JP6532575B2 - Anisotropic conductive film, connection method, bonded body, and method of manufacturing bonded body - Google Patents
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Description
本発明は、異方性導電フィルム、接続方法、及び接合体に関する。 The present invention relates to an anisotropic conductive film, a connection method, and a joined body.
従来より、電子部品同士を接続する手段として、異方性導電フィルム（ＡＣＦ；Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｆｉｌｍ）、異方性導電ペースト（ＡＣＰ；Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｐａｓｔｅ）などの接続材料が用いられている。 Conventionally, as a means for connecting electronic parts, connecting materials such as anisotropic conductive film (ACF) and anisotropic conductive paste (ACP) have been used.
前記異方性導電フィルムは、例えば、熱硬化性樹脂を含んだ絶縁性バインダーに導電性粒子が分散されてなるフィルム状の接続材料である。異方導電接続したい電子部品同士の電極部分を、前記ＡＣＦを介して熱圧着することで、前記熱硬化性樹脂を含んだバインダーを熱硬化させて接続を行う。 The anisotropic conductive film is, for example, a film-like connecting material in which conductive particles are dispersed in an insulating binder containing a thermosetting resin. The electrode portions of the electronic components to be anisotropically conductively connected are thermocompression-bonded through the ACF to thermally cure the binder containing the thermosetting resin to perform connection.
前記異方性導電ペーストは、例えば、絶縁性バインダーと、導電性粒子と、溶剤とを含有する（例えば、特許文献１及び２参照）。前記溶剤を含有する前記ＡＣＰの使用方法は、例えば、以下のとおりである。フレキシブルプリント基板（ＦＰＣ；Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔｓ）などの電子部品に前記ＡＣＰを印刷して加熱乾燥させると、前記電子部品の電極部に前記ＡＣＰからなる塗膜が形成される。前記ＡＣＰによる前記塗膜が形成された前記ＦＰＣは、この状態で室温輸送されることが多い。そのため、前記ＡＣＰは、熱で硬化しない非反応型バインダーを用いるタイプも使用されている。 The anisotropic conductive paste contains, for example, an insulating binder, conductive particles, and a solvent (see, for example, Patent Documents 1 and 2). The usage method of the said ACP containing the said solvent is as follows, for example. When the ACP is printed on an electronic component such as a flexible printed circuit (FPC) and heated and dried, a coating film made of the ACP is formed on the electrode portion of the electronic component. The FPC on which the coating film is formed by the ACP is often transported at room temperature in this state. Therefore, the type of ACP that uses a non-reactive binder that does not cure with heat is also used.
ところで、近年、電子部品同士の接続には、低温、低圧力、及び短時間での接続が要求されている。低温での接続は、電子部品の熱的ダメージを低減する点、接続の際の加熱温度のバラツキ（電極部に接続した配線の先に部品が繋がっているかどうかによって、電極部における加熱温度が変わり、バラツキになる。実装密度が高密度になるとバラツキは特に顕著になる。）を防ぐ点、及び実装設備への負荷の低減の点で要求されている。低圧力での接続は、薄い基板やタッチパネルへのダメージの低減の点で要求されている。短時間での接続は、生産性の点で要求されている。 By the way, in recent years, connection of low temperature, low pressure, and a short time is required for connection of electronic parts. The connection at low temperature reduces the thermal damage of the electronic parts, and the variation of the heating temperature at the time of connection (the heating temperature at the electrode changes depending on whether the part is connected to the end of the wiring connected to the electrode) It is required from the point of preventing the problem that the mounting density becomes high especially when the mounting density becomes high) and the reduction of the load on the mounting equipment. Low pressure connections are required in terms of reducing damage to thin substrates and touch panels. Connection in a short time is required in terms of productivity.
しかし、従来の前記異方性導電フィルムでは、熱硬化性樹脂を用いるため、低温及び短時間での接続に対応しようとすると、保管中に硬化が生じるために、保管期間を短くする必要があり、実用上適さないという問題がある。 However, in the conventional anisotropic conductive film, since thermosetting resin is used, it is necessary to shorten the storage period in order to cure during storage if it is intended to cope with connection at a low temperature and a short time. There is a problem that it is not suitable for practical use.
