JP2008252098A - Method of manufacturing circuit board apparatus - Google Patents
Method of manufacturing circuit board apparatus Download PDFInfo
- Publication number
- JP2008252098A JP2008252098A JP2008092915A JP2008092915A JP2008252098A JP 2008252098 A JP2008252098 A JP 2008252098A JP 2008092915 A JP2008092915 A JP 2008092915A JP 2008092915 A JP2008092915 A JP 2008092915A JP 2008252098 A JP2008252098 A JP 2008252098A
- Authority
- JP
- Japan
- Prior art keywords
- circuit
- connection
- heating
- light irradiation
- connection terminal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Wire Bonding (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Combinations Of Printed Boards (AREA)
Abstract
Description
本発明は光硬化成分と導電性粒子を含有する回路接続材料を用いて相対峙する電極同士が電気的に接続された回路板装置の製造法に関する。 The present invention relates to a method for manufacturing a circuit board device in which electrodes facing each other are electrically connected using a circuit connecting material containing a photocuring component and conductive particles.
フィルム状回路接続材料は、金属粒子等の導電性粒子を所定量含有した接着剤からなるもので、このフィルム状回路接続材料を電子部品と電極や回路の間に設け、加圧または加熱加圧を行うことによって、両者の電極同士が電気的に接続されると共に、隣接電極間の絶縁性を付与して、電子部品と回路とが接着固定されるものである。フィルム状回路接続材料に用いられる接着剤としては、スチレン系やポリエステル系等の熱可塑性物質や、エポキシ系やシリコーン系等の熱硬化性物質が知られている。これらの物質を含む接着剤を硬化させるには硬化剤が必要であり、さらにその硬化剤には、フィルム状回路接続材料の保存安定性を高めるために、常温では不活性であり、活性温度以上でのみ反応するという潜在性が伴っていなければならない。このため接着剤を硬化させるためには、樹脂成分の流動性の向上および硬化反応の促進のための加熱加圧が必要となる。すなわち、接着剤を溶融、流動させ、導電性粒子を変形して回路との接触面積を増大し、かつ回路部材との密着性を高めるために温度や圧力が必要となり、これらは接着剤の種類や硬化成分による。この他にフィルム状以外の形態を有する回路接続材料としては、光硬化性樹脂を用いたペースト状材料が知られているが、これらの回路接続材料は加圧もしくは加熱加圧によって回路部材を接続し、その後光照射によって接着剤を硬化させることを特徴としている。 The film-like circuit connection material is made of an adhesive containing a predetermined amount of conductive particles such as metal particles. This film-like circuit connection material is provided between an electronic component and an electrode or circuit, and is pressurized or heated and pressurized. By performing the above, both electrodes are electrically connected to each other, and insulation between adjacent electrodes is imparted, so that the electronic component and the circuit are bonded and fixed. As adhesives used for the film-like circuit connecting material, thermoplastic materials such as styrene and polyester, and thermosetting materials such as epoxy and silicone are known. In order to cure the adhesive containing these substances, a curing agent is required. Further, the curing agent is inactive at room temperature and is higher than the activation temperature in order to enhance the storage stability of the film-like circuit connecting material. It must be accompanied by the potential to react only with. For this reason, in order to cure the adhesive, it is necessary to apply heat and pressure to improve the fluidity of the resin component and accelerate the curing reaction. That is, the temperature and pressure are required to melt and flow the adhesive, deform the conductive particles to increase the contact area with the circuit, and improve the adhesion to the circuit member. Depending on the curing component. In addition, paste materials using photo-curing resins are known as circuit connection materials having forms other than film-like, but these circuit connection materials connect circuit members by pressurization or heating and pressurization. The adhesive is then cured by light irradiation.
しかしながら、樹脂硬化の際の加熱加圧に伴う回路部材に対する熱や圧力の影響はその大小を問わず存在し、特に熱的な影響に関しては、回路部材自体への影響のみならず、回路部材接続時の影響も大きい。すなわち前者の場合、例えば液晶パネル等の回路部材を接続する際、偏光板等液晶パネル自体に対する影響が懸念され、これによって従来より低温での接続、あるいは従来より短時間での接続が要求されている。また後者の場合、加熱加圧時の温度が高い条件で接続を行うと、対向する2つの回路部材が異なっておりそれぞれの熱膨張係数(α)の差が大きい場合には、回路の位置ずれが発生する可能性が高い。これは隣接回路間のピッチが狭くなるにつれてさらに発生確率が高くなる。本発明は、光照射を併用することによって従来より低温での接続が可能で、回路部材に対する熱的影響を軽減し、かつ接続後における接続部の信頼性に優れ、さらには従来より有する簡便な取扱い性の品質に影響を与えないフィルム状回路接続材料を用い、相対峙する電極同士を電気的に接続することによって得られる回路板装置を提供するものである。 However, the effects of heat and pressure on the circuit members due to heating and pressurization during resin curing exist regardless of their size. Especially regarding the thermal effects, not only the effects on the circuit members themselves, but also the connection of the circuit members. The influence of time is also great. That is, in the former case, for example, when connecting circuit members such as a liquid crystal panel, there is a concern about the influence on the liquid crystal panel itself such as a polarizing plate, thereby requiring a connection at a lower temperature than in the past or a connection in a shorter time than in the past. Yes. In the latter case, if the connection is performed under a condition where the temperature at the time of heating and pressurization is high, the two circuit members facing each other are different, and if the difference between the respective thermal expansion coefficients (α) is large, the circuit position shifts. Is likely to occur. This is more likely to occur as the pitch between adjacent circuits becomes narrower. The present invention enables connection at a lower temperature than in the past by using light irradiation in combination, reduces the thermal influence on the circuit member, is excellent in reliability of the connection part after connection, and has a simpler than in the past. The present invention provides a circuit board device obtained by electrically connecting electrodes facing each other using a film-like circuit connecting material that does not affect the quality of handleability.
本発明は、少なくとも一方が光透過性を有する2つの回路部材、すなわち第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に、(1)ラジカル重合性物質、(2)光照射によって活性ラジカルを発生する化合物、(3)導電性粒子を必須とする回路接続材料であって、示差走査熱量測定(DSC)における発熱ピーク温度が110〜150℃である回路接続材料を介在させ、一定時間の加熱加圧および一定時間の光照射を併用することによって、前記対向配置した第一の接続端子と第二の接続端子を電気的に接続させることを特徴とするものである。また、一定時間の加熱加圧の開始後、所定間隔経過後に一定時間の光照射を開始し、光照射が行なわれている間は加熱加圧状態が保持されていることを特徴とするものである。 According to the present invention, at least one of two circuit members having light transparency, that is, a first circuit member having a first connection terminal, and a second circuit member having a second connection terminal, A connection terminal and a second connection terminal are arranged to face each other, and (1) a radical polymerizable substance and (2) an active radical by light irradiation between the first connection terminal and the second connection terminal arranged to face each other. (3) a circuit connecting material that requires conductive particles, and a circuit connecting material having an exothermic peak temperature of 110 to 150 ° C. in differential scanning calorimetry (DSC) is interposed for a certain period of time. By using heating and pressurization and light irradiation for a predetermined time in combination, the first connection terminal and the second connection terminal arranged to face each other are electrically connected. In addition, after the start of heating and pressurization for a fixed time, light irradiation for a fixed time is started after a predetermined interval has elapsed, and the heat and pressure state is maintained while the light irradiation is performed. is there.
