、N,N’-4,4’-二苯基醚雙馬來醯亞胺、N,N’-3,3’-二苯碸雙馬來醯亞胺、2,2-雙(4-(4-馬來醯亞胺苯 氧基)苯基)丙烷、2,2-雙(3-仲丁基-4-(4-馬來醯亞胺苯氧基)苯基)丙烷、1,1-雙(4-(4-馬來醯亞胺苯氧基)苯基)癸烷、4,4’-環亞己基-雙(1-(4-馬來醯亞胺苯氧基)-2-環己基苯)、2,2-雙(4-(4-馬來醯亞胺苯氧基)苯基)六氟丙烷等。此等係可以單獨或組合多種使用。It is preferred that the maleic imine compound has at least two or more maleimine groups. Examples of the maleic imine compound having two or more maleimine groups include 1-methyl-2,4-bismaleimide benzene and N,N'-meta-phenylene double. Maleic imine, N, N'-p-phenylene bismaleimide, N, N'-m-methyl phenyl bismaleimide, N, N'-4, 4-stretch Biphenylenebismaleimide, N,N'-4,4'-(3,3'-dimethyl extended phenyl) bismaleimide, N,N'-4 , 4'-(3,3'-dimethyldiphenylmethane) bismaleimide, N,N'-4,4'-(3,3'-diethyldiphenylmethane) double Maleate, N,N'-4,4'-diphenylmethane, bismaleimide, N,N'-4,4'-diphenylpropane, bismaleimide, N, N'-4,4'-diphenyl ether bis-maleimide, N,N'-3,3'-diphenyl bis-maleimide, 2,2-bis(4-(4- Malay imiline benzene Oxy)phenyl)propane, 2,2-bis(3-sec-butyl-4-(4-maleimidophenoxy)phenyl)propane, 1,1-bis(4-(4- Maleimide phenoxy)phenyl)decane, 4,4'-cyclohexylene-bis(1-(4-maleimidophenoxy)-2-cyclohexylbenzene), 2, 2-bis(4-(4-maleimidophenoxy)phenyl)hexafluoropropane or the like. These systems can be used individually or in combination.
作為自由基聚合性化合物，因應需要，可單獨或混合多種上述化合物使用。尤其，因為可抑制電路連接材料之硬化收縮，或可賦予硬化物柔軟性，所以以胺基甲酸酯丙烯酸酯低聚物為宜，併用此胺基甲酸酯丙烯酸酯及1種以上之聚合性單體尤佳。As the radically polymerizable compound, a plurality of the above compounds may be used singly or in combination as needed. In particular, since the curing shrinkage of the circuit connecting material can be suppressed or the flexibility of the cured product can be imparted, it is preferable to use a urethane acrylate oligomer, and to use the urethane acrylate and one or more kinds of polymerization. Sexual monomers are especially preferred.
藉由加熱或光產生自由基的自由基起始劑，可使用如有機過氧化物、偶氮系化合物、光起始劑，藉由加熱或光照射中至少任一種之處理而產生活性自由基的化合物。By heating or photoradically generating a radical initiator, active radicals can be produced by treatment with at least any one of heating, light irradiation, such as an organic peroxide, an azo compound, or a photoinitiator. compound of.
有機過氧化物及偶氮系化合物，主要藉由加熱而產生自由基。使用此等化合物作為自由基起始劑時，可依目的之連接溫度、連接時間、適用期等而自有機過氧化物及/或偶氮系化合物適當選擇1種或2種以上。Organic peroxides and azo compounds generate radicals mainly by heating. When such a compound is used as the radical initiator, one or two or more kinds of organic peroxides and/or azo compounds may be appropriately selected depending on the connection temperature, the connection time, the pot life, and the like.
就兼具高反應性及充分的適用期，有機過氧化物之半衰期10小時之溫度為40℃以上，而且，半衰期1分鐘之溫度為180℃以下為宜，半衰期10小時之溫度為60℃以上，而且，半衰期1分鐘之溫度為170℃以下尤佳。另外，為防止電路構件之電路電極(連接端子)之腐蝕，有機過氧化物係以氯離子或有機酸之含量為5000ppm以下 為宜，進而，以加熱分解後產生有機酸少者尤佳。The combination has a high reactivity and a sufficient pot life. The half-life of the organic peroxide is 40 ° C or more, and the half-life of 1 minute is preferably 180 ° C or less. The half-life of 10 hours is 60 ° C or higher. Moreover, the temperature at which the half-life is 1 minute is preferably 170 ° C or less. Further, in order to prevent corrosion of the circuit electrode (connection terminal) of the circuit member, the organic peroxide has a chlorine ion or an organic acid content of 5000 ppm or less. Preferably, it is preferred that the organic acid is produced by decomposition after heating.
作為有機過氧化物，具體上適合使用二醯基過氧化物、二烷基過氧化物、過氧二碳酸鹽、過氧酯、過氧化縮酮、氫過氧化物、矽烷基過氧化物等。As the organic peroxide, specifically, a decyl peroxide, a dialkyl peroxide, a peroxydicarbonate, a peroxyester, a peroxy ketal, a hydroperoxide, a decyl peroxide, etc. are suitably used. .
作為二醯基過氧化物，可舉例如異丁基過氧化物、2,4-二氯苯醯基過氧化物、3,5,5-三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、琥珀醯基過氧化物、苯醯基過氧甲苯、苯醯基過氧化物等。As the dimercapto peroxide, for example, isobutyl peroxide, 2,4-dichlorophenylhydrazine peroxide, 3,5,5-trimethylhexyl peroxide, and octyl peroxide are oxidized. , laurel-based peroxide, stearic acid-based peroxide, amber-based peroxide, benzoyl peroxytoluene, phenylhydrazine peroxide, and the like.
作為二烷基過氧化物，可舉例如α,α’雙(叔丁基過氧)二異丙基苯、二枯烯基過氧化物、2,5-二甲基-2,5-二(叔丁基過氧)己烷、叔丁基枯烯基過氧化物等。The dialkyl peroxide may, for example, be α,α' bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di. (tert-butylperoxy)hexane, tert-butyl cumenyl peroxide, and the like.
作為過氧二碳酸鹽，可舉例如二正丙基過氧二碳酸鹽、二異丙基過氧二碳酸鹽、雙(4-叔丁基環己基)過氧二碳酸鹽、二-2-乙氧基甲氧基過氧二碳酸鹽、二(2-乙基己基)過氧二碳酸鹽、二甲氧基丁基過氧二碳酸鹽、二(3-甲基-3-甲氧基丁基)過氧二碳酸鹽等。Examples of the peroxydicarbonate include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and di-2-. Ethoxymethoxy peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, dimethoxybutylperoxydicarbonate, bis(3-methyl-3-methoxyl) Butyl) peroxydicarbonate and the like.
作為過氧酯，可舉例如枯烯基過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、1-環己基-1-甲基乙基過氧新癸酸酯、叔己基過氧新癸酸酯、叔丁基過氧三甲基乙酸酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧)己烷、1-環己基-1-甲基乙基過氧-2-乙基己酸酯、叔己基過氧-2-乙基己酸酯、叔丁基過氧-2-乙基己酸酯、叔丁基過氧異丁酸酯、 1,1-雙(叔丁基過氧)環己烷、叔己基過氧異丙基單碳酸酯、叔丁基過氧-3,5,5-三甲基己酸酯、叔丁基過氧月桂酸酯、2,5-二甲基-2,5-二(間甲苯醯基過氧)己烷、叔丁基過氧異丙基單碳酸酯、叔丁基過氧-2-乙基己基單碳酸酯、叔己基過氧苯酸酯、叔丁基過氧乙酸酯、二(叔丁基過氧)六氫對苯二甲酯等。As the peroxyester, for example, cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl Oxygen neodecanoate, tert-hexyl peroxy neodecanoate, t-butyl peroxytrimethyl acetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate 2,5-Dimethyl-2,5-di(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, Tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl Oxylaurate, 2,5-dimethyl-2,5-di(m-tolylperoxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethyl Hexyl monocarbonate, tert-hexyl peroxybenzoate, t-butyl peroxyacetate, di(tert-butylperoxy)hexahydroterephthalate, and the like.