また、従来の前記異方性導電ペーストでは、低圧力での接続に対応しようとすると、前記ＡＣＰの粘度を下げる必要がある。前記ＡＣＰの粘度を下げると、熱圧着の終了直後に発生する電子部品の復元力に前記ＡＣＰ中のバインダーが耐えきれずに、導電性粒子の潰れが維持できなくなり、接続抵抗が不十分になるという問題がある。 Further, in the conventional anisotropic conductive paste, in order to cope with connection at low pressure, it is necessary to lower the viscosity of the ACP. If the viscosity of the ACP is lowered, the binder in the ACP can not withstand the resilience of the electronic component generated immediately after the completion of the thermocompression bonding, and the conductive particles can not be maintained to be crushed, and the connection resistance becomes insufficient. There is a problem of
したがって、十分な接続抵抗を維持しつつ、低温、低圧力、及び短時間での接続が可能な異方性導電フィルム、並びに該異方性導電フィルムを用いた接続方法、及び前記異方性導電フィルムを用いた接合体の提供が求められているのが現状である。 Therefore, an anisotropic conductive film capable of connection at low temperature, low pressure and short time while maintaining sufficient connection resistance, a connection method using the anisotropic conductive film, and the anisotropic conduction At present, provision of a bonded body using a film is required.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、十分な接続抵抗を維持しつつ、低温、低圧力、及び短時間での接続が可能な異方性導電フィルム、並びに該異方性導電フィルムを用いた接続方法、及び前記異方性導電フィルムを用いた接合体を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems in the prior art and to achieve the following objects. That is, according to the present invention, an anisotropic conductive film capable of connection at low temperature, low pressure and short time while maintaining sufficient connection resistance, a connection method using the anisotropic conductive film, and the above An object of the present invention is to provide a bonded body using an anisotropic conductive film.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 第１の電子部品の端子と第２の電子部品の端子とを異方性導電接続させる異方性導電フィルムであって、
結晶性樹脂と、非晶性樹脂と、導電性粒子とを含有し、
前記結晶性樹脂が、前記非晶性樹脂が有する樹脂を特徴づける結合と同じ、樹脂を特徴づける結合を有する結晶性樹脂を含有することを特徴とする異方性導電フィルムである。
＜２＞ 下記の測定温度範囲、昇温速度、及び降温速度での示差走査熱量測定において、昇温時の溶融開始温度と吸熱ピーク温度との差の絶対値（ΔＴ１）と、降温時の結晶化開始温度と発熱ピーク温度との差の絶対値（ΔＴ２）とが、次式ΔＴ１＞ΔＴ２を満たす前記＜１＞に記載の異方性導電フィルムである。
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間
＜３＞ 結晶性樹脂と非晶性樹脂との質量比（結晶性樹脂：非晶性樹脂）が、２５：７５〜７５：２５である前記＜１＞から＜２＞のいずれかに記載の異方性導電フィルムである。
＜４＞ 結晶性樹脂が、結晶性ポリエステル樹脂を含有し、
非晶性樹脂が、非晶性ポリエステル樹脂を含有する前記＜１＞から＜３＞のいずれかに記載の異方性導電フィルムである。
＜５＞ 更にエラストマーを含有する前記＜１＞から＜４＞のいずれかに記載の異方性導電フィルムである。
＜６＞ 結晶性樹脂の含有量及び非晶性樹脂の含有量の和（Ｘ）と、エラストマーの含有量（Ｙ）との質量比（Ｘ：Ｙ）が、１６０：４０〜６０：１４０である前記＜５＞に記載の異方性導電フィルムである。
＜７＞ 導電性粒子の平均粒子径が、２μｍ〜４０μｍである前記＜１＞から＜６＞のいずれかに記載の異方性導電フィルムである。
＜８＞ 下記の測定温度範囲、昇温速度、及び降温速度での示差走査熱量測定において、昇温時の吸熱ピーク温度（Ｐ１）と、降温時の発熱ピーク温度（Ｐ２）との差（Ｐ１−Ｐ２）が、１１．０℃以上である前記＜１＞から＜７＞のいずれかに記載の異方性導電フィルムである。
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間
＜９＞ 下記の測定温度範囲、昇温速度、及び降温速度での示差走査熱量測定において、昇温時の吸熱量が、１．０Ｊ／ｇ〜１２Ｊ／ｇであり、降温時の発熱量が、１．０Ｊ／ｇ〜６．０Ｊ／ｇである前記＜１＞から＜８＞のいずれかに記載の異方性導電フィルムである。
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間
＜１０＞ 第１の電子部品の端子と第２の電子部品の端子とを異方性導電接続させる接続方法であって、
前記第２の電子部品の端子上に前記＜１＞から＜９＞のいずれかに記載の異方性導電フィルムを配置する第１の配置工程と、
前記異方性導電フィルム上に前記第１の電子部品を、前記第１の電子部品の端子が前記異方性導電フィルムと接するように配置する第２の配置工程と、
前記第１の電子部品を加熱押圧部材により加熱及び押圧する加熱押圧工程とを含むことを特徴とする接続方法である。
＜１１＞ 端子を有する第１の電子部品と、端子を有する第２の電子部品と、前記第１の電子部品と前記第２の電子部品との間に介在して前記第１の電子部品の端子と前記第２の電子部品の端子とを電気的に接続する異方性導電フィルムとを有し、
前記異方性導電フィルムが、前記＜１＞から＜９＞のいずれかに記載の異方性導電フィルムであることを特徴とする接合体である。
The means for solving the problems are as follows. That is,
<1> An anisotropic conductive film for anisotropically conductively connecting a terminal of a first electronic component and a terminal of a second electronic component,
Contains a crystalline resin, an amorphous resin, and conductive particles,
The anisotropic conductive film is characterized in that the crystalline resin contains a crystalline resin having a bond characterizing the resin, which is the same as a bond characterizing the resin possessed by the non-crystalline resin.
<2> In the differential scanning calorimetry at the following measurement temperature range, heating rate, and cooling rate, the absolute value (ΔT1) of the difference between the melting start temperature at heating and the endothermic peak temperature, and the crystal at cooling It is an anisotropic conductive film as described in said <1> in which the absolute value ((DELTA) T2) of the difference of the crystallization start temperature and exothermic peak temperature satisfy | fills following Formula (DELTA) T1> (DELTA) T2.
Measurement temperature range: 30 ° C to 250 ° C
Temperature rising rate: 10 ° C./min Temperature falling rate: 20 ° C./min <3> The mass ratio of crystalline resin to amorphous resin (crystalline resin: amorphous resin) is 25: 75 to 75: 25 It is an anisotropic conductive film in any one of said <1> to <2>.
<4> The crystalline resin contains a crystalline polyester resin,
It is an anisotropic conductive film in any one of said <1> to <3> in which amorphous resin contains amorphous polyester resin.
<5> The anisotropic conductive film according to any one of <1> to <4>, further containing an elastomer.
The mass ratio (X: Y) of the sum (X) of the content of the crystalline resin and the content of the amorphous resin and the content (Y) of the elastomer is 160: 40 to 60: 140. It is an anisotropic conductive film as described in a certain said <5>.
The average particle diameter of <7> electroconductive particle is an anisotropic conductive film in any one of said <1> to <6> which is 2 micrometers-40 micrometers.