本発明において、回路部材としては半導体チップ、抵抗体チップ、コンデンサチップ等のチップ部品、プリント基板等の基板、ポリイミドやポリエステルを基材としたフレキシブル配線板、液晶パネル等ガラス上に酸化インジウム(ITO)やクロム等で配線した透明電極等が用いられる。半導体チップや基板の電極パッド上には、めっきで形成されるバンプや金ワイヤの先端をトーチ等により溶融させ、金ボールを形成し、このボールを電極パッド上に圧着した後、ワイヤを切断して得られるワイヤバンプ等の特記電極を設け、接続端子として用いることができる。 In the present invention, as circuit members, chip parts such as semiconductor chips, resistor chips, capacitor chips, substrates such as printed boards, flexible wiring boards based on polyimide and polyester, indium oxide (ITO) on glass such as liquid crystal panels ) Or a transparent electrode wired with chromium or the like. On the electrode pad of the semiconductor chip or substrate, the bump formed by plating or the tip of the gold wire is melted with a torch or the like to form a gold ball, and after the ball is pressed onto the electrode pad, the wire is cut. Special electrodes such as wire bumps obtained in this way can be provided and used as connection terminals.
これらの回路部材には接続端子が通常は多数(場合によっては単数でも良い)設けられており、少なくとも一方が光透過性を有する前記回路部材の少なくとも1組を、それらの回路部材に設けられた接続端子の少なくとも1部を対向配置し、対向配置した接続端子間に接着剤を介在させ、加熱加圧および光照射して対向配置した接続端子同士を電気的に接続して接続体とする。この時、光透過性を有する回路部材の厚みは、1.2mm以下が光透過性の面で好ましい。また、ラジカル重合性物質を含有する回路接続材料の形態をフィルム状とすることで、従来のペースト状回路接続材料に比べて取扱い性が優れている点や接続厚みの均一化が図れる点等で有利である。さらに、回路部材との密着性を高めるために、硬化反応がほとんど進行せず樹脂が流動する程度の加熱を行う場合、接続材料の加熱を行って接続端子−導電性粒子−接続端子間の導通を確保した後、冷却工程を導入することによって接続材料の溶融粘度を再上昇させることが可能であり、これによって加熱−冷却のみによる導電性粒子の圧接状態を維持し樹脂の固定が図れる。 These circuit members are usually provided with a large number of connection terminals (or a single connection terminal in some cases), and at least one of the circuit members having light transparency is provided on those circuit members. At least one part of the connection terminals is arranged oppositely, an adhesive is interposed between the oppositely arranged connection terminals, and the connection terminals arranged opposite to each other by heating and pressurizing and irradiating light are electrically connected to form a connection body. At this time, the thickness of the light transmissive circuit member is preferably 1.2 mm or less in terms of light transmissive property. In addition, by making the circuit connection material containing the radical polymerizable substance into a film form, it is easier to handle than the conventional paste-like circuit connection material, and the connection thickness can be made uniform. It is advantageous. Furthermore, in order to improve the adhesiveness with the circuit member, when heating is performed to such an extent that the curing reaction hardly proceeds and the resin flows, conduction between the connection terminal-conductive particle-connection terminal is performed by heating the connection material. It is possible to re-increase the melt viscosity of the connection material by introducing a cooling step after securing the above, whereby the pressure contact state of the conductive particles only by heating and cooling can be maintained and the resin can be fixed.
本発明では、第一の接続端子と第二の接続端子とを対向配置し、その間に(1)ラジカル重合性物質、(2)光照射によって活性ラジカルを発生する化合物、(3)導電性粒子の各成分を必須成分とする回路接続材料を介在させ、加熱加圧および光照射によって前記対向配置した第一の接続端子と第二の接続端子を電気的に接続させる。フィルム状回路接続材料の硬化は主として光硬化によって行なわれるために、加熱加圧工程の役割としては、接着剤を溶融、流動させ、接続端子と導電性粒子が接触する部分周辺の樹脂成分を十分に排除し、接続端子間に導電性粒子を充分に圧接させることである、と考えることができる。このため接着剤のTg以上、もしくは導電性粒子の十分な変形に必要な接着剤の流動が得られる温度まで加熱すればよく、その温度はフィルム形成材料である高分子樹脂の種類にもよるが、概ね80〜140℃の範囲内である。これは従来の熱硬化性樹脂を硬化成分として用いているフィルム状回路接続材料の接続に必要な加熱温度である150〜190℃よりも低い。したがって上記方法によって回路部材の接続温度の低温化を図ることができる。また、示差走査熱量測定(DSC)における接着剤成分の発熱ピーク温度を110〜150℃とすることによって、前記した接着剤の溶融、流動する際に与える温度を接着剤成分、特に光照射によって活性ラジカル発生物質を熱的に活性にする温度に利用することが可能である。したがって、光硬化単独の場合と比較して、熱的効果によって反応系全体がより活性になり、接着剤の硬化特性がより向上することが期待される。しかし、DSC発熱ピーク温度が110℃より低い場合は、温度によるポットライフ(可使時間)が短くなることから注意を要する。これらの示差走査熱量測定は、例えばTAインスツルメンツ(株)製910型DSCを用い、試料重量1〜10mg、昇温速度10℃/min、温度範囲25〜300℃の各条件で測定することが可能である。 In the present invention, the first connection terminal and the second connection terminal are arranged to face each other, and (1) a radical polymerizable substance, (2) a compound that generates an active radical by light irradiation, and (3) conductive particles. A circuit connection material having each of the above components as an essential component is interposed, and the first connection terminal and the second connection terminal that are arranged to face each other are electrically connected by heating and pressurization and light irradiation. Since the curing of the film-like circuit connection material is mainly carried out by photocuring, the role of the heating and pressurizing step is to melt and flow the adhesive so that the resin component around the part where the connection terminals and the conductive particles are in contact is sufficient. It can be considered that the conductive particles are sufficiently pressed between the connection terminals. For this reason, it may be heated to Tg of the adhesive or a temperature at which the flow of the adhesive necessary for sufficient deformation of the conductive particles can be obtained, and the temperature depends on the type of polymer resin that is a film forming material. The temperature is generally within the range of 80 to 140 ° C. This is lower than 150 to 190 ° C., which is a heating temperature necessary for connection of a film-like circuit connecting material using a conventional thermosetting resin as a curing component. Therefore, the connection temperature of the circuit member can be lowered by the above method. Further, by setting the exothermic peak temperature of the adhesive component in differential scanning calorimetry (DSC) to 110 to 150 ° C., the temperature given when the adhesive melts and flows is activated by the adhesive component, particularly by light irradiation. It can be used at a temperature at which the radical generator is thermally activated. Therefore, compared to the case of photocuring alone, the entire reaction system becomes more active due to the thermal effect, and it is expected that the curing properties of the adhesive are further improved. However, when the DSC exothermic peak temperature is lower than 110 ° C., the pot life (potential time) depending on the temperature is shortened. These differential scanning calorimetry can be measured, for example, under the conditions of a sample weight of 1 to 10 mg, a heating rate of 10 ° C./min, and a temperature range of 25 to 300 ° C. using a TA Instruments 910 DSC. It is.
また(1)ラジカル重合性物質、(2)光照射によって活性ラジカルを発生する化合物、(3)導電性粒子を必須成分に、フィルム形成能を有する高分子樹脂をさらに配合分散することによって、光硬化が可能なフィルム状の回路接続材料を提供することが可能である。これは、用いる高分子樹脂は分子量が10,000以上であって常温で固形であり、フィルム形成能力が高いことに起因している。この高分子樹脂とラジカル重合性物質を混合することによって、従来の、光硬化性樹脂を用いた回路接続材料の短所であった、取扱い性の向上や接続厚みの均一化等を図ることが可能である。 In addition, (1) a radical polymerizable substance, (2) a compound that generates active radicals upon irradiation with light, and (3) a conductive resin is an essential component, and a polymer resin having film-forming ability is further blended and dispersed to produce light. It is possible to provide a film-like circuit connecting material that can be cured. This is because the polymer resin used has a molecular weight of 10,000 or more, is solid at room temperature, and has a high film forming ability. By mixing this polymer resin and radically polymerizable substance, it is possible to improve the handleability and make the connection thickness uniform, which is a disadvantage of conventional circuit connection materials using photo-curing resin. It is.