作為過氧化縮酮，可舉例如1,1-雙(叔己基過氧)-3,5,5-三甲基環己烷、1,1-雙(叔己基過氧)環己烷、1,1-雙(叔丁基過氧)-3,5,5-三甲基環己烷、1,1-雙(叔丁基過氧)環十二烷、2,2-雙(叔丁基過氧)癸烷等。The peroxy ketal may, for example, be 1,1-bis(tert-hexylperoxy)-3,5,5-trimethylcyclohexane or 1,1-bis(tert-hexylperoxy)cyclohexane; , 1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, 2,2-bis(tert-butyl) Base peroxy) decane and the like.
作為氫過氧化物，可舉例如二異丙基苯氫過氧化物、枯烯氫過氧化物等。Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
作為矽烷基過氧化物，可舉例如叔丁基三甲基矽烷基過氧化物、雙(叔丁基)二甲基矽烷基過氧化物、叔丁基三乙烯基矽烷基過氧化物、雙(叔丁基)二乙烯基矽烷基過氧化物、三(叔丁基)乙烯基矽烷基過氧化物、叔丁基三烯丙基矽烷基過氧化物、雙(叔丁基)二烯丙基矽烷基過氧化物、三(叔丁基)烯丙基矽烷基過氧化物等。Examples of the decyl-based peroxide include t-butyl trimethyl decyl peroxide, bis (tert-butyl) dimethyl decyl peroxide, t-butyl trivinyl decyl peroxide, and double (tert-butyl)divinyldecyl peroxide, tri(tert-butyl)vinyl fluorenyl peroxide, tert-butyl triallyl decyl peroxide, bis(tert-butyl)diene Based on alkyl peroxide, tri(tert-butyl) allyl fluorenyl peroxide, and the like.
此等有機過氧化物及偶氮系化合物係可單獨或混合數種使用。另外，亦可併用分解促進劑、抑制劑等。進而，將此等化合物以胺基甲酸酯系、聚酯系之高分子化合物等被覆，形成微膠囊化者，因為可得到長可使用時間，所以適宜。These organic peroxides and azo compounds may be used singly or in combination of several kinds. Further, a decomposition accelerator, an inhibitor, or the like may be used in combination. Further, these compounds are coated with a urethane-based or polyester-based polymer compound to form a microencapsulated one, and since a long usable time can be obtained, it is suitable.
作為光起始劑，適合使用例如苯偶因***、異丙基苯偶因醚等之苯偶因醚、聯苯甲醯、羥基環己基苯基酮等之聯苯甲醯縮酮、二苯甲酮、乙醯苯等之酮類及其衍生物、噻噸酮、雙咪唑類等。As the photoinitiator, a benzamidine ketal such as benzoin ether or cumene ether, a benzamidine, a hydroxycyclohexyl phenyl ketone or the like is preferably used. Ketones and derivatives thereof such as ketone and acetophenone, thioxanthone and biimidazole.
使用光起始劑時，因應使用光源之波長或所需之硬化特性等，選擇最適合之光起始劑。另外，光起始劑係可因應需要而以任意比率併用胺類、硫化合物、磷化合物等之增感劑。When a photoinitiator is used, the most suitable photoinitiator is selected in accordance with the wavelength of the light source or the desired hardening characteristics. Further, the photoinitiator may be used in combination with a sensitizer such as an amine, a sulfur compound or a phosphorus compound in an arbitrary ratio as needed.
作為增感劑，以脂肪族胺、芳香族胺、具有含氮環狀結構之哌啶等之環狀胺、鄰甲苯基硫脲、二乙基二硫磷酸鈉、芳香族亞磺酸之可溶性鹽、N,N’-二甲基-對胺基苯甲腈、N,N’-二乙基-對胺基苯甲腈、N,N’-二(β-氰基乙基)-對胺基苯甲腈、N,N’-二(β-氯乙基)-對胺基苯甲腈、三正丁基膦等為宜。As a sensitizer, the solubility of an aliphatic amine, an aromatic amine, a cyclic amine such as piperidine having a nitrogen-containing cyclic structure, o-tolylthiourea, sodium diethyldithiophosphate, and aromatic sulfinic acid Salt, N,N'-dimethyl-p-aminobenzonitrile, N,N'-diethyl-p-aminobenzonitrile, N,N'-bis(β-cyanoethyl)-pair Aminobenzonitrile, N,N'-bis(?-chloroethyl)-p-aminobenzonitrile, tri-n-butylphosphine, and the like are preferred.
或可使用苯丙酮、乙醯苯、呫噸酮、4-甲基乙醯苯、二苯甲酮、芴、聯三伸苯(triphenylene)、聯苯、噻噸酮、蒽醌、4,4’-雙(二甲基胺基)二苯甲酮、4,4’-雙(二乙基胺基)二苯甲酮、菲、萘、4-苯基乙醯苯、4-苯基二苯甲酮、1-碘萘、2-碘萘、苊、2-萘甲腈、1-萘甲腈、1,2-苯并菲、聯苯甲醯、熒蒽、芘、1,2-苯幷蒽、吖啶、蒽、苝、稠四苯、2-甲氧基萘等之非色素系增感劑、硫堇、甲基藍、光黃素、核黃素、光色素、香豆素、呋喃香豆素(psoralen)、8-甲氧基呋喃香豆素、6-甲基香豆素、5-甲氧基呋喃香豆素、5-羥基 呋喃香豆素、香豆基吡喃酮(Coumarylpyrone)、吖啶橙、吖啶黃、二胺基吖啶(proflavine)、螢光素(fluorescein)、伊紅Y、伊紅B、赤藻紅、孟加拉玫瑰紅(Rose Bengale)等之色素系增感劑。Or use phenylacetone, ethyl benzene, xanthone, 4-methyl acetophenone, benzophenone, hydrazine, triphenylene, biphenyl, thioxanthone, hydrazine, 4, 4 '-Bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, phenanthrene, naphthalene, 4-phenylethylbenzene, 4-phenyl di Benzophenone, 1-iodonaphthalene, 2-iodonaphthalene, anthracene, 2-naphthonitrile, 1-naphthonitrile, 1,2-benzophenanthrene, biphenylguanidine, fluoranthene, anthracene, 1,2- Non-pigment sensitizers such as benzoquinone, acridine, anthracene, anthracene, fused tetraphenyl, 2-methoxynaphthalene, thiopurine, methyl blue, light flavin, riboflavin, photochromic, and coumarin Phenol, psoralen, 8-methoxyfurocoumarin, 6-methylcoumarin, 5-methoxyfurancoumarin, 5-hydroxyl Furan coumarin, Coumarylpyrone, acridine orange, acridine yellow, proflavine, fluorescein, eosin Y, eosin B, red algae red , pigment sensitizers such as Rose Bengale.
作為自由基起始劑，亦可併用如上述之光起始劑，及有機過氧化物、偶氮系化合物等之藉由加熱產生自由基之化合物。As the radical initiator, a photoinitiator as described above, and a compound which generates a radical by heating, such as an organic peroxide or an azo compound, may be used in combination.
黏合劑組成物係可為含有環氧樹脂及該硬化劑者。作為環氧樹脂，可單獨或混合2種以上之1個分子內具有2個以上縮水甘油基之各種環氧化合物等使用。具體上可舉例如自環氧氯丙烷及雙酚A、F、AD等所衍生之雙酚型環氧樹脂、自環氧氯丙烷及苯酚酚醛清漆樹脂或甲酚酚醛清漆樹脂所衍生之環氧酚醛清漆樹脂、或具有含萘環骨架之萘型環氧樹脂、縮水甘油胺型環氧樹脂、聯苯型環氧樹脂、脂環式環氧樹脂等。環氧樹脂係減低不純物離子(Na+、Cl-等)、或水解性氯等於300ppm以下之高純度品，因為可防止電子遷移，所以適宜。The binder composition may be an epoxy resin and the hardener. The epoxy resin may be used alone or in combination of two or more kinds of epoxy compounds having two or more glycidyl groups in one molecule. Specifically, for example, a bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A, F, AD or the like, an epoxy derived from epichlorohydrin and a phenol novolak resin or a cresol novolak resin may be mentioned. A novolak resin, or a naphthalene type epoxy resin having a naphthalene ring skeleton, a glycidylamine type epoxy resin, a biphenyl type epoxy resin, an alicyclic epoxy resin, or the like. The epoxy resin is a high-purity product in which impure ions (Na+, Cl-, etc.) or hydrolyzable chlorine is equal to or less than 300 ppm, and is suitable because it can prevent electron migration.
