JP2006299177A - Anisotropically conductive adhesive sheet and fine connection structure - Google Patents
Anisotropically conductive adhesive sheet and fine connection structure Download PDFInfo
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- JP2006299177A JP2006299177A JP2005126133A JP2005126133A JP2006299177A JP 2006299177 A JP2006299177 A JP 2006299177A JP 2005126133 A JP2005126133 A JP 2005126133A JP 2005126133 A JP2005126133 A JP 2005126133A JP 2006299177 A JP2006299177 A JP 2006299177A
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- 239000011248 coating agent Substances 0.000 claims abstract description 112
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- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- WIBOKTQZOPHFAJ-UHFFFAOYSA-N [Zr].[Bi] Chemical class [Zr].[Bi] WIBOKTQZOPHFAJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000004840 adhesive resin Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical class [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 1
- KVGIAPSCKHLYEF-UHFFFAOYSA-N chromium;indium;oxotin Chemical compound [Cr].[In].[Sn]=O KVGIAPSCKHLYEF-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Images
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- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Electrical Connectors (AREA)
- Non-Insulated Conductors (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、微細回路接続性に優れた異方導電性接着シート及び接続構造体に関する。 The present invention relates to an anisotropic conductive adhesive sheet excellent in fine circuit connectivity and a connection structure.
これまで、微細回路を接続するための異方導電性接着シートに関して、接続性改良、短絡防止のために、種々の導電性粒子の検討および、異方導電性接着剤構成の検討がなされている。例えば、導電性粒子と同等の熱膨張係数をもつ絶縁粒子を配合する方法（特許文献１参照）、短絡防止のため、導電性粒子の表面に絶縁性粒子を付着させる方法（特許文献２参照）、あるいは、導電性粒子の表面を電気絶縁性樹脂で被覆する方法（特許文献３参照）、導電性粒子を含む層と含まない層を積層し、隣接する回路間の短絡を防止する方法（特許文献４、５参照）、端子回路を感光性樹脂で覆い、接続部以外の部分を選択硬化して粘着性を消失させ、粘着性を有する部分に導電性粒子を付着させ、次いで粘着性樹脂で覆って隣接する端子回路間の短絡を防止する方法（特許文献６参照）等が公知である。
So far, with regard to anisotropic conductive adhesive sheets for connecting microcircuits, various conductive particles and anisotropic conductive adhesive configurations have been studied in order to improve connectivity and prevent short circuits. . For example, a method of blending insulating particles having a thermal expansion coefficient equivalent to that of the conductive particles (see Patent Document 1), and a method of attaching the insulating particles to the surface of the conductive particles to prevent a short circuit (see Patent Document 2) Alternatively, a method of covering the surface of conductive particles with an electrically insulating resin (see Patent Document 3), a method of stacking a layer containing conductive particles and a layer not containing conductive particles, and preventing a short circuit between adjacent circuits (
しかしながら、導電性粒子に絶縁性を持たせる等の従来技術においては、端子接続方向においては導電性粒子と導電性粒子ないし接続端子とが接触することにより導電性を確保しなければならないので、絶縁性被覆、あるいは絶縁性粒子を圧着時に、導電性粒子表面から排除しなければならないため、強固な絶縁層を形成することは出来ず、よって、充分な粒子数を配合することには限界があり、微細回路接続の場合、絶縁性確保と接続粒子数確保の両立を満足できるものではなかった。また、接着剤構成による短絡防止等の従来技術においても、微細回路接続の場合は、絶縁性確保と電気接続性を同時に満足できるものではなかった。 However, in the prior art such as providing the conductive particles with insulation, the conductivity must be ensured by contacting the conductive particles with the conductive particles or connection terminals in the terminal connection direction. Insulating particles or insulating particles must be excluded from the surface of the conductive particles during pressure bonding, so a strong insulating layer cannot be formed. Therefore, there is a limit to blending a sufficient number of particles. In the case of fine circuit connection, it was not possible to satisfy both the insulation and the number of connected particles. Further, even in the prior art such as short circuit prevention by the adhesive configuration, in the case of the fine circuit connection, insulation and electrical connectivity cannot be satisfied at the same time.
本発明は、微細回路の隣接する回路間の絶縁性を損なうことなく、良好な電気的接続性を実現する異方導電性接着シート、その製造方法、およびそれを用いた微細接続構造体を提供することを目的とする。 The present invention provides an anisotropic conductive adhesive sheet that realizes good electrical connectivity without impairing insulation between adjacent circuits of a fine circuit, a method for producing the same, and a finely connected structure using the same. The purpose is to do.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、ある特定の平均粒子径を有する絶縁被覆導電性粒子が、ある特定の範囲内に、ある特定割合以上の絶縁被覆導電性粒子とは接触せずに存在しており、粒子の存在する片側面上に絶縁被覆導電性粒子表面の一部が露出しており、かつ露出部分に絶縁被覆のない部分を有することを特徴とする異方導電性接着シートを用いることによって、上記課題を解決できることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that the insulating coated conductive particles having a certain average particle diameter are within a certain specific range and have a certain ratio or more of the insulating coated conductive particles. It is present without contacting with the conductive particles, and a part of the surface of the insulating coating conductive particles is exposed on one side where the particles exist, and the exposed portion has a portion without the insulating coating. It was found that the above problems can be solved by using the anisotropic conductive adhesive sheet.
すなわち、本発明の一は、少なくとも硬化剤、硬化性の絶縁性樹脂、及び導電性粒子の表面に絶縁被覆を有する絶縁被覆導電性粒子からなる異方導電性接着シートであって、異方導電性接着シートの片側表面において一部または全部の絶縁被覆導電性粒子の一部分が露出しており、該露出している一部分を有する絶縁被覆導電性粒子の一部又は全部が、その露出している部分に絶縁被覆を有しない表面部分が存在する部分絶縁被覆導電性粒子であり、かつ近接する該絶縁被覆導電性粒子同士の平均粒子間隔が該絶縁被覆導電性粒子の平均粒径の１倍以上５倍以下であることを特徴とする異方導電性接着シート。である。
上記異方導電性接着シートにおいては、絶縁被覆導電性粒子の平均粒径が１〜８μｍであり、近接する該絶縁被覆導電性粒子同士の平均粒子間隔が２０μｍ以下であり、かつ、異方導電性接着シートの片側表面において８０％以上の個数の該絶縁被覆導電性粒子の一部分が露出していることが好ましい。また、導電性粒子が、貴金属被覆された樹脂粒子、貴金属被覆された金属粒子、金属粒子、貴金属被覆された合金粒子、及び合金粒子からなる群から選ばれる少なくとも１種の導電性粒子であることが好ましい。さらに、絶縁被覆が、ガラス転移温度が２５℃以上１５０℃以下かつ、厚みが０．０１μｍ以上０．５μｍ以下の樹脂からなることが好ましい。
That is, one aspect of the present invention is an anisotropic conductive adhesive sheet comprising at least a curing agent, a curable insulating resin, and insulating coated conductive particles having an insulating coating on the surface of the conductive particles. A part of all or part of the insulating coated conductive particles is exposed on one surface of the conductive adhesive sheet, and part or all of the insulating coated conductive particles having the exposed part are exposed. Partially insulating coated conductive particles having a surface portion that does not have an insulating coating in the portion, and the average particle interval between the adjacent insulating coated conductive particles is one or more times the average particle diameter of the insulating coated conductive particles An anisotropic conductive adhesive sheet characterized by being 5 times or less. It is.
In the anisotropic conductive adhesive sheet, the average particle diameter of the insulating coated conductive particles is 1 to 8 μm, the average particle interval between the adjacent insulating coated conductive particles is 20 μm or less, and anisotropic conductive It is preferable that a part of 80% or more of the insulating coating conductive particles is exposed on one surface of the conductive adhesive sheet. The conductive particles are at least one conductive particle selected from the group consisting of resin particles coated with noble metal, metal particles coated with noble metal, metal particles, alloy particles coated with noble metal, and alloy particles. Is preferred. Furthermore, the insulating coating is preferably made of a resin having a glass transition temperature of 25 ° C. or more and 150 ° C. or less and a thickness of 0.01 μm or more and 0.5 μm or less.
本発明の二は、２軸延伸可能なフィルム上に粘着層を設けて積層体を形成し、該積層体の上に導電性粒子の表面に樹脂で構成される絶縁被覆を有する平均粒径１〜８μｍの絶縁被覆導電性粒子を付着させて絶縁被覆導電性粒子付着フィルムを作製し、該絶縁被覆導電性粒子付着フィルムを該絶縁被覆を構成する樹脂のガラス転移温度以下の温度で近接する該絶縁被覆導電性粒子同士の平均粒子間隔が該絶縁被覆導電性粒子の平均粒径の１倍以上５倍以下になるように２軸延伸し、該絶縁被覆を構成する樹脂のガラス転移温度以上の温度で熱処理した後、少なくとも硬化剤、及び硬化性の絶縁性樹脂を含んでなる接着シートに該絶縁被覆導電性粒子を転写することによって絶縁被覆を有さない表面の一部分が露出した部分絶縁被覆導電性粒子を有する接着シートを作製する工程を含むことを特徴とする、本発明の一の異方導電性接着シートの製造方法である。
上記異方導電性接着シートの製造方法においては、２軸延伸可能なフィルムが長尺のフィルムであり、接着シートが長尺の接着シートであることが好ましい。
In the second aspect of the present invention, an
In the method for producing the anisotropic conductive adhesive sheet, it is preferable that the biaxially stretchable film is a long film and the adhesive sheet is a long adhesive sheet.
本発明の三は、微細接続端子を有する電子回路部品と回路基板とを本発明の一の異方導電性接着シートで電気的に接続する接続方法において、微細接続端子の高さが近接する絶縁被覆導電性粒子の平均粒子間隔の３〜１５倍かつ４０μｍ以下であり、該微細接続端子の間隔が該平均粒子間隔の１〜１０倍かつ４０μｍ以下であり、該微細接続端子のピッチが該平均粒子間隔の３〜３０倍かつ８０μｍ以下であることを特徴とする接続方法である。
本発明の四は、本発明の三の接続方法により接続された電子回路部品と回路基板を含むことを特徴とする微細接続構造体である。
The third aspect of the present invention is a connection method in which an electronic circuit component having a fine connection terminal and a circuit board are electrically connected with one anisotropic conductive adhesive sheet of the present invention, wherein the insulation of the fine connection terminals is close in height. 3 to 15 times the average particle interval of the coated conductive particles and 40 μm or less, the interval between the fine connection terminals is 1 to 10 times the average particle interval and 40 μm or less, and the pitch of the fine connection terminals is the average The connection method is characterized by being 3 to 30 times the particle interval and 80 μm or less.
A fourth aspect of the present invention is a finely connected structure characterized by including an electronic circuit component and a circuit board connected by the third connection method of the present invention.
本発明の異方導電性接着シート及び微細接続構造体は、隣接する接続端子間の良好な絶縁特性を有し、かつ接続した接続端子間の良好な電気的接続性を有する。すなわち、絶縁性が必要な異方導電接着シートの面内方向には絶縁被覆され、接続面の一方には、絶縁被覆のない部分を有する部分絶縁被覆導電性粒子を特定の間隔で配置させることにより、圧着時の絶縁被覆膜の排除性を増し、良好な接続性を確保することが出来る。 The anisotropic conductive adhesive sheet and the fine connection structure of the present invention have good insulation characteristics between adjacent connection terminals and good electrical connectivity between connected connection terminals. That is, insulative coating is applied in the in-plane direction of the anisotropic conductive adhesive sheet that requires insulation, and partially insulating coated conductive particles having a portion without insulation coating are arranged at specific intervals on one of the connection surfaces. As a result, it is possible to increase the exclusion of the insulating coating film at the time of pressure bonding and to ensure good connectivity.
以下、本発明について具体的に説明する。
まず、本発明の異方導電接着シートにおける絶縁被覆導電性粒子について説明する。以下においては、導電性粒子の表面の全部が絶縁被覆で覆われたものを完全絶縁被覆導電性粒子、導電性粒子の表面の一部が絶縁被覆で覆われたものを部分絶縁被覆導電性粒子、両方をあわせて絶縁被覆導電性粒子とよぶこととする。
Hereinafter, the present invention will be specifically described.