<8> The difference (P1) between the endothermic peak temperature (P1) at the time of temperature rise and the exothermic peak temperature (P2) at the time of temperature drop in differential scanning calorimetry at the following measurement temperature range, temperature raising rate and temperature lowering rate It is an anisotropic conductive film in any one of said <1> to <7> whose -P2) is 11.0 degreeC or more.
Measurement temperature range: 30 ° C to 250 ° C
Temperature rising rate: 10 ° C./min Temperature falling rate: 20 ° C./min The anisotropic conductive film according to any one of <1> to <8>, wherein the calorific value at the time of temperature decrease is 1.0 J / g to 6.0 J / g. .
Measurement temperature range: 30 ° C to 250 ° C
Temperature rising rate: 10 ° C./min Temperature falling rate: 20 ° C./min <10> A connection method in which the terminal of the first electronic component and the terminal of the second electronic component are anisotropically conductively connected,
A first disposing step of disposing the anisotropic conductive film according to any one of <1> to <9> on a terminal of the second electronic component;
A second disposing step of disposing the first electronic component on the anisotropic conductive film such that a terminal of the first electronic component is in contact with the anisotropic conductive film;
And a heating and pressing step of heating and pressing the first electronic component with a heating and pressing member.
<11> A first electronic component having a terminal, a second electronic component having a terminal, and the first electronic component interposed between the first electronic component and the second electronic component And an anisotropic conductive film electrically connecting the terminal and the terminal of the second electronic component,
The said anisotropic conductive film is an anisotropic conductive film in any one of said <1> to <9>, It is a joined body characterized by the above-mentioned.
本発明によれば、従来における前記諸問題を解決し、前記目的を達成することができ、十分な接続抵抗を維持しつつ、低温、低圧力、及び短時間での接続が可能な異方性導電フィルム、並びに該異方性導電フィルムを用いた接続方法、及び前記異方性導電フィルムを用いた接合体を提供することができる。 According to the present invention, the above problems in the prior art can be solved and the above object can be achieved, and an anisotropy that allows connection at low temperature, low pressure and short time while maintaining sufficient connection resistance. A conductive film, a connection method using the anisotropic conductive film, and a bonded body using the anisotropic conductive film can be provided.
（異方性導電フィルム）
本発明の異方性導電フィルムは、結晶性樹脂と、非晶性樹脂と、導電性粒子とを少なくとも含有し、好ましくはエラストマーを含有し、更に必要に応じて、その他の成分を含有する。
前記異方性導電フィルムは、第１の電子部品の端子と第２の電子部品の端子とを異方性導電接続させる異方性導電フィルムである。
(Anisotropic conductive film)
The anisotropic conductive film of the present invention contains at least a crystalline resin, an amorphous resin, and conductive particles, preferably contains an elastomer, and further contains other components as required.
The said anisotropic conductive film is an anisotropic conductive film which carries out anisotropic conductive connection of the terminal of a 1st electronic component, and the terminal of a 2nd electronic component.
＜結晶性樹脂、及び非晶性樹脂＞
前記結晶性樹脂としては、前記非晶性樹脂が有する樹脂を特徴づける結合と同じ、樹脂を特徴づける結合を有する結晶性樹脂（以下、「前記非晶性樹脂と同種の結晶性樹脂」と称することがある。）を含有する限り、特に制限はなく、目的に応じて適宜選択することができる。
<Crystalline resin and Amorphous resin>
The crystalline resin is a crystalline resin having a bond characterizing the resin, which is the same as a bond characterizing the resin possessed by the amorphous resin (hereinafter, referred to as “a crystalline resin of the same type as the amorphous resin”) There is no particular limitation as long as it contains (1), and can be appropriately selected depending on the purpose.
前記結晶性樹脂が、前記非晶性樹脂と同種の結晶性樹脂を含有しない場合は、平滑性のある異方性導電フィルムが得られず、その結果、接続抵抗が不十分となる。
一方、前記結晶性樹脂が、前記非晶性樹脂と同種の結晶性樹脂を含有することにより、前記結晶性樹脂と前記非晶性樹脂とを混合して前記結晶性樹脂が溶媒に溶解しやすい状態を作製できるため、前記結晶性樹脂がほぼ均一に含有された異方性導電フィルムを得ることができる。
そして、得られる異方性導電フィルムは、低温、低圧力、及び短時間での接続を可能にする。これは、得られる異方性導電フィルムを加熱して軟化した後に、加熱状態が解かれて常温に戻る際に、前記結晶性樹脂に由来して速やかに凝固するためと考えられる。
When the crystalline resin does not contain the same kind of crystalline resin as the non-crystalline resin, a smooth anisotropic conductive film can not be obtained, and as a result, the connection resistance becomes insufficient.
On the other hand, when the crystalline resin contains the same kind of crystalline resin as the non-crystalline resin, the crystalline resin and the non-crystalline resin are mixed and the crystalline resin is easily dissolved in the solvent. Since a state can be produced, it is possible to obtain an anisotropic conductive film in which the crystalline resin is contained substantially uniformly.
And the obtained anisotropic conductive film enables connection in low temperature, low pressure, and a short time. This is considered to be caused by the above-mentioned crystalline resin and rapidly coagulating when the obtained anisotropic conductive film is heated and softened and then the heated state is released and returned to normal temperature.