作為環氧樹脂之硬化劑，為得到充分長的適用期，以潛在性硬化劑為宜。作為潛在性硬化劑，有咪唑系、醯胼系、三氟化硼-胺配位化合物、鋶鹽、胺醯亞胺(amineimide)、多胺、雙氰胺(Dicyandiamide)。也可以是將此等硬化劑以胺基甲酸酯系、聚酯系之高分子物質等被覆，形成微膠囊化者。此等係可單獨或混合使用，亦可併用分解促進劑、抑制劑等。As the hardener of the epoxy resin, in order to obtain a sufficiently long pot life, a latent hardener is preferably used. Examples of the latent curing agent include imidazole, lanthanide, boron trifluoride-amine complex, sulfonium salt, amineimide, polyamine, and dicyandiamide. The curing agent may be coated with a urethane-based or polyester-based polymer material to form a microencapsulated product. These may be used singly or in combination, and a decomposition accelerator, an inhibitor, or the like may be used in combination.
本發明之電路連接材料係組合如上述之黏合劑組成物、與具有胺基甲酸酯基及酯基之有機化合物(以下有時稱為「酯胺基甲酸酯化合物」)者。酯胺基甲酸酯化合物係於該主鏈中具有胺基甲酸酯基及酯基為宜。The circuit connecting material of the present invention is a combination of the above-described binder composition and an organic compound having a urethane group and an ester group (hereinafter sometimes referred to as an "ester urethane compound"). The ester urethane compound preferably has a urethane group and an ester group in the main chain.
此酯胺基甲酸酯化合物係藉由例如聚酯多元醇、與二異氰酸酯進行反應所得。由此反應所得之酯胺基甲酸酯化合物，一般稱為聚酯胺基甲酸酯樹脂。The ester urethane compound is obtained by, for example, a polyester polyol and a reaction with a diisocyanate. The ester carbamate compound thus obtained is generally referred to as a polyester urethane resin.
作為二異氰酸酯，適合使用2,4-甲苯二異氰酸酯(TDI)、4,4’-二苯基甲烷二異氰酸酯(MDI)、1,6-六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)等之芳香族、脂環族、或脂肪族之二異氰酸酯。As the diisocyanate, 2,4-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), isophorone are suitably used. An aromatic, alicyclic or aliphatic diisocyanate such as diisocyanate (IPDI).
聚酯多元醇係具有複數個之酯基及複數個之羥基之聚合物。聚酯多元醇係藉由例如二羧酸與二元醇進行反應所得。作為二羧酸係以對苯二甲酸、間苯二甲酸、己二酸、癸二酸等之芳香族或脂肪族二羧酸為宜。作為二元醇，係以如乙二醇、丙二醇、1,4-丁二醇、己二醇、新戊二醇、二乙二醇、三乙二醇等之二醇類為宜。The polyester polyol is a polymer having a plurality of ester groups and a plurality of hydroxyl groups. The polyester polyol is obtained by, for example, reacting a dicarboxylic acid with a glycol. The dicarboxylic acid is preferably an aromatic or aliphatic dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid. As the diol, a glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, neopentyl glycol, diethylene glycol or triethylene glycol is preferred.
酯胺基甲酸酯化合物之玻璃轉移溫度係以50℃以上為宜。酯胺基甲酸酯化合物係藉由適當調整聚酯多元醇或二異氰酸酯之種類或分子量等，可使該玻璃轉移溫度為50℃以上。The glass transition temperature of the ester carbamate compound is preferably 50 ° C or higher. The ester urethane compound can be made to have a glass transition temperature of 50 ° C or more by appropriately adjusting the kind or molecular weight of the polyester polyol or the diisocyanate.
酯胺基甲酸酯化合物係以具有陰離子性為宜。由此更加提昇黏合強度。具有陰離子性之酯胺基甲酸酯化合物係藉由聚酯多元醇與二異氰酸酯進行反應時，與支鏈上具有 磺酸基或羧基之二元醇或二胺類共聚所得。亦即，酯胺基甲酸酯化合物係以具有磺酸基或羧基為宜。The ester carbamate compound is preferably anionic. This further increases the bond strength. An anionic ester urethane compound is obtained by reacting a polyester polyol with a diisocyanate Copolymerization of a sulfonic acid group or a carboxyl group of a glycol or a diamine. That is, the ester urethane compound preferably has a sulfonic acid group or a carboxyl group.
酯胺基甲酸酯化合物係以具有含苯環之芳香族基或環己烷環等之環狀脂肪族基為宜。The ester urethane compound is preferably a cyclic aliphatic group having a benzene ring-containing aromatic group or a cyclohexane ring.
酯胺基甲酸酯化合物係可混合2種以上使用。可組合例如藉由芳香族聚酯多元醇與脂肪族二異氰酸酯進行反應所得者，與藉由脂肪族聚酯多元醇與芳香族二異氰酸酯進行反應所得者。The ester urethane compound can be used in combination of two or more kinds. For example, those obtained by reacting an aromatic polyester polyol with an aliphatic diisocyanate, and reacting with an aliphatic polyester polyol and an aromatic diisocyanate may be combined.
酯胺基甲酸酯化合物之重量平均分子量係以5000至100000為宜。重量平均分子量若未滿5000時，成形薄膜狀時之薄膜形成性有降低之趨勢，重量平均分子量若超過100000時，對溶劑之溶解性或相溶性降低，有難以調製用以成形薄膜狀之塗工液之趨勢。The weight average molecular weight of the ester carbamate compound is preferably from 5,000 to 100,000. When the weight average molecular weight is less than 5,000, the film formability in the form of a film is reduced. When the weight average molecular weight exceeds 100,000, the solubility or compatibility with a solvent is lowered, and it is difficult to prepare a film for forming a film. The trend of working fluids.
酯胺基甲酸酯化合物係以具有自由基聚合性之不飽和雙鍵及環氧基中之任一種為宜。由此，硬化電路連接材料時，黏合劑組成物中之環氧樹脂或自由基聚合性化合物進行反應，提昇電路連接材料之硬化物之彈性率或耐熱性。The ester urethane compound is preferably one of a radical polymerizable unsaturated double bond and an epoxy group. Thereby, when the material is hardened, the epoxy resin or the radically polymerizable compound in the binder composition reacts to increase the modulus of elasticity or heat resistance of the cured material of the circuit connecting material.
電路連接材料係除了上述說明成份以外，亦可含有含羥基樹脂。作為含羥基樹脂，可使用聚乙烯醇縮丁醛、聚乙烯醇縮甲醛、聚醯胺、聚酯、酚醛樹脂、環氧樹脂、苯氧樹脂、聚胺基甲酸酯樹脂(上述酯胺基甲酸酯樹脂除外。)等之樹脂。其中，以苯氧樹脂尤佳。藉由使用此等含羥基樹脂，硬化時之應力緩和性優異，由於羥基黏合性更加提昇。The circuit connecting material may contain a hydroxyl group-containing resin in addition to the above-described components. As the hydroxyl group-containing resin, polyvinyl butyral, polyvinyl formal, polyamine, polyester, phenol resin, epoxy resin, phenoxy resin, polyurethane resin (the above ester amine group) can be used. Resin other than formic acid resin.). Among them, phenoxy resin is particularly preferred. By using such a hydroxyl group-containing resin, the stress relaxation property at the time of hardening is excellent, and the hydroxyl group adhesiveness is further improved.
