WO2017145801A1 - Anisotropic conductive film - Google Patents

Anisotropic conductive film Download PDF

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Publication number
WO2017145801A1
WO2017145801A1 PCT/JP2017/004887 JP2017004887W WO2017145801A1 WO 2017145801 A1 WO2017145801 A1 WO 2017145801A1 JP 2017004887 W JP2017004887 W JP 2017004887W WO 2017145801 A1 WO2017145801 A1 WO 2017145801A1
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WO
WIPO (PCT)
Prior art keywords
anisotropic conductive
conductive film
anion
alicyclic epoxy
epoxy compound
Prior art date
Application number
PCT/JP2017/004887
Other languages
French (fr)
Japanese (ja)
Inventor
慎一 林
憲司 徳久
恵津子 山口
Original Assignee
デクセリアルズ株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2016096768A external-priority patent/JP6776609B2/en
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to KR1020187019787A priority Critical patent/KR102363322B1/en
Priority to CN201780010511.3A priority patent/CN108602970A/en
Priority to KR1020217013728A priority patent/KR102513546B1/en
Priority to KR1020247000952A priority patent/KR20240010091A/en
Priority to CN202410926871.XA priority patent/CN118791984A/en
Priority to KR1020237009590A priority patent/KR102624920B1/en
Priority to US16/071,858 priority patent/US10964440B2/en
Publication of WO2017145801A1 publication Critical patent/WO2017145801A1/en

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Definitions

  • the present invention relates to an anisotropic conductive film.
  • an anisotropic conductive film in which conductive particles are dispersed in an insulating binder composition containing a polymerizable compound has been widely used.
  • an anisotropic conductive film in order to achieve low temperature fast curability, an alicyclic epoxy compound having higher cationic polymerization reactivity than a general-purpose glycidyl ether compound is used as a polymerizable compound, It has been proposed to use a sulfonium salt thermal acid generator that generates protons by heat as a polymerization initiator that does not inhibit polymerization by oxygen and exhibits dark reactivity (Patent Documents 1 to 3).
  • Such a conventional anisotropic conductive film containing an alicyclic epoxy compound and a sulfonium salt-based thermal acid generator has a relatively low curing temperature (for example, about 100 ° C.).
  • the anisotropic conductive film as described above may be stored in a warehouse where air-conditioning is not provided, and there is a problem that the time from manufacture to actual use becomes long due to internationalization of commercial transactions. As a result, there are concerns about a decrease in storage stability (storage life) from the viewpoints of temporary sticking properties and indentations, and a decrease in connection reliability from the viewpoint of adhesion characteristics.
  • the problem of the present invention is that the cationic polymerizable anisotropic conductive film using the alicyclic epoxy compound has better storage than ever before while ensuring the same curing temperature and connection reliability as before. It is to be able to realize life.
  • the present inventor uses a low-polar oxetane compound in a specific ratio in addition to an alicyclic epoxy compound as a cationic polymerizable compound, and a quaternary quaternary polymerization initiator instead of a sulfonium salt-based thermal acid generator.
  • a quaternary quaternary polymerization initiator instead of a sulfonium salt-based thermal acid generator.
  • the present invention is an anisotropic conductive film containing a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles
  • a cationic polymerization initiator is a quaternary ammonium salt thermal acid generator
  • the cationic polymerizable component contains an alicyclic epoxy compound and a low polarity oxetane compound.
  • the present invention also provides a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected using the anisotropic conductive film described above.
  • the anisotropic conductive film of the present invention containing a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles is a quaternary ammonium as a cationic polymerization initiator.
  • a salt-based thermal acid generator is used, and an alicyclic epoxy compound and a low-polar oxetane compound are contained as a cationic polymerizable component. For this reason, while ensuring the same curing temperature and connection reliability as before, it is possible to realize better storage life than ever.
  • the anisotropic conductive film of the present invention contains a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles.
  • the binder composition containing and holding the conductive particles contains a film forming component and a cationic polymerizable component.
  • the film-forming component is a component used for forming an anisotropic conductive film into a film and is a component having film-forming ability.
  • the film forming component include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. The above can be used together. Among these, a phenoxy resin can be preferably used from the viewpoints of film formability, processability, and connection reliability.
  • the blending ratio of the film-forming component in the binder composition is preferably 10 to 70% by mass, more preferably 20 to 50% by mass. If it is this range, sufficient film formation ability can be exhibited.
  • the cationic polymerizable component is a component that cures the anisotropic conductive film and contains an alicyclic epoxy compound and a low-polar oxetane compound.
  • the blending amount of the cationically polymerizable component in the binder composition is preferably 10 to 80% by mass, more preferably 20 to 60% by mass. If it is this range, the binder composition which has a higher hardening rate can be given.
  • the reason for using the alicyclic epoxy compound is to impart good low-temperature rapid curability to the anisotropic conductive film by utilizing its reactivity higher than that of a general-purpose glycidyl ether type epoxy compound.
  • Preferred examples of such alicyclic epoxy compounds include those having two or more epoxy groups in the molecule. These may be liquid or solid. Specific examples include diglycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, diepoxybicyclohexyl and the like. Among these, diglycidyl hexahydrobisphenol A, particularly diepoxybicyclohexyl, can be preferably used from the viewpoint that the light transmittance of the cured product can be ensured and the fast curability is excellent.
  • a low polarity oxetane compound is used in combination with an alicyclic epoxy compound.
  • a low-polar oxetane compound is an oxetane compound having a dipole moment of 3.0 d or less, has a relatively low surface tension, and can impart good leveling properties to the film of an anisotropic conductive film. It becomes possible to improve the storage life of the anisotropic conductive film.
  • a low polarity oxetane compound has the effect
  • Examples of such low polarity oxetane compounds include 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl and the like.
  • the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound is preferably 25:75 to 60:40, more preferably 45:55 to 60:40, and particularly preferably 50:50 to 55:45 on a mass basis. It is.
  • the blending amount of the low-polar oxetane compound is higher than this range, the reaction start temperature and the reaction end temperature tend to increase, and conversely, when it decreases, the storage life tends to decrease. Therefore, by adjusting the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound, it is possible to control the reaction start temperature and the reaction end temperature of the anisotropic conductive film, and further, the temperature rise during the reaction.
  • the reaction time can be controlled by adjusting the temperature rate and the like.
  • Binder composition is bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, other epoxy resins such as their modified epoxy resin, silane coupling agent, filler, softener, acceleration as required Agents, anti-aging agents, colorants (pigments, dyes), organic solvents, ion catchers and the like.
  • a (meth) acrylate compound and a radical polymerization initiator can be contained as needed.
  • the (meth) acrylate compound a conventionally known (meth) acrylate monomer can be used as the (meth) acrylate compound.
  • a monofunctional (meth) acrylate monomer or a bifunctional or higher polyfunctional (meth) acrylate monomer can be used as the (meth) acrylate compound.
  • (meth) acrylate includes acrylate and methacrylate.
  • radical polymerization initiator well-known radical polymerization initiators, such as an organic peroxide and an azobis britonitrile, can be contained.
  • the anisotropic conductive film of the present invention contains conductive particles in the binder composition in order to enable anisotropic conductive connection.
  • the conductive particles can be appropriately selected from those used in conventionally known anisotropic conductive films.
  • metal particles such as nickel, cobalt, silver, copper, gold, and palladium, alloy particles such as solder, metal-coated resin particles, and the like can be given. Two or more kinds can be used in combination.
  • the average particle size of the conductive particles is preferably 2.5 ⁇ m or more and 30 ⁇ m or less in order to be able to cope with variations in wiring height, to suppress increase in conduction resistance, and to suppress occurrence of short circuit. Preferably they are 3 micrometers or more and 9 micrometers or less.
  • the particle size of the conductive particles can be measured by a general particle size distribution measuring device, and the average particle size can also be obtained using the particle size distribution measuring device.
  • the particle hardness (20% K value; compression elastic deformation characteristic K 20 ) of the resin core particles is preferably 100 to 1000 kgf in order to obtain good connection reliability. / Mm 2 , more preferably 200 to 500 kgf / mm 2 .
  • the compression elastic deformation characteristic K 20 can be measured at a measurement temperature of 20 ° C. using, for example, a micro compression tester (MCT-W201, Shimadzu Corporation).