First, the insulating coated conductive particles in the anisotropic conductive adhesive sheet of the present invention will be described. In the following, a conductive particle in which the entire surface of the conductive particle is covered with an insulating coating is a conductive particle having a completely insulating coating, and a conductive particle in which a part of the surface of the conductive particle is covered with an insulating coating is used. Both are referred to as insulating coated conductive particles.
絶縁被覆導電性粒子は、公知の導電性粒子に絶縁被覆したものを用いることができる。導電性粒子としては、貴金属被覆された樹脂粒子、貴金属被覆された金属粒子、金属粒子、貴金属被覆された合金粒子、融点が１５０℃以上５００℃以下の合金粒子のなかから選ばれた１種以上を用いることが好ましい。 As the insulating coated conductive particles, those obtained by insulating coating known conductive particles can be used. As the conductive particles, one or more selected from resin particles coated with noble metal, metal particles coated with noble metal, metal particles, alloy particles coated with noble metal, and alloy particles having a melting point of 150 ° C. or higher and 500 ° C. or lower. Is preferably used.
貴金属被覆された樹脂粒子としては、ポリスチレン、ベンゾグアナミン、ポリメチルメタアクリレート等の球状粒子にニッケル、および金をこの順に被覆したものを用いることが好ましい。本発明の異方導電接着シートにおいては、シートの片側表面に絶縁被覆の無い部分を有する部分絶縁被覆導電性粒子が露出した構造である（該部分絶縁被覆導電性粒子の製造方法は後述する。）。 As the resin particles coated with the noble metal, it is preferable to use those obtained by coating spherical particles such as polystyrene, benzoguanamine, and polymethyl methacrylate with nickel and gold in this order. The anisotropic conductive adhesive sheet of the present invention has a structure in which partially insulating coated conductive particles having a portion without an insulating coating are exposed on one surface of the sheet (a method for producing the partially insulating coated conductive particles will be described later). ).
従って、導電性粒子が絶縁被覆で完全に被覆された完全絶縁被覆導電性粒子であれば圧着による接続時に排除しなければならないであろう絶縁被覆を排除する必要がないので、接続する微細接続端子（バンプ）硬度に応じて、より柔軟な樹脂粒子を用いて貴金属被覆された樹脂粒子を形成することができる。
接続するバンプ硬度がビッカース硬度で５０Ｈｖ未満である場合は、ポリメタアクリレート樹脂等の柔軟な樹脂粒子を用いることが好ましい。また、バンプ硬度が５０Ｈｖ以上である場合は、ベンゾグアナミン樹脂等の硬質樹脂粒子を用いることが好ましい。
Therefore, if the conductive particles are completely insulated conductive particles that are completely covered with an insulating coating, it is not necessary to exclude the insulating coating that would have to be eliminated during the crimping connection. Depending on the (bump) hardness, resin particles coated with noble metal can be formed using more flexible resin particles.
When the bump hardness to be connected is less than 50 Hv in terms of Vickers hardness, it is preferable to use flexible resin particles such as polymethacrylate resin. Moreover, when bump hardness is 50 Hv or more, it is preferable to use hard resin particles, such as a benzoguanamine resin.
貴金属被覆された金属粒子としては、ニッケル、銅等の金属粒子に金、パラジウム、ロジウム等の貴金属を最外層に被覆したものを用いることが好ましい。被覆する方法としては、蒸着法、スパッタリング法等の薄膜形成法、乾式ブレンド法によるコーティング法、無電解めっき法、電解めっき法等の湿式法を用いることができる。量産性の点から、無電解めっき法が好ましい。 As the metal particles coated with the noble metal, it is preferable to use a metal particle such as nickel or copper coated with a noble metal such as gold, palladium or rhodium on the outermost layer. As a coating method, a thin film forming method such as a vapor deposition method or a sputtering method, a coating method using a dry blend method, a wet method such as an electroless plating method or an electrolytic plating method can be used. From the viewpoint of mass productivity, the electroless plating method is preferable.
金属粒子としては、銀、銅、ニッケル等の金属から選ばれるものを用いることが好ましい。合金粒子としては、融点が１５０℃以上５００℃以下のものが好ましく、さらには１５０℃以上３５０℃以下の低融点合金粒子を用いることがより好ましい。融点が５００℃以下であると、接続端子間に金属結合を形成することも可能であり、接続信頼性の点から好ましい。また、耐熱接続信頼性の観点から、融点が１５０℃以上であることが好ましい。 As the metal particles, those selected from metals such as silver, copper and nickel are preferably used. The alloy particles preferably have a melting point of 150 ° C. or more and 500 ° C. or less, and more preferably low melting point alloy particles having a melting point of 150 ° C. or more and 350 ° C. or less. When the melting point is 500 ° C. or less, a metal bond can be formed between the connection terminals, which is preferable from the viewpoint of connection reliability. Moreover, it is preferable that melting | fusing point is 150 degreeC or more from a viewpoint of heat-resistant connection reliability.
導電性粒子を絶縁被覆して完全絶縁被覆導電性粒子を製造する方法は、公知の方法を用いることができる。具体的には、導電性粒子の周りに樹脂微粒子を静電気等で付着させ、それらを高速気流中で撹拌することにより、導電性粒子表面に付着した樹脂微粒子を融着させる方法、あるいは、樹脂溶液中に導電性粒子を分散させ、その分散体を微細な液滴として噴霧しながら加温し、溶剤を乾燥することにより導電性粒子表面に樹脂皮膜を絶縁被覆として形成する方法等を用いることができる。絶縁被覆する際の粒子の凝集を防止しやすいため、樹脂微粒子を融着させる方法が好ましい。 A known method can be used as a method for producing conductive particles having a completely insulating coating by insulatingly coating the conductive particles. Specifically, a method in which resin fine particles adhering to the surface of conductive particles are fused by adhering resin fine particles around the conductive particles by static electricity or the like and stirring them in a high-speed air current, or a resin solution It is possible to use a method in which conductive particles are dispersed therein, heated while spraying the dispersion as fine droplets, and a solvent is dried to form a resin film as an insulating coating on the surface of the conductive particles. it can. A method of fusing resin fine particles is preferable because it is easy to prevent aggregation of particles during insulation coating.
絶縁被覆としては、充分な絶縁性と加圧接続時の接続性確保が可能であれば、どのようなものでも使用可能である。加圧接続時に接続性確保の点から、ガラス転移温度が１５０℃以下の樹脂であることが好ましく、１００℃以下が更に好ましい。
ガラス転移温度の測定方法としては、公知の方法を用いることができる。具体的には、島津製作所製のＴＭＡ―５０熱機械分析装置を用いて昇温速度１０℃／分の条件で測定することができる。
Any insulation coating can be used as long as sufficient insulation and connectivity during pressure connection can be ensured. From the viewpoint of securing connectivity during pressure connection, a resin having a glass transition temperature of 150 ° C. or lower is preferable, and 100 ° C. or lower is more preferable.
As a method for measuring the glass transition temperature, a known method can be used. Specifically, it can be measured using a TMA-50 thermomechanical analyzer manufactured by Shimadzu Corporation under a temperature increase rate of 10 ° C./min.
本発明の異方導電性接着シートにおいては、接続する面の一方に絶縁被覆の無い部分を有する部分絶縁被覆導電性粒子を有する構造のため、圧着時に該接続面の絶縁被覆を排除する必要が無く、絶縁被覆導電性粒子を有する構造に比較してより強固な絶縁被覆の形成が可能である。 In the anisotropic conductive adhesive sheet of the present invention, it is necessary to eliminate the insulating coating on the connecting surface during crimping because of the structure having the partially insulating coated conductive particles having a portion without the insulating coating on one of the connecting surfaces. In addition, a stronger insulating coating can be formed as compared with a structure having insulating coating conductive particles.
また、通常の製法では、絶縁被覆導電性粒子を予め、絶縁性接着剤溶液中に配合する方式をとる場合が多いが、その場合は、溶剤の影響を無視できず、絶縁性接着剤溶液中での絶縁被覆膜の膨潤、ゲル化、凝集等の懸念から絶縁被覆として使用可能な樹脂に制限があった。本発明の異方導電性接着シートの製造方法では、既に溶剤を含まない状態の絶縁性接着シートへ、乾式で絶縁被覆導電性粒子を転写する方法も可能である。従って、溶剤に対する使用可能な絶縁被覆樹脂の制限も無く、また、より薄い絶縁被覆でもその効果を発揮することができる。 In addition, in the usual manufacturing method, insulative coating conductive particles are often pre-mixed in an insulating adhesive solution, but in this case, the influence of the solvent cannot be ignored, and in the insulating adhesive solution Resin that can be used as an insulating coating is limited due to concerns such as swelling, gelation, and aggregation of the insulating coating film. In the method for producing the anisotropic conductive adhesive sheet of the present invention, a method of transferring the insulating coated conductive particles in a dry manner to an insulating adhesive sheet that already contains no solvent is also possible. Therefore, there is no limitation on the usable insulating coating resin with respect to the solvent, and the effect can be exhibited even with a thinner insulating coating.
樹脂微粒子を融着させる方法に用いる樹脂微粒子の粒径は、被覆する導電性粒子の粒径の１／５から１／２０が好ましい。導電性粒子への初期付着が容易になることから、該樹脂微粒子は、被覆する導電性粒子と逆に帯電することが好ましい。具体的には、アクリル樹脂、スチレン樹脂、アクリル−スチレン共重合体樹脂等を用いることができる。 The particle size of the resin fine particles used in the method for fusing the resin fine particles is preferably 1/5 to 1/20 of the particle size of the conductive particles to be coated. Since the initial adhesion to the conductive particles is facilitated, the resin fine particles are preferably charged oppositely to the conductive particles to be coated. Specifically, an acrylic resin, a styrene resin, an acrylic-styrene copolymer resin, or the like can be used.
樹脂溶液中に導電性粒子を分散させ、その分散体を微細な液滴として噴霧しながら加温し、溶剤を乾燥することにより導電性粒子表面に絶縁被覆として樹脂皮膜を形成する方法に用いる樹脂としては、固形エポキシ樹脂、フェノキシ樹脂、アクリル樹脂、ポリエステル樹脂、アルキル化セルロース樹脂、フラックス樹脂等を用いることができる。 Resin used in a method for forming a resin film as an insulating coating on the surface of conductive particles by dispersing conductive particles in a resin solution, heating the dispersion while spraying it as fine droplets, and drying the solvent For example, solid epoxy resin, phenoxy resin, acrylic resin, polyester resin, alkylated cellulose resin, and flux resin can be used.
低融点合金粒子を用いる場合は、予め粒子表面にフラックス等を被覆しておくことが好ましい。いわゆるフラックスを絶縁被覆として用いることにより、絶縁被覆に加えて表面の酸化物等を取り除くことができ好ましい。フラックスとしては、アビエチン酸等の脂肪酸等を用いることができる。 When using low melting point alloy particles, it is preferable to coat the surface of the particles with a flux or the like in advance. By using a so-called flux as the insulating coating, it is preferable to remove oxides on the surface in addition to the insulating coating. As the flux, fatty acids such as abietic acid can be used.
絶縁被覆の厚みは、０．０１μｍ以上０．５μｍ以下であることが好ましい。絶縁性の点から０．０１μｍ以上であることが好ましく、接続性の点から０．５μｍ以下であることが好ましい。
絶縁被覆の厚みは、絶縁被覆導電性粒子をエポキシ樹脂等に包埋固定した後に、断面研磨し、研磨面を電子顕微鏡観察することにより測定することができる。
The thickness of the insulating coating is preferably 0.01 μm or more and 0.5 μm or less. It is preferable that it is 0.01 micrometer or more from an insulating point, and it is preferable that it is 0.5 micrometer or less from the point of connectivity.
The thickness of the insulating coating can be measured by embedding and fixing the insulating coated conductive particles in an epoxy resin or the like, then polishing the cross section and observing the polished surface with an electron microscope.
絶縁被覆導電性粒子の平均粒径と最大粒径の比は２以下であることが好ましく、１．５以下であることがより好ましい。該絶縁被覆導電性粒子の粒度分布はより狭いほうが好ましく、該絶縁被覆導電性粒子の粒径分布の幾何標準偏差は、１．２〜２．５であることが好ましく、１．２〜１．４であることが特に好ましい。幾何標準偏差が上記値であると粒径のバラツキが小さくなる。通常、接続する２端子間に一定のギャップが存在する場合には、粒径が揃っているほど、絶縁被覆導電性粒子が有効に機能すると考えられる。 The ratio of the average particle diameter to the maximum particle diameter of the insulating coated conductive particles is preferably 2 or less, and more preferably 1.5 or less. The particle size distribution of the insulating coating conductive particles is preferably narrower, and the geometric standard deviation of the particle size distribution of the insulating coating conductive particles is preferably 1.2 to 2.5, and 1.2 to 1. 4 is particularly preferred. When the geometric standard deviation is the above value, the variation in particle size is reduced. Usually, when there is a certain gap between two connected terminals, it is considered that the insulating coated conductive particles function more effectively as the particle diameters become uniform.