さらには、加熱加圧と光照射を同時に行う場合は、接着剤の流動によって導電性粒子の接触を十分に行うために、溶融流動性と光照射能力との調整が必要である。ここでいう光照射能力は、用いる光照射装置の光源に依存しており、光量の少ない光源を使用している光照射装置の場合には、接着剤の硬化速度が遅くなり、その間に樹脂流動が十分に行なわれるため、加熱加圧と光照射を全く同時に行うことができる。また光量の多い光源を使用している光照射装置の場合には、樹脂流動を優先させるために加熱加圧工程と光照射工程の間に1〜数秒の間隔を設け、加熱加圧開始後に光照射を行うこともできる。この場合光照射を遅延して行うため、樹脂が流動し導電性粒子による接続端子の導通が確保された後、光量を増加して短時間で急速に硬化させてもよい。 Furthermore, when performing heating and pressurization and light irradiation at the same time, it is necessary to adjust the melt fluidity and the light irradiation ability in order to sufficiently contact the conductive particles by the flow of the adhesive. The light irradiation capability here depends on the light source of the light irradiation device to be used, and in the case of a light irradiation device using a light source with a small amount of light, the curing rate of the adhesive is slowed, Therefore, heating and pressurization and light irradiation can be performed at the same time. In the case of a light irradiation device using a light source with a large amount of light, an interval of 1 to several seconds is provided between the heating and pressurizing step and the light irradiation step in order to prioritize resin flow, and light is emitted after the start of heating and pressing. Irradiation can also be performed. In this case, since the light irradiation is delayed, after the resin flows and the conduction of the connection terminal by the conductive particles is ensured, the amount of light may be increased to rapidly cure in a short time.
一定時間の加熱加圧および一定時間の光照射を行う際の順序に関しては、前述した様に溶融流動性と光照射能力との調整を行い、加熱加圧と光照射を同時に開始し同時に終了するのが、その所要時間を考えると最も理想的であるが、より優れた接続信頼性を確実に得るには、加熱加圧工程と光照射工程との間に適当な間隔を設け、接着剤樹脂が十分に流動するための時間を確保する方法が最適である。設ける間隔は加熱加圧を開始し、接着剤樹脂の流動がほぼ完全に終了するまでの時間とするのが理想的であり、この場合0.5〜10秒とするのが好ましいが、加熱加圧時間および接着剤樹脂の溶融粘度の点から2〜5秒とすることがより好ましい。 Regarding the order of heating and pressing for a certain period of time and light irradiation for a certain period of time, as described above, the melt fluidity and the light irradiation ability are adjusted, and the heating and pressurization and the light irradiation are started and ended simultaneously. However, in view of the time required, it is most ideal, but in order to ensure better connection reliability, an appropriate interval is provided between the heating and pressurizing process and the light irradiation process. The method of ensuring the time for sufficient flow is optimal. It is ideal to set the interval between heating and pressurization and the time until the flow of the adhesive resin is almost completely completed. In this case, it is preferably 0.5 to 10 seconds. The pressure time and the melt viscosity of the adhesive resin are more preferably 2 to 5 seconds.
本発明によれば、接着剤にラジカル重合性物質をおよび導電性粒子を必須成分とするフィルム状回路接続材料を介在させ、加熱加圧と同時に、あるいは加熱加圧後に光照射によって回路部材を接続するため、接続に要する温度を従来より低くすることが可能で、また熱的にも活性な光開始剤を含有することによって、より効率的に優れた接着強度や良好な電気的導通を得ることができ、優れた信頼性を有する回路板装置を得ることができる。 According to the present invention, a film-like circuit connecting material containing a radically polymerizable substance and conductive particles as essential components is interposed in an adhesive, and circuit members are connected by light irradiation simultaneously with heating or pressing. Therefore, it is possible to lower the temperature required for connection than before, and by obtaining a thermally active photoinitiator, it is possible to obtain better adhesive strength and good electrical continuity more efficiently. Thus, a circuit board device having excellent reliability can be obtained.
本発明に用いる回路接続材料としては(1)ラジカル重合性物質および(2)光照射によって活性ラジカルを発生する化合物から成る光硬化成分を必須とする接着剤成分、そして(3)導電性粒子から成っており、さらにフィルム形成能を有する高分子樹脂を含有させ、接続材料をフィルム状とすることで回路部材接続時の取扱い性の向上を図ることができる。 The circuit connection material used in the present invention includes (1) a radically polymerizable substance and (2) an adhesive component essentially comprising a photocuring component comprising a compound that generates active radicals upon irradiation with light, and (3) from conductive particles. Furthermore, the polymer resin which has film-forming ability is further contained, and the connection material can be made into a film shape to improve the handleability when connecting circuit members.
本発明に用いるラジカル重合性物質としては、エポキシアクリレートオリゴマー、ウレタンアクリレートオリゴマー、ポリエーテルアクリレートオリゴマー、ポリエステルアクリレートオリゴマー等の光重合性オリゴマー、トリメチロールプロパントリアクリレート、ポリエチレングリコールジアクリレート、ポリアルキレングリコールジアクリレート、ペンタエリスリトールアクリレート2−シアノエチルアクリレート、シクロヘキシルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニロキシエチルアクリレート、2(2−エトキシエトキシ)エチルアクリレート、2−エトキシエチルアクリレート、2−エチルヘキシルアクリレート、n−ヘキシルアクリレート、2ーヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、イソボルニルアクリレート、イソデシルアクリレート、イソオクチルアクリレート、n−ラウリルアクリレート、2−メトキシエチルアクリレート、2−フェノキシエチルアクリレート、テトラヒドロフルフリールアクリレート、ネオペンチルグリコールジアクリレート、ジペンタエリスリトールヘキサアクリレート等の光重合性単官能および多官能アクリレートモノマー等といったアクリル酸エステル等、およびこれらと類似したtーブチルアミノエチルメタクリレート、シクロヘキシルメタクリレート、ジシクロペンテニロキシエチルメタクリレート、2-ヒドロキシエチルメタクリレート、イソボルニルメタクリレート、イソデシルメタクリレート、n−ラウリルアクリレート、ステアリルメタクリレート、トリデシルメタクリレート、グリシジルメタクリレート等の光重合性単官能および多官能メタクリレートモノマーといったメタクリル酸エステル等に代表される光重合型の樹脂があり、必要に応じてこれらの樹脂を単独あるいは混合して用いてもよいが、接着剤硬化物の硬化収縮を抑制し、柔軟性を与えるためにはウレタンアクリレートオリゴマーを配合するのが好ましい。また上述した光重合性オリゴマーは高粘度であるために、粘度調整のために低粘度の光重合性多官能アクリレートモノマー等のモノマーを配合するのが好ましいが、その際には所望の接着剤特性を得るために1種あるいは2種類以上を混合して用いてもよい。 Examples of the radical polymerizable substance used in the present invention include photopolymerizable oligomers such as epoxy acrylate oligomers, urethane acrylate oligomers, polyether acrylate oligomers, and polyester acrylate oligomers, trimethylolpropane triacrylate, polyethylene glycol diacrylate, and polyalkylene glycol diacrylate. , Pentaerythritol acrylate 2-cyanoethyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2 (2-ethoxyethoxy) ethyl acrylate, 2-ethoxyethyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate 2-hydroxyethyl acrylate, hydroxypro Acrylate, isobornyl acrylate, isodecyl acrylate, isooctyl acrylate, n-lauryl acrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofurfryl acrylate, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate Acrylic esters such as photopolymerizable monofunctional and polyfunctional acrylate monomers, etc., and similar tert-butylaminoethyl methacrylate, cyclohexyl methacrylate, dicyclopentenyloxyethyl methacrylate, 2-hydroxyethyl methacrylate, isobol Nyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, stearyl methacrylate, tridecyl There are photopolymerization resins typified by methacrylic acid esters such as photopolymerizable monofunctional and polyfunctional methacrylate monomers such as methacrylate and glycidyl methacrylate, and these resins may be used alone or in combination as required. However, in order to suppress the curing shrinkage of the cured adhesive and give flexibility, it is preferable to add a urethane acrylate oligomer. In addition, since the above-mentioned photopolymerizable oligomer has a high viscosity, it is preferable to blend a monomer such as a low-viscosity polyfunctional acrylate monomer for adjusting the viscosity. In order to obtain 1 type, you may use 1 type or in mixture of 2 or more types.
