WO2010073885A1 - フィルム状接着剤及び異方導電性接着剤 - Google Patents

フィルム状接着剤及び異方導電性接着剤 Download PDF

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WO2010073885A1
WO2010073885A1 PCT/JP2009/070289 JP2009070289W WO2010073885A1 WO 2010073885 A1 WO2010073885 A1 WO 2010073885A1 JP 2009070289 W JP2009070289 W JP 2009070289W WO 2010073885 A1 WO2010073885 A1 WO 2010073885A1
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Prior art keywords
film
epoxy resin
adhesive
resin
conductive particles
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PCT/JP2009/070289
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English (en)
French (fr)
Inventor
年岡　英昭
奥田　泰弘
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住友電気工業株式会社
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to US13/141,497 priority Critical patent/US20110256342A1/en
Priority to CN2009801522260A priority patent/CN102264853A/zh
Priority to EP09834689A priority patent/EP2377903A1/en
Publication of WO2010073885A1 publication Critical patent/WO2010073885A1/ja

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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24174—Structurally defined web or sheet [e.g., overall dimension, etc.] including sheet or component perpendicular to plane of web or sheet

Definitions

  • the present invention relates to a film adhesive for bonding and electrically connecting a substrate or an electronic component provided with electrodes, circuits and the like.
  • the film-like adhesive examples include an anisotropic conductive adhesive (ACF) containing conductive particles in the resin composition and a non-conductive film (NCF: Non Conductive film) containing no conductive particles. is there. Both are sandwiched between connection objects and heated and pressurized to bond the connection objects.
  • anisotropic conductive adhesives the resin in the adhesive flows by heating and pressurization, sealing the gaps between the opposing electrodes on each connection object, and at the same time, a part of the conductive particles face each other In between, electrical connection is achieved.
  • the resin component flows by heating and pressurization, so that the electrodes to be connected are in direct contact with each other to achieve electrical connection.
  • the film adhesive is used for connection around precision equipment such as a liquid crystal display (LCD), high connection reliability is required. Therefore, environmental resistance is required in addition to conduction / insulation performance, and the performance is evaluated by, for example, a high-temperature and high-humidity test or a heat cycle test.
  • LCD liquid crystal display
  • an epoxy thermosetting resin composition is mainly used.
  • a resin composition in which a thermosetting resin such as an epoxy resin or a phenoxy resin and a curing agent are combined is widely used.
  • the epoxy resin is excellent in heat resistance and moisture resistance, but this cured product is very brittle and lacks toughness (flexibility). Therefore, peeling may occur due to the occurrence of cracks, resulting in a low adhesive force.
  • the epoxy resin develops an adhesive force by being cured and shrunk by heat at the time of connection, but stress is generated in the adhesive interface and inside the adhesive due to the curing shrinkage.
  • the stress at the time of curing shrinkage increases in proportion to the storage modulus of the adhesive, but since the epoxy resin has a high storage modulus after curing, the stress at the time of curing shrinkage becomes high, and the adhesive interface and the inside of the adhesive If the residual stress remains in the film and then released to a high temperature and high humidity state, interfacial debonding occurs.
  • Patent Document 1 discloses an anisotropically conductive circuit connecting member that uses epoxidized polybutadiene as a component that imparts flexibility and is used in combination with a naphthalene-based epoxy resin or a phenoxy resin.
  • the above-mentioned materials for imparting flexibility have very low compatibility with epoxy resins, and in a film adhesive using such materials, the epoxy resin and the rubber material are completely dissolved. Instead, it is in a so-called sea-island structure in which an epoxy resin is dispersed in a rubber material or the like. In order to create such a dispersed state, it is necessary to sufficiently mix the components constituting the film adhesive, and it is necessary to mix them using a special stirring device or to strictly control the production conditions.
  • An object of the present invention is to solve the above-mentioned problems, and to provide a film-like adhesive that is highly flexible and can increase adhesive strength and that can easily be mixed with its constituent components.
  • the present invention relates to a film-like adhesive comprising bisphenol A phenoxy resin having a molecular weight of 30,000 or more, an epoxy resin having a molecular weight of 500 or less, a glycidyl methacrylate copolymer, a rubber-modified epoxy resin, and a latent curing agent as essential components. (First invention of the present application).
  • the glycidyl methacrylate copolymer is a polymer obtained by copolymerizing glycidyl methacrylate and another copolymerization monomer, and has an epoxy group in a branched shape with respect to the polymer main chain. Therefore, compatibility with an epoxy resin becomes high and phase separation hardly occurs, so that mixing with the epoxy resin is easy. Moreover, since it is a soft component, flexibility can be imparted to the film adhesive and the adhesive force can be improved.
  • the epoxy equivalent of the glycidyl methacrylate copolymer is preferably 1000 or less (second invention of the present application).
  • the epoxy equivalent is large, that is, when the number of epoxy groups in the molecular chain is small, the compatibility with the epoxy resin is lowered.
  • the epoxy group in the molecular chain can react with the epoxy resin at the time of curing to form a network structure. As a result, thermal expansion under high temperature and high humidity conditions can be suppressed, and excellent long-term connection reliability.
  • the epoxy equivalent is greater than 1000, since there are few reaction points with the epoxy resin, an effective network structure cannot be formed, and heat resistance and moisture resistance are poor.
  • the glass transition temperature (Tg) of the glycidyl methacrylate copolymer is preferably lower than the glass transition temperature of the bisphenol A type phenoxy resin (the third invention of the present application).
  • Tg glass transition temperature
  • the film adhesive further contains conductive particles (the fourth invention of the present application).
  • a film adhesive containing conductive particles can be used as an anisotropic conductive adhesive.
  • the conductive particles having an aspect ratio of 5 or more are oriented in the thickness direction of the film because anisotropic conductivity is further improved (the fifth invention of the present application).
  • the orientation in the thickness direction means that the longitudinal direction of the conductive particles is aligned in a direction perpendicular to the film surface.
  • FIG. 1A and FIG. 1B are schematic views for explaining a method for measuring the aspect ratio of conductive particles used in the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a state where conductive particles are oriented in the thickness direction of the film.