粒度分布の幾何標準偏差とは、粒度分布のσ値（累積８４．１３％の粒径値）を累積５０％の粒径値で除した値である。粒度分布のグラフの横軸に粒径（対数）を設定し、縦軸に累積値（％、累積個数比、対数）を設定すると粒径分布はほぼ直線になり、粒径分布は対数正規分布に従う。累積値とは全粒子数に対して、ある粒径以下の粒子の個数比を示したもので、％で表す。粒径分布のシャープさはσ（累積８４．１３％の粒径値）と平均粒径（累積５０％の粒径値）の比で表現される。σ値は実測値あるいは、前述グラフのプロット値からの読み取り値である。平均粒径及び粒度分布は、公知の方法、装置を用いて測定することができ、湿式粒度分布計、レーザー式粒度分布計等を用いることができる。あるいは、電子顕微鏡等で粒子を観察し、平均粒径、粒度分布を算出しても構わない。本発明の平均粒径及び粒度分布はレーザー式粒度分布計により求めることが出来る。 The geometric standard deviation of the particle size distribution is a value obtained by dividing the σ value of the particle size distribution (particle size value of 84.13% cumulative) by the particle size value of 50% cumulative. When the particle size distribution (logarithm) is set on the horizontal axis of the particle size distribution graph and the cumulative value (%, cumulative number ratio, logarithm) is set on the vertical axis, the particle size distribution is almost linear, and the particle size distribution is lognormal distribution. Follow. The cumulative value indicates the number ratio of particles having a certain particle size or less with respect to the total number of particles, and is expressed in%. The sharpness of the particle size distribution is expressed by the ratio of σ (the cumulative particle size value of 84.13%) and the average particle size (the cumulative particle size value of 50%). The σ value is an actual measurement value or a read value from the plot value of the graph. The average particle size and particle size distribution can be measured using a known method and apparatus, and a wet particle size distribution meter, a laser particle size distribution meter, or the like can be used. Alternatively, the average particle size and particle size distribution may be calculated by observing the particles with an electron microscope or the like. The average particle size and particle size distribution of the present invention can be determined by a laser particle size distribution meter.
本発明において平均粒径は、絶縁被覆を含んだ絶縁性被覆導電性粒子の直径を意味する。
絶縁被覆導電性粒子の平均粒径は１〜８μｍであり、２〜６μｍであることが好ましい。絶縁性の観点から８μｍ以下が好ましく、接続端子等の高さバラツキ等の影響を受けにくく、また、電気的接続性の観点から１μｍ以上が好ましい。
In the present invention, the average particle diameter means the diameter of the insulating coated conductive particles including the insulating coating.
The average particle diameter of the insulating coating conductive particles is 1 to 8 μm, and preferably 2 to 6 μm. The thickness is preferably 8 μm or less from the viewpoint of insulation, and is preferably less than 1 μm from the viewpoint of electrical connectivity, and is not easily affected by variations in height of connection terminals and the like.
次いで本発明の異方導電性接着シートについて説明する。
本発明の異方導電性接着シートにおいて、近接する絶縁被覆導電性粒子との平均粒子間隔は、２０μｍ以下で、かつ平均粒径の１倍以上５倍以下であることが好ましく、２０μｍ以下で、かつ平均粒径の１．５倍以上３倍以下であることがより好ましい。接続時の粒子流動による粒子凝集の防止、及び絶縁性確保の観点から、平均粒径の１倍以上であることが好ましく、微細接続の観点から２０μｍ以下、かつ平均粒径の５倍以下が好ましい。
本発明において、近接する絶縁被覆導電性粒子とは、任意の絶縁被覆導電性粒子を選定し、該絶縁被覆導電性粒子に最も近い６個の絶縁被覆導電性粒子を言う。近接する絶縁被覆導電性粒子との平均粒子間隔は以下の通りである。
Next, the anisotropic conductive adhesive sheet of the present invention will be described.
In the anisotropic conductive adhesive sheet of the present invention, the average particle interval between adjacent insulating coating conductive particles is preferably 20 μm or less, and preferably 1 to 5 times the average particle size, and is 20 μm or less. In addition, the average particle diameter is more preferably 1.5 times or more and 3 times or less. From the viewpoint of preventing particle aggregation due to particle flow at the time of connection and ensuring insulation, the average particle size is preferably 1 time or more, and from the viewpoint of fine connection, 20 μm or less and preferably 5 times or less the average particle size. .
In the present invention, the adjacent insulating coating conductive particles refers to six insulating coating conductive particles closest to the insulating coating conductive particles by selecting arbitrary insulating coating conductive particles. The average particle spacing between adjacent insulating coating conductive particles is as follows.
まず、本発明の異方導電性接着シートを、絶縁被覆導電性粒子が露出した面側から光学顕微鏡で拡大した写真を撮影する。次に、任意の２０個の絶縁被覆導電性粒子を選定し、そのそれぞれの絶縁被覆導電性粒子に最も近い６個の絶縁被覆導電性粒子との距離を測定し、全体の平均値を求めて、平均粒子間隔とする。 First, the photograph which expanded the anisotropically conductive adhesive sheet of this invention with the optical microscope from the surface side which the insulation coating electroconductive particle was exposed is image | photographed. Next, arbitrary 20 insulating coated conductive particles are selected, the distance from the six insulating coated conductive particles closest to the respective insulating coated conductive particles is measured, and the average value of the whole is obtained. , The average particle spacing.
異方導電性接着シートの厚みは上述の平均粒子間隔の１．５倍以上４０μｍ以下であることが好ましく、２倍以上４０μｍ以下であることがより好ましい。機械的接続強度の観点から平均粒子間隔の１．５倍以上が好ましく、接続時の粒子流動による接続粒子数減少を防止する観点から４０μｍ以下であることが好ましい。 The thickness of the anisotropic conductive adhesive sheet is preferably 1.5 times or more and 40 μm or less, more preferably 2 times or more and 40 μm or less of the above average particle interval. From the viewpoint of mechanical connection strength, the average particle spacing is preferably 1.5 times or more, and from the viewpoint of preventing reduction in the number of connected particles due to particle flow during connection, it is preferably 40 μm or less.
異方導電性接着シートにおける絶縁被覆導電性粒子の配合量としては、硬化剤及び硬化性の絶縁性樹脂を合わせた成分１００質量部に対して、０．５質量部から２０質量部であることが好ましく、１質量部から１０質量部であることが特に好ましい。絶縁性の観点から２０質量部以下が好ましく、電気的接続性の観点から０．５質量部以上が好ましい。 As a compounding quantity of the insulation coating electroconductive particle in an anisotropically conductive adhesive sheet, it is 0.5 mass part to 20 mass parts with respect to 100 mass parts which combined the hardening | curing agent and the curable insulating resin. Is preferably 1 to 10 parts by mass. 20 parts by mass or less is preferable from the viewpoint of insulation, and 0.5 parts by mass or more is preferable from the viewpoint of electrical connectivity.
本発明の異方導電性接着シートは、異方導電性接着シートの片側表面から一部または全部の部分絶縁被覆導電性粒子の一部分が露出しており、該露出している一部分には絶縁被覆を有さない表面の一部分が存在している。露出している絶縁被覆導電性粒子は絶縁被覆導電性粒子個数の８０％以上であることが好ましく、９０％以上であることがより好ましい。部分絶縁被覆導電性粒子の露出している部分には絶縁被覆の無い表面の一部分が存在しているが、該部分絶縁被覆導電性粒子の個数は、露出している絶縁被覆導電性粒子全体の個数の８０％以上であることが好ましく、９０％以上であることがより好ましい。 In the anisotropic conductive adhesive sheet of the present invention, a part of a part or all of the partially insulated conductive particles are exposed from one side surface of the anisotropic conductive adhesive sheet, and the exposed part is insulated. A portion of the surface that does not have is present. The exposed insulating coating conductive particles are preferably 80% or more, more preferably 90% or more of the number of insulating coating conductive particles. A part of the surface without the insulation coating exists in the exposed portion of the partially insulated conductive particles, but the number of the partially insulated conductive particles is the total number of the exposed insulated conductive particles. The number is preferably 80% or more, more preferably 90% or more.
絶縁被覆導電性粒子の露出している部分は、その表面積の１％以上であることが好ましく、更に好ましくは、５％以上である。また、部分絶縁被覆導電性粒子の露出している表面における絶縁被覆の無い部分は、露出している面積の３０％以上であることが好ましく、５０％以上であることがさらに好ましい。 The exposed portion of the insulating coated conductive particles is preferably 1% or more of the surface area, more preferably 5% or more. Further, the portion of the exposed surface of the partially insulating coated conductive particles that has no insulating coating is preferably 30% or more of the exposed area, and more preferably 50% or more.
本発明の異方導電性接着シートにおいて、該異方導電性接着シートの厚み方向に対して、絶縁被覆導電性粒子の存在している位置は、焦点方向の変位を測定できるレーザー顕微鏡により測定することができる。従って、無作為に選んだ１００個の絶縁被覆導電性粒子の焦点方向の位置を測定し表面より深いか否かを判定することにより、該絶縁被覆導電性粒子が表面に露出している割合を求めることができる。またこのとき同時に、絶縁被覆導電性粒子が他の絶縁被覆導電性粒子と接触せずに存在している個数を測定することもできる。前記レーザー顕微鏡を用いて焦点方向の変位を測定する場合、その変位測定分解能は０．１μｍ以下であることが好ましく、０．０１μｍ以下であることが特に好ましい。 In the anisotropic conductive adhesive sheet of the present invention, the position where the insulating coated conductive particles are present with respect to the thickness direction of the anisotropic conductive adhesive sheet is measured by a laser microscope capable of measuring the displacement in the focal direction. be able to. Therefore, by measuring the position in the focal direction of 100 insulating coating conductive particles selected at random and determining whether or not it is deeper than the surface, the ratio of the insulating coating conductive particles exposed to the surface is determined. Can be sought. At the same time, it is also possible to measure the number of insulating coating conductive particles that are present without contacting other insulating coating conductive particles. When the displacement in the focal direction is measured using the laser microscope, the displacement measurement resolution is preferably 0.1 μm or less, and particularly preferably 0.01 μm or less.
本発明の異方導電性接着シートにおいて、表面に露出した絶縁被覆導電性粒子のうち絶縁被覆の無い部分を有する部分絶縁被覆導電性粒子個数は、電子顕微鏡により、無作為に１００個の露出した絶縁被覆導電性粒子を観察することで測定できる。電子顕微鏡観察により、露出部分に絶縁被覆のない部分があるかどうかは、容易に判別可能である。本発明の異方導電性接着シートの厚みは、絶縁被覆導電性粒子の平均粒径の３倍以上から２０倍未満であることが好ましく、５倍から１０倍であることが更に好ましい。接続構造体の接着強度の点から３倍以上であることが好ましく、接続性の点から２０倍未満であることが好ましい。 In the anisotropic conductive adhesive sheet of the present invention, the number of partially insulated coating conductive particles having a portion without insulation coating among the insulated coating conductive particles exposed on the surface was randomly exposed to 100 by an electron microscope. It can be measured by observing the insulating coated conductive particles. By observation with an electron microscope, it can be easily determined whether or not there is a portion without an insulating coating in the exposed portion. The thickness of the anisotropic conductive adhesive sheet of the present invention is preferably 3 times to less than 20 times the average particle diameter of the insulating coated conductive particles, and more preferably 5 times to 10 times. It is preferably 3 times or more from the viewpoint of the adhesive strength of the connection structure, and preferably less than 20 times from the viewpoint of connectivity.