これらのラジカル重合性物質は光照射によって活性ラジカルを発生する化合物を用いて重合、硬化させる。本発明に用いる光開始剤としてはベンゾインエチルエーテル、イソプロピルベンゾインエーテル等のベンゾインエーテル、ベンジル、ヒドロキシシクロヘキシルフェニルケトン等のベンジルケタール、ベンゾフェノン、アセトフェノン等のケトン類およびその誘導体、チオキサントン類、ビスイミダゾール類等があり、これらの光開始剤に必要に応じてアミン類、イオウ化合物、リン化合物等の増感剤を任意の比で添加してもよい。この際、用いる光源の波長や所望の硬化特性等に応じて最適な光開始剤を選択する必要がある。本発明に用いるフィルム形成能を有する高分子樹脂としては、含有した場合の取扱い性がよく硬化時の応力緩和に優れるものが好ましく、水酸基等の官能基を有する場合には被着体との接着性が向上するためより好ましい。各ポリマーをラジカル重合性の官能基で変性したものがより好ましい。これらポリマーの分子量は10000以上が好ましいが1000000以上になると混合性が悪くなる。また、これらのラジカル重合性物質とポリスチレン、ポリエチレン、ポリビニルブチラール、ポリビニルホルマール、ポリイミド、ポリアミド、ポリエステル、ポリ塩化ビニル、ポリフェニレンオキサイド、尿素樹脂、メラミン樹脂、フェノール樹脂、キシレン樹脂、エポキシ樹脂、ポリイソシアネート樹脂、フェノキシ樹脂等があり、これらを1種あるいは2種類以上を混合して用いることができる。また、被着体が無機物の場合にはシランカップリング剤を接着剤樹脂に混合して被着体との接着強度を高めることが可能である。シランカップリング剤としてはビニルトリクロルシラン、ビニルトリエトキシシラン、ビニル−トリス−(βメトキシエトキシ)シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、β−(3,4エポキシシクロヘキシル)エチルトリメトキシシラン、イソシアン酸プロピルトリエトキシシラン等があるが、ラジカル重合性物質との反応性を高めるにはγ−メタクリロキシプロピルトリメトキシシランを用いるのがより好ましい。 These radically polymerizable substances are polymerized and cured using a compound that generates active radicals upon irradiation with light. Photoinitiators used in the present invention include benzoin ethers such as benzoin ethyl ether and isopropyl benzoin ether, benzyl ketals such as benzyl and hydroxycyclohexyl phenyl ketone, ketones such as benzophenone and acetophenone and derivatives thereof, thioxanthones, and bisimidazoles Sensitizers such as amines, sulfur compounds and phosphorus compounds may be added to these photoinitiators in any ratio as necessary. At this time, it is necessary to select an optimal photoinitiator according to the wavelength of the light source to be used, desired curing characteristics, and the like. The polymer resin having film-forming ability used in the present invention preferably has good handleability when contained and is excellent in stress relaxation during curing, and adheres to an adherend when it has a functional group such as a hydroxyl group. It is more preferable because of improved properties. What modified each polymer with the radically polymerizable functional group is more preferable. The molecular weight of these polymers is preferably 10,000 or more, but if they are 1,000,000 or more, the mixing property is deteriorated. In addition, these radical polymerizable substances and polystyrene, polyethylene, polyvinyl butyral, polyvinyl formal, polyimide, polyamide, polyester, polyvinyl chloride, polyphenylene oxide, urea resin, melamine resin, phenol resin, xylene resin, epoxy resin, polyisocyanate resin There are phenoxy resins and the like, and these can be used alone or in combination of two or more. Further, when the adherend is an inorganic substance, it is possible to increase the adhesive strength with the adherend by mixing a silane coupling agent with the adhesive resin. Examples of silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris- (βmethoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltri There are ethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, propyltriethoxysilane isocyanate, etc., but γ-methacryloxypropyltrimethoxysilane is used to increase the reactivity with the radical polymerizable substance. Is more preferable.
硬化に用いる光は、一般的に広く使用されている紫外線を用いることができ、水銀ランプ、メタルハライドランプ、無電極ランプ等で発生させることができる。また、硬化反応としてラジカル反応を用いた場合、酸素が反応禁止剤として作用するので、光照射の雰囲気中の酸素量はラジカル重合性物質の硬化に影響を与える。これはラジカル重合性物質、光開始剤、増感剤等の種類や濃度にも大きく左右されるので、個々の配合系で詳細に検討する必要がある。本発明に用いる導電性粒子としては、Au、Ag、Ni、Cu、はんだ等の金属粒子やカーボン等があり、これらおよび非導電性のガラス、セラミック、プラスチック等に前記した導通層を被覆等によって形成したものでもよい。プラスチックを核とした場合や熱溶融金属粒子の場合、加熱加圧によって変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。導電性粒子は、接着剤成分100体積部に対して、0.1〜30体積部の広範囲で用途によって使い分ける。過剰な導電性粒子による隣接回路の短絡等を防止するためには、0.2〜15体積部とするのがより好ましい。この時の導電性粒子の平均粒径は、その添加量にもよるが1〜15μmとするのがより好ましい。また導電性粒子の圧縮弾性率は、加熱加圧および光照射を中断した時に、接着剤の弾性による粒子の復元を抑制するために、1000〜10000MPaの範囲内とすることが好ましい。 The light used for curing can be ultraviolet light that is widely used in general, and can be generated by a mercury lamp, a metal halide lamp, an electrodeless lamp, or the like. In addition, when a radical reaction is used as the curing reaction, oxygen acts as a reaction inhibitor, so the amount of oxygen in the light irradiation atmosphere affects the curing of the radical polymerizable substance. This greatly depends on the types and concentrations of radical polymerizable substances, photoinitiators, sensitizers, and the like, and therefore needs to be examined in detail for each compounding system. As the conductive particles used in the present invention, there are metal particles such as Au, Ag, Ni, Cu, solder, carbon, etc., and these and non-conductive glass, ceramic, plastic, etc. are coated with the conductive layer described above. It may be formed. In the case of using plastic as a core or hot-melt metal particles, it is preferable because it has deformability by heating and pressurization, so that the contact area with the electrode is increased at the time of connection and reliability is improved. The conductive particles are selectively used in a wide range of 0.1 to 30 parts by volume with respect to 100 parts by volume of the adhesive component. In order to prevent an adjacent circuit from being short-circuited by excessive conductive particles, the amount is more preferably 0.2 to 15 parts by volume. The average particle size of the conductive particles at this time is more preferably 1 to 15 μm, although it depends on the amount of addition. Further, the compression elastic modulus of the conductive particles is preferably in the range of 1000 to 10,000 MPa in order to suppress the restoration of particles due to the elasticity of the adhesive when heating and pressurization and light irradiation are interrupted.