  • the abundance of the conductive particles in the anisotropic conductive film is preferably 50 or more and 100,000 or less per square mm, more preferably, in order to suppress a decrease in the efficiency of capturing the conductive particles and suppress the occurrence of short circuit. 200 or more and 70000 or less. This abundance can be measured by observing a thin film of material with an optical microscope.
  • anisotropic conductive connection since the electroconductive particle in an anisotropic conductive film exists in a binder composition, it may be difficult to observe with an optical microscope. In such a case, the anisotropic conductive film after anisotropic conductive connection may be observed. In this case, the abundance can be determined in consideration of the film thickness change before and after connection.
  • the abundance of the conductive particles in the anisotropic conductive film can also be expressed on a mass basis.
  • the abundance is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass. It is an amount that is equal to or less than part by mass.
  • the anisotropic conductive film of the present invention contains a quaternary ammonium salt thermal acid generator instead of a sulfonium salt thermal acid generator as a cationic polymerization initiator. This is to improve the storage life.
  • quaternary ammonium salt thermal acid generator a quaternary ammonium cation, a hexafluoroantimonate anion, a hexafluorophosphate anion, a trifluoromethanesulfonate anion, a perfluorobutanesulfonate anion
  • examples thereof include salts with dinonylnaphthalene sulfonate anion, p-toluene sulfonate anion, dodecylbenzene sulfonate anion, or tetrakis (pentafluorophenyl) borate anion.
  • R1, R2, R3 and R4 are linear, branched or cyclic alkyl groups or aryl groups having 1 to 12 carbon atoms, each having a hydroxyl group, a halogen, an alkoxyl group, an amino group, an ester group or the like. You may do it.
  • quaternary ammonium salt thermal acid generator examples include King Industries, Inc. Examples thereof include CXC-1612, CXC-1733, CXC-1738, TAG-2678, CXC-1614, TAG-2690, TAG-2690, TAG-2700, CXC1802-60, and CXC-1821. These are available from Enomoto Kasei Co., Ltd.
  • the layer thickness of the anisotropic conductive film of the present invention is preferably 3 to 50 ⁇ m, more preferably 5 to 20 ⁇ m.
  • the anisotropic conductive film of the present invention is obtained by dissolving conductive particles and a cationic polymerization initiator in the binder composition described above in an organic solvent such as toluene to form a paint, and using the known film-forming technique. It can be manufactured by forming a film.
  • the anisotropic conductive film of the present invention may be a single layer, but reduces the production cost by reducing the amount of conductive particles used without reducing the particle trapping property during anisotropic conductive connection.
  • an insulating resin layer may be laminated.
  • the anisotropic conductive film of the present invention has a two-layer structure of conductive particle containing layer / insulating resin layer.
  • Such an insulating resin layer can be basically formed from a composition obtained by blending a binder composition used in an anisotropic conductive film with a cationic polymerization initiator without containing conductive particles.
  • the reaction start temperature of the reaction peak measured with a differential scanning calorimeter is adjusted to 60 to 80 ° C., and the reaction end temperature is 155 to 185 ° C. It is preferable to adjust to. These adjustments can be made by adjusting the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound.
  • the anisotropic conductive film of the present invention anisotropically conducts a first electronic component such as an IC chip, an IC module, and an FPC and a second electronic component such as a plastic substrate, a glass substrate, a rigid substrate, a ceramic substrate, and an FPC. It can be preferably applied when connecting.
  • a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected in the anisotropic conductive film of the present invention is also a part of the present invention.
  • a well-known method can be utilized as a connection method of the electronic component using an anisotropic conductive film.
  • Example 1 (Formation of conductive particle-containing layer) 60 parts by mass of phenoxy resin (YP-50, Nippon Steel & Sumikin Chemical Co., Ltd.), 10 parts by mass of diepoxybicyclohexyl (Celoxide 8000, Daicel Co., Ltd.) as an alicyclic epoxy compound, low polarity oxetane compound (OXBP, Ube Industries) 20 parts by mass, thermal cationic polymerization initiator (quaternary ammonium salt thermal acid generator, trade name CXC-1612, Enomoto Kasei Co., Ltd.) 2 parts by mass, and conductive particles having an average particle size of 3 ⁇ m 50 parts by mass (Ni / Au plating resin particles, AUL704, Sekisui Chemical Co., Ltd.) was added to toluene to prepare a mixed solution so that the solid content was 50% by mass.
  • phenoxy resin YP-50, Nippon Steel & Sumikin Chemical Co., Ltd.
  • the obtained mixed liquid was applied on a polyethylene terephthalate release film (PET release film) having a thickness of 50 ⁇ m so as to have a dry thickness of 6 ⁇ m, and dried in an oven at 60 ° C. for 5 minutes to thereby obtain a conductive particle-containing layer. Formed.
  • PET release film polyethylene terephthalate release film
  • the obtained mixed solution was applied onto a PET peel film having a thickness of 50 ⁇ m so that the dry thickness was 12 ⁇ m, and dried in an oven at 60 ° C. for 5 minutes to form an insulating resin layer.
  • Examples 2-4 An alicyclic epoxy compound (Celoxide 8000, Daicel Corp.) and 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl as a low-polar oxetane compound in the conductive particle-containing layer and the insulating resin layer
  • An anisotropic conductive film was obtained in the same manner as in Example 1 except that the blending amount (ratio) with (0XBP, Ube Industries, Ltd.) was changed as shown in Table 1.
  • Comparative Example 5 Table 1 shows the blending amounts (ratio) of the alicyclic epoxy compound (Celoxide 8000, Daicel Corporation) and the low-polar oxetane compound (0XBP, Ube Industries, Ltd.) in the conductive particle-containing layer and the insulating resin layer.
  • An anisotropic conductive film was prepared in the same manner as in Example 1 except for the change as shown.
  • the PET release film on the conductive particle-containing layer side of the anisotropic conductive film is peeled off, the anisotropic conductive film is attached to the raw glass from the conductive particle-containing layer side, and a laminate of the raw glass and the anisotropic conductive film is formed. Produced.
  • This laminated body was mounted so that the raw glass side was in contact with a hot plate set to 45 ° C., pressure was applied manually from the anisotropic conductive film side, and then cooled to room temperature. After cooling, the PET release film on the insulating resin layer side was peeled from the laminate, and it was confirmed whether only the PET release film was peeled off without peeling the anisotropic conductive film from the raw glass.
  • the reaction rate of the anisotropic conductive film in this connection was measured as described below, and the curing temperature was determined from the measurement result. The obtained results are shown in Table 1.
  • reaction rate measurement The IC chip of the connection object for evaluation was picked and peeled by hand, the cured anisotropic conductive film was exposed, and the anisotropic conductive film was sampled. The obtained sample was dissolved in acetonitrile so as to have a concentration of 0.1 g / mL. Separately, the anisotropic conductive film before curing was dissolved in acetonitrile so as to have the same concentration, and the peak intensity of each monomer was confirmed using HPLC-MS (WaterS) under the following conditions. The reaction rate at each temperature was determined from the amount of decrease in peak intensity after curing, and the temperature at which the reaction rate reached 80% or more was taken as the curing temperature.
  • ⁇ Reaction time> About 5 mg of a sample cut out from the obtained anisotropic conductive film was stored in aluminum PAN (TA Instruments Inc.), which was set in a DSC measuring apparatus (Q2000, TA Instruments Inc.), and 30 ° C. to 250 ° C. Differential scanning calorimetry (DSC) measurement was performed at a temperature rising rate of 10 ° C./min up to ° C. From the obtained DSC chart, the temperature when the exothermic peak rose was read as the reaction start temperature, and the temperature when the exothermic peak changed to the baseline was read as the reaction end temperature. The reaction time was calculated according to the following formula. The obtained results are shown in Table 1.
  • the cationic conductive anisotropic conductive film of the present invention using an alicyclic epoxy compound has the same curing temperature and connection reliability as a conventional anisotropic conductive film using a sulfonium salt thermal acid generator. While guaranteeing, it is possible to realize a better storage life than ever, which is useful for anisotropic conductive connection of an electronic component such as an IC chip to a wiring board.