ここで、前記樹脂を特徴づける結合とは、その樹脂を重合により合成する際に形成される結合を意味する。例えば、ポリエステル樹脂においては、その樹脂を重合により合成する際に形成されるエステル結合を指し、ポリウレタン樹脂においては、その樹脂を重合により合成する際に形成されるウレタン結合を指し、ポリオレフィン樹脂については、その樹脂を重合により合成する際に形成される炭素−炭素結合を指す。前記樹脂を特徴づける結合とは、言い換えれば、その樹脂の主たる結合ということもできる。
そのため、前記非晶性樹脂と、前記非晶性樹脂が有する樹脂を特徴づける結合と同じ、樹脂を特徴づける結合を有する結晶性樹脂との組合せとしては、例えば、非晶性ポリエステル樹脂と結晶性ポリエステル樹脂との組合せ、非晶性ポリオレフィン樹脂と結晶性ポリオレフィン樹脂との組合せ、非晶性ポリウレタン樹脂と結晶性ポリウレタン樹脂との組合せなどが挙げられる。
Here, the bond that characterizes the resin means a bond that is formed when the resin is synthesized by polymerization. For example, in the case of a polyester resin, it refers to an ester bond formed when the resin is synthesized by polymerization, and in the polyurethane resin, it refers to a urethane bond formed when the resin is synthesized by polymerization. Refers to a carbon-carbon bond formed when the resin is synthesized by polymerization. The bond that characterizes the resin can be, in other words, the main bond of the resin.
Therefore, as a combination of the amorphous resin and a crystalline resin having a bond that characterizes the same resin as the bond that characterizes the resin included in the amorphous resin, for example, a crystalline polyester resin and a crystalline resin are combined. A combination with a polyester resin, a combination of an amorphous polyolefin resin and a crystalline polyolefin resin, a combination of an amorphous polyurethane resin and a crystalline polyurethane resin, and the like can be mentioned.
前記結晶性樹脂は、前記非晶性樹脂が有する樹脂を特徴づける結合と同じ、樹脂を特徴づける結合を有する結晶性樹脂以外の結晶性樹脂を含有していてもよい。
前記非晶性樹脂と、前記結晶性樹脂との組合せとしては、例えば、非晶性ポリエステル樹脂と、結晶性ポリエステル樹脂及び結晶性ポリオレフィン樹脂を含有する結晶性樹脂との組合せなどが挙げられる。
The crystalline resin may contain a crystalline resin other than the crystalline resin having the bond characterizing the resin, which is the same as the bond characterizing the resin possessed by the amorphous resin.
Examples of combinations of the amorphous resin and the crystalline resin include combinations of an amorphous polyester resin and a crystalline resin containing a crystalline polyester resin and a crystalline polyolefin resin.
ここで、前記結晶性樹脂とは、結晶領域を有する樹脂をいい、前記結晶性樹脂かどうかは、例えば、示差走査熱量分析において、昇温過程で吸熱ピークが観察されることにより確認できる。
前記結晶性樹脂は、結晶領域を有する樹脂の混合物であってもよい。
Here, the crystalline resin refers to a resin having a crystalline region, and whether it is the crystalline resin can be confirmed, for example, by observing an endothermic peak in a temperature rising process in differential scanning calorimetry.
The crystalline resin may be a mixture of resins having crystalline regions.
前記結晶性樹脂と前記非晶性樹脂との質量比（結晶性樹脂：非晶性樹脂）としては、特に制限はなく、目的に応じて適宜選択することができるが、１５：８５〜８５：１５が好ましく、２５：７５〜７５：２５がより好ましい。 There is no restriction | limiting in particular as mass ratio (crystalline resin: amorphous resin) with the said crystalline resin and the said amorphous resin, Although it can select suitably according to the objective, 15: 85-85: 15 is preferable and 25: 75-75: 25 is more preferable.
＜導電性粒子＞
前記導電性粒子としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、金属粒子、金属被覆樹脂粒子などが挙げられる。
<Conductive particles>
There is no restriction | limiting in particular as said conductive particle, According to the objective, it can select suitably, For example, a metal particle, metal coating resin particle, etc. are mentioned.
前記金属粒子としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ニッケル、コバルト、銀、銅、金、パラジウム、半田などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
これらの中でも、ニッケル、銀、銅が好ましい。これらの金属粒子は、表面酸化を防ぐ目的で、その表面に金、パラジウムを施していてもよい。更に、表面に金属突起や有機物で絶縁皮膜を施したものを用いてもよい。
There is no restriction | limiting in particular as said metal particle, According to the objective, it can select suitably, For example, nickel, cobalt, silver, copper, gold | metal | money, palladium, solder etc. are mentioned. These may be used alone or in combination of two or more.
Among these, nickel, silver and copper are preferable. These metal particles may have gold and palladium on the surface for the purpose of preventing surface oxidation. Furthermore, the surface may be provided with an insulating film with metal protrusions or organic substances.
前記金属被覆樹脂粒子としては、樹脂粒子の表面を金属で被覆した粒子であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、樹脂粒子の表面をニッケル、銀、半田、銅、金、及びパラジウムの少なくともいずれかの金属で被覆した粒子などが挙げられる。更に、表面に金属突起や有機物で絶縁皮膜を施したものを用いてもよい。低抵抗を考慮した接続の場合、樹脂粒子の表面を銀で被覆した粒子が好ましい。
前記樹脂粒子への金属の被覆方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、無電解めっき法、スパッタリング法などが挙げられる。
前記樹脂粒子の材質としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、スチレン−ジビニルベンゼン共重合体、ベンゾグアナミン樹脂、架橋ポリスチレン樹脂、アクリル樹脂、スチレン−シリカ複合樹脂などが挙げられる。
The metal-coated resin particle is not particularly limited as long as it is a particle in which the surface of the resin particle is coated with a metal, and can be appropriately selected according to the purpose. For example, the surface of the resin particle is nickel, silver, solder And particles coated with at least one of copper, gold, and palladium. Furthermore, the surface may be provided with an insulating film with metal protrusions or organic substances. In the case of connection considering low resistance, particles in which the surface of resin particles is coated with silver are preferable.
There is no restriction | limiting in particular as a coating method of the metal to the said resin particle, According to the objective, it can select suitably, For example, the electroless-plating method, sputtering method, etc. are mentioned.
There is no restriction | limiting in particular as a material of the said resin particle, According to the objective, it can select suitably, For example, a styrene divinylbenzene copolymer, a benzoguanamine resin, a crosslinked polystyrene resin, an acrylic resin, styrene-silica composite resin etc. Can be mentioned.