本発明には用途に応じて無機充填剤、有機充填剤、白色顔料、重合抑制剤、増感剤およびその組合せから選択される添加物を含有してもよい。その添加量としては接着剤樹脂成分100重量部に対して1〜100重量部が好ましいが、添加物の種類や性質が得られる回路板の信頼性に悪影響を及ぼす可能性がない、あるいは著しく低くなるような範囲内で用いる必要がある。 The present invention may contain an additive selected from an inorganic filler, an organic filler, a white pigment, a polymerization inhibitor, a sensitizer, and combinations thereof depending on the application. The addition amount is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the adhesive resin component, but there is no possibility of adversely affecting the reliability of the circuit board from which the kind and properties of the additive are obtained, or extremely low. It is necessary to use within such a range.
以下に、本発明を実施例に基づいて詳細に説明するが、本発明はこれに限定されるものではない。
実施例1
フェノキシ樹脂(ユニオンカーバイド株式会社製、商品名PKHC、平均分子量45,000)40gを、重量比でトルエン(沸点110.6℃、SP値8.90)/酢酸エチル(沸点77.1℃、SP値9.10)=50/50の混合溶剤60gに溶解して、固形分40%の溶液とした。ラジカル重合性物質は、エポキシアクリレートオリゴマー(新中村化学工業株式会社製、商品名NKオリゴEA−1020)およびアクリレートモノマー(新中村化学工業株式会社製、商品名NKエステルA−TMM−3L)を、3/1の重量比で用いた。光開始剤はビスイミダゾール型光開始剤(黒金化成製、2,2’−ビス(o−クロロフェニル)4,4’,5,5’−テトラフェニル1,2−ビイミダゾール)を用い、これに増感剤として4,4’−ビスジエチルアミノベンゾフェノン(保土ケ谷化学工業株式会社製、商品名EAB)を、光開始剤/増感剤=5/1となるように混合して用いた。またポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設け、このニッケル層の外側に、厚み0.02μmの金層を設け、平均粒径5μm、比重2.5の導電性粒子を作製した。固形重量比でフェノキシ樹脂50、ラジカル重合製物質50、光開始剤5、増感剤1となるように配合し、さらに導電性粒子を3体積%配合分散させ、厚み80μmのフッ素樹脂フィルムに塗工装置を用いて塗布し、70℃、10分の熱風乾燥によって接着剤層の厚みが20μmのフィルム状回路接続材料を得た。得られた接着剤成分のDSCにおける発熱ピーク温度は約130℃であった。上記製法によって得たフィルム状回路接続材料を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、紫外線照射併用型熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて130℃、2MPaで20秒間の加熱加圧およびITOガラス側からの紫外線照射を同時に行って幅2mmにわたり接続し、時間経過後圧力開放して、接続体を作製した。接着剤に照射される紫外線照射量は2.0J/cm2とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。
Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
Example 1
40 g of phenoxy resin (trade name PKHC, manufactured by Union Carbide Co., Ltd., average molecular weight 45,000) in weight ratio with toluene (boiling point 110.6 ° C., SP value 8.90) / ethyl acetate (boiling point 77.1 ° C., SP Value 9.10) = dissolved in 60 g of 50/50 mixed solvent to obtain a solution having a solid content of 40%. The radical polymerizable substance includes an epoxy acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK Oligo EA-1020) and an acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK Ester A-TMM-3L). It was used at a weight ratio of 3/1. As the photoinitiator, a bisimidazole type photoinitiator (manufactured by Kurogane Kasei Co., Ltd., 2,2′-bis (o-chlorophenyl) 4,4 ′, 5,5′-tetraphenyl1,2-biimidazole) is used. In addition, 4,4′-bisdiethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name EAB) was used as a sensitizer in a mixture so that the photoinitiator / sensitizer = 5/1. Further, a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided on the outside of the nickel layer. The conductivity is an average particle diameter of 5 μm and a specific gravity of 2.5. Particles were made. The phenoxy resin 50, the radical polymerization product 50, the photoinitiator 5 and the sensitizer 1 are blended in a solid weight ratio, and 3% by volume of conductive particles are further dispersed and coated on a fluororesin film having a thickness of 80 μm. The film-like circuit connecting material having an adhesive layer thickness of 20 μm was obtained by hot air drying at 70 ° C. for 10 minutes. The exothermic peak temperature in DSC of the obtained adhesive component was about 130 ° C. A flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm of indium oxide (ITO) using the film-like circuit connecting material obtained by the above manufacturing method Glass (thickness 1.1 mm, surface resistance 20 Ω / □) is used at 130 ° C. and 2 MPa for 20 seconds using an ultraviolet irradiation combined thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). The heating and pressurization and the ultraviolet irradiation from the ITO glass side were simultaneously performed to connect over a width of 2 mm, and the pressure was released after the lapse of time to prepare a connection body. The ultraviolet irradiation amount irradiated to the adhesive was 2.0 J / cm 2 . At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body.
実施例2
実施例1で使用したフィルム状回路接続材料を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、紫外線照射併用型熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて130℃、2MPaで20秒間の加熱加圧およびITOガラス側からの紫外線照射を同時に行って幅2mmにわたり接続し、時間経過後圧力開放して、接続体を作製した。接着剤に照射される紫外線照射量は2.0J/cm2とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。また20秒間の接続の際、加熱加圧のみを開始して3秒経過した後17秒間の紫外線照射を開始し、加熱加圧20秒後に2工程が同時に終了するようにした。
Example 2
A flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm and a thin film of 0.2 μm of indium oxide (ITO) using the film-like circuit connecting material used in Example 1. The layer-formed glass (thickness 1.1 mm, surface resistance 20Ω / □) is 20 at 130 ° C. and 2 MPa using an ultraviolet irradiation combined thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Second heating and pressurization and UV irradiation from the ITO glass side were performed simultaneously to connect over a width of 2 mm, and after a lapse of time, the pressure was released to prepare a connection body. The ultraviolet irradiation amount irradiated to the adhesive was 2.0 J / cm 2 . At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body. When connecting for 20 seconds, only heating and pressurization was started, and after 3 seconds had elapsed, ultraviolet irradiation was started for 17 seconds, and after 20 seconds of heating and pressurization, the two steps were completed simultaneously.
実施例3
実施例1で使用したフィルム状回路接続材料のラジカル重合性物質を、ウレタンアクリレートオリゴマー(新中村化学工業株式会社製、商品名NKオリゴUA−512)およびアクリレートモノマー(A−TMM−3L)に代えた他は、実施例2と同様にして接続体を作製した。
Example 3
The radically polymerizable substance of the film-like circuit connecting material used in Example 1 was replaced with a urethane acrylate oligomer (made by Shin-Nakamura Chemical Co., Ltd., trade name NK Oligo UA-512) and an acrylate monomer (A-TMM-3L). Otherwise, a connection body was fabricated in the same manner as in Example 2.