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Abstract

A cationically polymerizable anisotropic conductive film using an alicyclic epoxy compound, which has more excellent storage life than ever before, while ensuring curing temperature and connection reliability that are the same as before. This anisotropic conductive film contains a binder composition containing a film formation component and a cationically polymerizable component, a cationic polymerization initiator and conductive particles. This anisotropic conductive film uses, as the cationic polymerization initiator, a quaternary ammonium salt-based thermal acid generator, while containing, as the cationically polymerizable component, an alicyclic epoxy compound and an oxetane compound with low polarity.

Description

異方性導電フィルムAnisotropic conductive film
　本発明は、異方性導電フィルムに関する。 The present invention relates to an anisotropic conductive film.
　従来より、ＩＣチップなどの電子部品を配線基板に実装する際に、重合性化合物を含有する絶縁性のバインダ組成物に導電粒子が分散している異方性導電フィルムが広く用いられている。このような異方性導電フィルムには、低温速硬化性を実現するために、重合性化合物として、汎用のグリシジルエーテル系化合物よりもカチオン重合反応性の高い脂環式エポキシ化合物を使用すると共に、酸素による重合阻害がなく、暗反応性を示す重合開始剤として、熱によりプロトンを発生するスルホニウム塩系熱酸発生剤を使用することが提案されている（特許文献1～３）。このような、脂環式エポキシ化合物とスルホニウム塩系熱酸発生剤とを含有する従来の異方性導電フィルムは、比較的低温（例えば１００℃程度）の硬化温度を示している。 Conventionally, when an electronic component such as an IC chip is mounted on a wiring board, an anisotropic conductive film in which conductive particles are dispersed in an insulating binder composition containing a polymerizable compound has been widely used. In such an anisotropic conductive film, in order to achieve low temperature fast curability, an alicyclic epoxy compound having higher cationic polymerization reactivity than a general-purpose glycidyl ether compound is used as a polymerizable compound, It has been proposed to use a sulfonium salt thermal acid generator that generates protons by heat as a polymerization initiator that does not inhibit polymerization by oxygen and exhibits dark reactivity (Patent Documents 1 to 3). Such a conventional anisotropic conductive film containing an alicyclic epoxy compound and a sulfonium salt-based thermal acid generator has a relatively low curing temperature (for example, about 100 ° C.).
特開平９－１７６１１２号公報JP-A-9-176112 特開２００８－３０８５９６号公報JP 2008-308596 A 国際公開２０１２／０１８１２３号International Publication 2012/018123
　しかしながら、前述したような異方性導電フィルムについては、商取引の国際化等により製造から実使用までの時間が長くなるという問題や、また、空調が整備されていない倉庫で保管される場合があるといった問題があり、仮貼り性や圧痕等の観点からの保存安定性（保管ライフ性）の低下や、密着特性等の観点からの接続信頼性の低下が懸念されるようになっている。 However, the anisotropic conductive film as described above may be stored in a warehouse where air-conditioning is not provided, and there is a problem that the time from manufacture to actual use becomes long due to internationalization of commercial transactions. As a result, there are concerns about a decrease in storage stability (storage life) from the viewpoints of temporary sticking properties and indentations, and a decrease in connection reliability from the viewpoint of adhesion characteristics.
　本発明の課題は、脂環式エポキシ化合物を使用するカチオン重合性の異方性導電フィルムに対し、従前と変わらない硬化温度と接続信頼性とを担保しながらも、今まで以上に優れた保管ライフ性を実現できるようにすることである。 The problem of the present invention is that the cationic polymerizable anisotropic conductive film using the alicyclic epoxy compound has better storage than ever before while ensuring the same curing temperature and connection reliability as before. It is to be able to realize life.
　本発明者は、カチオン重合性化合物として、脂環式エポキシ化合物に加えて低極性オキセタン化合物を特定割合で併用し、且つカチオン重合開始剤として、スルホニウム塩系熱酸発生剤に代えて第４級アンモニウム塩系熱酸発生剤を使用することにより、今までと変わらない硬化温度と接続信頼性とを担保しながらも、今まで以上に優れた保管ライフ性を実現できることを見出し、本発明を完成させるに至った。 The present inventor uses a low-polar oxetane compound in a specific ratio in addition to an alicyclic epoxy compound as a cationic polymerizable compound, and a quaternary quaternary polymerization initiator instead of a sulfonium salt-based thermal acid generator. By using an ammonium salt thermal acid generator, we have found that it is possible to achieve better storage life than ever, while ensuring the same curing temperature and connection reliability as ever, and completed the present invention. I came to let you.
　即ち、本発明は、成膜用成分とカチオン重合性成分とを含有するバインダ組成物と、カチオン重合開始剤と、導電粒子とを含有する異方性導電フィルムであって、
　カチオン重合開始剤が、第４級アンモニウム塩系熱酸発生剤であり、カチオン重合性成分が、脂環式エポキシ化合物と低極性オキセタン化合物とを含有している異方性導電フィルムを提供する。 That is, the present invention is an anisotropic conductive film containing a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles,
Provided is an anisotropic conductive film in which the cationic polymerization initiator is a quaternary ammonium salt thermal acid generator, and the cationic polymerizable component contains an alicyclic epoxy compound and a low polarity oxetane compound.
　また、本発明は、上述の異方性導電フィルムで、第１電子部品と第２電子部品とが異方性導電接続されている接続構造体を提供する。 The present invention also provides a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected using the anisotropic conductive film described above.
　成膜用成分とカチオン重合性成分とを含有するバインダ組成物と、カチオン重合開始剤と、導電粒子とを含有する本発明の異方性導電フィルムは、カチオン重合開始剤として、第４級アンモニウム塩系熱酸発生剤を使用し、カチオン重合性成分として、脂環式エポキシ化合物と低極性オキセタン化合物とを含有している。このため、今までと変わらない硬化温度と接続信頼性とを担保しながらも、今まで以上に優れた保管ライフ性を実現できる。 The anisotropic conductive film of the present invention containing a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles is a quaternary ammonium as a cationic polymerization initiator. A salt-based thermal acid generator is used, and an alicyclic epoxy compound and a low-polar oxetane compound are contained as a cationic polymerizable component. For this reason, while ensuring the same curing temperature and connection reliability as before, it is possible to realize better storage life than ever.
　以下、本発明の一例を、詳細に説明する。 Hereinafter, an example of the present invention will be described in detail.
＜異方性導電フィルム＞
　本発明の異方性導電フィルムは、成膜用成分とカチオン重合性成分とを含有するバインダ組成物と、カチオン重合開始剤と、導電粒子とを含有している。 <Anisotropic conductive film>
The anisotropic conductive film of the present invention contains a binder composition containing a film-forming component and a cationic polymerizable component, a cationic polymerization initiator, and conductive particles.
（バインダ組成物）
　本発明において、導電粒子を含有保持するバインダ組成物は、成膜用成分とカチオン重合性成分とを含有している。 (Binder composition)
In the present invention, the binder composition containing and holding the conductive particles contains a film forming component and a cationic polymerizable component.
（成膜用成分）
　成膜用成分は、異方性導電フィルムをフィルム化するために使用される成分であり、膜形成能を有する成分である。このような成膜用成分としては、フェノキシ樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ウレタン樹脂、ブタジエン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリオレフィン樹脂等を挙げることができ、これらの２種以上を併用することができる。これらの中でも、成膜性、加工性、接続信頼性の観点から、フェノキシ樹脂を好ましく使用することができる。 (Components for film formation)
The film-forming component is a component used for forming an anisotropic conductive film into a film and is a component having film-forming ability. Examples of the film forming component include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. The above can be used together. Among these, a phenoxy resin can be preferably used from the viewpoints of film formability, processability, and connection reliability.
　バインダ組成物中の成膜用成分の配合割合は、好ましくは１０～７０質量％、より好ましくは２０～５０質量％である。この範囲であれば、十分なフィルム形成能を発揮することができる。 The blending ratio of the film-forming component in the binder composition is preferably 10 to 70% by mass, more preferably 20 to 50% by mass. If it is this range, sufficient film formation ability can be exhibited.
（カチオン重合性成分）
　カチオン重合性成分は、異方性導電フィルムを硬化させる成分であり、脂環式エポキシ化合物と低極性オキセタン化合物とを含有している。バインダ組成物中におけるカチオン重合性成分の配合量は、好ましくは１０～８０質量％、より好ましくは２０～６０質量％である。この範囲であれば、より高い硬化速度を有するバインダ組成物を与えることができる。 (Cationically polymerizable component)
The cationic polymerizable component is a component that cures the anisotropic conductive film and contains an alicyclic epoxy compound and a low-polar oxetane compound. The blending amount of the cationically polymerizable component in the binder composition is preferably 10 to 80% by mass, more preferably 20 to 60% by mass. If it is this range, the binder composition which has a higher hardening rate can be given.