  • the present invention relates to a film-like adhesive comprising bisphenol A phenoxy resin having a molecular weight of 30,000 or more, an epoxy resin having a molecular weight of 500 or less, a glycidyl methacrylate copolymer, a rubber-modified epoxy resin, and a latent curing agent as essential components. It is an agent.
  • the glycidyl methacrylate copolymer is a polymer obtained by copolymerizing glycidyl methacrylate and another copolymerization monomer, and has an epoxy group in a branched shape with respect to the polymer main chain. Therefore, compatibility with an epoxy resin becomes high and phase separation hardly occurs, so that mixing with the epoxy resin is easy. Moreover, since it is a soft component, flexibility can be imparted to the film adhesive and the adhesive force can be improved.
  • the film adhesive further contains a rubber-modified epoxy resin.
  • the rubber-modified epoxy resin is a flexible component similar to the glycidyl methacrylate copolymer. By using the rubber-modified epoxy resin and glycidyl methacrylate copolymer in combination, the flexibility of the film adhesive can be further increased. Can increase the sex.
  • the compounding amount of the rubber-modified epoxy resin is preferably 1% by weight or more and 30% by weight or less based on the total amount of the epoxy resin and the phenoxy resin.
  • the rubber-modified epoxy resin is not particularly limited as long as it is an epoxy resin having rubber and / or polyether in the skeleton. Specifically, for example, an epoxy chemically bonded to a carboxy group-modified butadiene-acrylonitrile elastomer in the molecule. Examples thereof include rubber-modified epoxy resins such as resin (CTBN-modified epoxy resin), acrylonitrile-butadiene rubber-modified epoxy resin (NBR-modified epoxy resin), urethane-modified epoxy resin, and silicone-modified epoxy resin. These may be used alone or in combination of two or more.
  • NBR-modified epoxy resins are preferably used because of excellent compatibility with epoxy resins and phenoxy resins.
  • the epoxy equivalent of the glycidyl methacrylate copolymer is preferably 1000 or less.
  • the epoxy equivalent is large, that is, when the number of epoxy groups in the molecular chain is small, the compatibility with the epoxy resin is lowered.
  • the epoxy group in the molecular chain can react with the epoxy resin at the time of curing to form a network structure. As a result, thermal expansion under high temperature and high humidity conditions can be suppressed, and excellent long-term connection reliability.
  • the epoxy equivalent is greater than 1000, since there are few reaction points with the epoxy resin, an effective network structure cannot be formed, and heat resistance and moisture resistance are poor.
  • the glass transition temperature (Tg) of the glycidyl methacrylate copolymer is preferably lower than the glass transition temperature of the bisphenol A type phenoxy resin.
  • Tg glass transition temperature
  • a phenoxy resin having a high glass transition temperature is often used as a resin component.
  • Film adhesive is sandwiched between the objects to be connected and heated and pressurized to bond the objects to be connected, but phenoxy resin with a high glass transition temperature does not have sufficient flow characteristics when heated and pressed.
  • a resin component remains more than a necessary amount between electrodes to be connected, and the remaining resin component is cured to form an insulating film and cause a connection failure. Therefore, when a glycidyl methacrylate copolymer having a glass transition temperature lower than that of the phenoxy resin is used, the flow characteristics of the entire film adhesive can be improved.
  • the glass transition temperature is a value measured using a dynamic viscoelasticity measuring device (DMA).
  • the glycidyl methacrylate copolymer is a polymer obtained by copolymerizing glycidyl methacrylate and other copolymerization monomers.
  • examples of other copolymerization monomers include acrylic acid such as acrylic acid, methyl acrylate, and acrylate ester.
  • examples include derivatives, fumaric acid derivatives such as dimethyl fumarate and diethyl fumarate, and styrene derivatives such as styrene and ⁇ -methylstyrene.
  • an acrylic acid derivative is used as another copolymer monomer, the compatibility between the glycidyl methacrylate copolymer and the epoxy resin and phenoxy resin can be increased, which is preferable.
  • the molecular weight of the glycidyl methacrylate copolymer is not particularly limited, but preferably has a weight average molecular weight of 100,000 or less in consideration of compatibility with the epoxy resin.
  • the content of the glycidyl methacrylate copolymer is preferably 1% by weight or more and 30% by weight or less based on the total amount of the epoxy resin and the phenoxy resin. This is because if the content of the glycidyl methacrylate copolymer resin exceeds 30%, the heat resistance after curing becomes insufficient. On the other hand, if it is less than 1% by weight, a sufficient flexibility improvement effect cannot be obtained, and the adhesive strength is lowered.
  • the resin component here refers to a thermosetting resin and a thermoplastic resin such as an epoxy resin, a phenoxy resin, a glycidyl methacrylate copolymer, and a rubber-modified epoxy resin.
  • the epoxy resin used in the present invention reacts quickly with a curing agent during heating and develops adhesive performance.
  • the type of epoxy resin is not particularly limited, but in addition to bisphenol type epoxy resins having skeletons of bisphenol A, F, S, AD, etc., novolac type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, etc. Illustrated.
  • the molecular weight of the epoxy resin is 500 or less.
  • the crosslinking density can be increased and the adhesion performance can be enhanced.
  • adhesive force increases.
  • the phenoxy resin used in the present invention has a high molecular weight among the epoxy resins.
  • a bisphenol A type phenoxy resin having a molecular weight of 30,000 or more is used.
  • film formability is enhanced.
  • the melt viscosity of the resin at the connection temperature can be increased, and there is an effect that the connection can be made without disturbing the orientation of the conductive particles described later.
  • molecular weight means the weight average molecular weight of polystyrene conversion calculated
  • a latent curing agent is a curing agent that has excellent storage stability at low temperatures and hardly undergoes a curing reaction at room temperature, but rapidly performs a curing reaction under a predetermined condition by heating or the like.
  • latent curing agents include imidazoles, hydrazides, boron trifluoride-amine complexes, amine imides, polyamines, tertiary amines, alkyl ureas, and other amines, dicyandiamide, and modified products thereof. These can be used alone or as a mixture of two or more.
  • imidazole-based latent curing agents are preferably used.