実施例4
実施例1で使用したフィルム状回路接続材料の導電性粒子を、平均粒径5μmのニッケル粒子(大同特殊綱株式会社製、商品名DSP3101、比重8.5)に代えた他は、実施例2と同様にして接続体を作製した。
Example 4
Example 2 except that the conductive particles of the film-like circuit connecting material used in Example 1 were replaced with nickel particles having an average particle diameter of 5 μm (trade name DSP3101, specific gravity 8.5, manufactured by Daido Special Tuna Co., Ltd.). A connected body was produced in the same manner as described above.
実施例5
実施例1で使用したフィルム状回路接続材料の光開始剤を、ベンゾフェノン誘導体(日本油脂株式会社製、商品名BTTB)に代えた他は、実施例2と同様にして接続体を作製した。得られた接着剤成分のDSCにおける発熱ピーク温度は約120℃であった。
Example 5
A connector was prepared in the same manner as in Example 2 except that the photoinitiator of the film-like circuit connecting material used in Example 1 was replaced with a benzophenone derivative (trade name BTTB manufactured by NOF Corporation). The exothermic peak temperature in DSC of the obtained adhesive component was about 120 ° C.
実施例6
フェノキシ樹脂(ユニオンカーバイド株式会社製、商品名PKHC、平均分子量45,000)40gを、重量比でトルエン(沸点110.6℃、SP値8.90)/酢酸エチル(沸点77.1℃、SP値9.10)=50/50の混合溶剤60gに溶解して、固形分40%の溶液とした。ラジカル重合性物質は、エポキシアクリレートオリゴマー(新中村化学工業株式会社製、商品名NKオリゴEA−1020)およびアクリレートモノマー(新中村化学工業株式会社製、商品名NKエステルA−TMM−3L)を、3/1の重量比で用いた。光開始剤はビスイミダゾール型光開始剤(黒金化成製、2,2’−ビス(o−クロロフェニル)4,4’,5,5’−テトラフェニル1,2−ビイミダゾール)を用い、これに増感剤として4,4’−ビスジエチルアミノベンゾフェノン(保土ケ谷化学工業株式会社製、商品名EAB)を、光開始剤/増感剤=5/1となるように混合して用いた。またポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設け、このニッケル層の外側に、厚み0.02μmの金層を設け、平均粒径5μm、比重2.5の導電性粒子を作製した。固形重量比でフェノキシ樹脂50、ラジカル重合製物質50、光開始剤5、増感剤1となるように配合し、さらに導電性粒子を3体積%、および無機充填剤(無水シリカ微粒子、1次粒子平均径約12nm)を5重量%配合分散し、、厚み80μmのフッ素樹脂フィルムに塗工装置を用いて塗布し、70℃、10分の熱風乾燥によって接着剤層の厚みが20μmのフィルム状回路接続材料を得た。上記製法によって得たフィルム状回路接続材料を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、紫外線照射併用型熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて130℃、2MPaで20秒間の加熱加圧およびITOガラス側からの紫外線照射を同時に行って幅2mmにわたり接続し、時間経過後圧力開放して、接続体を作製した。接着剤に照射される紫外線照射量は2.0J/cm2とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。また10秒間の接続の際、加熱加圧のみを開始して2秒経過した後8秒間の紫外線照射を開始し、加熱加圧10秒後に2工程が同時に終了するようにした。
Example 6
40 g of phenoxy resin (trade name PKHC, manufactured by Union Carbide Co., Ltd., average molecular weight 45,000) in weight ratio with toluene (boiling point 110.6 ° C., SP value 8.90) / ethyl acetate (boiling point 77.1 ° C., SP Value 9.10) = dissolved in 60 g of 50/50 mixed solvent to obtain a solution having a solid content of 40%. The radical polymerizable substance includes an epoxy acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK Oligo EA-1020) and an acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK Ester A-TMM-3L). It was used at a weight ratio of 3/1. As the photoinitiator, a bisimidazole type photoinitiator (manufactured by Kurogane Kasei Co., Ltd., 2,2′-bis (o-chlorophenyl) 4,4 ′, 5,5′-tetraphenyl1,2-biimidazole) is used. In addition, 4,4′-bisdiethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name EAB) was used as a sensitizer in a mixture so that the photoinitiator / sensitizer = 5/1. Further, a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided on the outside of the nickel layer. The conductivity is an average particle diameter of 5 μm and a specific gravity of 2.5. Particles were made. It is blended so that it becomes phenoxy resin 50, radical polymerization product 50, photoinitiator 5, and sensitizer 1 in a solid weight ratio, and further 3% by volume of conductive particles, and inorganic filler (anhydrous silica fine particles, primary particles). 5% by weight (average particle diameter of about 12 nm) is dispersed and applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, followed by drying with hot air at 70 ° C. for 10 minutes to form a film with a thickness of 20 μm. A circuit connection material was obtained. A flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm of indium oxide (ITO) using the film-like circuit connecting material obtained by the above manufacturing method Glass (thickness 1.1 mm, surface resistance 20 Ω / □) is used at 130 ° C. and 2 MPa for 20 seconds using an ultraviolet irradiation combined thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). The heating and pressurization and the ultraviolet irradiation from the ITO glass side were simultaneously performed to connect over a width of 2 mm, and the pressure was released after the lapse of time to prepare a connection body. The ultraviolet irradiation amount irradiated to the adhesive was 2.0 J / cm 2 . At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body. In addition, at the time of connection for 10 seconds, only heating and pressurization was started, and after 2 seconds had elapsed, ultraviolet irradiation was started for 8 seconds, and two steps were completed simultaneously after 10 seconds of heating and pressurization.
比較例1
実施例1で使用したフィルム状回路接続材料の光開始剤を、ベンゾインエチルエーテルに代えた他は、実施例2と同様にして接続体を作製した。得られた接着剤成分のDSCにおける発熱ピーク温度は約190℃であった。
Comparative Example 1
A connector was prepared in the same manner as in Example 2 except that the photoinitiator of the film-like circuit connecting material used in Example 1 was replaced with benzoin ethyl ether. The exothermic peak temperature in DSC of the obtained adhesive component was about 190 ° C.
比較例2
実施例1で使用したフィルム状回路接続材料を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、紫外線照射併用型熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて130℃、2MPaで10秒間の加熱加圧およびITOガラス側からの紫外線照射を同時に行って幅2mmにわたり接続し、時間経過後圧力開放して、接続体を作製した。紫外線照射量は5.0J/cm2とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。
Comparative Example 2
A flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm and a thin film of 0.2 μm of indium oxide (ITO) using the film-like circuit connecting material used in Example 1. The layer-formed glass (thickness 1.1 mm, surface resistance 20Ω / □) is 10 at 130 ° C. and 2 MPa using an ultraviolet irradiation combined thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Second heating and pressurization and ultraviolet irradiation from the ITO glass side were simultaneously performed to connect over a width of 2 mm, and after a lapse of time, the pressure was released to prepare a connection body. The ultraviolet irradiation amount was 5.0 J / cm 2 . At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body.