（脂環式エポキシ化合物）
　脂環式エポキシ化合物を使用する理由は、汎用のグリシジルエーテル型エポキシ化合物よりも高いその反応性を利用して、異方性導電フィルムに良好な低温速硬化性を付与するためである。このような脂環式エポキシ化合物としては、分子内に２つ以上のエポキシ基を有するものが好ましく挙げられる。これらは液状であっても、固体状であってもよい。具体的には、ジグリシジルヘキサヒドロビスフェノールＡ、３，４－エポキシシクロヘキセニルメチル－３′，４′－エポキシシクロヘキセンカルボキシレート、ジエポキシビシクロヘキシル等を挙げることができる。中でも、硬化物の光透過性を確保でき、速硬化性にも優れている点から、ジグリシジルヘキサヒドロビスフェノールＡ、特にジエポキシビシクロヘキシルを好ましく使用することができる。 (Alicyclic epoxy compound)
The reason for using the alicyclic epoxy compound is to impart good low-temperature rapid curability to the anisotropic conductive film by utilizing its reactivity higher than that of a general-purpose glycidyl ether type epoxy compound. Preferred examples of such alicyclic epoxy compounds include those having two or more epoxy groups in the molecule. These may be liquid or solid. Specific examples include diglycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, diepoxybicyclohexyl and the like. Among these, diglycidyl hexahydrobisphenol A, particularly diepoxybicyclohexyl, can be preferably used from the viewpoint that the light transmittance of the cured product can be ensured and the fast curability is excellent.
（低極性オキセタン化合物）
　本発明においては、脂環式エポキシ化合物に低極性オキセタン化合物を併用する。低極性オキセタン化合物は、双極子モーメントが３．０ｄ以下のオキセタン化合物であり、表面張力が比較的低く、異方性導電フィルムの膜に良好なレベリング性を付与することができ、結果的に異方性導電フィルムの保管ライフ性を向上させることが可能となる。他方、低極性オキセタン化合物は、脂環式エポキシ化合物に由来する異方性導電フィルムの示差走査熱量計（ＤＳＣ）で測定される反応開始温度と反応終了温度とを上昇させる作用を有する。このような低極性オキセタン化合物としては、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、３－エチル－３－ヒドロキシメチルオキセタン、ジ［１－エチル（３－オキセタニル）］メチルエーテル、４，４′－ビス[（３－エチル－３－オキセタニル）メトキシメチル]ビフェニル等が挙げられる。中でも、表面張力が低く、濡れ性に優れることから、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、特に４，４′－ビス[（３－エチル－３－オキセタニル）メトキシメチル]ビフェニルが好ましい。 (Low polarity oxetane compound)
In the present invention, a low polarity oxetane compound is used in combination with an alicyclic epoxy compound. A low-polar oxetane compound is an oxetane compound having a dipole moment of 3.0 d or less, has a relatively low surface tension, and can impart good leveling properties to the film of an anisotropic conductive film. It becomes possible to improve the storage life of the anisotropic conductive film. On the other hand, a low polarity oxetane compound has the effect | action which raises the reaction start temperature and reaction end temperature which are measured with the differential scanning calorimeter (DSC) of the anisotropic conductive film derived from an alicyclic epoxy compound. Examples of such low polarity oxetane compounds include 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl and the like. Among them, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, particularly 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] because of its low surface tension and excellent wettability Biphenyl is preferred.
　脂環式エポキシ化合物と低極性オキセタン化合物との配合割合は、質量基準で好ましくは２５：７５～６０：４０、より好ましくは４５：５５～６０：４０、特に好ましくは５０：５０～５５：４５である。この範囲よりも低極性オキセタン化合物の配合量が増加すると、反応開始温度と反応終了温度とを上昇させる傾向があり、逆に減少すると保管ライフが低下する傾向がある。従って、脂環式エポキシ化合物と低極性オキセタン化合物との配合割合を調整することにより、異方性導電フィルムの反応開始温度と反応終了温度とをコントロールすることが可能となり、更に、反応時の昇温速度等を調整することにより、反応時間をコントロールすることも可能となる。 The blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound is preferably 25:75 to 60:40, more preferably 45:55 to 60:40, and particularly preferably 50:50 to 55:45 on a mass basis. It is. When the blending amount of the low-polar oxetane compound is higher than this range, the reaction start temperature and the reaction end temperature tend to increase, and conversely, when it decreases, the storage life tends to decrease. Therefore, by adjusting the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound, it is possible to control the reaction start temperature and the reaction end temperature of the anisotropic conductive film, and further, the temperature rise during the reaction. The reaction time can be controlled by adjusting the temperature rate and the like.
　バインダ組成物は、必要に応じ、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、それらの変性エポキシ樹脂等の他のエポキシ樹脂、シランカップリング剤、充填剤、軟化剤、促進剤、老化防止剤、着色剤（顔料、染料）、有機溶剤、イオンキャッチャー剤などを含有することができる。また、必要に応じて、（メタ）アクリレート化合物とラジカル重合開始剤とを含有することができる。ここで、（メタ）アクリレート化合物としては、従来公知の（メタ）アクリレートモノマーを使用することができる。例えば、単官能（メタ）アクリレート系モノマー、二官能以上の多官能（メタ）アクリレート系モノマーを使用することができる。ここで、（メタ）アクリレートには、アクリレートとメタクリレートとが包含される。また、ラジカル重合開始剤としては、有機過酸化物、アゾビスブリトニトリル等の公知のラジカル重合開始剤を含有することができる。 Binder composition is bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, other epoxy resins such as their modified epoxy resin, silane coupling agent, filler, softener, acceleration as required Agents, anti-aging agents, colorants (pigments, dyes), organic solvents, ion catchers and the like. Moreover, a (meth) acrylate compound and a radical polymerization initiator can be contained as needed. Here, as the (meth) acrylate compound, a conventionally known (meth) acrylate monomer can be used. For example, a monofunctional (meth) acrylate monomer or a bifunctional or higher polyfunctional (meth) acrylate monomer can be used. Here, (meth) acrylate includes acrylate and methacrylate. Moreover, as a radical polymerization initiator, well-known radical polymerization initiators, such as an organic peroxide and an azobis britonitrile, can be contained.
（導電粒子）
　本発明の異方性導電フィルムは、異方性導電接続を可能とするために、バインダ組成物中に導電粒子を含有する。導電粒子としては、従来公知の異方性導電フィルムに用いられているものの中から適宜選択して使用することができる。例えばニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、ハンダなどの合金粒子、金属被覆樹脂粒子などが挙げられる。２種以上を併用することもできる。 (Conductive particles)
The anisotropic conductive film of the present invention contains conductive particles in the binder composition in order to enable anisotropic conductive connection. The conductive particles can be appropriately selected from those used in conventionally known anisotropic conductive films. For example, metal particles such as nickel, cobalt, silver, copper, gold, and palladium, alloy particles such as solder, metal-coated resin particles, and the like can be given. Two or more kinds can be used in combination.
　導電粒子の平均粒径としては、配線高さのばらつきに対応できるようにし、また、導通抵抗の上昇を抑制し、且つショートの発生を抑制するために、好ましくは２．５μｍ以上３０μｍ以下、より好ましくは３μｍ以上９μｍ以下である。導電粒子の粒径は、一般的な粒度分布測定装置により測定することができ、また、その平均粒径も粒度分布測定装置を用いて求めることができる。 The average particle size of the conductive particles is preferably 2.5 μm or more and 30 μm or less in order to be able to cope with variations in wiring height, to suppress increase in conduction resistance, and to suppress occurrence of short circuit. Preferably they are 3 micrometers or more and 9 micrometers or less. The particle size of the conductive particles can be measured by a general particle size distribution measuring device, and the average particle size can also be obtained using the particle size distribution measuring device.