次に、本発明における絶縁被覆導電性粒子が他の絶縁被覆導電性粒子と接触せずに存在することを特徴とする異方導電性接着シートの製造方法について説明する。
本発明において「絶縁被覆導電性粒子が他の絶縁被覆導電性粒子と接触せずに存在する」とは、絶縁被覆導電性粒子同士が凝集せずに各々単独に存在することを意味する。以下、この意味で「単独に存在する」、「単独粒子」なる表現を用いることがある。
Next, a method for producing an anisotropic conductive adhesive sheet, in which the insulating coated conductive particles in the present invention exist without being in contact with other insulating coated conductive particles, will be described.
In the present invention, “the insulating coating conductive particles are present without being in contact with other insulating coating conductive particles” means that the insulating coating conductive particles are present independently without aggregation. Hereinafter, the expressions “exist alone” and “single particle” may be used in this sense.
本発明の異方導電性接着シートの製造方法としては、２軸延伸可能なフィルム又はシート上に、粘着層を形成し、その上に絶縁被覆導電性粒子を単層配列し、それらを延伸することにより、該絶縁被覆導電性粒子を分散配列させ、延伸した状態を保った状態で絶縁被覆の一部を該粘着層に残したまま、少なくとも硬化剤及び硬化性の絶縁性樹脂からなる接着シートに転写させる方法が好ましい。 As a method for producing the anisotropic conductive adhesive sheet of the present invention, an adhesive layer is formed on a biaxially stretchable film or sheet, and a single layer of insulating coated conductive particles is arranged thereon, and then they are stretched. Thus, an adhesive sheet comprising at least a curing agent and a curable insulating resin while the insulating coating conductive particles are dispersed and arranged, and a part of the insulating coating is left in the adhesive layer in a stretched state. The method of transferring to the surface is preferred.
２軸延伸可能なフィルムとしては、公知の樹脂フィルム等を用いることができるが、ポリエチレン樹脂、ポリプロピレン樹脂、ポリエステル樹脂、ポリビニルブチラール樹脂、ポリビニルアルコール樹脂、ポリ塩化ビニリデン樹脂等の単独あるいは共重合体等、又は、ニトリルゴム、ブタジエンゴム、シリコーンゴム等のゴムシート等の柔軟で延伸可能な樹脂フィルムを用いることが好ましい。ポリプロピレン樹脂、ポリエステル樹脂が特に好ましい。延伸後の収縮率は１０％以下になることが好ましい。 As the biaxially stretchable film, a known resin film or the like can be used, but a polyethylene resin, a polypropylene resin, a polyester resin, a polyvinyl butyral resin, a polyvinyl alcohol resin, a polyvinylidene chloride resin alone or a copolymer, etc. Alternatively, it is preferable to use a flexible and stretchable resin film such as a rubber sheet such as nitrile rubber, butadiene rubber, or silicone rubber. Polypropylene resin and polyester resin are particularly preferable. The shrinkage after stretching is preferably 10% or less.
２軸延伸可能なフィルム上に絶縁被覆導電性粒子を分散配列し、固定する方法としては、公知の方法を用いることができる。例えば、少なくとも熱可塑性樹脂を含む粘着層を該２軸延伸可能なフィルム上に形成し、その上に絶縁被覆導電性粒子を接触させて付着させ、ゴムロール等で荷重をかけて単層に配置する方法を採ることができる。この場合、隙間無く充填するためには、付着−ロール操作を数回繰り返す方法が好ましい。球状の絶縁被覆導電性粒子の場合、最密充填が最も安定した構造なので比較的容易に充填することができる。あるいは、該２軸延伸可能なフィルム上に粘着剤を塗布して接着層を形成し、その上に絶縁被覆導電性粒子を付着させ、必要なら数回付着を繰り返し、単層で分散配置する方法等を用いることができる。 As a method for dispersing and fixing insulating coated conductive particles on a biaxially stretchable film, a known method can be used. For example, an adhesive layer containing at least a thermoplastic resin is formed on the biaxially stretchable film, and the insulating coating conductive particles are brought into contact therewith and placed in a single layer by applying a load with a rubber roll or the like. The method can be taken. In this case, a method of repeating the adhesion-roll operation several times is preferable for filling without gaps. In the case of spherical insulating coated conductive particles, the closest packing is the most stable structure, so that it can be filled relatively easily. Alternatively, a method of applying a pressure-sensitive adhesive on the biaxially stretchable film to form an adhesive layer, attaching insulating coating conductive particles thereon, repeating the adhesion several times if necessary, and dispersing and arranging in a single layer Etc. can be used.
絶縁被覆導電性粒子を単層配列させた２軸延伸可能なフィルムを延伸させる方法としては、公知の方法を用いることができるが、均一分散配列という点から、２軸延伸装置を用いることが好ましい。粒子間隔の点から延伸度合いは、８０％以上、４００％以下であることが好ましく、１００％以上、３００％以下であることがより好ましい。なお、１００％延伸するとは、延伸方向に沿って延伸した部分の長さが延伸前の長さの１００％であることを言う。延伸方向は、任意であるが、延伸角度が９０°の２軸延伸が好ましく、同時延伸が好ましい。２軸延伸の場合、各方向の延伸度合いは同じであっても異なっていても構わない。 As a method of stretching a biaxially stretchable film in which insulating coated conductive particles are arranged in a single layer, a known method can be used, but a biaxial stretching device is preferably used from the viewpoint of uniform dispersion alignment. . The degree of stretching is preferably 80% or more and 400% or less, and more preferably 100% or more and 300% or less in terms of particle spacing. In addition, 100% stretching means that the length of the portion stretched along the stretching direction is 100% of the length before stretching. The stretching direction is arbitrary, but biaxial stretching with a stretching angle of 90 ° is preferable, and simultaneous stretching is preferable. In the case of biaxial stretching, the degree of stretching in each direction may be the same or different.
２軸延伸装置としては、同時２軸連続延伸装置が好ましい。
同時２軸連続延伸装置としては、公知のものを使用することができるが、長辺側をチャック金具で固定し、それらの間隔を縦横同時に延伸することにより連続延伸するテンター型延伸機が好ましい。延伸度を調整する方式としては、スクリュー方式、パンタグラフ方式を用いることが可能だが、調整の精度の観点から、パンタグラフ方式がより好ましい。加熱しながら延伸する場合は、延伸部分の手前に予熱ゾーンを設けて、延伸部分の後方に熱固定ゾーンを設けることが好ましい。
As the biaxial stretching apparatus, a simultaneous biaxial continuous stretching apparatus is preferable.
As the simultaneous biaxial continuous stretching apparatus, a known one can be used, but a tenter type stretching machine that continuously stretches by fixing the long side with a chuck fitting and simultaneously stretching the distance in the vertical and horizontal directions is preferable. As a method for adjusting the degree of stretching, a screw method or a pantograph method can be used, but a pantograph method is more preferable from the viewpoint of accuracy of adjustment. When stretching while heating, it is preferable to provide a preheating zone before the stretched portion and a heat setting zone behind the stretched portion.
本発明の異方導電性接着シートは、少なくとも硬化剤、硬化性の絶縁性樹脂、及び絶縁被覆導電性粒子からなる単層のシートであってもよいし、さらに該シートに絶縁被覆導電性粒子を含まず少なくとも絶縁性樹脂を含む樹脂シートを積層した複層のシートであっても構わない。 The anisotropic conductive adhesive sheet of the present invention may be a single-layer sheet composed of at least a curing agent, a curable insulating resin, and insulating coated conductive particles, and further the insulating coated conductive particles on the sheet. It may be a multilayer sheet obtained by laminating a resin sheet containing at least an insulating resin.
本発明の異方導電性接着シートに用いる硬化性の絶縁性樹脂としては、熱硬化性樹脂、光硬化性樹脂、光及び熱硬化性樹脂、電子線硬化性樹脂等を用いることができる。取り扱いの容易さから、熱硬化性の絶縁性樹脂を用いることが好ましい。熱硬化性樹脂としては、エポキシ樹脂、アクリル樹脂等を用いることができるが、エポキシ樹脂が特に好ましい。 As the curable insulating resin used for the anisotropic conductive adhesive sheet of the present invention, a thermosetting resin, a photocurable resin, light and thermosetting resin, an electron beam curable resin, or the like can be used. In view of ease of handling, it is preferable to use a thermosetting insulating resin. As the thermosetting resin, an epoxy resin, an acrylic resin, or the like can be used, and an epoxy resin is particularly preferable.
エポキシ樹脂は、１分子中に２個以上のエポキシ基を有する化合物であり、グリシジルエーテル基、グリシジルエステル基、脂環式エポキシ基を有する化合物、分子内の二重結合をエポキシ化した化合物が好ましい。具体的には、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、ナフタレン型エポキシ樹脂、ノボラックフェノール型エポキシ樹脂あるいは、それらの変性エポキシ樹脂を用いることができる。 The epoxy resin is a compound having two or more epoxy groups in one molecule, and is preferably a compound having a glycidyl ether group, a glycidyl ester group or an alicyclic epoxy group, or a compound obtained by epoxidizing a double bond in the molecule. . Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, novolac phenol type epoxy resin, or modified epoxy resins thereof can be used.
本発明に用いる硬化剤は、前記硬化性の絶縁性樹脂を硬化できるものであればよい。硬化性の絶縁性樹脂として、熱硬化性樹脂を用いる場合は、１００℃以上で熱硬化性樹脂と反応し、硬化できるものが好ましい。エポキシ樹脂の場合は、保存性の点から、潜在性硬化剤であることが好ましく、例えば、イミダゾール系硬化剤、カプセル型イミダゾール系硬化剤、カチオン系硬化剤、ラジカル系硬化剤、ルイス酸系硬化剤、アミンイミド系硬化剤、ポリアミン塩系硬化剤、ヒドラジド系硬化剤等を用いることができる。保存性、低温反応性の点から、カプセル型のイミダゾール系硬化剤が好ましい。 The curing agent used in the present invention may be any one that can cure the curable insulating resin. When a thermosetting resin is used as the curable insulating resin, a resin that can be cured by reacting with the thermosetting resin at 100 ° C. or higher is preferable. In the case of an epoxy resin, a latent curing agent is preferable from the viewpoint of storage stability. For example, an imidazole curing agent, a capsule type imidazole curing agent, a cationic curing agent, a radical curing agent, a Lewis acid curing agent. An agent, an amine imide curing agent, a polyamine salt curing agent, a hydrazide curing agent, and the like can be used. From the viewpoint of storage stability and low-temperature reactivity, capsule-type imidazole curing agents are preferred.
本発明の異方導電性接着シートには、硬化剤及び硬化性の絶縁性樹脂以外に、熱可塑性樹脂等を配合しても構わない。熱可塑性樹脂を配合することにより、容易にシート状に形成することが出来る。この場合の配合量は、硬化剤及び硬化性の絶縁性樹脂を合わせた成分１００質量部に対して２００質量部以下であることが好ましく、１００質量部以下であることが特に好ましい。本発明の硬化性の絶縁性樹脂に配合できる熱可塑性樹脂は、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリビニルブチラール樹脂、アルキル化セルロース樹脂、ポリエステル樹脂、アクリル樹脂、スチレン樹脂、ウレタン樹脂、ポリエチレンテレフタレート樹脂等であり、それらから選ばれる１種または２種以上の樹脂を組み合わせても差し支えない。これらの樹脂の中、水酸基、カルボキシル基等の極性基を有する樹脂は、接着強度の点から好ましい。また、熱可塑性樹脂は、ガラス転移温度が８０℃以上である熱可塑性樹脂を１種以上含むことが好ましい。 The anisotropic conductive adhesive sheet of the present invention may contain a thermoplastic resin or the like in addition to the curing agent and the curable insulating resin. By blending a thermoplastic resin, it can be easily formed into a sheet. In this case, the blending amount is preferably 200 parts by mass or less, particularly preferably 100 parts by mass or less, based on 100 parts by mass of the components including the curing agent and the curable insulating resin. Thermoplastic resins that can be blended with the curable insulating resin of the present invention include phenoxy resin, polyvinyl acetal resin, polyvinyl butyral resin, alkylated cellulose resin, polyester resin, acrylic resin, styrene resin, urethane resin, polyethylene terephthalate resin, etc. There may be a combination of one or more resins selected from them. Among these resins, a resin having a polar group such as a hydroxyl group or a carboxyl group is preferable from the viewpoint of adhesive strength. Moreover, it is preferable that a thermoplastic resin contains 1 or more types of thermoplastic resins whose glass transition temperature is 80 degreeC or more.