前記導電性粒子は、異方性導電接続の際に、導電性を有していればよい。例えば、金属粒子の表面に絶縁皮膜を施した粒子であっても、異方性導電接続の際に前記粒子が変形し、前記金属粒子が露出するものであれば、前記導電性粒子である。 The conductive particles may have conductivity at the time of anisotropic conductive connection. For example, even in the case of particles in which an insulating film is applied to the surface of metal particles, the particles are the conductive particles as long as the particles are deformed at the time of anisotropic conductive connection and the metal particles are exposed.
前記導電性粒子の平均粒子径としては、特に制限はなく、目的に応じて適宜選択することができるが、２μｍ〜４０μｍが好ましく、５μｍ〜３０μｍがより好ましく、１０μｍ〜２５μｍが更により好ましく、１０μｍ〜２０μｍが特に好ましい。
前記平均粒子径は、任意に１０個の導電性粒子について測定した粒子径の平均値である。
前記粒子径は、例えば、走査型電子顕微鏡観察により測定できる。
There is no restriction | limiting in particular as an average particle diameter of the said electroconductive particle, Although it can select suitably according to the objective, 2 micrometers-40 micrometers are preferable, 5 micrometers-30 micrometers are more preferable, 10 micrometers-25 micrometers are still more preferable, 10 micrometers -20 μm is particularly preferred.
The said average particle diameter is an average value of the particle diameter arbitrarily measured about ten electroconductive particles.
The particle size can be measured, for example, by scanning electron microscopy.
前記導電性粒子の含有量としては、特に制限はなく、目的に応じて適宜選択することができる。 There is no restriction | limiting in particular as content of the said electroconductive particle, According to the objective, it can select suitably.
＜エラストマー＞
前記エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリウレタン樹脂（ポリウレタン系エラストマー）、アクリルゴム、シリコーンゴム、ブタジエンゴムなどが挙げられる。
<Elastomer>
There is no restriction | limiting in particular as said elastomer, According to the objective, it can select suitably, For example, a polyurethane resin (polyurethane-type elastomer), acrylic rubber, silicone rubber, butadiene rubber etc. are mentioned.
前記エラストマーは、ゴム状の弾力性を有する点で、前記結晶性樹脂、及び前記非晶性樹脂とは異なる。 The elastomer is different from the crystalline resin and the amorphous resin in that the elastomer has rubbery elasticity.
前記結晶性樹脂の含有量及び前記非晶性樹脂の含有量の和（Ｘ）と、前記エラストマーの含有量（Ｙ）との質量比（Ｘ：Ｙ）としては、特に制限はなく、目的に応じて適宜選択することができるが、１６０：４０〜６０：１４０が好ましい。 The mass ratio (X: Y) of the sum (X) of the content of the crystalline resin and the content of the amorphous resin and the content (Y) of the elastomer is not particularly limited, and Although it can select suitably according to, 160: 40-60: 140 is preferable.
前記エラストマーの含有量としては、特に制限はなく、目的に応じて適宜選択することができる。 There is no restriction | limiting in particular as content of the said elastomer, According to the objective, it can select suitably.
＜第１の電子部品及び第２の電子部品＞
前記第１の電子部品及び前記第２の電子部品としては、前記異方性導電フィルムを用いた異方性導電接続の対象となる、端子を有する電子部品であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ガラス基板、フレキシブル基板、リジッド基板、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ Ｃｉｒｃｕｉｔ）チップ、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）、液晶パネルなどが挙げられる。前記ガラス基板としては、例えば、Ａｌ配線形成ガラス基板、ＩＴＯ配線形成ガラス基板などが挙げられる。前記ＩＣチップとしては、例えば、フラットパネルディスプレイ（ＦＰＤ）における液晶画面制御用ＩＣチップなどが挙げられる。
<First Electronic Component and Second Electronic Component>
The first electronic component and the second electronic component are not particularly limited as long as they are electronic components having terminals, which are targets of anisotropic conductive connection using the anisotropic conductive film. For example, a glass substrate, a flexible substrate, a rigid substrate, an IC (Integrated Circuit) chip, a TAB (Tape Automated Bonding), a liquid crystal panel and the like can be mentioned. As said glass substrate, Al wiring formation glass substrate, ITO wiring formation glass substrate etc. are mentioned, for example. Examples of the IC chip include a liquid crystal screen control IC chip in a flat panel display (FPD).
前記異方性導電フィルムは、下記の測定条件Ａ（測定温度範囲、昇温速度、及び降温速度）での示差走査熱量測定において、昇温時の溶融開始温度と吸熱ピーク温度との差の絶対値（ΔＴ１）と、降温時の結晶化開始温度と発熱ピーク温度との差の絶対値（ΔＴ２）とが、次式ΔＴ１＞ΔＴ２を満たすことが好ましい。
〔測定条件Ａ〕
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間
The said anisotropic conductive film is the absolute difference of the melting start temperature at the time of temperature rising, and the endothermic peak temperature in the differential scanning calorimetry measurement on the following measurement conditions A (measurement temperature range, temperature rising rate, and temperature lowering rate) It is preferable that the value (ΔT1) and the absolute value (ΔT2) of the difference between the crystallization start temperature and the exothermic peak temperature at the time of temperature decrease satisfy the following expression ΔT1> ΔT2.
[Measurement condition A]
Measurement temperature range: 30 ° C to 250 ° C
Heating rate: 10 ° C / min Cooling rate: 20 ° C / min
前記式ΔＴ１＞ΔＴ２を満たすことは、前記結晶性樹脂の結晶化が速やかに起こることを意味する。
前記式ΔＴ１＞ΔＴ２を満たすことにより、前記異方性導電フィルムを加熱して軟化した後に、加熱状態が解かれて常温に戻る際に、前記結晶性樹脂に由来する凝固がより速やかに起こるようになる。その結果、低温、低圧力、及び短時間での接続をより確実に実現でき、前記接続においても接続抵抗に優れた異方性導電フィルムが得られる。
Satisfying the formula ΔT1> ΔT2 means that the crystallization of the crystalline resin occurs rapidly.