　なお、導電粒子が金属被覆樹脂粒子である場合、樹脂コア粒子の粒子硬さ（２０％Ｋ値；圧縮弾性変形特性Ｋ２０）は、良好な接続信頼性を得るために、好ましくは１００～１０００ｋｇｆ／ｍｍ２、より好ましくは２００から５００ｋｇｆ／ｍｍ２である。圧縮弾性変形特性Ｋ２０は、例えば、微小圧縮試験機（ＭＣＴ－Ｗ２０１、（株）島津製作所）を使用して測定温度２０℃で測定することができる。 When the conductive particles are metal-coated resin particles, the particle hardness (20% K value; compression elastic deformation characteristic K 20 ) of the resin core particles is preferably 100 to 1000 kgf in order to obtain good connection reliability. / Mm 2 , more preferably 200 to 500 kgf / mm 2 . The compression elastic deformation characteristic K 20 can be measured at a measurement temperature of 20 ° C. using, for example, a micro compression tester (MCT-W201, Shimadzu Corporation).
　導電粒子の異方性導電フィルム中の存在量は、導電粒子捕捉効率の低下を抑制し、且つショートの発生を抑制するために、好ましくは１平方ｍｍ当たり５０個以上１０００００個以下、より好ましくは２００個以上７００００個以下である。この存在量の測定は材料の薄膜を光学顕微鏡で観察することにより行うことができる。なお、異方性導電接続前において、異方性導電フィルム中の導電粒子がバインダ組成物中に存在しているために光学顕微鏡で観察し難い場合がある。そのような場合には、異方性導電接続後の異方性導電フィルムを観察してもよい。この場合には、接続前後のフィルム厚変化を考慮して存在量を割り出すことができる。 The abundance of the conductive particles in the anisotropic conductive film is preferably 50 or more and 100,000 or less per square mm, more preferably, in order to suppress a decrease in the efficiency of capturing the conductive particles and suppress the occurrence of short circuit. 200 or more and 70000 or less. This abundance can be measured by observing a thin film of material with an optical microscope. In addition, before anisotropic conductive connection, since the electroconductive particle in an anisotropic conductive film exists in a binder composition, it may be difficult to observe with an optical microscope. In such a case, the anisotropic conductive film after anisotropic conductive connection may be observed. In this case, the abundance can be determined in consideration of the film thickness change before and after connection.
　なお、導電粒子の異方性導電フィルム中の存在量は質量基準で表すこともができる。この場合、その存在量は、異方性導電フィルムの全質量を１００質量部としたときに、その１００質量部中に好ましくは１質量部以上３０質量部以下、より好ましくは３質量部以上１０質量部以下となる量である。 Note that the abundance of the conductive particles in the anisotropic conductive film can also be expressed on a mass basis. In this case, when the total mass of the anisotropic conductive film is 100 parts by mass, the abundance is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass. It is an amount that is equal to or less than part by mass.
（カチオン重合開始剤）
　本発明の異方性導電フィルムは、カチオン重合開始剤として、スルホニウム塩系熱酸発生剤ではなく第４級アンモニウム塩系熱酸発生剤を含有する。保管ライフ性を向上させるためである。このような第４級アンモニウム塩系熱酸発生剤としては、第４級アンモニウムカチオンと、６フッ化アンチモン酸アニオン、６フッ化リン酸アニオン、トリフルオロメタンスルホン酸アニオン、パーフルオロブタンスルホン酸アニオン、ジノニルナフタレンスルホン酸アニオン、ｐ－トルエンスルホン酸アニオン、ドデシルベンゼンスルホン酸アニオン、またはテトラキス（ペンタフルオロフェニル）ボレートアニオンとの塩等を挙げることができる。また、第４級アンモニウムカチオンとしては、ＮＲ１Ｒ２Ｒ３Ｒ４＋で表されるカチオンを挙げることができる。ここで、Ｒ１、Ｒ２、Ｒ３及びＲ４は、直鎖、分岐鎖または環状の炭素数１～１２のアルキル基またはアリール基であり、それぞれ水酸基、ハロゲン、アルコキシル基、アミノ基、エステル基等を有していてもよい。 (Cationic polymerization initiator)
The anisotropic conductive film of the present invention contains a quaternary ammonium salt thermal acid generator instead of a sulfonium salt thermal acid generator as a cationic polymerization initiator. This is to improve the storage life. As such a quaternary ammonium salt thermal acid generator, a quaternary ammonium cation, a hexafluoroantimonate anion, a hexafluorophosphate anion, a trifluoromethanesulfonate anion, a perfluorobutanesulfonate anion, Examples thereof include salts with dinonylnaphthalene sulfonate anion, p-toluene sulfonate anion, dodecylbenzene sulfonate anion, or tetrakis (pentafluorophenyl) borate anion. Moreover, as a quaternary ammonium cation, the cation represented by NR1R2R3R4 + can be mentioned. Here, R1, R2, R3 and R4 are linear, branched or cyclic alkyl groups or aryl groups having 1 to 12 carbon atoms, each having a hydroxyl group, a halogen, an alkoxyl group, an amino group, an ester group or the like. You may do it.
　第４級アンモニウム塩系熱酸発生剤の具体例としては、Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ，Ｉｎｃ．製造のＣＸＣ－１６１２、ＣＸＣ－１７３３、ＣＸＣ－１７３８、ＴＡＧ－２６７８、ＣＸＣ－１６１４、ＴＡＧ－２６８９、ＴＡＧ－２６９０、ＴＡＧ－２７００、ＣＸＣ－１８０２－６０、ＣＸＣ－１８２１等が挙げられる。これらは、楠本化成（株）から入手可能である。 Specific examples of the quaternary ammonium salt thermal acid generator include King Industries, Inc. Examples thereof include CXC-1612, CXC-1733, CXC-1738, TAG-2678, CXC-1614, TAG-2690, TAG-2690, TAG-2700, CXC1802-60, and CXC-1821. These are available from Enomoto Kasei Co., Ltd.
　本発明の異方性導電フィルムの層厚は、好ましくは３～５０μｍ、より好ましくは５～２０μｍである。 The layer thickness of the anisotropic conductive film of the present invention is preferably 3 to 50 μm, more preferably 5 to 20 μm.
（異方性導電フィルムの製造）
　本発明の異方性導電フィルムは、上述したバインダ組成物に導電粒子とカチオン重合開始剤とを、トルエン等の有機溶媒に溶解して塗料とし、その塗料を公知のフィルム化手法を利用してフィルム化することにより製造することができる。 (Manufacture of anisotropic conductive film)
The anisotropic conductive film of the present invention is obtained by dissolving conductive particles and a cationic polymerization initiator in the binder composition described above in an organic solvent such as toluene to form a paint, and using the known film-forming technique. It can be manufactured by forming a film.
　なお、本発明の異方性導電フィルムは、単層であってもよいが、異方性導電接続時の粒子捕捉性を低下させることなく、導電粒子の使用量を減じて製造コストを減少させ、且つアンダーフィル充填操作を省くために、絶縁性樹脂層を積層させてもよい。その場合、本発明の異方性導電フィルムは、導電粒子含有層／絶縁性樹脂層の２層構成となる。このような絶縁性樹脂層は、基本的には異方性導電フィルムで使用したバインダ組成物に、導電粒子を含有させることなくカチオン重合開始剤を配合させた組成物から形成することができる。 The anisotropic conductive film of the present invention may be a single layer, but reduces the production cost by reducing the amount of conductive particles used without reducing the particle trapping property during anisotropic conductive connection. In order to omit the underfill filling operation, an insulating resin layer may be laminated. In that case, the anisotropic conductive film of the present invention has a two-layer structure of conductive particle containing layer / insulating resin layer. Such an insulating resin layer can be basically formed from a composition obtained by blending a binder composition used in an anisotropic conductive film with a cationic polymerization initiator without containing conductive particles.
　本発明の異方性導電フィルムは、反応速度コントロールとの観点から、示差走査熱量計で測定した反応ピークの反応開始温度を６０～８０℃に調整し、また、反応終了温度を１５５～１８５℃に調整することが好ましい。これらの調整は、脂環式エポキシ化合物と低極性オキセタン化合物との配合割合を調整すること等により行うことができる。 In the anisotropic conductive film of the present invention, from the viewpoint of reaction rate control, the reaction start temperature of the reaction peak measured with a differential scanning calorimeter is adjusted to 60 to 80 ° C., and the reaction end temperature is 155 to 185 ° C. It is preferable to adjust to. These adjustments can be made by adjusting the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound.