本発明の異方導電性接着シートには、上記構成成分に添加剤を配合しても差し支えない。異方導電性接着シートと被着物との密着性を向上させるために、添加剤として、カップリング剤を配合することができる。該カップリング剤としては、シランカップリング剤、チタンカップリング剤、アルミカップリング剤等を用いることができるが、シランカップリング剤が好ましい。該シランカップリング剤としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メルカプトトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、β−アミノエチル−γ−アミノプロピルトリメトキシシラン、γ−ウレイドプロピルトリメトキシシラン等を用いることができる。 In the anisotropic conductive adhesive sheet of the present invention, an additive may be blended with the above components. In order to improve the adhesion between the anisotropic conductive adhesive sheet and the adherend, a coupling agent can be blended as an additive. As the coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like can be used, and a silane coupling agent is preferable. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptotrimethoxysilane, γ-aminopropyltrimethoxysilane, β-aminoethyl-γ- Aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and the like can be used.
該カップリング剤の配合量は硬化剤および硬化性の絶縁性樹脂を合わせた成分１００質量部に対して、０．０１質量部から１質量部が好ましい。密着性向上の観点から０．０１質量部以上が好ましく、信頼性の観点から１質量部以下が好ましい。 The blending amount of the coupling agent is preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the components including the curing agent and the curable insulating resin. 0.01 mass part or more is preferable from a viewpoint of adhesive improvement, and 1 mass part or less is preferable from a reliability viewpoint.
さらに、吸湿時において、異方導電性接着シート中のイオン性成分による絶縁性低下を防止するため、添加剤としてイオン捕捉剤を配合することができる。該イオン捕捉剤としては、有機イオン交換体、無機イオン交換体、無機イオン吸着剤等を用いることができるが、耐熱性に優れる無機イオン交換体が好ましい。該無機イオン交換体としては、ジルコニウム系化合物、ジルコニウムビスマス系化合物、アンチモンビスマス系化合物、マグネシウムアルミニウム化合物を用いることができる。交換するイオンのタイプとしては、陽イオンタイプ、陰イオンタイプ、両イオンタイプがあるが、イオンマイグレーション直接の原因になる金属イオン（陽イオン）、電気伝導度を上昇し、金属イオンの生成原因になる陰イオンを両方とも交換できるため両イオンタイプが好ましい。 Furthermore, an ion scavenger can be blended as an additive in order to prevent a decrease in insulation due to an ionic component in the anisotropic conductive adhesive sheet during moisture absorption. As the ion scavenger, an organic ion exchanger, an inorganic ion exchanger, an inorganic ion adsorbent, and the like can be used, but an inorganic ion exchanger excellent in heat resistance is preferable. As the inorganic ion exchanger, zirconium compounds, zirconium bismuth compounds, antimony bismuth compounds, and magnesium aluminum compounds can be used. There are positive ion type, negative ion type, and both ion types as ion types to be exchanged, but metal ions (positive ions) that cause direct ion migration, increase electrical conductivity, and cause generation of metal ions. Both anions are preferred because both anions can be exchanged.
配合する該イオン捕捉剤の平均粒径は、０．０１μｍ以上５μｍ以下であることが好ましく、０．０１μｍ以上１μｍ以下であることがより好ましい。
イオン捕捉剤の配合量としては、樹脂成分１００質量部に対して０．０１質量部から３質量部であることが好ましい。配合量が０．０１質量部未満の場合は、イオン捕捉効果が不充分であり、電気的接続の観点から３質量部以下が好ましい。
The average particle size of the ion scavenger to be blended is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.01 μm or more and 1 μm or less.
The compounding amount of the ion scavenger is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the resin component. When the blending amount is less than 0.01 parts by mass, the ion trapping effect is insufficient, and 3 parts by mass or less is preferable from the viewpoint of electrical connection.
次に本発明の異方導電性接着シートの製造方法について説明する。
まず、２軸延伸可能なフィルム上に粘着層を設けて積層体を形成し、該積層体の上に平均粒径１〜８μｍの絶縁被覆導電性粒子を付着させ絶縁被覆導電性粒子付着フィルムを作製し、該絶縁被覆導電性粒子付着フィルムを該絶縁被覆導電性粒子の近接する粒子との平均粒子間隔が絶縁被覆導電性粒子の平均粒径の１倍以上５倍以下かつ２０μｍ以下となるように２軸延伸して保持し、延伸した状態を保ったまま、絶縁被覆の一部を粘着層に残して、少なくとも硬化剤及び硬化性の絶縁性樹脂を含んでなる接着シートに転写することにより、部分絶縁被覆導電性粒子を有する本発明の異方導電性接着シートを製造することができる。好ましくは、２軸延伸可能なフィルムは長尺のフィルムであり、接着シートも長尺の接着シートである。本願において長尺とは長さが１０ｍ以上であることを指す。長尺の接着シートを用いれば連続して接続構造体を生産でき効率がよい。
Next, the manufacturing method of the anisotropically conductive adhesive sheet of this invention is demonstrated.
First, an adhesive layer is provided on a biaxially stretchable film to form a laminate, and insulating coated conductive particles having an average particle diameter of 1 to 8 μm are adhered on the laminated body to form an insulating coated conductive particle-adhered film. The insulating coated conductive particle-adhered film is prepared so that the average particle interval between the insulating coated conductive particles and the adjacent particles is 1 to 5 times the average particle diameter of the insulating coated conductive particles and 20 μm or less. Biaxially stretched and held, while keeping the stretched state, leaving a part of the insulating coating on the adhesive layer and transferring it to an adhesive sheet comprising at least a curing agent and a curable insulating resin The anisotropic conductive adhesive sheet of the present invention having partially insulating coated conductive particles can be produced. Preferably, the biaxially stretchable film is a long film, and the adhesive sheet is also a long adhesive sheet. In the present application, the long length means that the length is 10 m or more. If a long adhesive sheet is used, a connection structure can be produced continuously, which is efficient.
接着シートは硬化剤及び硬化性の絶縁性樹脂を含んでなる接着層であり、この接着シートは通常は剥離可能なベースフィルム（保持フィルム）上に形成される。このため、得られる異方導電性接着シートは、通常は剥離可能なベースフィルム上に形成される。
本願明細書では、この異方導電性接着シートとベースフィルムとの積層体を異方導電性接着シートと言うことがある。
The adhesive sheet is an adhesive layer comprising a curing agent and a curable insulating resin, and this adhesive sheet is usually formed on a peelable base film (holding film). For this reason, the anisotropically conductive adhesive sheet obtained is normally formed on the peelable base film.
In the present specification, the laminate of the anisotropic conductive adhesive sheet and the base film may be referred to as an anisotropic conductive adhesive sheet.
粘着層に使用する粘着剤は、公知のものを使用することができるが、加熱しながら２軸延伸する場合は、非熱架橋性の粘着剤を用いることが好ましい。具体的には、天然ゴムラテックス系粘着剤、合成ゴムラテックス系粘着剤、合成樹脂エマルジョン系粘着剤、シリコーン系粘着剤、エチレン−酢酸ビニル共重合体粘着剤等を単独で、又は組み合わせて用いることができる。使用する絶縁被覆導電性粒子表面の絶縁被覆膜に対する粘着剤の粘着力は、導電性粒子に対する絶縁被覆の粘着力より強いことが好ましい。 As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, a known one can be used, but when biaxial stretching is performed while heating, it is preferable to use a non-thermal crosslinkable pressure-sensitive adhesive. Specifically, natural rubber latex adhesives, synthetic rubber latex adhesives, synthetic resin emulsion adhesives, silicone adhesives, ethylene-vinyl acetate copolymer adhesives, etc. may be used alone or in combination. Can do. The adhesive force of the adhesive to the insulating coating film on the surface of the insulating coating conductive particles to be used is preferably stronger than the adhesive strength of the insulating coating to the conductive particles.
粘着層の厚みは、使用する絶縁被覆導電性粒子の平均粒径の１／５０から３倍の範囲が好ましく、１／１０から２倍の範囲がより好ましい。絶縁被覆導電性粒子付着時及び延伸時に導電性粒子を保持する観点から、粘着層の厚みは該完全絶縁被覆導電性粒子の平均粒径の１／５０以上が好ましく、延伸後の接着シートへの粒子転写の観点から３倍以下が好ましい。粘着層形成方法としては、溶剤又は水に分散又は溶解したものを、グラビアコーター、ダイコーター、ナイフコーター、バーコーター等の公知の方法で塗布し、乾燥する方法を用いることができる。ホットメルトタイプの粘着剤を使用する場合は、無溶剤でロールコートすることができる。 The thickness of the adhesive layer is preferably in the range of 1/50 to 3 times the average particle diameter of the insulating coated conductive particles to be used, and more preferably in the range of 1/10 to 2 times. From the viewpoint of retaining the conductive particles when the insulating coating conductive particles are attached and stretched, the thickness of the adhesive layer is preferably 1/50 or more of the average particle diameter of the completely insulating coating conductive particles, From the viewpoint of particle transfer, it is preferably 3 times or less. As the method for forming the adhesive layer, a method in which a dispersion or solution in a solvent or water is applied and dried by a known method such as a gravure coater, a die coater, a knife coater, or a bar coater can be used. When a hot-melt type pressure-sensitive adhesive is used, it can be roll-coated without a solvent.
該絶縁被覆導電性粒子を粘着層に塗布するにあたっては、ほぼ隙間無く単層に配置すること（密集充填）が好ましい。密集充填する方法としては、前述の、２軸延伸可能なフィルム上に絶縁被覆導電性粒子を分散配列し、固定する方法を用いることができる。なお、密集充填とは、充填された粒子間の平均粒子間隔が、平均粒径の１／２以下であるように充填することをいうものとする。より好ましくは、充填された粒子間の平均粒子間隔が、平均粒径の１／５以下である。 In applying the insulating coating conductive particles to the adhesive layer, it is preferable to dispose the insulating coating conductive particles in a single layer with almost no gap (dense packing). As a method of densely packing, the above-described method can be used in which insulating coated conductive particles are dispersed and arranged on a biaxially stretchable film. In addition, close packing means filling so that the average particle | grain space | interval between the filled particles may be 1/2 or less of an average particle diameter. More preferably, the average particle interval between the filled particles is 1/5 or less of the average particle size.
２軸延伸後のフィルムの膜厚は、転写する接着性シート及び接着性シートのベースフィルムの膜厚を合計した厚みの１／１０から１倍であることが好ましく、１／５から１／２であることが特に好ましい。延伸後のフィルムのハンドリング性の観点から、１／１０以上であることが好ましく、延伸後の接着性シートへの粒子転写の観点から１倍以下であることが好ましい。 The film thickness of the biaxially stretched film is preferably 1/10 to 1 times the total thickness of the adhesive sheet to be transferred and the base film of the adhesive sheet, and 1/5 to 1/2. It is particularly preferred that From the viewpoint of handling properties of the stretched film, it is preferably 1/10 or more, and from the viewpoint of particle transfer to the adhesive sheet after stretching, it is preferably 1 time or less.
延伸した状態を保ったまま、絶縁被覆の一部を粘着層に残して、少なくとも硬化剤及び硬化性の絶縁性樹脂を含んでなる接着シートに転写する方法としては、絶縁被覆を構成する樹脂のガラス転移温度以上の温度で熱処理することが好ましい。該熱処理により軟化した絶縁被覆の粘着層と融合し、接着シートに完全絶縁被覆導電性粒子を転写するときに絶縁被覆の一部が粘着層に残ることで部分絶縁被覆導電性粒子とすることができる。 While maintaining the stretched state, a part of the insulating coating is left in the adhesive layer and transferred to an adhesive sheet comprising at least a curing agent and a curable insulating resin. Heat treatment is preferably performed at a temperature equal to or higher than the glass transition temperature. Fusing with the insulating coating adhesive layer softened by the heat treatment, when transferring the completely insulating coated conductive particles to the adhesive sheet, a part of the insulating coating remains in the adhesive layer, so that partially insulating coated conductive particles can be obtained it can.