By satisfying the formula ΔT1> ΔT2, after the heating and softening of the anisotropic conductive film, when the heating state is released and returned to normal temperature, the solidification derived from the crystalline resin occurs more rapidly become. As a result, connection at low temperature, low pressure and short time can be realized more reliably, and an anisotropic conductive film excellent in connection resistance can be obtained also in the connection.
前記ΔＴ１と前記ΔＴ２との差（ΔＴ１−ΔＴ２）としては、１５℃以上がより好ましく、１８℃〜５０℃が特に好ましい。 As a difference ((DELTA) T1- (DELTA) T2) between said (DELTA) T1 and said (DELTA) T2, 15 degreeC or more is more preferable, and 18 degreeC-50 degreeC is especially preferable.
前記測定条件Ａでの示差走査熱量測定における吸熱ピーク温度（Ｐ１）としては、特に制限はなく、目的に応じて適宜選択することができるが、７０℃〜１１５℃が好ましく、１００℃〜１１５℃がより好ましく、１０５℃〜１１０℃が特に好ましい。 There is no restriction | limiting in particular as an endothermic peak temperature (P1) in the differential scanning calorimetry measurement on the said measurement conditions A, Although it can select suitably according to the objective, 70 to 115 degreeC is preferable, 100 to 115 degreeC Is more preferable, and 105 ° C. to 110 ° C. is particularly preferable.
前記測定条件Ａでの示差走査熱量測定における発熱ピーク温度（Ｐ２）としては、特に制限はなく、目的に応じて適宜選択することができるが、６０℃〜１０５℃が好ましく、８５℃〜１０５℃がより好ましく、９０℃〜１００℃が特に好ましい。 There is no restriction | limiting in particular as exothermic peak temperature (P2) in the differential scanning calorimetry measurement on the said measurement conditions A, Although it can select suitably according to the objective, 60 to 105 degreeC is preferable, 85 to 105 degreeC Is more preferable, and 90 ° C. to 100 ° C. is particularly preferable.
前記異方性導電フィルムは、前記測定条件Ａでの示差走査熱量測定において、昇温時の吸熱ピーク温度（Ｐ１）と、降温時の発熱ピーク温度（Ｐ２）との差（Ｐ１−Ｐ２）が、１１．０℃以上が好ましく、１１．０℃〜１４．０℃がより好ましい。 In the anisotropic conductive film, in differential scanning calorimetry under the measurement condition A, the difference (P1-P2) between the endothermic peak temperature (P1) at the time of temperature rise and the exothermic peak temperature (P2) at the time of temperature decrease is 11.0 degreeC or more is preferable, and 11.0 degreeC-14.0 degreeC is more preferable.
前記異方性導電フィルムは、前記測定条件Ａでの示差走査熱量測定において、昇温時の吸熱量が、１．０Ｊ／ｇ〜１２Ｊ／ｇであり、降温時の発熱量が、１．０Ｊ／ｇ〜６．０Ｊ／ｇであることが好ましい。
昇温時に吸熱現象が観察されることは、結晶性樹脂成分の結晶状態が解かれて溶融することを意味する。そして、前記吸熱量が、１．０Ｊ／ｇ〜１２Ｊ／ｇであると、前記異方性導電フィルムは、異方性導電接続において前記導電性粒子を潰す際に潰し易い溶融状態になる。前記吸熱量が、１．０Ｊ／ｇ未満であると、異方性導電接続において前記導電性粒子が潰し難いために導通不良を起こすことがある。前記吸熱量が、１２Ｊ／ｇを超えると、前記異方性導電フィルムの溶融時の粘度変化が大きいため、前記異方性導電フィルムの圧着部の気泡が多くなり接続外観が損なわれ、場合によっては気泡過多により接続信頼性が劣ることがある。
一方、降温時に発熱現象が観察されることは、結晶性樹脂成分の溶融状態が結晶化により急速に固化することを意味する。そして、前記発熱量は、結晶化で固化する度合いを示す。前記発熱量が、１．０Ｊ／ｇ未満であると、環境試験で接続抵抗が上昇し、接続信頼性が劣ることがある。前記発熱量が、６．０Ｊ／ｇを超えると、室温で前記異方性導電フィルム自体が硬くなり過ぎることにより、前記異方性導電フィルムを貼り付ける時の仮接着性などの使い勝手が劣ったり、ピール強度の低下を招くことがある。
In the anisotropic conductive film, the heat absorption amount at the time of temperature rise is 1.0 J / g to 12 J / g in the differential scanning calorimetry measurement under the measurement condition A, and the calorific value at the time of temperature fall is 1.0 J It is preferable that it is / g-6.0 J / g.
The fact that the endothermic phenomenon is observed when the temperature rises means that the crystalline state of the crystalline resin component is melted and melted. Then, when the heat absorption amount is 1.0 J / g to 12 J / g, the anisotropic conductive film is in a molten state that tends to be crushed when the conductive particles are crushed in the anisotropic conductive connection. If the heat absorption amount is less than 1.0 J / g, conduction defects may occur because the conductive particles are hard to be crushed in the anisotropic conductive connection. When the heat absorption amount exceeds 12 J / g, the viscosity change at the time of melting of the anisotropic conductive film is large, so that the number of bubbles in the pressure-bonded portion of the anisotropic conductive film is increased, and the connection appearance is impaired. There are cases where connection reliability is poor due to excessive air bubbles.