＜接続構造体＞
　本発明の異方性導電フィルムは、ＩＣチップ、ＩＣモジュール、ＦＰＣなどの第１電子部品と、プラスチック基板、ガラス基板、リジッド基板、セラミック基板、ＦＰＣなどの第２電子部品とを異方性導電接続する際に好ましく適用することができる。このような本発明の異方性導電フィルムで、第１電子部品と第２電子部品とが異方性導電接続されている接続構造体も本発明の一部である。なお、異方性導電フィルムを用いた電子部品の接続方法としては、公知の手法を利用することができる。 <Connection structure>
The anisotropic conductive film of the present invention anisotropically conducts a first electronic component such as an IC chip, an IC module, and an FPC and a second electronic component such as a plastic substrate, a glass substrate, a rigid substrate, a ceramic substrate, and an FPC. It can be preferably applied when connecting. A connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected in the anisotropic conductive film of the present invention is also a part of the present invention. In addition, a well-known method can be utilized as a connection method of the electronic component using an anisotropic conductive film.
　以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
　　実施例１
（導電粒子含有層の形成）
　フェノキシ樹脂（ＹＰ－５０、新日鉄住金化学（株））６０質量部、脂環式エポキシ化合物としてジエポキシビシクロヘキシル（セロキサイド８０００、（株）ダイセル）１０質量部、低極性オキセタン化合物（ＯＸＢＰ、宇部興産（株））２０質量部、熱カチオン重合開始剤（第４級アンモニウム塩系熱酸発生剤、商品名ＣＸＣ－１６１２、楠本化成（株））２質量部、および平均粒径３μｍの導電性粒子（Ｎｉ／Ａｕメッキ樹脂粒子、ＡＵＬ７０４、積水化学工業（株））５０質量部を、トルエンに添加し、固形分が５０質量％となるよう混合液を調製した。 Example 1
(Formation of conductive particle-containing layer)
60 parts by mass of phenoxy resin (YP-50, Nippon Steel & Sumikin Chemical Co., Ltd.), 10 parts by mass of diepoxybicyclohexyl (Celoxide 8000, Daicel Co., Ltd.) as an alicyclic epoxy compound, low polarity oxetane compound (OXBP, Ube Industries) 20 parts by mass, thermal cationic polymerization initiator (quaternary ammonium salt thermal acid generator, trade name CXC-1612, Enomoto Kasei Co., Ltd.) 2 parts by mass, and conductive particles having an average particle size of 3 μm 50 parts by mass (Ni / Au plating resin particles, AUL704, Sekisui Chemical Co., Ltd.) was added to toluene to prepare a mixed solution so that the solid content was 50% by mass.
　得られた混合液を、厚さ５０μｍのポリエチレンテレフタレート剥離フィルム（ＰＥＴ剥離フィルム）上に、乾燥厚が６μｍとなるよう塗布し、６０℃のオーブン中で５分間乾燥することにより、導電粒子含有層を形成した。 The obtained mixed liquid was applied on a polyethylene terephthalate release film (PET release film) having a thickness of 50 μm so as to have a dry thickness of 6 μm, and dried in an oven at 60 ° C. for 5 minutes to thereby obtain a conductive particle-containing layer. Formed.
（絶縁性樹脂層の形成）
　導電粒子を用いない以外は、導電粒子含有層の形成の際に使用した原材料と同じ原材料をトルエンに添加し、固形分が５０質量％となるよう混合液を調製した。 (Formation of insulating resin layer)
Except not using electroconductive particle, the raw material same as the raw material used in the case of formation of an electroconductive particle content layer was added to toluene, and the liquid mixture was prepared so that solid content might be 50 mass%.
　得られた混合液を、厚さ５０μｍのＰＥＴ剥離フィルム上に、乾燥厚が１２μｍとなるよう塗布し、６０℃のオーブン中で５分間乾燥することにより、絶縁性樹脂層を形成した。 The obtained mixed solution was applied onto a PET peel film having a thickness of 50 μm so that the dry thickness was 12 μm, and dried in an oven at 60 ° C. for 5 minutes to form an insulating resin layer.
（異方性導電フィルムの作成）
　導電粒子含有層に絶縁性樹脂層を、６０℃、５ＭＰａでラミネー卜することにより、厚さ５０μｍの一対のＰＥＴ剥離フィルムで挟持された異方性導電フィルムを得た。 (Creation of anisotropic conductive film)
By laminating the insulating resin layer on the conductive particle-containing layer at 60 ° C. and 5 MPa, an anisotropic conductive film sandwiched between a pair of PET release films having a thickness of 50 μm was obtained.
　　実施例２～４
　導電粒子含有層および絶縁性樹脂層における脂環式エポキシ化合物（セロキサイド８０００、（株）ダイセル）と低極性オキセタン化合物として４，４′－ビス[（３－エチル－３－オキセタニル）メトキシメチル]ビフェニル（０ＸＢＰ、宇部興産（株））との配合量（比率）を、表１に示すように変更した以外は、実施例１と同様に異方性導電フィルムを得た。 Examples 2-4
An alicyclic epoxy compound (Celoxide 8000, Daicel Corp.) and 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl as a low-polar oxetane compound in the conductive particle-containing layer and the insulating resin layer An anisotropic conductive film was obtained in the same manner as in Example 1 except that the blending amount (ratio) with (0XBP, Ube Industries, Ltd.) was changed as shown in Table 1.
　　比較例１～４
　導電粒子含有層および絶縁性樹脂層における熱カチオン重合開始剤を、表１に示すようにスルホニウム塩系熱酸発生剤（ＳＩ－６０Ｌ、三新化学工業（株））に代えた以外は、実施例１～４と同様に異方性導電フィルムを作成した。 Comparative Examples 1 to 4
Implementation was performed except that the thermal cationic polymerization initiator in the conductive particle-containing layer and the insulating resin layer was replaced with a sulfonium salt thermal acid generator (SI-60L, Sanshin Chemical Industry Co., Ltd.) as shown in Table 1. An anisotropic conductive film was prepared in the same manner as in Examples 1 to 4.
　　実施例５～１３、比較例５
　導電粒子含有層及び絶縁性樹脂層における脂環式エポキシ化合物（セロキサイド８０００、（株）ダイセル）と低極性オキセタン化合物（０ＸＢＰ、宇部興産（株））との配合量（比率）を、表１に示すよう変更した以外は、実施例１と同様に異方性導電フィルムを作成した。 Examples 5 to 13, Comparative Example 5
Table 1 shows the blending amounts (ratio) of the alicyclic epoxy compound (Celoxide 8000, Daicel Corporation) and the low-polar oxetane compound (0XBP, Ube Industries, Ltd.) in the conductive particle-containing layer and the insulating resin layer. An anisotropic conductive film was prepared in the same manner as in Example 1 except for the change as shown.
＜＜評価＞＞
　各実施例及び比較例で得られた異方性導電フィルムについて、以下に説明するように「保管ライフ特性」、「硬化温度」、「密着特性」及び「反応時間」を試験もしくは測定し、評価した。 << Evaluation >>
For the anisotropic conductive films obtained in each of the examples and comparative examples, as described below, “storage life characteristics”, “curing temperature”, “adhesion characteristics”, and “reaction time” are tested or measured and evaluated. did.
＜保管ライフ特性＞
　一対のＰＥＴ剥離フィルムに挟持されている異方性導電フィルムを、湿度４０％、温度２５℃又は３０℃に設定されている恒温恒湿室に投入し、投入後２４時間毎にサンプリングを行い、以下の仮張り評価および圧着評価を実施し、それらの評価結果から総合的に保管ライフ特性を評価した。得られた結果を表１に示す。 <Storage life characteristics>
An anisotropic conductive film sandwiched between a pair of PET release films is placed in a constant temperature and humidity chamber set at a humidity of 40% and a temperature of 25 ° C. or 30 ° C., and sampling is performed every 24 hours after the insertion, The following temporary tension evaluation and pressure bonding evaluation were performed, and the storage life characteristics were comprehensively evaluated from the evaluation results. The obtained results are shown in Table 1.