次に、微細接続端子を有する電子回路部品とそれに対応する回路を有する回路基板とを異方導電性接着シートで電気的に接続する、本発明の接続方法を説明する。該接続方法において、該電子回路部品の微細接続端子の高さは絶縁被覆導電性粒子の平均粒子間隔の３〜１５倍かつ４０μｍ以下であり、該微細接続端子の間隔は該平均粒子間隔の１〜１０倍かつ４０μｍ以下であり、該微細接続端子のピッチは該平均粒子間隔の３〜３０倍かつ８０μｍ以下である。該電子回路部品とそれに対応する回路を有する回路基板とは、本発明の異方導電性接着シートを用いて電気的に接続する。 Next, the connection method of the present invention, in which an electronic circuit component having fine connection terminals and a circuit board having a corresponding circuit are electrically connected with an anisotropic conductive adhesive sheet, will be described. In the connection method, the height of the fine connection terminal of the electronic circuit component is 3 to 15 times the average particle interval of the insulating coated conductive particles and 40 μm or less, and the interval of the fine connection terminal is 1 of the average particle interval. 10 to 40 μm or less, and the pitch of the fine connection terminals is 3 to 30 times the average particle interval and 80 μm or less. The electronic circuit component and a circuit board having a corresponding circuit are electrically connected using the anisotropic conductive adhesive sheet of the present invention.
微細接続端子の高さは、絶縁被覆導電性粒子の平均粒子間隔の３〜１５倍かつ４０μｍ以下であり、４倍〜１０倍が好ましい。微細接続構造体の機械的強度の観点から３倍以上が好ましく、接続時に接着性シートの樹脂流動により絶縁被覆導電性粒子の移動が起こり、該微細接続端子下部にある絶縁被覆導電性粒子数の減少による接続性低下の観点から、１５倍以下であり、かつ４０μｍ以下が好ましい。該微細接続端子間隔は平均粒子間隔の１〜１０倍かつ４０μｍ以下であり、１〜１０倍かつ２０μｍ以下が好ましく、２〜５倍かつ１５μｍ以下がより好ましい。絶縁性の観点から１倍以上が好ましく、微細接続の観点から１０倍以下かつ４０μｍ以下が好ましい。ピッチは、平均粒子間隔の３〜３０倍かつ８０μｍ以下であり、５〜２０倍かつ４０μｍ以下であることが好ましい。接続性の観点から３倍以上が好ましく、微細接続の観点から３０倍以下かつ８０μｍ以下が好ましい。 The height of the fine connection terminal is 3 to 15 times and 40 μm or less, and preferably 4 to 10 times the average particle interval of the insulating coated conductive particles. Three times or more is preferable from the viewpoint of the mechanical strength of the fine connection structure, and the movement of the insulating coated conductive particles occurs due to the resin flow of the adhesive sheet at the time of connection. From the viewpoint of lowering the connectivity due to the decrease, it is 15 times or less and preferably 40 μm or less. The fine connection terminal interval is 1 to 10 times the average particle interval and 40 μm or less, preferably 1 to 10 times and 20 μm or less, more preferably 2 to 5 times and 15 μm or less. 1 times or more is preferable from the viewpoint of insulation, and 10 times or less and 40 μm or less are preferable from the viewpoint of fine connection. The pitch is 3 to 30 times the average particle interval and 80 μm or less, and preferably 5 to 20 times and 40 μm or less. It is preferably 3 times or more from the viewpoint of connectivity, and preferably 30 times or less and 80 μm or less from the viewpoint of fine connection.
本発明はまた、上記微細接続方法により接続された微細接続構造体にも関する。
本発明の微細接続構成体を構成する回路基板の材質は、有機基板でも無機基板でも、差し支えない。有機基板としては、ポリイミドフィルム基板、ポリアミドフィルム基板、ポリエーテルスルホンフィルム基板、エポキシ樹脂をガラスクロスに含浸させたリジッド基板、ビスマレイミド−トリアジン樹脂をガラスクロスに含浸させたリジッド基板等を用いることができる。無機基板としては、シリコン基板、ガラス基板、アルミナ基板、窒化アルミ基板等を用いることができる。配線基板の配線材料は、インジウム錫酸化物、インジウム亜鉛酸化物等の無機配線材料、金メッキ銅、クロム−銅、アルミニウム、金バンプ等の金属配線材料、アルミニウム、クロム等の金属材料でインジウム錫酸化物等の無機配線材料を覆った複合配線材料等を用いることができる。
The present invention also relates to a fine connection structure connected by the fine connection method.
The material of the circuit board constituting the finely connected structure of the present invention may be an organic substrate or an inorganic substrate. As the organic substrate, a polyimide film substrate, a polyamide film substrate, a polyethersulfone film substrate, a rigid substrate obtained by impregnating a glass cloth with an epoxy resin, a rigid substrate obtained by impregnating a glass cloth with a bismaleimide-triazine resin, or the like may be used. it can. As the inorganic substrate, a silicon substrate, a glass substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. The wiring material of the wiring board is inorganic wiring materials such as indium tin oxide and indium zinc oxide, metal wiring materials such as gold-plated copper, chromium-copper, aluminum and gold bumps, and metal materials such as aluminum and chromium indium tin oxide. A composite wiring material covering an inorganic wiring material such as an object can be used.
本発明の異方導電性接着シートを適応する用途、あるいは本発明の微細接続構造体を構成する電子回路部品としては、液晶ディスプレイ機器、プラズマディスプレイ機器、エレクトロルミネッセンスディスプレイ機器等の表示機器の配線板接続用途および、それら機器のＬＳＩ等の電子部品実装用途、その他の機器の配線基板接続部分、ＬＳＩ等の電子部品実装用途に使用することができる。上記表示機器の中でも、信頼性を必要とされるプラズマディスプレイ機器、エレクトロルミネッセンスディスプレイ機器に用いるのが好ましい。
次に、実施例および比較例によって本発明を説明する。
As an application to which the anisotropic conductive adhesive sheet of the present invention is applied, or as an electronic circuit component constituting the finely connected structure of the present invention, a wiring board of a display device such as a liquid crystal display device, a plasma display device, an electroluminescence display device, etc. It can be used for connection applications, electronic component mounting applications such as LSIs for those devices, wiring board connection parts of other devices, and electronic component mounting applications such as LSIs. Among the display devices, it is preferably used for plasma display devices and electroluminescence display devices that require reliability.
Next, the present invention will be described with reference to examples and comparative examples.
[実施例１]
フェノキシ樹脂（ガラス転移温度９８℃、数平均分子量１４０００）３９ｇ、ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９０、２５℃粘度、１４０００ｍＰａ・Ｓ）２４ｇ、γ−グリシドキシプロピルトリメトキシシラン０．４ｇを酢酸エチル−トルエンの混合溶剤（混合比１：１）に溶解し、固形分５０％溶液とする。
マイクロカプセル型潜在性イミダゾール硬化剤を含有する液状エポキシ樹脂（マイクロカプセルの平均粒径５μｍ、活性温度１２５℃）３７ｇ、前記固形分５０％溶液に配合分散させる。その後、厚さ５０μｍのポリエチレンテレフタレートフィルム（ベースフィルム）上に塗布し、６０℃で１５分間送風乾燥し、膜厚１８μｍのフィルム状の接着シートを得た。
[Example 1]
Acetic acid is 39 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), bisphenol A type epoxy resin (epoxy equivalent 190, viscosity at 25 ° C., 14000 mPa · S) 24 g, and 0.4 g of γ-glycidoxypropyltrimethoxysilane. Dissolve in a mixed solvent of ethyl-toluene (mixing ratio 1: 1) to obtain a 50% solid content solution.
A liquid epoxy resin containing a microcapsule-type latent imidazole curing agent (average particle diameter of microcapsule 5 μm, active temperature 125 ° C.) 37 g is mixed and dispersed in the 50% solid content solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film (base film), and air-dried at 60 degreeC for 15 minute (s), and obtained the film-form adhesive sheet of 18-micrometer-thickness.
平均粒径３．０μｍの金めっきプラスチック粒子２０ｇに平均粒径０．１５μｍのポリメチルメタアクリレート樹脂（ガラス転移温度１１８℃）粒子１ｇを混合し、高速気流中（周速度、１００ｍ／ｓ）で７分間処理し、絶縁被覆導電性粒子を得た。該絶縁被覆導電性粒子の平均粒径は、レーザー式粒度分布計（ＪＥＯＬ社製、ＨＥＬＯＳ ＳＹＳＴＥＭ）にて測定し、積算値５０％になる値を平均粒径とした。平均粒径は、３．３μｍであった。エポキシ樹脂に包埋して断面研磨し、電子顕微鏡観察し、絶縁被覆の膜厚を測定したところ、０．１５μｍであった。厚さ４０μｍの無延伸ポリプロピレンフィルム上に、粘着層としてニトリルゴムラテックス−メチルメタアクリレートのグラフト共重合体接着剤を５μｍの厚みを塗布したものに平均粒径３．３μｍの上記絶縁被覆導電性粒子をほぼ隙間無く単層塗布した。すなわち、該絶縁被覆導電性粒子を該フィルム幅より大きい容器内に数層以上の厚みになるよう敷き詰めたものを用意し、該絶縁被覆導電性粒子に対して粘着剤の塗布面を下向きにして押し付けて付着させ、その後過剰な粒子を不織布からなるスクレバーで掻き落とした。この操作を２回繰り返すことにより、隙間無く単層塗布した絶縁被覆導電性粒子付着フィルムを得た。 20 g of gold-plated plastic particles having an average particle size of 3.0 μm and 1 g of polymethyl methacrylate resin (glass transition temperature 118 ° C.) particles having an average particle size of 0.15 μm are mixed in a high-speed air stream (circumferential speed, 100 m / s). Treatment was performed for 7 minutes to obtain insulating coated conductive particles. The average particle size of the insulating coating conductive particles was measured with a laser particle size distribution meter (manufactured by JEOL, HELOS SYSTEM), and the value at which the integrated value was 50% was defined as the average particle size. The average particle size was 3.3 μm. It was 0.15 μm when embedded in an epoxy resin, cross-section polished, observed with an electron microscope, and the thickness of the insulating coating was measured. Insulating coated conductive particles having an average particle size of 3.3 μm applied to an unstretched polypropylene film having a thickness of 40 μm and a 5 μm thick nitrile rubber latex-methyl methacrylate graft copolymer adhesive applied as an adhesive layer Was applied with almost no gap. That is, prepare the insulating coating conductive particles spread in a container larger than the film width so as to have a thickness of several layers or more, with the adhesive coating surface facing the insulating coating conductive particles downward After pressing, the particles were scraped off with a scraper made of nonwoven fabric. By repeating this operation twice, an insulating coating conductive particle adhesion film coated with a single layer without any gap was obtained.
このフィルムを２軸延伸装置（東洋精機製Ｘ６Ｈ−Ｓ、パンタグラフ方式のコーナーストレッチ型の２軸延伸装置）を用いて縦横にそれぞれ１０個のチャックを用いて固定し１１５℃、１２０秒間予熱し、その後２０％／秒の速度で１００％延伸して固定した。固定後、１５０℃、２分間熱処理した。この延伸フィルムに前記接着シートをラミネートした後、剥離し、異方導電性接着シートを得た。
得られた異方導電性接着シートの絶縁被覆導電性粒子のうち、無作為に１００個を選び、焦点方向の変位を測定できるレーザー顕微鏡（キーエンス社製、ＶＫ９５００、形状測定分解能０．０１μｍ）を用いて、異方導電性接着シート表面からの距離を測定した。その結果、絶縁被覆導電性粒子の９０％が異方導電性接着シート表面より露出して存在することがわかった。また、電子顕微鏡観察の結果、露出している絶縁被覆導電性粒子１００個のうち８９％が部分絶縁被覆導電性粒子であった。また、平均粒子間隔は４．５８μｍであり、これは、平均粒径の１．３９倍であった。
This film was fixed using 10 chucks vertically and horizontally using a biaxial stretching device (X6H-S manufactured by Toyo Seiki, pantograph type corner stretching type biaxial stretching device), preheated at 115 ° C. for 120 seconds, Thereafter, the film was stretched 100% and fixed at a rate of 20% / second. After fixing, heat treatment was performed at 150 ° C. for 2 minutes. After laminating the adhesive sheet on the stretched film, it was peeled off to obtain an anisotropic conductive adhesive sheet.
A laser microscope (Keyence Co., VK9500, shape measurement resolution 0.01 μm) capable of measuring the displacement in the focal direction by randomly selecting 100 of the insulating coated conductive particles of the obtained anisotropic conductive adhesive sheet. Using, the distance from the anisotropic conductive adhesive sheet surface was measured. As a result, it was found that 90% of the insulating coated conductive particles were exposed from the anisotropic conductive adhesive sheet surface. As a result of observation with an electron microscope, 89% of 100 exposed insulating coated conductive particles were partially insulating coated conductive particles. Further, the average particle interval was 4.58 μm, which was 1.39 times the average particle size.