  • known imidazole-based latent curing agents can be used, and specific examples include adducts of imidazole compounds with epoxy resins.
  • the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-dodecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 4-methylimidazole.
  • the blending ratio of the resin component such as the epoxy resin, phenoxy resin, glycidyl methacrylate copolymer and the latent curing agent is preferably 5 to 90% by weight with respect to the total weight of the resin component.
  • the ratio of the latent curing agent is less than 5% by weight, the curing rate may decrease and curing may be insufficient.
  • the amount is more than 90% by weight, unreacted curing agent tends to remain, and heat resistance and moisture resistance may be lowered.
  • the film adhesive further contains conductive particles.
  • a film adhesive containing conductive particles can be used as an anisotropic conductive adhesive.
  • the conductive particles include metal particles such as gold, silver, copper, nickel, and alloys thereof, and carbon.
  • a non-conductive glass, ceramic, plastic, metal oxide or other core surface may be formed by coating a metal, ITO, or the like to form a conductive layer.
  • the shape of the conductive particles is not particularly limited, and spherical particles and elongated needle-like particles can be used.
  • the aspect ratio of the conductive particles is a ratio between the diameter R and the length L of the conductive particles 1 as shown in FIG.
  • the conductive particles are not necessarily required to have a straight shape, and can be used without any problem even if they are slightly bent or branched. In this case, as shown in FIG. 1B, the aspect ratio is obtained with the maximum length of the conductive particles (the length of the arrow in the figure) as the length L.
  • the diameter of the conductive particles is a diameter of a cross section perpendicular to the length direction. When the cross section is not a circle, the maximum length of the cross section is taken as the diameter of the conductive particles.
  • acicular conductive particles can be used as the conductive particles having an aspect ratio of 5 or more. Moreover, what formed many needle
  • Examples of the metal that forms fine metal particles include a single metal having ferromagnetism such as Fe, Ni, and Co, or a composite containing a metal containing ferromagnetism. When a metal having ferromagnetism is used, it is oriented by its own magnetism, and the conductive particles can be oriented using a magnetic field as will be described later.
  • the conductive particles having an aspect ratio of 5 or more are oriented in the thickness direction of the film because anisotropic conductivity is further improved.
  • the orientation in the thickness direction means that the longitudinal direction of the conductive particles is aligned in a direction perpendicular to the film surface.
  • FIG. 2 is a schematic cross-sectional view showing a state where conductive particles are oriented in the thickness direction of the film.
  • the acicular conductive particles 1 are oriented in the film thickness direction (arrow direction in the figure) in the resin component 2 of the film adhesive.
  • the method for orienting the conductive particles in the thickness direction of the film is not particularly limited. When conductive particles having ferromagnetism as described above are used, the conductive particles are obtained by dispersing them in a resin solution.
  • a preferred example is a method in which a dispersion solution is applied on a base to which a magnetic field is applied in a direction crossing the base surface, the conductive particles are oriented, and solidified and cured by removing the solvent on the base to fix the orientation. Is done.
  • the content of the conductive particles is selected from the range of 0.01 to 30% by volume with respect to the total volume of the film adhesive, and it is properly used depending on the application. In order to prevent deterioration of the insulation performance in the surface direction due to excessive conductive particles, the content is more preferably 0.01 to 10% by volume.
  • thermosetting resins thermoplastic resins and the like can be added in addition to the essential components as long as the gist of the present invention is not impaired.
  • additives such as a hardening accelerator, a polymerization inhibitor, a sensitizer, a silane coupling agent, a flame retardant, and a thixotropic agent.
  • the film adhesive of the present invention can be obtained by mixing the above-described components. Since the glycidyl methacrylate copolymer used in the present invention is excellent in compatibility with the epoxy resin and the phenoxy resin, it can be easily mixed without using a special stirring device.
  • a resin component solution can be easily prepared by placing the epoxy resin, phenoxy resin, glycidyl methacrylate copolymer, latent curing agent and the like in a container and performing simple mixing with a centrifugal mixer for several minutes. This solution is applied with a roll coater or the like to form a thin film, and then the solvent is removed by drying or the like to obtain a film adhesive.
  • a film is formed by coating in the same manner using a dispersion in which conductive particles are added and dispersed in a resin component solution, and then the solvent is removed by drying or the like to form a film.
  • An adhesive can be made.
  • the film thickness of the film adhesive is not particularly limited, but is usually 10 to 50 ⁇ m.
  • Example 1 (Preparation of coating solution) Bisphenol A type epoxy resin [Epicoat 1256 manufactured by Japan Epoxy Resin Co., Ltd. (molecular weight: about 50,000, Tg: about 98 ° C.)] as phenoxy resin, and bisphenol F type liquid epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd.] Epicoat 806 (molecular weight of about 350)], glycidyl methacrylate copolymer, styrene copolymer of glycidyl methacrylate [Nippon Yushi Co., Ltd.
  • Marproof G-0250S epoxy equivalent 310, molecular weight of about 20,000, Tg of about 74 ° C.
  • NBR-modified epoxy (DIC TSR960] as the rubber-modified epoxy
  • microcapsule-type imidazole curing agent [manufactured by Asahi Kasei Epoxy Co., Ltd., Novacure HX3932] as the latent curing agent in a weight ratio of 50 / 20/15/15/30 ratio
  • mixing ratio is 1: 1 by weight
  • acicular nickel particles (aspect ratio: 5 to 60) having a length distribution from 1 ⁇ m to 12 ⁇ m as conductive particles are added to the total amount of solid content (resin composition + nickel powder). It added so that it might become 0.2 volume%, and also it disperse
  • the coating solution prepared above is applied onto a release-treated PET film using a doctor knife, and then dried and solidified at 60 ° C. for 30 minutes in a magnetic field having a magnetic flux density of 100 mT to form a film having a thickness of 20 ⁇ m. A film adhesive was obtained.