（仮張り評価）
　異方性導電フィルムの導電粒子含有層側のＰＥＴ剥離フィルムを剥離し、導電粒子含有層側から異方性導電フィルムを素ガラスに貼り付け、素ガラスと異方性導電フィルムとの積層体を作製した。この積層体をその素ガラス側が４５℃に設定したホットプレートに接触するように載置し、異方性導電フィルム側から手で圧力をかけ、その後、室温にまで冷却した。冷却後、積層体から絶縁性樹脂層側のＰＥＴ剥離フィルムを剥がし、素ガラスから異方性導電フィルムが剥がれることなく、ＰＥＴ剥離フィルムだけが剥がれるか否かを確認した。 (Temporary tension evaluation)
The PET release film on the conductive particle-containing layer side of the anisotropic conductive film is peeled off, the anisotropic conductive film is attached to the raw glass from the conductive particle-containing layer side, and a laminate of the raw glass and the anisotropic conductive film is formed. Produced. This laminated body was mounted so that the raw glass side was in contact with a hot plate set to 45 ° C., pressure was applied manually from the anisotropic conductive film side, and then cooled to room temperature. After cooling, the PET release film on the insulating resin layer side was peeled from the laminate, and it was confirmed whether only the PET release film was peeled off without peeling the anisotropic conductive film from the raw glass.
（圧着評価）
　テスト用ＩＣチップとテスト用基板との間に、ＩＣチップ側に絶縁性樹脂層が配置されるよう異方性導電フィルムを挟み、加熱加圧（１２０℃、６０ＭＰａ、５秒）し、評価用接続物を作成した。作成した接続物の圧痕状態を確認し、圧痕が薄くならず、消失せずに残存するかを確認した。 (Crimp evaluation)
An anisotropic conductive film is sandwiched between the test IC chip and the test substrate so that an insulating resin layer is disposed on the IC chip side, and heated and pressurized (120 ° C., 60 MPa, 5 seconds) for evaluation. Created a connection. The indentation state of the created connection was confirmed, and it was confirmed whether the indentation did not become thin and remained without disappearing.
（保管ライフ特性評価）
　仮張り評価において、素ガラスから異方性導電フィルムが剥がれた時点を保管ライフとした。また、仮張り評価において、素ガラスから異方性導電フィルムが剥がれなかった場合でも、圧着評価において、圧痕が薄くなった（消失した）時点を保管ライフとした。 (Storage life characteristics evaluation)
In the temporary tension evaluation, the time when the anisotropic conductive film was peeled off from the raw glass was defined as the storage life. Further, even when the anisotropic conductive film was not peeled off from the raw glass in the temporary tension evaluation, the time when the indentation became thin (disappeared) in the pressure-bonding evaluation was defined as the storage life.
＜硬化温度＞
　テスト用ＩＣチップとテスト用基板との間に、ＩＣチップ側に絶縁性樹脂層が配置されるよう異方性導電フィルムを挟み、加熱加圧（８０℃、９０℃、１００℃、１１０℃、又は１２０℃、６０ＭＰａ、５秒）し、評価用接続物を得た。この接続物における異方性導電フィルムの反応率を以下に説明するように測定し、その測定結果から硬化温度を決定した。得られた結果を表１に示す。 <Curing temperature>
An anisotropic conductive film is sandwiched between the test IC chip and the test substrate so that an insulating resin layer is disposed on the IC chip side, and heating and pressurization (80 ° C., 90 ° C., 100 ° C., 110 ° C., Or 120 ° C., 60 MPa, 5 seconds) to obtain an evaluation connection. The reaction rate of the anisotropic conductive film in this connection was measured as described below, and the curing temperature was determined from the measurement result. The obtained results are shown in Table 1.
（反応率測定）
　評価用接続物のＩＣチップを手で摘まんで剥がし、硬化した異方性導電フィルムを露出させ、異方性導電フィルムをサンプリングした。得られたサンプルを、濃度０．１ｇ／ｍＬとなるようアセトニトリルに溶解した。別途、硬化前の異方性導電フィルムを同様の濃度となるようアセトニトリルに溶解し、ＨＰＬＣ－ＭＳ（ＷａｔｅｒＳ社）を用いて、以下の条件にて各モノマーのピーク強度を確認した。硬化後のピーク強度の減少量より各温度での反応率を求め、反応率８０％以上となる温度を、硬化温度とした。 (Reaction rate measurement)
The IC chip of the connection object for evaluation was picked and peeled by hand, the cured anisotropic conductive film was exposed, and the anisotropic conductive film was sampled. The obtained sample was dissolved in acetonitrile so as to have a concentration of 0.1 g / mL. Separately, the anisotropic conductive film before curing was dissolved in acetonitrile so as to have the same concentration, and the peak intensity of each monomer was confirmed using HPLC-MS (WaterS) under the following conditions. The reaction rate at each temperature was determined from the amount of decrease in peak intensity after curing, and the temperature at which the reaction rate reached 80% or more was taken as the curing temperature.
溶媒：水／アセ卜ニトリル混合溶液（９０／１０）６０質量部に、アセトニトリル４０質量部を混合した混合溶媒
流量：０．４ｍＬ／ｍｉｎ
カラム：１０ｃｍ、４０℃Ｃ
注入量：５μＬ
解析波：２１０－４１０ｎｍ Solvent: 60 parts by mass of water / acetonitrile mixed solution (90/10) and 40 parts by mass of acetonitrile mixed solvent Flow rate: 0.4 mL / min
Column: 10cm, 40 ° C
Injection volume: 5 μL
Analysis wave: 210-410nm
＜密着特性＞
　テスト用ＩＣチップとテスト用基板との間に、ＩＣチップ側に絶縁性樹脂層が配置されるよう異方性導電フィルムを挟み、加熱加圧（１２０℃、６０ＭＰａ、５秒）し、評価用接続物を得た。この接続物に対して、エタック社、型式ＥＨＳ－４１１Ｍを用いて、プレッシャークッカーテスト（ＰＣＴ）を実施した。具体的には、得られた評価用接続物を、１２１℃、２ａｔｍ、飽和水蒸気雰囲気という条件に設定された恒温恒湿槽に接続物を投入し、２４時間毎に以下の密着評価を行った。得られた結果を表１に示す。 <Adhesion characteristics>
An anisotropic conductive film is sandwiched between the test IC chip and the test substrate so that an insulating resin layer is disposed on the IC chip side, and heated and pressurized (120 ° C., 60 MPa, 5 seconds) for evaluation. I got a connection. A pressure cooker test (PCT) was performed on this connection using an ETAC model EHS-411M. Specifically, the obtained connection for evaluation was put into a constant temperature and humidity chamber set under conditions of 121 ° C., 2 atm, and saturated steam atmosphere, and the following adhesion evaluation was performed every 24 hours. . The obtained results are shown in Table 1.
（密着評価）
　ＰＣＴ試験に投入した接続物の外観確認を行い、異方性導電フィルムとＩＣチップもしくは基板との層間で剥離が生じているかを目視観察した。
ランク　基準
　〇：　ＩＣ圧着後、４８時間のＰＣＴでも剥離が観察されない場合
　△：　ＩＣ圧着後、２４時間のＰＣＴでは剥離が観察されないが、４８時間のＰＣＴ試験では剥離が観察された場合
　×：　ＩＣ圧着後、ＰＣＴを行う前にすでに剥離が観察されていたか、２４時間のＰＣＴで剥離が観察された場合 (Adhesion evaluation)
The appearance of the connected object put in the PCT test was confirmed, and it was visually observed whether peeling occurred between the layers of the anisotropic conductive film and the IC chip or the substrate.