[実施例２]
フェノキシ樹脂（ガラス転移温度９８℃、数平均分子量１４０００）４１ｇ、ナフタレン型エポキシ樹脂（エポキシ当量１３６、半固形）３３ｇ、γ−ウレイドプロピルトリメトキシシラン０．０６ｇを酢酸エチル−トルエンの混合溶剤（混合比１：１）に溶解し、固形分５０％溶液とする。マイクロカプセル型潜在性イミダゾール硬化剤を含有する液状エポキシ樹脂（マイクロカプセルの平均粒径７μｍ、活性温度１２５℃）２６ｇ、前記固形分５０％溶液に配合分散させる。その後、厚さ５０μｍのポリエチレンテレフタレートフィルム上に塗布し、６０℃で１５分間送風乾燥し、膜厚１７μｍのフィルム状の接着シートを得た。
[Example 2]
41 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), 33 g of naphthalene type epoxy resin (epoxy equivalent 136, semi-solid), 0.06 g of γ-ureidopropyltrimethoxysilane were mixed in ethyl acetate-toluene mixed solvent (mixed) To a 50% solid content solution. A liquid epoxy resin containing a microcapsule-type latent imidazole curing agent (average particle diameter of microcapsule 7 μm, active temperature 125 ° C.) 26 g is mixed and dispersed in the 50% solid content solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, and air-dried at 60 degreeC for 15 minute (s), and obtained the film-like adhesive sheet of film thickness of 17 micrometers.
平均粒径３．８μｍの金めっきプラスチック粒子２０ｇに平均粒径０．２μｍのポリメチルメタアクリレート樹脂（ガラス転移温度１１８℃）粒子１ｇを混合し、高速気流中（周速度、１００ｍ／ｓ）で７分間処理し、絶縁被覆導電性粒子を得た。該絶縁被覆導電性粒子の平均粒径は、レーザー式粒度分布計（ＪＥＯＬ社製、ＨＥＬＯＳ ＳＹＳＴＥＭ）にて測定し、積算値５０％になる値を平均粒径とした。平均粒径は、４．２μｍであった。エポキシ樹脂に包埋して断面研磨し、電子顕微鏡観察し、絶縁被覆の膜厚を測定したところ、０．１９μｍであった。
厚さ４５μｍの無延伸ポリエチレンフィルム上に実施例１と同じニトリルゴムラテックス−メチルメタアクリレートのグラフト共重合体接着剤を３μｍ塗布したものに平均粒径４．２μｍの上記絶縁被覆導電性粒子を実施例１と同様の方法によりほぼ隙間無く単層塗布した絶縁被覆導電性粒子付着フィルムを得た。
1 g of polymethyl methacrylate resin (glass transition temperature 118 ° C.) particles having an average particle size of 0.2 μm is mixed with 20 g of gold-plated plastic particles having an average particle size of 3.8 μm, and in a high-speed air current (circumferential speed, 100 m / s). Treatment was performed for 7 minutes to obtain insulating coated conductive particles. The average particle diameter of the insulating coated conductive particles was measured with a laser particle size distribution meter (manufactured by JEOL, HELOS SYSTEM), and the value at which the integrated value was 50% was defined as the average particle diameter. The average particle size was 4.2 μm. It was 0.19 μm when embedded in an epoxy resin, cross-sectional polished, observed with an electron microscope, and the thickness of the insulating coating was measured.
Conducting the above insulating coated conductive particles having an average particle diameter of 4.2 μm on a non-stretched polyethylene film having a thickness of 45 μm coated with 3 μm of the same nitrile rubber latex-methyl methacrylate graft copolymer adhesive as in Example 1. An insulating coated conductive particle-adhered film coated with a single layer with almost no gap was obtained in the same manner as in Example 1.
このフィルムを延伸温度を８０℃にする以外は実施例１と同様の方法により２軸延伸装置を用いて縦横にそれぞれ１２０％延伸して固定した。固定後、１２５℃、２分間熱処理した。この延伸フィルムに前記接着シートをラミネートした後、剥離し、異方導電性接着シートを得た。
得られた異方導電性接着シートの絶縁被覆導電性粒子のうち、無作為に１００個を選び、焦点方向の変位を測定できるレーザー顕微鏡（キーエンス社製、ＶＫ９５００、形状測定分解能０．０１μｍ）を用いて、異方導電性接着シート表面からの距離を測定した。その結果、絶縁被覆導電性粒子の９２％が異方導電性接着シート表面より露出して存在することがわかった。また、電子顕微鏡観察の結果、露出している絶縁被覆導電性粒子１００個のうち８８％が部分絶縁被覆導電性粒子であった。また、平均粒子間隔は７．０６μｍであり、これは、平均粒径の１．６８倍であった。
The film was stretched and fixed 120% vertically and horizontally by the same method as in Example 1 except that the stretching temperature was 80 ° C. After fixing, heat treatment was performed at 125 ° C. for 2 minutes. After laminating the adhesive sheet on the stretched film, it was peeled off to obtain an anisotropic conductive adhesive sheet.
A laser microscope (Keyence Co., VK9500, shape measurement resolution 0.01 μm) capable of measuring the displacement in the focal direction by randomly selecting 100 of the insulating coated conductive particles of the obtained anisotropic conductive adhesive sheet. Using, the distance from the anisotropic conductive adhesive sheet surface was measured. As a result, it was found that 92% of the insulating coated conductive particles were exposed from the surface of the anisotropic conductive adhesive sheet. As a result of observation with an electron microscope, 88% of 100 exposed insulating coated conductive particles were partially insulating coated conductive particles. The average particle spacing was 7.06 μm, which was 1.68 times the average particle size.
[実施例３]
フェノキシ樹脂（ガラス転移温度４５℃、数平均分子量１２０００）１０ｇ、フェノキシ樹脂（ガラス転移温度９８℃、数平均分子量１４０００）３３ｇ、ナフタレン型エポキシ樹脂（エポキシ当量１３６、半固形）２６ｇ、γ−グリシドキシプロピルトリエトキシシラン０．１ｇを酢酸エチル−トルエンの混合溶剤（混合比１：１）に溶解し、固形分５０％溶液とする。マイクロカプセル型潜在性イミダゾール硬化剤を含有する液状エポキシ樹脂（マイクロカプセルの平均粒径７μｍ、活性温度１２５℃）３１ｇ、前記固形分５０％溶液に配合分散させる。その後、厚さ５０μｍのポリエチレンテレフタレートフィルム上に塗布し、６０℃で１５分間送風乾燥し、膜厚１５μｍのフィルム状の接着シートを得た。
[Example 3]
10 g of phenoxy resin (glass transition temperature 45 ° C., number average molecular weight 12000), 33 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), 26 g of naphthalene type epoxy resin (epoxy equivalent 136, semi-solid), γ-glycid 0.1 g of xylpropyltriethoxysilane is dissolved in a mixed solvent of ethyl acetate-toluene (mixing ratio 1: 1) to obtain a 50% solid content solution. A liquid epoxy resin containing a microcapsule-type latent imidazole curing agent (average particle diameter of microcapsule 7 μm, active temperature 125 ° C.) 31 g is mixed and dispersed in the 50% solid content solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, and it air-dried for 15 minutes at 60 degreeC, and obtained the film-form adhesive sheet of 15-micrometer-thickness.
平均粒径３．２μｍの金めっき銅粒子２０ｇに平均粒径０．１０μｍのポリメチルメタアクリレート樹脂（ガラス転移温度１１８℃）粒子０．３ｇを混合し、高速気流中（周速度、１００ｍ／ｓ）で５分間処理し、絶縁被覆導電性粒子を得た。該絶縁被覆導電性粒子の平均粒径は、レーザー式粒度分布計（ＪＥＯＬ社製、ＨＥＬＯＳ ＳＹＳＴＥＭ）にて測定し、積算値５０％になる値を平均粒径とした。平均粒径は、３．４μｍであった。エポキシ樹脂に包埋して断面研磨し、電子顕微鏡観察し、絶縁被覆の膜厚を測定したところ、０．０９μｍであった。
厚さ４５μｍの無延伸ポリプロピレンフィルム上にエチレン−酢酸ビニル共重合体接着剤を５μｍ塗布したものに上記の平均粒径３．４μｍの絶縁被覆導電性粒子を実施例１と同様の方法によりほぼ隙間無く単層塗布した絶縁被覆導電性粒子付着フィルムを得た。
このフィルムを実施例１と同様の方法により２軸延伸装置を用いて縦横にそれぞれ１５０％延伸して固定した。固定後、１５０℃、２分間保持した。この延伸フィルムに前記接着シートをラミネートした後、剥離し、異方導電性接着シートを得た。
20 g of gold-plated copper particles having an average particle diameter of 3.2 μm are mixed with 0.3 g of polymethyl methacrylate resin (glass transition temperature 118 ° C.) particles having an average particle diameter of 0.10 μm in a high-speed air stream (peripheral speed, 100 m / s). ) For 5 minutes to obtain insulating coated conductive particles. The average particle diameter of the insulating coated conductive particles was measured with a laser particle size distribution meter (manufactured by JEOL, HELOS SYSTEM), and the value at which the integrated value was 50% was defined as the average particle diameter. The average particle size was 3.4 μm. It was 0.09 μm when embedded in an epoxy resin, cross-section polished, observed with an electron microscope, and the thickness of the insulating coating was measured.
The insulating coated conductive particles having an average particle diameter of 3.4 μm were applied to a non-stretched polypropylene film having a thickness of 45 μm coated with 5 μm of an ethylene-vinyl acetate copolymer adhesive. An insulating coated conductive particle-adhered film coated without a single layer was obtained.
This film was fixed by stretching 150% in the longitudinal and lateral directions using a biaxial stretching apparatus in the same manner as in Example 1. After fixing, it was kept at 150 ° C. for 2 minutes. After laminating the adhesive sheet on the stretched film, it was peeled off to obtain an anisotropic conductive adhesive sheet.
得られた異方導電性接着シートの絶縁被覆導電性粒子のうち、無作為に１００個を選び、焦点方向の変位を測定できるレーザー顕微鏡（キーエンス社製、ＶＫ９５００、形状測定分解能０．０１μｍ）を用いて、異方導電性接着シート表面からの距離を測定した。その結果、絶縁被覆導電性粒子の８５％が異方導電性接着シート表面より露出して存在することがわかった。また、電子顕微鏡観察の結果、露出している絶縁被覆導電性粒子１００個のうち９２％が部分絶縁被覆導電性粒子であった。また、平均粒子間隔は７．２１μｍであり、これは、平均粒径の２．１２倍であった。 A laser microscope (Keyence Co., VK9500, shape measurement resolution 0.01 μm) capable of measuring the displacement in the focal direction by randomly selecting 100 of the insulating coated conductive particles of the obtained anisotropic conductive adhesive sheet. Using, the distance from the anisotropic conductive adhesive sheet surface was measured. As a result, it was found that 85% of the insulating coated conductive particles were exposed from the surface of the anisotropic conductive adhesive sheet. Further, as a result of observation with an electron microscope, 92% of 100 exposed insulating coated conductive particles were partially insulating coated conductive particles. The average particle spacing was 7.21 μm, which was 2.12 times the average particle size.
[比較例１]
フェノキシ樹脂（ガラス転移温度９８℃、数平均分子量１４０００）３７ｇ、ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９０、２５℃粘度、１４０００ｍＰａ・Ｓ）２６ｇ、γ−グリシドキシプロピルトリメトキシシラン０．３ｇを酢酸エチル−トルエンの混合溶剤（混合比１：１）に溶解し、固形分５０％溶液とする。
マイクロカプセル型潜在性イミダゾール硬化剤を含有する液状エポキシ樹脂（マイクロカプセルの平均粒径５μｍ、活性温度１２５℃）３７ｇ、平均粒径３．８μｍの金めっきプラスチック粒子２．０ｇを前記固形分５０％溶液に配合分散させる。その後、厚さ５０μｍのポリエチレンテレフタレートフィルム上に塗布し、６０℃で１５分間送風乾燥し、膜厚２０μｍのフィルム状の異方導電性接着シートを得た。
得られた異方導電性接着シートの導電性粒子のうち、無作為に１００個を選び、レーザー式の変位計を用いて、異方導電性接着シート表面からの距離を測定した。その結果、導電性粒子は異方導電性接着シートの膜厚方向においてランダムに存在することがわかった。また、測定した導電性粒子１００個のうち７５％が単独粒子であった。また、表面に露出している粒子は１％であった。
[Comparative Example 1]
Acetic acid containing 37 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), 26 g of bisphenol A type epoxy resin (epoxy equivalent 190, viscosity at 25 ° C., 14000 mPa · S), 0.3 g of γ-glycidoxypropyltrimethoxysilane Dissolve in a mixed solvent of ethyl-toluene (mixing ratio 1: 1) to obtain a 50% solid content solution.