含羥基樹脂之重量平均分子量係以10000以上為宜，以10000至1000000尤佳。含羥基樹脂之重量平均分子量若超過1000000時，有難以與其他成份混合之趨勢。另外，含羥基樹脂之玻璃轉移溫度係以-50℃以上為宜。The weight average molecular weight of the hydroxyl group-containing resin is preferably 10,000 or more, and more preferably 10,000 to 1,000,000. When the weight average molecular weight of the hydroxyl group-containing resin exceeds 1,000,000, there is a tendency that it is difficult to mix with other components. Further, the glass transition temperature of the hydroxyl group-containing resin is preferably -50 ° C or higher.
為更提昇耐熱性，含羥基樹脂係以具有自由基聚合性官能基為宜。具有自由基聚合性官能基之含羥基樹脂係作為上述之自由基聚合性化合物使用。含羥基樹脂亦可藉由含羧基之彈性體、含環氧基之彈性體等而變性。In order to further improve the heat resistance, the hydroxyl group-containing resin preferably has a radical polymerizable functional group. A hydroxyl group-containing resin having a radical polymerizable functional group is used as the above-mentioned radical polymerizable compound. The hydroxyl group-containing resin may also be denatured by a carboxyl group-containing elastomer, an epoxy group-containing elastomer, or the like.
為使電路連接材料成為應力緩和優異者，以含有丙烯酸橡膠為宜。作為丙烯酸橡膠，可使用丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯腈中至少1種之丙烯酸系單體聚合之聚合物或共聚物。丙烯酸橡膠係可為上述單體與縮水甘油丙烯酸酯或縮水甘油甲基丙烯酸酯之共聚物。丙烯酸橡膠之重量平均分子量(重量平均)，就提高電路連接材料之凝聚力之觀點，係以20萬以上為宜。In order to make the circuit connecting material excellent in stress relaxation, it is preferred to contain an acrylic rubber. As the acrylic rubber, a polymer or copolymer obtained by polymerizing at least one of acrylic monomers such as acrylic acid, acrylate, methacrylate or acrylonitrile can be used. The acrylic rubber may be a copolymer of the above monomer and glycidyl acrylate or glycidyl methacrylate. The weight average molecular weight (weight average) of the acrylic rubber is preferably 200,000 or more in terms of improving the cohesive force of the circuit connecting material.
電路連接材料係可含有苯乙烯樹脂。苯乙烯樹脂係可為將苯乙烯單體聚合者，亦可為將苯乙烯與馬來酸酐化合物、馬來醯亞胺化合物中之至少一種共聚之共聚物。苯乙烯樹脂之重量平均分子量(重量平均)，就提高電路連接材料之凝聚力之觀點，係以10萬以上為宜。The circuit connecting material may contain a styrene resin. The styrene resin may be a copolymer of styrene monomer or a copolymer of styrene and at least one of a maleic anhydride compound and a maleimide compound. The weight average molecular weight (weight average) of the styrene resin is preferably 100,000 or more from the viewpoint of improving the cohesive force of the circuit connecting material.
電路連接材料係可再含有充填劑、軟化劑、促進劑、抗老化劑、著色劑、難燃化劑、觸變劑、偶合劑及酚醛樹脂或三聚氰胺樹脂、異氰酸酯類等。The circuit connecting material may further comprise a filler, a softener, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin or a melamine resin, an isocyanate or the like.
含有充填劑時，因為可得到連接信賴性等，所以適 宜。充填劑之最大徑係以未滿於導電性粒子之粒徑為宜，該量係於5至60體積份(相對100體積份之黏合劑組成物)之範圍為宜。超過60體積份時，提昇信賴性之效果成飽和，未滿5體積份時，添加的功效少。作為偶合劑，就提昇黏合性之觀點，以乙烯基、丙烯醯基、胺基、環氧基及異氰酸酯基含有物為宜。When a filler is included, it is possible to obtain connection reliability and the like. should. The maximum diameter of the filler is preferably not more than the particle diameter of the conductive particles, and the amount is preferably in the range of 5 to 60 parts by volume (relative to 100 parts by volume of the binder composition). When the amount is more than 60 parts by volume, the effect of improving the reliability is saturated, and when it is less than 5 parts by volume, the effect of addition is small. As the coupling agent, a vinyl group, an acryl group, an amine group, an epoxy group, and an isocyanate group-containing substance are preferable from the viewpoint of improving the adhesion.
電路連接材料係以含有導電性粒子為宜。即使不含有導電性粒子，雖可藉由電路電極彼此間直接接觸，連接電路構件，但藉由含有導電粒子，將可更安定地連接。The circuit connecting material preferably contains conductive particles. Even if the conductive particles are not contained, the circuit members can be connected by direct contact between the circuit electrodes, but the conductive particles can be connected to each other more stably.
作為導電性粒子，可舉例如Au、Ag、Ni、Cu、焊料等之金屬粒子或碳粒子等。為充分地延長適用期，導電性粒子以含有Au、Ag、鉑族之金屬為宜，含有Au更好。Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, or carbon particles. In order to sufficiently extend the pot life, the conductive particles are preferably a metal containing Au, Ag or a platinum group, and it is more preferable to contain Au.
導電性粒子係以Ni等之過渡金屬、或非導電性之玻璃、陶瓷、塑膠等所形成之粒子為核，將其表面以由Au等之貴金屬所形成之被覆層被覆者為宜。具有如此貴金屬被覆層之導電性粒子係藉由將電路連接材料加熱及加壓時之變形，增加與電路電極之接觸面積，更提昇信賴性。為得到良好連接電阻，貴金屬被覆層之厚度係以100埃以上為宜。進而，核為Ni等之過渡金屬之粒子時，被覆層之厚度係以300埃以上尤佳。被覆層之厚度若未滿300埃時，分散導電性粒子於樹脂中等時，被覆層部份缺損時，藉由氧化還原作用而產生游離自由基，而有降低電路連接材料之保存安定性之趨勢。The conductive particles are preferably a transition metal made of Ni or the like, or a particle formed of a non-conductive glass, ceramic, plastic or the like, and the surface of the conductive particle is coated with a coating layer made of a noble metal such as Au. The conductive particles having such a noble metal coating layer are deformed by heating and pressurizing the circuit connecting material, thereby increasing the contact area with the circuit electrodes and improving the reliability. In order to obtain a good connection resistance, the thickness of the noble metal coating layer is preferably 100 angstroms or more. Further, when the core is a transition metal particle such as Ni, the thickness of the coating layer is preferably 300 angstroms or more. When the thickness of the coating layer is less than 300 angstroms, when the conductive particles are dispersed in the resin or the like, when the coating layer is partially deficient, free radicals are generated by redox, and the storage stability of the circuit connecting material is lowered. .
導電性粒子的量係相對於100體積份之黏合劑組成 物，係以0.1至30體積份為宜。為防止因過剩導電性粒子造成相鄰電路之短路，以0.1至10體積份尤佳。The amount of conductive particles is based on 100 parts by volume of the binder composition The substance is preferably 0.1 to 30 parts by volume. In order to prevent short-circuiting of adjacent circuits due to excessive conductive particles, it is particularly preferable to use 0.1 to 10 parts by volume.
圖1係表示依據本發明之薄膜狀電路連接材料之一種實施形態之斷面圖。薄膜狀電路連接材料1係複數個導電性粒子5分散於含有黏合劑組成物及酯胺基甲酸酯化合物等之樹脂組成物層3中之電路連接材料，成形成薄膜狀者。薄膜狀電路連接材料1係例如以所定之厚度塗工電路連接材料於支持薄膜上而可製作。作為支持薄膜，適合使用表面處理過之具有離型性之PET(聚乙烯對苯二甲酸酯)薄膜等。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a film-like circuit connecting material according to the present invention. The film-like circuit connecting material 1 is a circuit connecting material in which a plurality of conductive particles 5 are dispersed in a resin composition layer 3 including a binder composition and an ester urethane compound, and is formed into a film. The film-like circuit connecting material 1 can be produced, for example, by applying a circuit-bonding material to a support film with a predetermined thickness. As the support film, a surface-treated PET (polyethylene terephthalate) film having a release property or the like is suitably used.