比較例3
実施例1で使用したフィルム状回路接続材料の配合樹脂であるフェノキシ樹脂と、マイクロカプセル型潜在性硬化剤を含有する液状エポキシ樹脂を、固形重量比でフェノキシ樹脂50、液状エポキシ樹脂50となるように配合し、さらに実施例1で用いた導電性粒子を3体積%配合分散させ、厚み80μmのフッ素樹脂フィルムに塗工装置を用いて塗布し、70℃、10分の熱風乾燥によって接着剤層の厚みが20μmのフィルム状回路接続材料を得た。上記製法によって得たフィルム状回路接続材料を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、コンスタントヒート型熱圧着装置(当社製)を用いて130℃、2MPaで20秒間加熱加圧して幅2mmにわたり接続し、時間経過後圧力開放して、これを接続終了とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。
Comparative Example 3
The phenoxy resin, which is a compounded resin of the film-like circuit connecting material used in Example 1, and the liquid epoxy resin containing the microcapsule-type latent curing agent are converted into the phenoxy resin 50 and the liquid epoxy resin 50 in a solid weight ratio. In addition, 3% by volume of the conductive particles used in Example 1 were mixed and dispersed, applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, and dried by hot air at 70 ° C. for 10 minutes. A film-like circuit connecting material having a thickness of 20 μm was obtained. A flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm of indium oxide (ITO) using the film-like circuit connecting material obtained by the above manufacturing method The glass (thickness 1.1 mm, surface resistance 20 Ω / □) formed was connected to a 2 mm width by heating and pressing at 130 ° C. and 2 MPa for 20 seconds using a constant heat type thermocompression bonding apparatus (manufactured by our company). After the elapse of time, the pressure was released, and this was terminated. At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body.
比較例4
ラジカル重合性物質は、エポキシアクリレートオリゴマー(新中村化学工業株式会社製、商品名NKオリゴEA−1020)およびアクリレートモノマー(新中村化学工業株式会社製、商品名NKエステルA−TMM−3L)を、3/1の重量比で用い、光開始剤にはビスイミダゾール型光開始剤(黒金化成製、2,2’−ビス(o−クロロフェニル)4,4’,5,5’−テトラフェニル1,2−ビイミダゾール)を用い、これに増感剤として4,4’−ビスジエチルアミノベンゾフェノン(保土ケ谷化学工業株式会社製、商品名EAB)を、光開始剤/増感剤=5/1となるように混合して用いた。また、ポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設け、このニッケル層の外側に、厚み0.02μmの金層を設け、平均粒径5μm、比重2.5の導電性粒子を作製した。これらを用い、固形重量比でラジカル重合性物質100、光開始剤5、増感剤1となるように配合し、さらに導電性粒子を3体積%配合分散させ、ペースト状回路接続材料を得た。上記製法によって得たペースト状回路接続材料を用いて、イン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、紫外線照射併用型熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて130℃、2MPaで20秒間の加熱加圧およびITOガラス側からの紫外線照射を同時に行って幅2mmにわたり接続し、時間経過後圧力開放して、接続体を作製した。接着剤に照射される紫外線照射量は2.0J/cm2とした。この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を貼り付けた後、70℃、0.5MPaで5秒間加熱加圧して仮接続し、その後、フッ素樹脂フィルムを剥離してもう一方の被着体であるFPCと接続した。また10秒間の接続の際、加熱加圧のみを開始して2秒経過した後8秒間の紫外線照射を開始し、加熱加圧10秒後に2工程が同時に終了するようにした。
Comparative Example 4
The radical polymerizable substance includes an epoxy acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK Oligo EA-1020) and an acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK Ester A-TMM-3L). The photoinitiator is a bisimidazole type photoinitiator (manufactured by Kurokin Kasei, 2,2′-bis (o-chlorophenyl) 4,4 ′, 5,5′-tetraphenyl 1). , 2-biimidazole), and 4,4′-bisdiethylaminobenzophenone (made by Hodogaya Chemical Co., Ltd., trade name EAB) as a sensitizer, photoinitiator / sensitizer = 5/1. Were used as mixed. In addition, a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a nucleus, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer, and a conductive material having an average particle diameter of 5 μm and a specific gravity of 2.5. Particles were prepared. Using these, they were blended so as to be a radically polymerizable substance 100, a photoinitiator 5, and a sensitizer 1 in a solid weight ratio, and further 3% by volume of conductive particles were mixed and dispersed to obtain a paste-like circuit connection material. . A flexible circuit board (FPC) having 500 copper circuits with an in width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm indium oxide (ITO) using the paste-like circuit connecting material obtained by the above-mentioned manufacturing method Glass (thickness 1.1 mm, surface resistance 20 Ω / □) is used at 130 ° C. and 2 MPa for 20 seconds using an ultraviolet irradiation combined thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). The heating and pressurization and the ultraviolet irradiation from the ITO glass side were simultaneously performed to connect over a width of 2 mm, and the pressure was released after the lapse of time to prepare a connection body. The ultraviolet irradiation amount irradiated to the adhesive was 2.0 J / cm 2 . At this time, after adhering the adhesive surface of the film-like circuit connecting material on the ITO glass in advance, the film is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off. It connected with FPC which is one to-be-adhered body. In addition, at the time of connection for 10 seconds, only heating and pressurization was started, and after 2 seconds had elapsed, ultraviolet irradiation was started for 8 seconds, and two steps were completed simultaneously after 10 seconds of heating and pressurization.
実施例1〜6、比較例1〜4で得た接続体について初期抵抗および接着性について評価した。初期抵抗については、回路部材の接続後、上記接続部を含むFPCの隣接回路間の抵抗値を、マルチメータで測定した。測定電流は1mAとし、抵抗値は隣接回路間の抵抗150点の平均(x+3σ)で示した。FPCならびにITOガラスに対する接着性については、接着強度をJIS−Z0237に準じて90度剥離法で測定し、評価した。測定装置は東洋ボールドウィン株式会社製テンシロンUTM−4(剥離速度50mm/min、25℃)を使用した。 The initial resistance and adhesiveness of the connectors obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated. Regarding the initial resistance, after connecting the circuit members, the resistance value between adjacent circuits of the FPC including the connection portion was measured with a multimeter. The measurement current was 1 mA, and the resistance value was shown as an average (x + 3σ) of 150 resistances between adjacent circuits. About the adhesiveness with respect to FPC and ITO glass, adhesive strength was measured and evaluated by the 90 degree | times peeling method according to JIS-Z0237. As a measuring device, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used.
加熱加圧と紫外線照射を同時に開始、終了している実施例1では、初期抵抗、接着強度のいずれも良好な値を示した。また実施例2の場合、20秒の加熱加圧、17秒の紫外線照射を3秒の間隔を設けて行っているため、接着剤樹脂が加熱によって十分に流動し、接続端子と導電性粒子との接触面積がより大きくなるため、特に初期抵抗に関して実施例1よりさらに良好な接続特性を有する回路板が得られた。さらに導電性粒子、ラジカル重合性物質、光開始剤を代えた実施例3〜5においても良好な接続状態の確保が可能であった。さらに無機充填剤を添加した実施例6の場合、無添加の場合とほぼ同等の良好な初期接着強度が得られたことから、充填剤による光硬化反応の阻害はほとんど起こらず、また耐湿信頼性試験処理後の接着強度においても、無機充填剤の応力緩和作用によって無添加の場合に比べて向上する。 In Example 1 in which heating and pressurization and ultraviolet irradiation were started and ended at the same time, both initial resistance and adhesive strength showed good values. In the case of Example 2, since heating and pressurization for 20 seconds and ultraviolet irradiation for 17 seconds are performed at intervals of 3 seconds, the adhesive resin flows sufficiently by heating, and the connection terminals, conductive particles, Thus, a circuit board having better connection characteristics than that of Example 1 was obtained particularly with respect to the initial resistance. Furthermore, in Examples 3 to 5 in which the conductive particles, the radical polymerizable substance, and the photoinitiator were replaced, it was possible to ensure a good connection state. Further, in the case of Example 6 in which an inorganic filler was added, good initial adhesive strength almost equal to that in the case of no addition was obtained, so that the photocuring reaction was hardly inhibited by the filler, and the moisture resistance reliability The adhesive strength after the test treatment is improved as compared with the case of no addition due to the stress relaxation action of the inorganic filler.