On the other hand, that an exothermic phenomenon is observed when the temperature is lowered means that the molten state of the crystalline resin component is rapidly solidified by crystallization. And, the calorific value indicates the degree of solidification by crystallization. When the calorific value is less than 1.0 J / g, connection resistance may increase in an environmental test, and connection reliability may be degraded. When the calorific value exceeds 6.0 J / g, the anisotropic conductive film itself becomes too hard at room temperature, resulting in poor usability such as temporary adhesion when the anisotropic conductive film is attached. May cause a decrease in peel strength.
前記異方性導電フィルムは、硬化剤を含有せず、加熱により樹脂が架橋しない。そのため、低温、かつ短時間の接続に使用する異方性導電フィルムであっても、長期保存を可能にする。 The said anisotropic conductive film does not contain a hardening | curing agent, and resin does not bridge | crosslink by heating. Therefore, even if it is an anisotropic conductive film used for low temperature and a short time connection, long-term storage is enabled.
前記異方性導電フィルムの平均厚みとしては、特に制限はなく、目的に応じて適宜選択することができるが、５μｍ〜１００μｍが好ましく、１０μｍ〜６０μｍがより好ましく、２０μｍ〜５０μｍが特に好ましい。 There is no restriction | limiting in particular as average thickness of the said anisotropic conductive film, Although it can select suitably according to the objective, 5 micrometers-100 micrometers are preferable, 10 micrometers-60 micrometers are more preferable, and 20 micrometers-50 micrometers are especially preferable.
前記異方性導電フィルムの製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記結晶性樹脂と前記非晶性樹脂とを溶剤に溶解させて混合ワニスを得た後に、前記混合ワニスに必要に応じて前記エラストマーを混合し、更に前記導電性粒子を混合して得た異方性導電組成物を、剥離処理したポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗布する方法などが挙げられる。
前記溶剤としては、特に制限はなく、目的に応じて適宜選択することができる。
There is no restriction | limiting in particular as a manufacturing method of the said anisotropic conductive film, According to the objective, it can select suitably, For example, the said crystalline resin and the said non-crystalline resin are dissolved in a solvent, After obtained, the elastomer is mixed with the mixed varnish as necessary, and the anisotropic conductive composition obtained by further mixing the conductive particles is applied on a peel-treated polyethylene terephthalate (PET) film. Methods etc.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably.
（接続方法）
本発明の接続方法は、第１の配置工程と、第２の配置工程と、加熱押圧工程とを少なくとも含み、更に必要に応じて、その他の工程を含む。
前記接続方法は、第１の電子部品の端子と第２の電子部品の端子とを異方性導電接続させる方法である。
(Connection method)
The connection method of the present invention at least includes a first arrangement step, a second arrangement step, and a heating and pressing step, and further includes other steps as necessary.
The connection method is a method in which the terminal of the first electronic component and the terminal of the second electronic component are anisotropically conductively connected.
前記第１の電子部品、及び前記第２の電子部品としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、本発明の前記異方性導電フィルムの説明で例示した前記第１の電子部品、及び前記第２の電子部品がそれぞれ挙げられる。 There is no restriction | limiting in particular as said 1st electronic component and said 2nd electronic component, According to the objective, it can select suitably, For example, the said illustrated in description of the said anisotropic conductive film of this invention A first electronic component and the second electronic component can be mentioned respectively.
＜第１の配置工程＞
前記第１の配置工程としては、前記第２の電子部品の端子上に本発明の前記異方性導電フィルムを配置する工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
<First arrangement step>
The first arrangement step is not particularly limited as long as it is a step of arranging the anisotropic conductive film of the present invention on the terminal of the second electronic component, and may be appropriately selected according to the purpose. it can.
＜第２の配置工程＞
前記第２の配置工程としては、前記異方性導電フィルム上に前記第１の電子部品を、前記第１の電子部品の端子が前記異方性導電フィルムと接するように配置する工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
<Second arrangement step>
In the second disposing step, the first electronic component is disposed on the anisotropic conductive film so that the terminal of the first electronic component is in contact with the anisotropic conductive film. There is no particular limitation, and it can be selected appropriately according to the purpose.
＜加熱押圧工程＞
前記加熱押圧工程としては、前記第１の電子部品を加熱押圧部材により加熱及び押圧する工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
前記加熱押圧部材としては、例えば、加熱機構を有する押圧部材などが挙げられる。前記加熱機構を有する押圧部材としては、例えば、ヒートツールなどが挙げられる。
前記加熱の温度としては、特に制限はなく、目的に応じて適宜選択することができるが、１００℃〜１４０℃が好ましい。
前記押圧の圧力としては、特に制限はなく、目的に応じて適宜選択することができるが、０．５ＭＰａ〜１０ＭＰａが好ましい。
前記加熱及び押圧の時間としては、特に制限はなく、目的に応じて適宜選択することができるが、０．５秒間〜１０秒間が好ましい。
<Heating and pressing process>
The heating and pressing step is not particularly limited as long as it is a step of heating and pressing the first electronic component by the heating and pressing member, and can be appropriately selected according to the purpose.
Examples of the heating and pressing member include a pressing member having a heating mechanism. Examples of the pressing member having the heating mechanism include a heat tool.
There is no restriction | limiting in particular as temperature of the said heating, Although it can select suitably according to the objective, 100 to 140 degreeC is preferable.
There is no restriction | limiting in particular as a pressure of the said press, Although it can select suitably according to the objective, 0.5 MPa-10 MPa are preferable.
There is no restriction | limiting in particular as time of the said heating and pressing, According to the objective, it can select suitably, Although 0.5 second-10 second are preferable.
（接合体）
本発明の接合体は、第１の電子部品と、第２の電子部品と、異方性導電フィルムとを少なくとも有し、更に必要に応じて、その他の部材を有する。
(Bonded body)
The joined body of the present invention has at least a first electronic component, a second electronic component, and an anisotropic conductive film, and further has other members as required.