薄膜狀電路連接材料1係以夾於對向的1對電路構件彼此間之狀態，加熱及加壓時，熔融流動而使成對峙之電路電極彼此間電性連接後，硬化而發生黏合強度。因此，薄膜狀電路連接材料1之流動性係重要的。具體上，使薄膜狀電路連接材料1(厚度為35μm，5mm×5mm)夾於2枚玻璃板(厚度為0.7mm，15mm×15mm)之間之狀態，進行150℃，2MPa，10秒鐘的加熱及加壓時，使用電路連接材料1之初期面積(A)與加熱及加壓後之面積(B)所表示之流動性之指標(B)/(A)的值係以1.3至3.0為宜，以1.5至2.5尤佳。(B)/(A)的值未滿1.3時流動性不足，而有不能得到良好連接之趨勢，若超過3.0時，產生氣泡而有信賴性降低之趨勢。The film-like circuit connecting material 1 is in a state of being sandwiched between the pair of opposing circuit members, and when heated and pressurized, melts and flows to electrically connect the pair of circuit electrodes to each other, and then hardens to cause adhesive strength. Therefore, the fluidity of the film-like circuit connecting material 1 is important. Specifically, the film-like circuit connecting material 1 (thickness: 35 μm, 5 mm × 5 mm) was sandwiched between two glass plates (thickness: 0.7 mm, 15 mm × 15 mm), and was subjected to 150 ° C, 2 MPa, and 10 seconds. When heating and pressurizing, the values of the fluidity index (B)/(A) expressed by the initial area (A) of the circuit connecting material 1 and the area (B) after heating and pressurization are 1.3 to 3.0. Preferably, it is preferably 1.5 to 2.5. When the value of (B)/(A) is less than 1.3, the fluidity is insufficient, and there is a tendency that good connection is not obtained. When it exceeds 3.0, bubbles are generated and the reliability is lowered.
薄膜狀電路連接材料1雖僅具有1層，但本發明之電路連接材料亦可取代它，而使用成形成具有組成相異之複 數層薄膜之狀態。尤其，電路連接材料含有導電性粒子，電路連接材料中之黏合劑組成物含有藉由加熱或光產生自由基的自由基起始劑時，將電路連接材料形成為分別具有含有藉由加熱或光產生自由基的自由基起始劑之層，與含有導電性粒子之層之多層薄膜為宜。由此而可得到更長的可使用時間。Although the film-like circuit connecting material 1 has only one layer, the circuit connecting material of the present invention can also be substituted for it, and can be used to form a complex composition. The state of several layers of film. In particular, the circuit connecting material contains conductive particles, and when the binder composition in the circuit connecting material contains a radical initiator which generates radicals by heating or light, the circuit connecting material is formed to have a heating or light respectively A layer of a radical generating initiator which generates a radical and a multilayer film of a layer containing a conductive particle are preferred. This results in a longer usable time.
薄膜狀電路連接材料1係使用於用以將例如半導體晶片、電阻體晶片、冷凝器晶片等之晶片零件、或印刷基板等之電路構件彼此間連接。The film-like circuit connecting material 1 is used to connect, for example, a wafer component such as a semiconductor wafer, a resistor wafer, or a condenser wafer, or a circuit member such as a printed circuit board.
圖2係表示依據本發明之電路構件之連接構造之一種實施形態之斷面圖。圖2所示之電路構件之連接構造101係具有第1基板11及於該第1基板的主面上介由黏合劑層12所形成的第1電路電極13之第1電路構件10，與具有第2基板21及於該第2基板的主面上所形成的第2電路電極23之第2電路構件20，藉由上述之電路連接材料硬化的硬化物所形成且形成於第1及第2電路構件10，20之間的電路連接構件1a所連接者。於電路構件之連接構造101中，第1電路電極13與該第2電路電極23成對峙的同時電性連接。Fig. 2 is a cross-sectional view showing an embodiment of a connection structure of a circuit member according to the present invention. The connection structure 101 of the circuit member shown in FIG. 2 includes a first substrate 11 and a first circuit member 10 of the first circuit electrode 13 formed on the main surface of the first substrate via the adhesive layer 12, and has The second substrate 21 and the second circuit member 20 of the second circuit electrode 23 formed on the main surface of the second substrate are formed of the cured material hardened by the above-described circuit connecting material and formed on the first and second sides. The circuit connecting member 1a between the circuit members 10, 20 is connected. In the connection structure 101 of the circuit member, the first circuit electrode 13 is electrically connected to the second circuit electrode 23 while being opposed to each other.
電路連接構件1a係由黏合劑組成物及含有酯胺基甲酸酯化合物等之樹脂組成物之硬化物3a及分散於其中之導電性粒子5所構成。第1電路電極13與該第2電路電極23係介由導電性粒子5而電性連接。電路連接構件1a於40℃之彈性率係以100至3000MPa為宜，以500至 2000MPa尤佳。The circuit connecting member 1a is composed of a binder composition, a cured product 3a containing a resin composition such as an ester urethane compound, and conductive particles 5 dispersed therein. The first circuit electrode 13 and the second circuit electrode 23 are electrically connected via the conductive particles 5 . The elastic modulus of the circuit connecting member 1a at 40 ° C is preferably 100 to 3000 MPa, and is 500 to 2000MPa is especially good.
第1基板11係含有至少1種選自聚對苯二甲酸乙二醇酯、聚醚碸、環氧樹脂、丙烯酸樹脂、聚醯亞胺樹脂所成群之樹脂之樹脂薄膜。The first substrate 11 is a resin film containing at least one resin selected from the group consisting of polyethylene terephthalate, polyether oxime, epoxy resin, acrylic resin, and polyimide resin.
電路電極13係以可作為電極運作程度之具有導電性材料(至少1種選自金、銀、錫、鉑族之金屬及銦-錫氧化物所成群為宜)所形成。複數個電路電極13係介由黏著劑層12黏合於第1基板11之主面上。黏著劑層12係以電路構件中通常所使用之黏合劑等所形成。The circuit electrode 13 is formed of a conductive material (at least one metal selected from the group consisting of gold, silver, tin, a platinum group, and an indium-tin oxide group) which can function as an electrode. The plurality of circuit electrodes 13 are bonded to the main surface of the first substrate 11 via the adhesive layer 12. The adhesive layer 12 is formed of a binder or the like which is generally used in circuit members.
第2基板21係玻璃基板，於第2基板21之主面上，形成複數個第2電路電極23。The second substrate 21 is a glass substrate, and a plurality of second circuit electrodes 23 are formed on the main surface of the second substrate 21.
電路構件之連接構造101係例如藉由對將第1電路構件10、與上述薄膜狀電路連接材料1、與第2電路構件20之順序層合第1電路電極13與第2電路電極23成對峙之層合體進行加熱及加壓後，連接第1電路構件10及該第2電路構件20而使該第1電路電極13與該第2電路電極23成電性連接之連接方法而得。The connection structure 101 of the circuit member is formed by, for example, laminating the first circuit member 10, the film-like circuit connecting material 1, and the second circuit member 20 in the order of the first circuit electrode 13 and the second circuit electrode 23. After the laminate is heated and pressurized, the first circuit member 10 and the second circuit member 20 are connected to each other, and the first circuit electrode 13 and the second circuit electrode 23 are electrically connected to each other.
於此方法中，首先將支持薄膜上所形成之薄膜狀電路連接材料1，以貼附於第2電路構件20上之狀態，進行加熱及加壓，暫時黏合電路連接材料1，剝離支持薄膜後，配合電路電極位置的同時，上載第1電路構件10，可準備層合體。In this method, first, the film-like circuit connecting material 1 formed on the support film is attached to the second circuit member 20, heated and pressurized, temporarily bonding the circuit connecting material 1 and peeling off the supporting film. The first circuit member 10 is loaded while the position of the circuit electrode is matched, and a laminate can be prepared.
加熱及加壓上述層合體之條件係因應電路連接材料中黏合劑組成物之硬化性等，適當的調整，將電路連接材料 硬化以得到充分的黏合強度。The conditions for heating and pressurizing the above-mentioned laminate are appropriate adjustments in accordance with the hardenability of the binder composition in the circuit connecting material, and the circuit connecting material Harden to obtain sufficient bond strength.