  • connection resistance evaluation An FPC in which 124 gold-plated copper circuits with a width of 50 ⁇ m and a height of 16 ⁇ m were arranged at intervals of 50 ⁇ m and a glass substrate on which ITO circuits with a width of 150 ⁇ m were formed at intervals of 50 ⁇ m were prepared. After that, both are placed facing each other so as to form a daisy chain capable of measuring 124 consecutive connection resistances, and the film-like adhesive obtained above is sandwiched between the FPC and the glass substrate, and the temperature is set to 190 ° C. While being heated, pressure was applied at a pressure of 5 MPa for 12 seconds to cause adhesion, and an FPC and empty bunt joined body was obtained. In this joined body, the resistance value of 124 consecutive points connected via the ITO electrode, the film adhesive, and the gold-plated copper circuit is obtained by the four-terminal method, and the value is divided by 124 to obtain the resistance value per location. The connection resistance was determined.
  • connection resistance was low, and the resistance value did not increase so much after 100 hours in a high temperature and high humidity environment. Also, the adhesive strength was good both in the initial stage and after high temperature and high humidity.
  • Comparative Example 1 since the rubber-modified epoxy was not added, the reaction rate was lowered, and it seems that curing did not proceed sufficiently. Accordingly, the initial characteristics of both connection resistance and adhesive strength are good, but the characteristics are degraded after the high temperature and high humidity test. In Comparative Example 2, since the glycidyl methacrylate copolymer is not added, the flexibility of the adhesive cannot be sufficiently obtained. Therefore, compared with Example 1, the adhesive strength is low both at the initial stage and after the high temperature and high humidity test.
  • the film adhesive of the present invention bonds and electrically connects substrates and electronic components in order to reduce the size of the connection terminals of components in fields where downsizing and high functionality of electronic devices are required. It is suitably used for this purpose.

Abstract

　分子量が３０，０００以上のビスフェノールＡ型フェノキシ樹脂、分子量が５００以下のエポキシ樹脂、メタクリル酸グリシジル共重合体、ゴム変性エポキシ樹脂、及び潜在性硬化剤を必須成分とし、好ましくは、メタクリル酸グリシジル共重合体のエポキシ当量は、１０００以下とすることにより、混合が容易であり、可撓性が高く接着力を高めることができるフィルム状接着剤を提供する。

Description

フィルム状接着剤及び異方導電性接着剤
　本発明は、電極、回路等を設けた基板や電子部品等を接着し、かつ電気的に接続するためのフィルム状接着剤に関するものである。
　近年の電子機器の小型化、高機能化の流れの中で、構成部品における接続端子の狭小化が進んでいる。このため、エレクトロニクス実装分野においては、そのような端子間の接続を容易に行える種々のフィルム状接着剤が使用されている。例えばＩＣチップとフレキシブルプリント配線板（ＦＰＣ）、ＩＣチップとＩＴＯ（Ｉｎｄｉｕｍ－Ｔｉｎ－Ｏｘｉｄｅ）電極回路が形成されたガラス基板、等の接合に使用されている。