37 g of liquid epoxy resin containing microcapsule type latent imidazole curing agent (average particle size of microcapsule 5 μm, active temperature 125 ° C.) and 2.0 g of gold-plated plastic particles having an average particle size of 3.8 μm are mixed with 50% solid content. Mix and disperse in the solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, air-dried at 60 degreeC for 15 minute (s), and the film-form anisotropic conductive adhesive sheet of 20-micrometer-thickness was obtained.
Of the conductive particles of the obtained anisotropic conductive adhesive sheet, 100 particles were randomly selected, and the distance from the anisotropic conductive adhesive sheet surface was measured using a laser displacement meter. As a result, it was found that the conductive particles exist randomly in the film thickness direction of the anisotropic conductive adhesive sheet. In addition, 75% of 100 measured conductive particles were single particles. Moreover, 1% of the particles were exposed on the surface.
[比較例２]
フェノキシ樹脂（ガラス転移温度４５℃、数平均分子量１２０００）４２ｇ、ナフタレン型エポキシ樹脂（エポキシ当量１３６、半固形）３２ｇ、γ−ウレイドプロピルトリメトキシシラン０．０６ｇを酢酸エチル−トルエンの混合溶剤（混合比１：１）に溶解し、固形分５０％溶液とする。マイクロカプセル型潜在性イミダゾール硬化剤を含有する液状エポキシ樹脂（マイクロカプセルの平均粒径５μｍ、活性温度１２５℃）２６ｇ、平均粒径３．２μｍの金めっき銅粒子６．０ｇを前記固形分５０％溶液に配合分散させる。その後、厚さ５０μｍのポリエチレンテレフタレートフィルム上に塗布し、６０℃で１５分間送風乾燥し、膜厚２０μｍのフィルム状の異方導電性接着シートを得る。
得られた異方導電性接着シートの導電性粒子のうち、無作為に１００個を選び、レーザー式の変位計を用いて、異方導電性接着シート表面からの距離を測定した。その結果、導電性粒子は異方導電性接着シートの膜厚方向においてランダムに存在することがわかった。また、測定した導電性粒子１００個のうち６０％が単独粒子であった。また、表面に露出している粒子は０％であった。
[Comparative Example 2]
42 g of phenoxy resin (glass transition temperature 45 ° C., number average molecular weight 12000), 32 g of naphthalene type epoxy resin (epoxy equivalent 136, semi-solid), 0.06 g of γ-ureidopropyltrimethoxysilane, mixed solvent of ethyl acetate-toluene (mixed) To a 50% solid content solution. 26 g of liquid epoxy resin containing microcapsule-type latent imidazole curing agent (average size of microcapsule 5 μm, active temperature 125 ° C.) and 6.0 g of gold-plated copper particles having an average particle size of 3.2 μm are mixed with 50% solid content. Mix and disperse in the solution. Then, it apply | coats on a 50-micrometer-thick polyethylene terephthalate film, and air-drys for 15 minutes at 60 degreeC, and obtains a film-form anisotropic conductive adhesive sheet with a film thickness of 20 micrometers.
Of the conductive particles of the obtained anisotropic conductive adhesive sheet, 100 particles were randomly selected, and the distance from the anisotropic conductive adhesive sheet surface was measured using a laser displacement meter. As a result, it was found that the conductive particles exist randomly in the film thickness direction of the anisotropic conductive adhesive sheet. Moreover, 60% of 100 measured conductive particles were single particles. Further, the number of particles exposed on the surface was 0%.
（接続抵抗値測定方法）
縦横が１．６ｍｍ×１５．１ｍｍのシリコン片（厚み０．５ｍｍ）全面に酸化膜を形成後、外辺部から４０μｍ内側に横７４．５μｍ、縦１２０μｍのアルミ薄膜（１０００Å）をそれぞれが０．１μｍ間隔になるように長辺側に各々１７５個、短辺側に各々１６個形成する。それらアルミ薄膜上に１５μｍ間隔になるように横２５μｍ、縦１００μｍの金バンプ（厚み１５μｍ）をそれぞれ２個ずつ形成するために、それぞれの金バンプ配置個所の外周部から７．５μｍ内側に横１０μｍ、縦８５μｍの開口部を残す以外の部分にポリイミドの保護膜を常法により前記開口部以外の全面に形成する。その後、前記金バンプを形成し、試験チップとする。
(Connection resistance measurement method)
After an oxide film is formed on the entire surface of a silicon piece (thickness 0.5 mm) of 1.6 mm × 15.1 mm in length and width, an aluminum thin film (1000 mm) having a width of 74.5 μm and a length of 120 μm is 40 μm inside from the outer side. 175 pieces are formed on the long side and 16 pieces are formed on the short side, respectively, so as to have an interval of 1 μm. In order to form two gold bumps (thickness: 15 μm) each having a width of 25 μm and a length of 100 μm on the aluminum thin film at intervals of 15 μm, a width of 10 μm inside 7.5 μm from the outer peripheral portion of each gold bump placement location. Then, a polyimide protective film is formed on the entire surface other than the opening by a conventional method except for leaving the opening having a length of 85 μm. Thereafter, the gold bump is formed to obtain a test chip.
厚み０．７ｍｍの無アルカリガラス上に前記アルミ薄膜上の金バンプが隣接するアルミ薄膜上の金バンプと対になる位置関係で接続されるようにインジウム錫酸化物膜（１４００Å）の接続パッド（横６６μｍ、縦１２０μｍ）を形成する。２０個の金バンプが接続される毎に前記接続パッドにインジウム錫酸化物薄膜の引き出し配線を形成し、引出し配線上はアルミニウム−チタン薄膜（チタン１％、３０００Å）を形成し、接続評価基板とする。前記接続評価基板上に、前記接続パッドがすべて覆われるように、幅２ｍｍ、長さ１７ｍｍの異方導電性接着シートの該絶縁被覆粒子の存在する側を仮張りし、２．５ｍｍ幅の圧着ヘッドを用いて、８０℃、０．３ＭＰａ、３秒間加圧した後、ポリエチレンテレフタレートのベースフィルムを剥離する。そこへ、前記接続パッドと金バンプの位置が合うように試験チップを載せ、２２０℃、５秒間５．２ＭＰａ加圧圧着する。圧着後、前記引出し配線間（金バンプ２０個のデイジーチェイン）の抵抗値を四端子法の抵抗計で抵抗測定し、接続抵抗値とする。
A connection pad of an indium tin oxide film (1400 mm) so that the gold bump on the aluminum thin film is connected to a gold bump on the adjacent aluminum thin film on a non-alkali glass having a thickness of 0.7 mm so as to be paired with each other. 66 μm wide and 120 μm long). Each time 20 gold bumps are connected, a lead wire of indium tin oxide thin film is formed on the connection pad, and an aluminum-titanium thin film (
（絶縁抵抗試験方法）
厚み０．７ｍｍの無アルカリガラス上に前記アルミ薄膜上の２個の金バンプがそれぞれ接続されるような位置関係にインジウム錫酸化物膜（１４００Å）の接続パッド（横６５μｍ、縦１２０μｍ）を形成する。前記接続パッドを１個おきに５個接続できるようにインジウム錫酸化物薄膜の接続配線を形成し、さらにそれらと対になり、櫛型パターンを形成するように１個おきに５個接続できるようにインジウム錫酸化物薄膜の接続配線を形成する。それぞれの接続配線にインジウム錫酸化物薄膜の引出し配線を形成し、引き出し配線上にアルミニウム−チタン薄膜（チタン１％、３０００Å）を形成して、絶縁性評価基板とする。前記絶縁性評価基板上に、前記接続パッドがすべて覆われるように、幅２ｍｍ、長さ１７ｍｍの異方導電性接着シートを仮張りし、２．５ｍｍ幅の圧着ヘッドを用いて、８０℃、０．３ＭＰａ、３秒間加圧した後、ポリエチレンテレフタレートのベースフィルムを剥離する。そこへ、前記接続パッドと金バンプの位置が合うように試験チップを載せ、１８０℃、１０秒間２．４ＭＰａ加圧圧着し、絶縁抵抗試験基板とする。
(Insulation resistance test method)
Indium tin oxide film (1400 mm) connection pads (width: 65 μm, height: 120 μm) are formed on a non-alkali glass with a thickness of 0.7 mm so that the two gold bumps on the aluminum thin film are connected to each other. To do. A connection wiring of an indium tin oxide thin film is formed so that every other five connection pads can be connected, and a pair of them is paired to form a comb pattern so that every fifth connection pad can be connected. Then, an indium tin oxide thin film connection wiring is formed. An indium tin oxide thin film lead-out wiring is formed on each connection wiring, and an aluminum-titanium thin film (
この絶縁抵抗試験基板を８５℃、８５％相対湿度中に保持しながら、定電圧定電流電源を用いて、対になる引き出し配線間に５０Ｖの直流電圧を印加する。この配線間の絶縁抵抗を５分間毎に測定し、絶縁抵抗値が１０ＭΩ以下になるまでの時間を測定し、その値を絶縁低下時間とする。この絶縁低下時間が２４０時間未満の場合を×、２４０時間以上の場合を○とする。
以上の結果を表１に示す。表１から明らかなように、本発明の異方導電性接着シートは、非常に優れた絶縁信頼性を示す。
While maintaining this insulation resistance test substrate at 85 ° C. and 85% relative humidity, a DC voltage of 50 V is applied between the pair of lead wires using a constant voltage constant current power source. The insulation resistance between the wires is measured every 5 minutes, the time until the insulation resistance value becomes 10 MΩ or less is measured, and the value is defined as the insulation decrease time. The case where the insulation decrease time is less than 240 hours is indicated as x, and the case where the insulation decrease time is 240 hours or more is indicated as ◯.
The results are shown in Table 1. As is clear from Table 1, the anisotropic conductive adhesive sheet of the present invention exhibits very excellent insulation reliability.
本発明は、低接続抵抗、高絶縁信頼性を示し、微細回路接続が求められるベアチップ接続用材料および、高精細なディスプレイ装置等の接続材料として好適である。 INDUSTRIAL APPLICABILITY The present invention is suitable as a connection material for bare chip connection materials that exhibit low connection resistance and high insulation reliability and require fine circuit connection, and high-definition display devices.
１．硬化剤と硬化性の絶縁性樹脂
２．絶縁被覆
３．貴金属被覆
４．樹脂粒子
５．導電性粒子
６．部分絶縁被覆導電性粒子
1. 1. Hardener and curable insulating
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Cited By (5)
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|---|---|---|---|---|
| JP2012007093A (en) * | 2010-06-25 | 2012-01-12 | Nitto Denko Corp | Conductive adhesive tape |
| JP2014062257A (en) * | 2013-11-05 | 2014-04-10 | Dexerials Corp | Anisotropic electroconductive adhesive sheet and connection method |
| US8698394B2 (en) | 2010-03-31 | 2014-04-15 | 3M Innovative Properties Company | Electronic articles for displays and methods of making same |
| JP2016138168A (en) * | 2015-01-26 | 2016-08-04 | 日立化成株式会社 | Adhesive for semiconductor, method of manufacturing semiconductor device, and semiconductor device |
| CN108604480A (en) * | 2016-02-10 | 2018-09-28 | 日立化成株式会社 | The manufacturing method of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive, connection structural bodies and conducting particles |
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| JP5445558B2 (en) * | 2011-10-24 | 2014-03-19 | デクセリアルズ株式会社 | Anisotropic conductive adhesive sheet and connection method |
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| CN108604480A (en) * | 2016-02-10 | 2018-09-28 | 日立化成株式会社 | The manufacturing method of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive, connection structural bodies and conducting particles |
| CN108604480B (en) * | 2016-02-10 | 2020-03-24 | 日立化成株式会社 | Conductive particle, insulation-coated conductive particle, anisotropic conductive adhesive, connection structure, and method for producing conductive particle |
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