圖3係表示依據本發明之電路構件之連接構造之其他實施形態之斷面圖。圖3所示之電路構件之連接構造102係除了於第1電路構件10，直接形成第1電路電極13於第1基板11之主面上以外，其他係與電路構件之連接構造101相同者。Fig. 3 is a cross-sectional view showing another embodiment of a connection structure of a circuit member according to the present invention. The connection structure 102 of the circuit member shown in FIG. 3 is the same as the first circuit member 10, and the first circuit electrode 13 is directly formed on the main surface of the first substrate 11, and the other connection structure 101 of the circuit member is the same.
如電路構件之連接構造102，電路連接構件1a係與以聚對苯二甲酸乙二醇酯、聚醚碸、環氧樹脂、丙烯酸樹脂、聚醯亞胺樹脂及玻璃之材料所成的基板直接密合之構成時，傳統的電路連接材料特別難以得到充分的黏合強度。相對於此，於電路構件之連接構造102，電路連接構件1a係藉由上述本發明之電路連接材料之硬化物，即使於高溫高濕環境下可維持充分的黏合強度。如此效果係於電路連接構件及電路構件之間，形成含有聚醯亞胺樹脂、丙烯酸樹脂、矽酮樹脂等之層時，亦可得之。For example, the connection structure 102 of the circuit member, the circuit connection member 1a is a substrate made of a material of polyethylene terephthalate, polyether oxime, epoxy resin, acrylic resin, polyimide resin, and glass. In the case of direct adhesion, it is particularly difficult to obtain sufficient bonding strength of a conventional circuit connecting material. On the other hand, in the connection structure 102 of the circuit member, the circuit connecting member 1a is a cured product of the circuit connecting material of the present invention, and maintains sufficient adhesive strength even in a high-temperature and high-humidity environment. Such an effect is obtained when a layer containing a polyimide resin, an acrylic resin, an anthrone resin or the like is formed between the circuit connecting member and the circuit member.
以下係舉實施例及比較例，更具體地說明本發明。但是，本發明並不侷限於以下之實施例者。The present invention will be more specifically described below by way of examples and comparative examples. However, the invention is not limited to the following embodiments.
將由二羧酸及二元醇之反應所得之聚酯多元醇溶解於甲基乙基酮之溶液，放入具備攪拌機、溫度計、冷凝器及真空發生裝置及氮氣導入管之附有加熱器之不鏽鋼製高壓釜。接著，加入所定量之異氰酸酯，加入相對於100重量 份之聚酯多元醇為0.02重量份之作為觸媒之二丁基錫月桂酸酯，以75℃反應10小時後，冷卻至40℃。進而由加入哌嗪反應30分鐘之鏈延長後，以三乙基胺中和。The polyester polyol obtained by the reaction of the dicarboxylic acid and the diol is dissolved in a solution of methyl ethyl ketone, and placed in a stainless steel with a heater equipped with a stirrer, a thermometer, a condenser, a vacuum generator, and a nitrogen introduction tube. Making an autoclave. Next, add the quantified isocyanate and add relative to 100 weight The polyester polyol was 0.02 parts by weight of dibutyltin laurate as a catalyst, and reacted at 75 ° C for 10 hours, and then cooled to 40 ° C. Further, the chain was extended by a piperazine reaction for 30 minutes, and then neutralized with triethylamine.
滴入上述反應後之溶液於純水時，溶劑及觸媒溶解於水的同時，亦析出作為酯胺基甲酸酯化合物之聚酯胺基甲酸酯樹脂。將析出之聚酯胺基甲酸酯樹脂，以真空乾燥機乾燥而得聚酯胺基甲酸酯樹脂。When the solution after the above reaction is added dropwise to pure water, the solvent and the catalyst are dissolved in water, and a polyester urethane resin as an ester urethane compound is also precipitated. The precipitated polyester urethane resin was dried in a vacuum dryer to obtain a polyester urethane resin.
將作為二羧酸之對苯二甲酸、作為二元醇之丙二醇、作為異氰酸酯之4,4’-二苯基甲烷二異氰酸酯，以對苯二甲酸/丙二醇/4,4’-二苯基甲烷二異氰酸酯之莫耳比為1.0/1.3/0.25之量，依據上述步驟而得聚酯胺基甲酸酯樹脂A。由凝膠滲透層析儀測定聚酯胺基甲酸酯樹脂A之重量分子量時，為27000。Terephthalic acid as dicarboxylic acid, propylene glycol as glycol, 4,4'-diphenylmethane diisocyanate as isocyanate, terephthalic acid/propylene glycol/4,4'-diphenylmethane The molar ratio of the diisocyanate was 1.0/1.3/0.25, and the polyester urethane resin A was obtained according to the above procedure. When the weight molecular weight of the polyester urethane resin A was measured by a gel permeation chromatography, it was 27,000.
將溶解聚酯胺基甲酸酯樹脂A於甲基乙基酮而成20重量%之甲基乙基酮溶液，使用塗工裝置塗佈於單面表面處理過之PET薄膜(厚度為80μm)，以70℃熱風乾燥10分鐘，形成厚度為35μm之薄膜。關於此薄膜，使用廣域動態黏彈性測定裝置，拉伸負荷為5gf，頻率為10Hz之條件，測定彈性率之溫度依賴性。於所得之彈性率-溫度曲線中，自延長玻璃轉移範圍之前後各基線之直線，於縱軸方向上處於等距離之直線，與玻璃轉移範圍之階段狀變化部份之曲線相交點之溫度(中間點玻璃轉移溫度)， 作為聚酯胺基甲酸酯樹脂A之玻璃轉移溫度，所求為105℃。A 20% by weight solution of methyl ethyl ketone in which the polyester urethane resin A was dissolved in methyl ethyl ketone was applied to a single-surface treated PET film (thickness: 80 μm) using a coating device. It was dried by hot air at 70 ° C for 10 minutes to form a film having a thickness of 35 μm. With respect to this film, the temperature dependence of the modulus of elasticity was measured using a wide-area dynamic viscoelasticity measuring apparatus under the conditions of a tensile load of 5 gf and a frequency of 10 Hz. In the obtained elastic modulus-temperature curve, the straight line from the baseline before and after the extension of the glass transition range, the line at an equidistant distance in the direction of the longitudinal axis, and the temperature at the point of intersection with the curve of the phase change portion of the glass transition range ( Intermediate point glass transfer temperature), The glass transition temperature of the polyester urethane resin A was found to be 105 °C.
將400重量份之重量平均分子量為800之聚己內酯二醇、131重量份之2-羥丙基丙烯酸酯、0.5重量份之作為觸媒之二丁基錫二月桂酸酯及1.0重量份之作為聚合禁止劑之氫輥單甲基醚，於50℃加熱下攪拌混合。接著，滴入222重量份之異氟爾酮二異氰酸酯，進一步攪拌下，昇溫至80℃，進行胺基甲酸酯化反應。確認異氰酸基之反應率為99%以上後，降低溫度，得到作為自由基聚合性化合物之胺基甲酸酯丙烯酸酯。400 parts by weight of polycaprolactone diol having a weight average molecular weight of 800, 131 parts by weight of 2-hydroxypropyl acrylate, 0.5 parts by weight of dibutyltin dilaurate as a catalyst, and 1.0 part by weight The hydrogen roller monomethyl ether of the polymerization inhibitor was stirred and mixed under heating at 50 °C. Next, 222 parts by weight of isophorone diisocyanate was added dropwise, and the mixture was further stirred to raise the temperature to 80 ° C to carry out a urethanization reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the temperature was lowered to obtain a urethane acrylate which is a radical polymerizable compound.
以聚苯乙烯為核之粒子表面上，使依序形成厚度為0.2μm之鎳層及厚度為0.04μm之金層，製作平均粒徑為10μm之導電性粒子。On the surface of the particles having polystyrene as a core, a nickel layer having a thickness of 0.2 μm and a gold layer having a thickness of 0.04 μm were sequentially formed to prepare conductive particles having an average particle diameter of 10 μm.