　フィルム状接着剤としては、樹脂組成物中に導電性粒子を含有する異方導電性接着剤（ＡＣＦ：Ａｎｉｓｏｔｏｒｏｐｉｃ　Ｃｏｎｄｕｃｔｉｖｅ　ｆｉｌｍ）と導電性粒子を含有しない非導電性フィルム（ＮＣＦ：Ｎｏｎ　Ｃｏｎｄｕｃｔｉｖｅ　ｆｉｌｍ）がある。どちらも接続対象の間に挟まれ、加熱、加圧されて接続対象を接着する。異方導電性接着剤では、加熱、加圧により接着剤中の樹脂が流動し、それぞれの接続対象上の相対峙する電極間の間隙を封止すると同時に導電性粒子の一部が対峙する電極間に噛み込まれて電気的接続が達成される。非導電性フィルムの場合は、加熱、加圧により樹脂成分が流動することで接続対象である電極同士が直接接触して電気的接続が達成される。これらのフィルム状接着剤では、厚み方向に相対峙する電極間の抵抗（接続抵抗）を低くするという導通性能と、面方向に隣り合う電極間の抵抗（絶縁抵抗）を高くするという絶縁性能が必要とされている。
　また、フィルム状接着剤は、液晶表示装置（ＬＣＤ）等の精密機器周辺の接続に使用されるため高い接続信頼性が要求されている。そこで導通／絶縁性能に加え、耐環境性が求められており、たとえば高温高湿試験やヒートサイクル試験等によりその性能を評価している。
　フィルム状接着剤を構成する絶縁性の樹脂組成物としては、主にエポキシ系の熱硬化性樹脂組成物が用いられている。例えばエポキシ樹脂、フェノキシ樹脂等の熱硬化性樹脂と硬化剤を組み合わせた樹脂組成物が広く使用されている。
　エポキシ樹脂は、耐熱性、耐湿性に優れているが、この硬化物は、非常に脆く靱性（可撓性）に欠けている。そのため、クラックの発生によって剥離を生じる場合があり、接着力が低くなる。また、エポキシ樹脂は、接続時の熱により硬化収縮することで接着力を発現するが、この硬化収縮によって接着界面や接着剤内部に応力が発生する。硬化収縮時の応力は、接着剤の貯蔵弾性率に比例して増大するが、エポキシ樹脂は、硬化後の貯蔵弾性率が高いことから硬化収縮時の応力が高くなり、接着界面や接着剤内部に残留応力が残り、その後高温高湿状態に解放されると界面剥離が生じることになる。
　上記のエポキシ樹脂の欠点を補うために、アクリルゴム、ＮＢＲ等のゴム系材料やアクリル樹脂等の熱可塑性樹脂をエポキシ樹脂と併用し、フィルム状接着剤に可撓性を付与している。たとえば特許文献１では、可撓性を付与する成分としてエポキシ化ポリブタジエンを用い、ナフタレン系エポキシ樹脂、フェノキシ樹脂と併用した異方導電性の回路接続用部材が開示されている。
　可撓性を付与するための上記の材料は、エポキシ樹脂との相溶性が非常に低く、このような材料を用いたフィルム状接着剤では、エポキシ樹脂とゴム材料等とが完全に溶解した状態ではなく、ゴム材料等の中にエポキシ樹脂が分散した、いわゆる海島構造と呼ばれる状態となっている。このような分散状態を作るためには、フィルム状接着剤を構成する成分を充分に混合する必要があり、特殊な攪拌装置を使って混合したり、製造条件を厳しく管理する必要がある。
　特許文献１では、可撓性を付与する成分に官能基（エポキシ基）を付与したエポキシ化ポリブタジエンを用いてエポキシ樹脂との相溶性を高めているが、その分子量に比べて官能基の割合が低いため、その効果は、低い。
　本発明は、上記の問題を解決し、可撓性が高く接着力を高めることができると共に、その構成成分の混合が容易であるフィルム状接着剤を提供することを課題とする。
　本発明は、分子量が３０，０００以上のビスフェノールＡ型フェノキシ樹脂、分子量が５００以下のエポキシ樹脂、メタクリル酸グリシジル共重合体、ゴム変性エポキシ樹脂、及び潜在性硬化剤を必須成分とするフィルム状接着剤である（本願第１の発明）。
　メタクリル酸グリシジル共重合体は、メタクリル酸グリシジルと他の共重合モノマーとを共重合させたポリマーであり、ポリマー主鎖に対して枝状にエポキシ基を有している。そのため、エポキシ樹脂との相溶性が高くなり、相分離が起こりにくくなるのでエポキシ樹脂との混合が容易である。また、柔軟な成分であるため、フィルム状接着剤に可撓性を付与でき、接着力を向上できる。
　メタクリル酸グリシジル共重合体のエポキシ当量は、１０００以下とすることが好ましい（本願第２の発明）。エポキシ当量が大きい、すなわち分子鎖中のエポキシ基の数が少ないとエポキシ樹脂との相溶性が低くなる。また、分子鎖中のエポキシ基は、硬化時にエポキシ樹脂と反応して網目構造をつくることができ、その結果、高温高湿条件下での熱膨張を抑制でき、長期接続信頼性に優れる。エポキシ当量が１０００より大きいと、エポキシ樹脂との反応点が少ないことから効果的な網目構造をつくることができなくなり、耐熱、耐湿性が劣る。
　メタクリル酸グリシジル共重合体のガラス転移温度（Ｔｇ）は、ビスフェノールＡ型フェノキシ樹脂のガラス転移温度よりも低いことが好ましい（本願第３の発明）。一般的に、耐熱性及び耐湿性の向上のためには、フィルム状接着剤に含まれる樹脂成分の硬化後のガラス転移温度を高くすることが必要である。ガラス転移温度が高いと高温域での熱膨張率が低減し、高温・高湿環境での特性変化が少なくなるからである。
　フィルム状接着剤には、さらに導電性粒子を含有すると好ましい（本願第４の発明）。導電性粒子を含有したフィルム状接着剤は、異方導電性接着剤として使用可能である。
　上記のアスペクト比が５以上の導電性粒子がフィルムの厚み方向に配向していると、異方導電性がさらに向上するので好ましい（本願第５の発明）。なお、厚み方向に配向とは、導電性粒子の長手方向がフィルムの面に対して垂直方向に並んだ状態になっていることをいう。
　本発明により、可撓性が高く接着力を高めることができると共に、その構成成分の混合が容易であるフィルム状接着剤が得られる。
図１(a)および図１(b)は、本発明に使用する導電性粒子のアスペクト比の測定方法を説明するための模式図である。 図２は、導電性粒子がフィルムの厚み方向に配向している状態を示す断面模式図である。
以下、本発明の実施の形態を説明する。なお、実施例は、本発明の範囲を限定するものではない。図面の説明においては、同一要素には同一符号を付し、重複する説明を省略する。また、図面の寸法比率は、説明のものと必ずしも一致していない。
　本発明は、分子量が３０，０００以上のビスフェノールＡ型フェノキシ樹脂、分子量が５００以下のエポキシ樹脂、メタクリル酸グリシジル共重合体、ゴム変性エポキシ樹脂、及び潜在性硬化剤を必須成分とするフィルム状接着剤である。