一方、光開始剤としてベンゾインエチルエーテルを用いた比較例1の場合、DSCにおける発熱ピーク温度が実施例1〜6に比べて高いため、硬化反応に及ぼす熱的効果がほとんどなく、実施例1〜6と比較して接着強度が低くなった。また光照射量5.0J/cm2の条件下で加熱加圧と紫外線照射を同時に行った比較例2では、接着剤の硬化反応が樹脂の流動よりも早く進行するため、導電性粒子が回路部材に十分に接触しておらず、導通不良となった。熱硬化性樹脂を主成分とした接着剤を用いている比較例3では、130℃、2MPa、20秒の接続条件では接着剤の反応率が低くなるため、十分な硬化が得られず、接着強度がかなり低くなり初期抵抗も高くなった。比較例4の場合には、フィルム形成性を付与する高分子樹脂が含有されていないために、硬化収縮が大きくなり、接着強度、特に耐湿信頼性試験処理後の接着強度が低くなった。 On the other hand, in the case of Comparative Example 1 using benzoin ethyl ether as a photoinitiator, since the exothermic peak temperature in DSC is higher than those in Examples 1 to 6, there is almost no thermal effect on the curing reaction. Compared with 6, the adhesive strength was low. In Comparative Example 2 in which heating and pressurization and ultraviolet irradiation were simultaneously performed under a light irradiation amount of 5.0 J / cm 2 , since the curing reaction of the adhesive proceeds faster than the flow of the resin, the conductive particles are in a circuit. Insufficient contact with the member resulted in poor conduction. In Comparative Example 3 using an adhesive mainly composed of a thermosetting resin, the reaction rate of the adhesive is low under the connection conditions of 130 ° C., 2 MPa, and 20 seconds, so that sufficient curing cannot be obtained. The strength decreased considerably and the initial resistance increased. In the case of Comparative Example 4, since the polymer resin imparting film-forming property was not contained, the curing shrinkage was increased, and the adhesive strength, particularly the adhesive strength after the moisture resistance reliability test treatment was lowered.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008092915A JP2008252098A (en) | 2008-03-31 | 2008-03-31 | Method of manufacturing circuit board apparatus |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008092915A JP2008252098A (en) | 2008-03-31 | 2008-03-31 | Method of manufacturing circuit board apparatus |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8516998A Division JPH11279500A (en) | 1998-03-31 | 1998-03-31 | Circuit-connecting material and production of circuit board device |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009201947A Division JP5000695B2 (en) | 2009-09-01 | 2009-09-01 | Circuit board device manufacturing method |
JP2009201946A Division JP2009290231A (en) | 2009-09-01 | 2009-09-01 | Method of manufacturing circuit board apparatus |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2008252098A true JP2008252098A (en) | 2008-10-16 |
Family
ID=39976615
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008092915A Pending JP2008252098A (en) | 2008-03-31 | 2008-03-31 | Method of manufacturing circuit board apparatus |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2008252098A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015167187A (en) * | 2014-03-04 | 2015-09-24 | 日立化成株式会社 | Electronic part manufacturing method and intermediate product of electronic part |
KR20160130977A (en) | 2014-03-11 | 2016-11-15 | 데쿠세리아루즈 가부시키가이샤 | Anisotropic conductive adhesive, method for producing connector and method for connecting electronic component |
KR20170056662A (en) | 2015-01-20 | 2017-05-23 | 데쿠세리아루즈 가부시키가이샤 | Method for producing connected body, method for connecting electronic component, and connected body |
JP2017134413A (en) * | 2017-03-31 | 2017-08-03 | 日東電工株式会社 | Polarizing film and production method of the same, optical film, and image display device |
US9937689B2 (en) | 2013-04-26 | 2018-04-10 | Nitto Denko Corporation | Polarizing film, method for manufacture thereof, optical film, and image display device |
JP2018074168A (en) * | 2017-11-24 | 2018-05-10 | 東洋インキScホールディングス株式会社 | Electromagnetic wave shield sheet and printed wiring board |
-
2008
- 2008-03-31 JP JP2008092915A patent/JP2008252098A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9937689B2 (en) | 2013-04-26 | 2018-04-10 | Nitto Denko Corporation | Polarizing film, method for manufacture thereof, optical film, and image display device |
JP2015167187A (en) * | 2014-03-04 | 2015-09-24 | 日立化成株式会社 | Electronic part manufacturing method and intermediate product of electronic part |
KR20160130977A (en) | 2014-03-11 | 2016-11-15 | 데쿠세리아루즈 가부시키가이샤 | Anisotropic conductive adhesive, method for producing connector and method for connecting electronic component |
KR20170056662A (en) | 2015-01-20 | 2017-05-23 | 데쿠세리아루즈 가부시키가이샤 | Method for producing connected body, method for connecting electronic component, and connected body |
JP2017134413A (en) * | 2017-03-31 | 2017-08-03 | 日東電工株式会社 | Polarizing film and production method of the same, optical film, and image display device |
JP2018074168A (en) * | 2017-11-24 | 2018-05-10 | 東洋インキScホールディングス株式会社 | Electromagnetic wave shield sheet and printed wiring board |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4469089B2 (en) | Film-like anisotropic conductive adhesive for circuit connection, electrode connection structure, and electrode connection method | |
CN101250386B (en) | Adhesive for electrode connection and connecting method using it | |
KR100875411B1 (en) | Low-temperature setting adhesive and anisotropically electroconductive adhesive film using the same | |
JP4304508B2 (en) | Adhesive composition, adhesive composition for circuit connection, connector and semiconductor device | |
CN1926675B (en) | Method for establishing anisotropic conductive connection and anisotropic conductive adhesive film | |
JP2009016133A (en) | Anisotropic conductive film and its manufacturing method, and joint | |
JP2008252098A (en) | Method of manufacturing circuit board apparatus | |
TW200946633A (en) | Conductive adhesive precursor, method of using the same, and article | |
JP6425899B2 (en) | ANISOTROPIC CONDUCTIVE ADHESIVE, METHOD FOR MANUFACTURING CONNECTION AND METHOD FOR CONNECTING ELECTRONIC COMPONENTS | |
JP2006173100A (en) | Method for connecting electrode | |
JPH1197482A (en) | Electrode connecting method and electrode connection structure | |
JP4907840B2 (en) | Anisotropic conductive film and circuit board using the same | |
JPH11279500A (en) | Circuit-connecting material and production of circuit board device | |
JP3871095B2 (en) | Circuit board device manufacturing method | |
JP5000695B2 (en) | Circuit board device manufacturing method | |
JP2009290231A (en) | Method of manufacturing circuit board apparatus | |
JP3759294B2 (en) | Electrode connection method | |
JP6046896B2 (en) | Film winding body and method for manufacturing film winding body | |
JP5111711B2 (en) | Adhesive composition, adhesive composition for circuit connection, and circuit connection method | |
JP2007009201A (en) | Electrode-connecting adhesive and connecting structure of fine electrode given by using the same | |
JP2002367692A (en) | Anisotropy conductive adhesive and connection structure using the same | |
JP2015109358A (en) | Method for manufacturing connection structure and anisotropic conductive film | |
JP4635312B2 (en) | Adhesive composition, circuit connection material, adhesive composition for circuit connection, connector and semiconductor device | |
JP2002167569A (en) | Adhesive composition, adhesive composition for connecting circuit, connected unit and semiconductor device | |
JP2016103634A (en) | Photo-curing anisotropic conductive adhesive material, method for manufacturing connection body, and method for connecting electronic part |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090310 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090511 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090602 |