以固形份之重量，混合各成份之50g之聚酯胺基甲酸酯樹脂A、49g之胺基甲酸酯丙烯酸樹脂、1g之磷酸酯型丙烯酸酯、5g之自由基起始劑之叔己基過氧2-乙基己酸酯，進一步加入導電性粒子，使量成為整體之3體積%，將此均勻分散，而得塗工用之分散液。調製分散液時，聚酯胺基甲酸酯樹脂A係以溶解於甲基乙基酮成20質量%之濃度之溶液狀態，叔己基過氧2-乙基己酸酯係50重量%DOP溶液(日本油脂股份有限公司製，商品名「PercureHO」)之狀態，與其他成份混合。將所得之分散液，使用塗工裝置塗佈於單面表面處理過之PET薄膜 (厚度為80μm)，以70℃熱風乾燥10分鐘，而得厚度為20μm之薄膜狀電路連接材料。Mix 50g of polyester urethane resin A, 49g of urethane acrylate resin, 1g of phosphate ester acrylate, and 5g of free radical initiator t-hexyl group by weight of solid content. Peroxy 2-ethylhexanoate was further added to the conductive particles to make the amount 3% by volume of the whole, and this was uniformly dispersed to obtain a dispersion for coating. When the dispersion is prepared, the polyester urethane resin A is in a solution state in which the concentration of methyl ethyl ketone is 20% by mass, and the tert- hexyl peroxy 2-ethylhexanoate is 50% by weight of the DOP solution. (The product made by Nippon Oil & Fat Co., Ltd., trade name "PercureHO") is mixed with other ingredients. Applying the obtained dispersion to a single-surface treated PET film using a coating device (thickness: 80 μm), dried by hot air at 70 ° C for 10 minutes to obtain a film-like circuit connecting material having a thickness of 20 μm.
將作為二羧酸之間苯二甲酸、對苯二甲酸及己二酸、作為二元醇之乙二醇、新戊二醇及1,6-己二醇、作為二異氰酸酯之4,4’-二苯基甲烷二異氰酸酯，以間苯二甲酸/對苯二甲酸/己二酸/乙二醇/新戊二醇/1,6-己二醇/4,4’-二苯基甲烷二異氰酸酯之莫耳比為0.21/0.21/0.58/0.19/0.55/0.46/0.3之量，依據上述步驟合成聚酯胺基甲酸酯樹脂B。由凝膠滲透層析儀測定聚酯胺基甲酸酯樹脂B之重量分子量時，為60000。另外，聚酯胺基甲酸酯樹脂B之玻璃轉移溫度係與實施例1同樣地測定時，為-3℃。It will be used as dicarboxylic acid, terephthalic acid and adipic acid, ethylene glycol as a glycol, neopentyl glycol and 1,6-hexanediol, as a diisocyanate 4,4' -diphenylmethane diisocyanate, isophthalic acid / terephthalic acid / adipic acid / ethylene glycol / neopentyl glycol / 1,6-hexanediol / 4,4'-diphenylmethane The molar ratio of the isocyanate was 0.21/0.21/0.58/0.19/0.55/0.46/0.3, and the polyester urethane resin B was synthesized in accordance with the above procedure. When the weight molecular weight of the polyester urethane resin B was measured by a gel permeation chromatography, it was 60,000. Further, the glass transition temperature of the polyester urethane resin B was -3 ° C when measured in the same manner as in Example 1.
除了使用聚酯胺基甲酸酯樹脂B取代聚酯胺基甲酸酯樹脂A以外，與實施例1同樣地製作薄膜狀電路連接材料。A film-like circuit connecting material was produced in the same manner as in Example 1 except that the polyester urethane resin B was used instead of the polyester urethane resin A.
除了將50g之聚酯胺基甲酸酯樹脂B中之20g，取代成苯氧樹脂(Union Carbide股份有限公司製，商品名「PKHC」，重量平均分子量為45000)以外，與實施例2同樣地製作薄膜狀電路連接材料。In the same manner as in Example 2 except that 20 g of 50 g of the polyester urethane resin B was replaced by a phenoxy resin (manufactured by Union Carbide Co., Ltd., trade name "PKHC", and the weight average molecular weight was 45,000). A film-like circuit connecting material is produced.
除了取代聚酯胺基甲酸酯樹脂A，改使用合成聚酯胺基甲酸酯樹脂A時所使用之聚酯多元醇(玻璃轉移溫度：85℃)以外，與實施例1同樣地製作薄膜狀電路連接 材料。A film was produced in the same manner as in Example 1 except that the polyester urethane resin A was used instead of the polyester polyol (glass transition temperature: 85 ° C) used in the synthesis of the polyester urethane resin A. Circuit connection material.
除了取代聚酯胺基甲酸酯樹脂B，改使用合成聚酯胺基甲酸酯樹脂B時所使用之聚酯多元醇(玻璃轉移溫度：-5℃)以外，與實施例2同樣地製作薄膜狀電路連接材料。The same procedure as in Example 2 was carried out except that the polyester urethane resin B was used instead of the polyester polyol (glass transition temperature: -5 ° C) used in the synthesis of the polyester urethane resin B. Film-like circuit connection material.
除了取代聚酯胺基甲酸酯樹脂B，使用合成聚酯胺基甲酸酯樹脂B時所使用之聚酯多元醇(玻璃轉移溫度：-5℃)以外，與實施例3同樣地製作薄膜狀電路連接材料。A film was produced in the same manner as in Example 3 except that the polyester urethane resin B was used instead of the polyester polyol (glass transition temperature: -5 ° C) used in the synthesis of the polyester urethane resin B. Circuit connection material.
除了取代聚酯胺基甲酸酯樹脂A，使用未具有酯基之聚胺基甲酸酯樹脂(DIC Bayer Polymer股份有限公司製，商品名「Pandex T-8175」)(玻璃轉移溫度：-30℃)以外，與實施例1同樣地製作薄膜狀電路連接材料。In addition to the polyester urethane resin A, a polyurethane resin having no ester group (manufactured by DIC Bayer Polymer Co., Ltd., trade name "Pandex T-8175") was used (glass transition temperature: -30). A film-like circuit connecting material was produced in the same manner as in Example 1 except for ° C).
準備形成500支之作為電路電極之鉻電路(線寬為50μm，間距為100μm，厚度為0.4μm)於玻璃基板(Corning社製，商品名「#1737」)上之電路構件。於該電路構件上，貼附以實施例1製作之薄膜狀電路連接材料，以70℃，0.5MPa加熱及加壓5秒鐘，將此暫時黏合。A circuit member of a chrome circuit (line width: 50 μm, pitch: 100 μm, thickness: 0.4 μm) as a circuit electrode was prepared on a glass substrate (manufactured by Corning Co., Ltd., trade name "#1737"). To the circuit member, the film-like circuit connecting material produced in Example 1 was attached, and heated and pressurized at 70 ° C, 0.5 MPa for 5 seconds to temporarily bond the film.
接著，將剝離PET薄膜，於聚醯亞胺薄膜(宇部興產股份有限公司製商品名「upilex」，厚度為75μm)上，介由黏合劑層黏著500支銅電路(線寬為50μm，間距為100μm，厚度為18μm)之3層構造之可撓式電路構件(FPC1)，上載於薄膜狀電路連接材料上，以160℃，3MPa加熱及加壓10秒鐘。由此，以寬度2mm連接具有玻璃基板之電路構件及FPC1。Next, the PET film was peeled off and a 500-copper circuit was adhered to the adhesive layer by a polyimide film (product name "upilex" manufactured by Ube Industries, Ltd., thickness: 75 μm) (line width 50 μm, pitch) A flexible circuit member (FPC1) having a three-layer structure of 100 μm and a thickness of 18 μm was placed on a film-like circuit connecting material, and heated and pressurized at 160 ° C, 3 MPa for 10 seconds. Thereby, the circuit member having the glass substrate and the FPC 1 were connected with a width of 2 mm.
另外，取代FPC1，改使用聚醯亞胺薄膜(宇部興產股份有限公司製商品名「upilex 25S」，厚度為25μm)上，直接形成500支之線寬為50μm，間距為100μm，厚度為8μm之銅電路之2層構造之可撓式電路板(FPC2)，與上述同樣地，以寬度2mm連接具有玻璃基板之電路構件及FPC2。In addition, instead of FPC1, a polyimide film (product name "upilex 25S" manufactured by Ube Industries, Ltd., thickness: 25 μm) was used, and 500 lines were directly formed to have a line width of 50 μm, a pitch of 100 μm, and a thickness of 8 μm. A flexible circuit board (FPC2) having a two-layer structure of a copper circuit is connected to a circuit member having a glass substrate and an FPC 2 in a width of 2 mm in the same manner as described above.