　メタクリル酸グリシジル共重合体は、メタクリル酸グリシジルと他の共重合モノマーとを共重合させたポリマーであり、ポリマー主鎖に対して枝状にエポキシ基を有している。そのため、エポキシ樹脂との相溶性が高くなり、相分離が起こりにくくなるのでエポキシ樹脂との混合が容易である。また、柔軟な成分であるため、フィルム状接着剤に可撓性を付与でき、接着力を向上できる。
　上記の成分に加えて、フィルム状接着剤には、さらにゴム変性エポキシ樹脂を含有する。ゴム変性エポキシ樹脂は、前記メタクリル酸グリシジル共重合体と同様に柔軟な成分であり、ゴム変性エポキシ樹脂とメタクリル酸グリシジル共重合体とを組み合わせて使用することで、さらにフィルム状接着剤の可撓性を高めることができる。ゴム変性エポキシ樹脂の配合量は、エポキシ樹脂及びフェノキシ樹脂の合計量に対して１重量％以上３０重量％以下であることが好ましい。
　ゴム変性エポキシ樹脂は、骨格にゴムおよび／またはポリエーテルを有するエポキシ樹脂であれば特に限定されないが、具体的には、例えば、カルボキシ基変性ブタジエン－アクリロニトリルエラストマーと分子内で化学的に結合したエポキシ樹脂（ＣＴＢＮ変性エポキシ樹脂）、アクリロニトリル－ブタジエンゴム変性エポキシ樹脂（ＮＢＲ変性エポキシ樹脂）、ウレタン変性エポキシ樹脂、シリコーン変性エポキシ樹脂等のゴム変性エポキシ樹脂が例示される。これらは単独で使用しても良く、二種類以上を併用しても良い。
　上記ゴム変性エポキシ樹脂の中でもＮＢＲ変性エポキシ樹脂を用いると、エポキシ樹脂及びフェノキシ樹脂との相溶性に優れ、好ましい。
　メタクリル酸グリシジル共重合体のエポキシ当量は１０００以下とすることが好ましい。エポキシ当量が大きい、すなわち分子鎖中のエポキシ基の数が少ないとエポキシ樹脂との相溶性が低くなる。また、分子鎖中のエポキシ基は、硬化時にエポキシ樹脂と反応して網目構造をつくることができ、その結果、高温高湿条件下での熱膨張を抑制でき、長期接続信頼性に優れる。エポキシ当量が１０００より大きいと、エポキシ樹脂との反応点が少ないことから効果的な網目構造をつくることができなくなり、耐熱、耐湿性が劣る。
　メタクリル酸グリシジル共重合体のガラス転移温度（Ｔｇ）は、ビスフェノールＡ型フェノキシ樹脂のガラス転移温度よりも低いことが好ましい。一般的に、耐熱性及び耐湿性の向上のためには、フィルム状接着剤に含まれる樹脂成分の硬化後のガラス転移温度を高くすることが必要である。ガラス転移温度が高いと高温域での熱膨張率が低減し、高温・高湿環境での特性変化が少なくなるからである。
　硬化後のガラス転移温度を高くするための方法として、ガラス転移温度の高いフェノキシ樹脂が樹脂成分として使用されることが多い。フィルム状接着剤は、接続対象の間に挟まれ、加熱、加圧されて接続対象を接着するが、ガラス転移温度が高いフェノキシ樹脂は、加熱、加圧時に充分な流動特性を有さないため、接続対象である電極間に樹脂成分が必要量以上に残留し、残留した樹脂成分が硬化したものが絶縁被膜を形成して接続不良の原因となる場合がある。そこで、フェノキシ樹脂のガラス転移温度よりもガラス転移温度が低いメタクリル酸グリシジル共重合体を使用すると、フィルム状接着剤全体の流動特性を向上させることができる。なお、ガラス転移温度は、動的粘弾性測定装置（ＤＭＡ）を用いて測定した値とする。
　メタクリル酸グリシジル共重合体は、メタクリル酸グリシジルと他の共重合モノマーとを共重合させたポリマーであるが、他の共重合モノマーとしては、アクリル酸、アクリル酸メチル、アクリル酸エステル等のアクリル酸誘導体、フマル酸ジメチル、フマル酸ジエチル等のフマル酸誘導体、または、スチレン、α－メチルスチレン等のスチレン誘導体等が例示できる。他の共重合体モノマーとしてアクリル酸誘導体を使用すると、メタクリル酸グリシジル共重合体とエポキシ樹脂及びフェノキシ樹脂との相溶性を高めることができ、好ましい。
　メタクリル酸グリシジル共重合体の分子量は、特に制限されないが、エポキシ樹脂との相溶性を考慮すると、重量平均分子量が１０万以下のものが好ましい。
　メタクリル酸グリシジル共重合体の含有量は、エポキシ樹脂及びフェノキシ樹脂の合計量に対して１重量％以上３０重量％以下であることが好ましい。メタクリル酸グリシジル共重合体樹脂の含有量が３０％を超えると硬化後の耐熱性が不充分となるからである。また、１重量％未満であると、充分な可撓性向上効果が得られず、接着力が低下する。なお、ここでいう樹脂成分とは、エポキシ樹脂、フェノキシ樹脂、メタクリル酸グリシジル共重合体、ゴム変性エポキシ樹脂等の熱硬化性樹脂及び熱可塑性樹脂を指すものとする。
　本発明に使用するエポキシ樹脂は、加熱時に速やかに硬化剤と反応し接着性能を発現するものである。エポキシ樹脂の種類は、特に限定されないが、ビスフェノールＡ、Ｆ、Ｓ、ＡＤ等を骨格とするビスフェノール型エポキシ樹脂等の他、ノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂等が例示される。
　エポキシ樹脂の分子量は、５００以下とする。低分子量のエポキシ樹脂を使用することで、架橋密度が高まって接着性能を高めることができる。また、加熱時に、硬化剤と速やかに反応するため、接着力が高まる。
　本発明に使用するフェノキシ樹脂は、前記エポキシ樹脂の中でも高分子量のものである。本発明では、分子量３０，０００以上のビスフェノールＡ型フェノキシ樹脂を使用する。高分子量のフェノキシ樹脂を使用することでフィルム成形性が高くなる。また、接続温度における樹脂の溶解粘度を高くでき、後述の導電性粒子の配向を乱すことなく接続できる効果がある。
　このように低分子量のエポキシ樹脂と高分子量のフェノキシ樹脂を組み合わせて使用することによって、フィルム状接着剤の性能のバランスを取ることが可能となる。エポキシ樹脂とフェノキシ樹脂の配合比は、エポキシ樹脂／フェノキシ樹脂＝１０／９０～７０／３０とすると好ましい。なお、分子量は、ＴＨＦ展開のゲルパーミッションクロマトグラフィー（ＧＰＣ）から求められたポリスチレン換算の重量平均分子量のことをいう。