Rank Criteria O: When peeling is not observed even after 48 hours PCT after IC crimping Δ: When peeling is not observed in PCT for 24 hours after IC crimping, but peeling is observed in the PCT test for 48 hours ×: IC After crimping, if peeling has already been observed before PCT, or has been observed after 24 hours of PCT
＜反応時間＞
　得られた異方性導電フィルムから切り出した約５ｍｇのサンプルを、アルミＰＡＮ（ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ　Ｉｎｃ．）に格納し、それをＤＳＣ測定装置（Ｑ２０００，ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ　Ｉｎｃ．）にセットし、３０℃から２５０℃まで、１０℃／分の昇温速度で示差走査熱量計（ＤＳＣ）測定を行った。得られたＤＳＣチャートから、発熱ピークが立ち上がった時点の温度を反応開始温度として読み取り、発熱ピークがベースラインに変化した時点の温度を反応終了温度として読み取った。また、反応時間を以下の式に従って算出した。得られた結果を表１に示す。 <Reaction time>
About 5 mg of a sample cut out from the obtained anisotropic conductive film was stored in aluminum PAN (TA Instruments Inc.), which was set in a DSC measuring apparatus (Q2000, TA Instruments Inc.), and 30 ° C. to 250 ° C. Differential scanning calorimetry (DSC) measurement was performed at a temperature rising rate of 10 ° C./min up to ° C. From the obtained DSC chart, the temperature when the exothermic peak rose was read as the reaction start temperature, and the temperature when the exothermic peak changed to the baseline was read as the reaction end temperature. The reaction time was calculated according to the following formula. The obtained results are shown in Table 1.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
＜＜評価結果の考察＞＞
　表１の結果（実施例１と比較例１との対比、実施例２と比較例２との対比、実施例３と比較例３との対比、実施例４と比較例４との対比）から、スルホニウム塩系熱酸発生剤に代えて第４級アンモニウム塩系熱酸発生剤を使用すると、脂環式エポキシ化合物と低極性オキセタン化合物との間の配合比に変動があっても、硬化温度や接続信頼性の評価指標となる密着特性を変化させずに保管ライフを大きく向上させ得ることがわかる。 << Consideration of evaluation results >>
From the results of Table 1 (Comparison between Example 1 and Comparative Example 1, Comparison between Example 2 and Comparative Example 2, Comparison between Example 3 and Comparative Example 3, Comparison between Example 4 and Comparative Example 4) When a quaternary ammonium salt thermal acid generator is used in place of the sulfonium salt thermal acid generator, the curing temperature may vary even if the blending ratio between the alicyclic epoxy compound and the low polarity oxetane compound varies. It can be seen that the storage life can be greatly improved without changing the adhesion characteristics which are evaluation indexes of connection reliability.
　また、実施例１、５～７及び比較例５の対比から、脂環式エポキシ化合物に対して低極性オキセタン化合物の配合割合が増加するにつれ、保管ライフが向上する傾向があるが、相対的に脂環式エポキシ化合物の配合量が減少すると密着特性が低下する傾向があることがわかる。逆に、実施例８～１３の対比から、脂環式エポキシ化合物に対して低極性オキセタン化合物の配合割合が減少するにつれ、保管ライフが低下する傾向があることがわかる。 Further, from the comparison of Examples 1, 5 to 7 and Comparative Example 5, the storage life tends to improve as the blending ratio of the low polarity oxetane compound to the alicyclic epoxy compound increases. It can be seen that the adhesion properties tend to decrease as the amount of the alicyclic epoxy compound decreases. On the contrary, it can be seen from the comparison between Examples 8 to 13 that the storage life tends to decrease as the blending ratio of the low-polar oxetane compound to the alicyclic epoxy compound decreases.
　なお、実施例１、実施例５～１３、比較例５において行ったＤＳＣ測定結果の対比から、低極性オキセタン化合物の配合量が増加すると、反応開始温度と反応終了温度とを上昇させる傾向があることが分かる。 From the comparison of DSC measurement results performed in Example 1, Examples 5 to 13 and Comparative Example 5, when the blending amount of the low polarity oxetane compound increases, the reaction start temperature and the reaction end temperature tend to increase. I understand that.
　脂環式エポキシ化合物を使用するカチオン重合性の本発明の異方性導電フィルムは、スルホニウム塩系熱酸発生剤を使用した従来の異方性導電フィルムと同等の硬化温度と接続信頼性とを担保しながらも、今まで以上に優れた保管ライフ性を実現できるので、ＩＣチップなどの電子部品の配線基板への異方性導電接続に有用である。 The cationic conductive anisotropic conductive film of the present invention using an alicyclic epoxy compound has the same curing temperature and connection reliability as a conventional anisotropic conductive film using a sulfonium salt thermal acid generator. While guaranteeing, it is possible to realize a better storage life than ever, which is useful for anisotropic conductive connection of an electronic component such as an IC chip to a wiring board.

Claims (9)

  1. 　成膜用成分とカチオン重合性成分とを含有するバインダ組成物と、カチオン重合開始剤と、導電粒子とを含有する異方性導電フィルムであって、
    　カチオン重合開始剤が、第４級アンモニウム塩系熱酸発生剤であり、カチオン重合性成分が、脂環式エポキシ化合物と低極性オキセタン化合物とを含有している異方性導電フィルム。     A binder composition containing a film forming component and a cationic polymerizable component, a cationic polymerization initiator, and an anisotropic conductive film containing conductive particles,
    An anisotropic conductive film in which the cationic polymerization initiator is a quaternary ammonium salt thermal acid generator, and the cationic polymerizable component contains an alicyclic epoxy compound and a low-polar oxetane compound.
  2. 　脂環式エポキシ化合物と低極性オキセタン化合物との配合割合が、質量基準で２５：７５～６０：４０である請求項１記載の異方性導電フィルム。 The anisotropic conductive film according to claim 1, wherein the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound is 25:75 to 60:40 on a mass basis.
  3. 　脂環式エポキシ化合物と低極性オキセタン化合物との配合割合が、質量基準で４５：５５～６０：４０である請求項１記載の異方性導電フィルム。 The anisotropic conductive film according to claim 1, wherein the blending ratio of the alicyclic epoxy compound and the low polarity oxetane compound is 45:55 to 60:40 on a mass basis.
  4. 　第４級アンモニウム塩系熱酸発生剤が、第４級アンモニウムカチオンと、６フッ化アンチモン酸アニオン、６フッ化リン酸アニオン、トリフルオロメタンスルホン酸アニオン、パーフルオロブタンスルホン酸アニオン、ジノニルナフタレンスルホン酸アニオン、ｐ－トルエンスルホン酸アニオン、ドデシルベンゼンスルホン酸アニオン、またはテトラキス（ペンタフルオロフェニル）ボレートアニオンとの塩である請求項１～３のいずれかに記載の異方性導電フィルム。 The quaternary ammonium salt thermal acid generator includes a quaternary ammonium cation, a hexafluoroantimonate anion, a hexafluorophosphate anion, a trifluoromethanesulfonate anion, a perfluorobutanesulfonate anion, and dinonylnaphthalenesulfone. The anisotropic conductive film according to any one of claims 1 to 3, which is a salt with an acid anion, p-toluenesulfonate anion, dodecylbenzenesulfonate anion, or tetrakis (pentafluorophenyl) borate anion.
  5. 　第４級アンモニウムカチオンが、ＮＲ１Ｒ２Ｒ３Ｒ４＋で表されるカチオンであり、Ｒ１、Ｒ２、Ｒ３及びＲ４は、直鎖、分岐鎖または環状の炭素数１～１２のアルキル基またはアリール基である請求項４記載の異方性導電フィルム。 The quaternary ammonium cation is a cation represented by NR1R2R3R4 + , and R1, R2, R3 and R4 are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms or aryl groups. The anisotropic conductive film as described.
  6. 　脂環式エポキシ化合物が、ジグリシジルヘキサヒドロビスフェノールＡ又はジエポキシビシクロヘキシルであり、低極性オキセタン化合物が、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン又は４，４′－ビス[（３－エチル－３－オキセタニル）メトキシメチル]ビフェニルである請求項１～５のいずれかに記載の異方性導電フィルム。 The alicyclic epoxy compound is diglycidyl hexahydrobisphenol A or diepoxybicyclohexyl, and the low polarity oxetane compound is 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane or 4,4′-bis [ The anisotropic conductive film according to any one of claims 1 to 5, which is (3-ethyl-3-oxetanyl) methoxymethyl] biphenyl.
  7. 　成膜用成分がフェノキシ樹脂である請求項１～６のいずれかに記載の異方性導電フィルム。 The anisotropic conductive film according to any one of claims 1 to 6, wherein the film-forming component is a phenoxy resin.
  8. 　示差走査熱量計で測定した反応ピークの反応開始温度が６０～８０℃であり、反応終了温度が１５５～１８５℃である請求項１～７のいずれかに記載の異方性導電フィルム。 The anisotropic conductive film according to any one of claims 1 to 7, wherein the reaction start temperature of the reaction peak measured with a differential scanning calorimeter is 60 to 80 ° C and the reaction end temperature is 155 to 185 ° C.
  9. 　請求項１～８のいずれかに記載の異方性導電フィルムで、第１電子部品と第２電子部品とが異方性導電接続されている接続構造体。 A connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected in the anisotropic conductive film according to any one of claims 1 to 8.
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