使用實施例2至3、比較例1至4所製作之薄膜狀電路連接材料，與上述同樣地，將FPC1及FPC2分別與具有玻璃基板之電路構件連接。Using the film-like circuit connecting materials produced in Examples 2 to 3 and Comparative Examples 1 to 4, FPC1 and FPC2 were respectively connected to a circuit member having a glass substrate in the same manner as described above.
關於所製作之電路構件之連接構造，使用電表(multimeter)測定對峙之電路電極間之電阻值(連接電阻)。測定係對於初期、及於85℃，85%RH之高溫高濕槽中保持500小時之高溫高濕處理後進行。表1顯示電阻值為150點之平均值(x+3σ)作為連接電阻。Regarding the connection structure of the circuit member to be fabricated, the resistance value (connection resistance) between the circuit electrodes of the pair was measured using a multimeter. The measurement was carried out after the high-temperature and high-humidity treatment in the initial stage and in the high-temperature and high-humidity tank of 85% RH at 85 ° C for 500 hours. Table 1 shows the average value of the resistance value of 150 points (x + 3σ) as the connection resistance.
關於所製作之電路構件之連接構造，將以90°剝離時 之黏合強度，以剝離速度50mm/min測定。測定係對於初期、及與上述同樣地高溫高濕處理後進行。Regarding the connection structure of the fabricated circuit member, when peeling at 90° The bonding strength was measured at a peeling speed of 50 mm/min. The measurement was carried out after the initial stage and the high-temperature and high-humidity treatment similar to the above.
使用實施例1至3之電路連接材料連接之電路構件之連接構造，於初期之連接電阻十分低，並且於高溫高濕處理後之連接電阻亦認為幾乎未上昇，顯示高耐久性。其中，使用玻璃轉移溫度為50℃以上之聚酯樹脂之實施例1時，耐久性尤其優異。另外，使用玻璃轉移溫度未滿50℃之聚酯胺基甲酸酯樹脂之實施例2時，雖然於高溫高濕處理後連接有些鬆動，連接電阻上昇亦相對地比實施例1大，但仍為實用上之容許範圍內。進一步，併用聚酯胺基甲酸酯樹脂及玻璃轉移溫度為50℃以上之苯氧樹脂之實施例3，與實施例1大約同等程度抑制因高溫高濕處理之連接電阻之上昇。The connection structure of the circuit members connected by the circuit connecting materials of Examples 1 to 3 was extremely low in the initial stage, and the connection resistance after the high-temperature and high-humidity treatment was considered to be hardly increased, showing high durability. Among them, in the case of Example 1 in which a polyester resin having a glass transition temperature of 50 ° C or higher was used, the durability was particularly excellent. Further, in the case of the second embodiment of the polyester urethane resin having a glass transition temperature of less than 50 ° C, although the connection was somewhat loose after the high-temperature and high-humidity treatment, the connection resistance was relatively increased as compared with the first embodiment, but still For practical purposes, the range is allowed. Further, in Example 3 in which a polyester urethane resin and a phenoxy resin having a glass transition temperature of 50 ° C or higher were used in combination, the increase in the connection resistance due to the high-temperature and high-humidity treatment was suppressed to about the same extent as in Example 1.
實施例1至3係於FPC1及FPC2中任一種時，初期及高溫高濕處理後，維持6N/cm以上。此試驗中，一般黏合強度為6N/cm以上時，認為十分實用。於實施例2及實施例3之比較，聚酯胺基甲酸酯樹脂含量更多之實施例2係比實施例3，於高溫高濕處理後之連接強度優異。In the case of any of FPC1 and FPC2, Examples 1 to 3 were maintained at 6 N/cm or more after the initial stage and high-temperature and high-humidity treatment. In this test, when the general bonding strength is 6 N/cm or more, it is considered to be very practical. In the comparison between Example 2 and Example 3, Example 2 in which the content of the polyester urethane resin was more than that of Example 3 was excellent in the connection strength after the high-temperature and high-humidity treatment.
相對於此，不具有酯鍵，以及玻璃轉移溫度為低至- 30℃之聚胺基甲酸酯樹脂之比較例4，於高溫高濕處理後之連接電阻大幅上昇。並且，比較例4雖於使用FPC1之連接構造，顯示比較良好的黏合強度，但於使用FPC2之連接構造，高溫高濕處理後之黏合強度大幅降低。比較例1至3中任一種之黏合強度皆為約6N/cm以下，至少就黏合強度上，並未顯示足以實用之特性。In contrast, there is no ester bond, and the glass transition temperature is as low as - In Comparative Example 4 of a 30 ° C polyurethane resin, the connection resistance after the high temperature and high humidity treatment was greatly increased. Further, in Comparative Example 4, although the connection structure of FPC1 was used, a relatively good adhesive strength was exhibited, but the bonding strength of the FPC2 was used, and the bonding strength after the high-temperature and high-humidity treatment was greatly lowered. The adhesive strength of any of Comparative Examples 1 to 3 was about 6 N/cm or less, and at least the adhesive strength did not exhibit sufficient practical properties.
1‧‧‧薄膜狀之電路連接材料1‧‧‧film-like circuit connecting materials
1a‧‧‧電路連接構件1a‧‧‧Circuit connection components
5‧‧‧導電性粒子5‧‧‧Electrical particles
10‧‧‧第1電路構件10‧‧‧1st circuit component
11‧‧‧第1基板11‧‧‧1st substrate
12‧‧‧黏合劑層12‧‧‧Binder layer
13‧‧‧第1電路電極13‧‧‧1st circuit electrode
20‧‧‧第2電路構件20‧‧‧2nd circuit component
21‧‧‧第2基板21‧‧‧2nd substrate
23‧‧‧第2電路電極23‧‧‧2nd circuit electrode
101‧‧‧電路構件之連接構造101‧‧‧ Connection structure of circuit components
102‧‧‧電路構件之連接構造102‧‧‧Connection structure of circuit components
〔圖1〕表示依據本發明之薄膜狀電路連接材料之一種實施形態之斷面圖。Fig. 1 is a cross-sectional view showing an embodiment of a film-like circuit connecting material according to the present invention.
〔圖2〕表示依據本發明之電路構件之連接構造之一種實施形態之斷面圖。Fig. 2 is a cross-sectional view showing an embodiment of a connection structure of a circuit member according to the present invention.
〔圖3〕表示依據本發明之電路構件之連接構造之其他實施形態之斷面圖。Fig. 3 is a cross-sectional view showing another embodiment of a connection structure of a circuit member according to the present invention.
1‧‧‧薄膜狀之電路連接材料1‧‧‧film-like circuit connecting materials
3‧‧‧樹脂組成物層3‧‧‧ resin composition layer
5‧‧‧導電性粒子5‧‧‧Electrical particles
Claims (16)
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| TW99104909A TWI412305B (en) | 2006-07-28 | 2006-07-28 | A circuit connection material, a connection structure of a circuit component, and a connection method of a circuit component |
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| TW99104909A TWI412305B (en) | 2006-07-28 | 2006-07-28 | A circuit connection material, a connection structure of a circuit component, and a connection method of a circuit component |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW480278B (en) * | 1997-10-20 | 2002-03-21 | Toyo Boseki | Adhesive resin composition and adhesive film |
| TW200538526A (en) * | 1999-08-25 | 2005-12-01 | Hitachi Chemical Co Ltd | Wiring-connecting material and wiring-connected board production process using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW480278B (en) * | 1997-10-20 | 2002-03-21 | Toyo Boseki | Adhesive resin composition and adhesive film |
| TW200538526A (en) * | 1999-08-25 | 2005-12-01 | Hitachi Chemical Co Ltd | Wiring-connecting material and wiring-connected board production process using the same |
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| TW201034533A (en) | 2010-09-16 |
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