　本発明に使用する潜在性硬化剤としては、エポキシ樹脂の硬化剤として公知のものを適宜選択して使用することができる。潜在性硬化剤は、低温での貯蔵安定性に優れ、室温では、ほとんど硬化反応を起こさないが、加熱等により所定の条件とすると、速やかに硬化反応を行う硬化剤である。潜在性硬化剤としては、イミダゾール系、ヒドラジド系、三フッ化ホウ素－アミン錯体、アミンイミド、ポリアミン系、第３級アミン、アルキル尿素系等のアミン系、ジシアンジアミド等、及びこれらの変性物が例示され、これらは、単独または２種以上の混合物として使用できる。
　前記の潜在性硬化剤の中でも、イミダゾール系潜在性硬化剤が好ましく使用される。イミダゾール系潜在性硬化剤としては、公知のイミダゾール系潜在性硬化剤を使用することができ、具体的には、イミダゾール化合物のエポキシ樹脂との付加物が例示される。イミダゾール化合物としては、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－プロピルイミダゾール、２－ドデシルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、４－メチルイミダゾールが例示される。
　さらに、これらの潜在性硬化剤をポリウレタン系、ポリエステル系等の高分子物質や、ニッケル、銅等の金属薄膜及びケイ酸カルシウム等の無機物で被覆してマイクロカプセル化したものは、長期保存性と速硬化性という矛盾した特性の両立をより充分に達成するため好ましい。従って、マイクロカプセル型イミダゾール系潜在性硬化剤が特に好ましい。
　前記エポキシ樹脂、フェノキシ樹脂、メタクリル酸グリシジル共重合体等の樹脂成分と潜在性硬化剤の配合割合は、樹脂成分の合計重量に対し、５～９０重量％とするのが好ましい。潜在性硬化剤の割合が５重量％より少ない場合、硬化速度が低下し、硬化が不十分になる場合がある。また、９０重量％より多い場合、未反応の硬化剤が残留しやすくなり、耐熱、耐湿性を低下させる場合がある。
　フィルム状接着剤には、さらに導電性粒子を含有すると好ましい。導電性粒子を含有したフィルム状接着剤は、異方導電性接着剤として使用可能である。導電性粒子としては、金、銀、銅、ニッケル及びそれらの合金などの金属粒子、カーボン等が挙げられる。又、非導電性のガラス、セラミック、プラスチック、金属酸化物等の核の表面に、金属やＩＴＯ等を被覆して導電層を形成したものでも良い。導電性粒子の形状は、特に限定されず、球状の粒子や細長い針状の粒子を使用することができる。
　導電性粒子として、径と長さの比（アスペクト比）が５以上の導電性粒子を用いると、導電性粒子の含有量を増やすことなく接続抵抗を低くすることができ、良好な電気的接続を達成出来ると共に、面方向の絶縁抵抗をより高く保つことができ好ましい。導電性粒子のアスペクト比は、ＣＣＤ顕微鏡観察等の方法により直接測定する図１(a)に示すように導電性粒子１の径Ｒと長さＬの比である。導電性粒子は、必ずしもまっすぐな形状を有する必要はなく、多少の曲がりや枝分かれがあっても問題なく使用できる。この場合は、図１(b)に示すように、導電性粒子の最大長（図中の矢印の長さ）を長さＬとしてアスペクト比を求める。また、導電性粒子の径とは、長さ方向に垂直な断面の径である。断面が円で無い場合は、断面の最大長さを導電性粒子の径とする。
　アスペクト比が５以上の導電性粒子としては、市販の針状導電性粒子を使用することができる。また、微細な金属粒子を多数つなげて針状に形成したものも好ましく使用できる。アスペクト比が１０～１００であると更に好ましい。また、導電性粒子の径が１μｍ以下であると、いわゆるファインピッチ電極の接続が可能となり好ましい。
　微細な金属粒子を形成する金属としては、Ｆｅ、Ｎｉ、Ｃｏ等の強磁性を有する金属の単体又は強磁性を含む金属を含む複合体が挙げられる。強磁性を有する金属を用いると、それ自体が有する磁性により配向し、また、後述するように磁場を用いて導電性粒子の配向を行うことができる。
　上記のアスペクト比が５以上の導電性粒子がフィルムの厚み方向に配向していると、異方導電性がさらに向上するので好ましい。なお、厚み方向に配向とは、導電性粒子の長手方向がフィルムの面に対して垂直方向に並んだ状態になっていることをいう。図２は、導電性粒子がフィルムの厚み方向に配向している状態を示す断面模式図である。針状の導電性粒子１は、フィルム状接着剤の樹脂成分２の中で、フィルムの厚み方向（図中の矢印方向）に配向している。導電性粒子をフィルムの厚み方向に配向させる方法は、特に限定されないが、前記のような強磁性を有する導電性粒子を用いる場合は、導電性粒子を樹脂用液中に分散し、得られた分散溶液を下地面と交差する方向に磁場を印加した下地上に塗布して、該導電性粒子を配向させ、下地上で溶媒の除去等により固化、硬化させて配向を固定する方法が好ましく例示される。
　導電性粒子の含有量は、フィルム状接着剤の全体積に対して０．０１～３０体積％の範囲から選ばれ、用途により使い分ける。過剰な導電性粒子による面方向の絶縁性能低下を防ぐためには、０．０１～１０体積％とするのがより好ましい。
　本発明のフィルム状接着剤には、本発明の趣旨を損なわない範囲で、前記の必須成分に加えて、他の熱硬化性樹脂、熱可塑性樹脂等を添加することが可能である。また、硬化促進剤、重合抑制剤、増感剤、シランカップリング剤、難燃化剤、チキソトロピック剤等の添加剤を含有しても良い。
　本発明のフィルム状接着剤は、前記の各成分を混合することにより得ることができる。本発明に使用するメタクリル酸グリシジル共重合体は、エポキシ樹脂、フェノキシ樹脂との相溶性に優れるため、特別な攪拌装置を使用しなくても容易に混合可能である。例えば前記エポキシ樹脂、フェノキシ樹脂、メタクリル酸グリシジル共重合体、潜在性硬化剤等と溶媒を容器に入れ、遠心攪拌ミキサーによる単純混合を数分行うことで容易に樹脂成分の溶液を作成できる。この溶液をロールコーター等で塗工して薄い膜を形成し、その後溶媒を乾燥等により除去することによりフィルム状接着剤が得られる。
　導電性粒子を用いる場合は、樹脂成分の溶液中に導電性粒子を加えて分散させた分散液を用いて同様に塗工して膜を形成し、その後溶媒を乾燥等により除去してフィルム状接着剤を作製することができる。導電性粒子を配向させるためには、膜の形成時に、フィルム状接着剤の厚み方向にかけた磁場の中を通過させると良い。磁場の中を通過する際に導電性粒子が配向し、その後溶媒を除去する工程で配向した導電性粒子の状態が固定化される。フィルム状接着剤の膜厚は、特に制限されないが、通常１０～５０μｍである。
（実施例１）
（塗工溶液の作製）
　フェノキシ樹脂としてビスフェノールＡ型のエポキシ樹脂［ジャパンエポキシレジン（株）製エピコート１２５６（分子量約５万、Ｔｇ約９８℃）］、エポキシ樹脂としてビスフェノールＦ型の液状エポキシ樹脂［ジャパンエポキシレジン（株）製エピコート８０６（分子量約３５０）］、メタクリル酸グリシジル共重合体として、メタクリル酸グリシジルのスチレン系共重合体［日本油脂（株）製マープルーフＧ－０２５０Ｓ（エポキシ当量３１０、分子量約２万、Ｔｇ約７４℃）］、ゴム変性エポキシとしてＮＢＲ変性エポキシ［ＤＩＣ（株）ＴＳＲ９６０］、潜在性硬化剤としてマイクロカプセル型イミダゾール系硬化剤［旭化成エポキシ（株）製、ノバキュアＨＸ３９３２］とを、重量比で５０／２０／１５／１５／３０の割合で用い、これらの材料にカルビトールアセテートと酢酸ブチルの混合溶媒（混合比率は、重量比で１：１）を加えた後、遠心攪拌ミキサーによる単純混合を３分行って個稀有分６０％の樹脂溶液を作製した。この樹脂用液に、導電性粒子として、１μｍから１２μｍまでの長さ分布を有する針状ニッケル粒子（アスペクト比：５～６０）を、固形分の総量（樹脂組成物＋ニッケル粉末）に対して０．２体積％となるように添加し、さらに遠心攪拌ミキサーを用いて３分間攪拌することで均一分散し、接着剤用の塗工溶液を調製した。
（フィルム状接着剤の作製）
　上記で調整した塗工溶液を、離型処理したＰＥＴフィルム上にドクターナイフを用いて塗布した後、磁束密度１００ｍＴの磁場中、６０℃で３０分間乾燥、固化させることによって、厚み２０μｍのフィルム状のフィルム状接着剤を得た。
（接続抵抗評価）
　幅５０μｍ、高さ１６μｍの金メッキした銅回路が５０μｍ間隔で１２４本個配列されたＦＰＣと、幅１５０μｍのＩＴＯ回路が５０μｍ間隔で形成されたガラス基板とを準備した。その後両者を、連続する１２４カ所の接続抵抗が測定可能なデイジーチェーンを形成するように向かい合わせて配置し、ＦＰＣとガラス基板との間に前記で得られたフィルム状接着剤挟み、１９０℃に加熱しながら５ＭＰａの圧力で１２秒間加圧して接着させ、ＦＰＣとがら空きバントの接合体を得た。この接合体において、ＩＴＯ電極、フィルム状接着剤、及び金メッキ銅回路を介して接続された連続する１２４箇所の抵抗値を四端子法により求め、その値を１２４で除することによって１箇所当たりの接続抵抗を求めた。
（耐熱・耐湿試験）
　上記のＦＰＣとガラス基板の接合体を温度８５℃、湿度８５％に設定した恒温恒湿槽内に投入し、１００時間経過後に取り出し、再び前記と同様にして接続抵抗値を測定した。
（接着力評価）
　上記のＦＰＣとガラス基板の接合体において、オートグラフＡＧ－５００Ｇ［（株）島津製作所製］を使用して、ＦＰＣを引きはがし、９０°剥離強度を測定した。なお接着力は、初期のものと、耐熱・耐湿試験後のものの両方で行った。
（比較例１）
　ゴム変性エポキシ樹脂を添加せず、各成分の配合割合をフェノキシ樹脂／エポキシ樹脂／メタクリル酸グリシジル共重合体／潜在性硬化剤＝５０／２０／３０／３０としたこと以外は実施例１と同様にして、厚みが２０μｍのフィルム状接着剤を作製し、一連の評価を行った。
（比較例２）
　メタクリル酸グリシジル共重合体を添加せず、各成分の配合割合をフェノキシ樹脂／エポキシ樹脂／ゴム変性エポキシ樹脂／潜在性硬化剤＝５０／２０／３０／３０としたこと以外は実施例１と同様にして、厚みが２０μｍのフィルム状接着剤を作製し、一連の評価を行った。
（比較例３）
　メタクリル酸グリシジル共重合体の代わりに、ＯＨ末端を有するアクリルゴム［根上工業（株）製ＡＳ－３０００Ｅ］を使用したこと以外は実施例１と同様にして、フィルム状接着剤の作製を試みたが、３分間の遠心攪拌では、エポキシ樹脂とアクリルゴムとがうまく混合せず、樹脂溶液が分離してシートの作製はできなかった。以上の結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　本発明のフィルム状接着剤を用いた実施例１では、接続抵抗が低く、また、高温高湿の環境で１００時間経過後も抵抗値は、さほど上昇していなかった。また、接着力も初期、高温高湿後共に良好であった。
　比較例１では、ゴム変性エポキシを添加していないため、反応速度が低下し、硬化が充分に進まなかったと思われる。従って接続抵抗、接着力共に初期の特性は良いが、高温高湿試験後には、特性が低下している。比較例２は、メタクリル酸グリシジルコポリマーを添加していないため、接着剤の可撓性が充分に得られない。従って実施例１に比べると、初期、高温高湿試験後共に接着力が低くなっている。
　今回開示された実施の形態および実施例は、全ての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記した説明でなく特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内のすべての変更が含まれることが意図される。
本発明フィルム状接着剤は、電子機器の小型化、高機能化が求められる分野において、構成部品の接続端子の狭小化を行うために、基板や電子部品等を接着し、かつ電気的に接続するために好適に用いられる。
　１　導電性粒子
　２　樹脂成分
特許第４１１０５８９号公報

Claims (5)

  1. 　分子量が３０，０００以上のビスフェノールＡ型フェノキシ樹脂、分子量が５００以下のエポキシ樹脂、メタクリル酸グリシジル共重合体、ゴム変性エポキシ樹脂、及び潜在性硬化剤を必須成分とするフィルム状接着剤。
  2. 　前記メタクリル酸グリシジル共重合体のエポキシ当量が１０００以下であることを特徴とする、請求項１に記載のフィルム状接着剤。
  3. 　前記メタクリル酸グリシジル共重合体のガラス転移温度が、前記ビスフェノールＡ型フェノキシ樹脂のガラス転移温度よりも低いことを特徴とする、請求項１又は２に記載のフィルム状接着剤。
  4. 　さらに導電性粒子を含有する、請求項１～３のいずれか１項に記載のフィルム状接着剤。
  5. 　前記導電性粒子は、径と長さの比（アスペクト比）が５以上であり、フィルムの厚み方向に配向していることを特徴とする、請求項４に記載のフィルム状接着剤。
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