前記第１の電子部品、及び前記第２の電子部品としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、本発明の前記異方性導電フィルムの説明で例示した前記第１の電子部品、及び前記第２の電子部品がそれぞれ挙げられる。 There is no restriction | limiting in particular as said 1st electronic component and said 2nd electronic component, According to the objective, it can select suitably, For example, the said illustrated in description of the said anisotropic conductive film of this invention A first electronic component and the second electronic component can be mentioned respectively.
前記異方性導電フィルムは、本発明の前記異方性導電フィルムである。
前記異方性導電フィルムは、前記第１の電子部品と前記第２の電子部品との間に介在して前記第１の電子部品の端子と前記第２の電子部品の端子とを電気的に接続している。
The anisotropic conductive film is the anisotropic conductive film of the present invention.
The anisotropic conductive film is interposed between the first electronic component and the second electronic component to electrically connect the terminal of the first electronic component and the terminal of the second electronic component. Connected
前記接合体は、例えば、本発明の前記接続方法により製造できる。 The bonded body can be manufactured, for example, by the connection method of the present invention.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（実施例１）
＜異方性導電フィルムの作製＞
結晶性樹脂であるアロンメルトＰＥＳ−１１１ＥＥ（東亜合成株式会社製、結晶性ポリエステル樹脂を主成分とする結晶性樹脂）２５質量部、非晶性樹脂であるエリーテルＵＥ３５００（ユニチカ株式会社製、非晶性ポリエステル樹脂）７５質量部、及び混合溶剤（トルエン：メチルエチルケトン＝１：１（質量比））４００質量部を混合及び撹拌し、混合ワニスを得た。
続いて、得られた混合ワニスに、固形分量で１００質量部に相当する量のニッポランＮ−５１９６（日本ポリウレタン工業株式会社製、ポリカーボネート骨格のポリウレタン系エラストマー、固形分３０質量％）を混合した。
続いて、平均粒子径２０μｍの球状Ａｇめっき樹脂粒子（下記の製造方法で得られた導電性粒子）７質量部を更に加えて、異方性導電組成物を得た。
得られた異方性導電組成物を、５０μｍ厚みのＰＥＴ（ポリエチレンテレフタレート）フィルム上に乾燥後の平均厚みが３５μｍとなるように塗布し、８０℃で１０分間乾燥させ、異方性導電フィルムを作製した。
Example 1
<Preparation of anisotropic conductive film>
25 parts by mass of crystalline resin Aronmelt PES-111EE (made by Toagosei Co., Ltd., a crystalline resin containing crystalline polyester resin as a main component), Eritel UE3500 (made by Unitika Co., Ltd., amorphous) A mixed varnish was obtained by mixing and stirring 75 parts by mass of a polyester resin and 400 parts by mass of a mixed solvent (toluene: methyl ethyl ketone = 1: 1 (mass ratio)).
Subsequently, Nipporan N-5196 (a polyurethane-based elastomer having a polycarbonate skeleton, solid content: 30% by mass, solid content: 30% by mass) was mixed with the obtained mixed varnish in an amount corresponding to 100 parts by mass in solid content.
Subsequently, 7 parts by mass of spherical Ag-plated resin particles (conductive particles obtained by the following production method) having an average particle diameter of 20 μm were further added to obtain an anisotropic conductive composition.
The resulting anisotropic conductive composition is coated on a 50 μm thick PET (polyethylene terephthalate) film so that the average thickness after drying is 35 μm, and dried at 80 ° C. for 10 minutes to obtain an anisotropic conductive film. Made.
−導電性粒子の製造−
−−ジビニルベンゼン系樹脂粒子の製造−−
ジビニルベンゼン、スチレン、及びブチルメタクリレートの混合比を調整した溶液に、重合開始剤としてベンゾイルパーオキサイドを投入して高速で均一攪拌しながら加熱を行い、重合反応を行うことにより微粒子分散液を得た。前記微粒子分散液をろ過し減圧乾燥することにより微粒子の凝集体であるブロック体を得た。更に、前記ブロック体を粉砕することにより、ジビニルベンゼン系樹脂粒子を得た。
−−樹脂粒子の銀めっき−−
銀塩として硝酸銀４．２５ｇを純水６２５ｍＬに室温で溶解した溶液に、還元剤としてベンズイミダゾール１５ｇを加えて溶解し、当初生成した沈殿が完全に溶解したのを確認した後、錯化剤としてコハク酸イミド５ｇ、及びクエン酸１水和物３ｇを溶解し、その後、結晶調整剤としてグリオキシル酸１３ｇを投入し完全溶解させ無電解銀メッキ液を調製した。
次に、上記で得られた前記ジビニルベンゼン系樹脂粒子を前記無電解銀メッキ液に投入し、この液を攪拌しながら加熱して温度を５０℃に保った。その後、ブフナー漏斗で濾別して粒子を分離し真空乾燥機で８０℃２時間乾燥し、平均粒子径２０μｍの球状Ａｇめっき樹脂粒子（導電性粒子）を得た。
-Production of conductive particles-
--Production of divinylbenzene resin particles-
Benzoyl peroxide as a polymerization initiator was added to a solution in which the mixing ratio of divinylbenzene, styrene, and butyl methacrylate was adjusted, and heating was carried out while uniformly stirring at high speed to obtain a fine particle dispersion by carrying out a polymerization reaction. . The fine particle dispersion was filtered and dried under reduced pressure to obtain a block body which is an aggregate of fine particles. Furthermore, divinylbenzene-based resin particles were obtained by grinding the block body.
-Silver plating of resin particles-
In a solution of 4.25 g of silver nitrate as silver salt dissolved in 625 mL of pure water at room temperature, 15 g of benzimidazole as a reducing agent is added and dissolved, and after confirming that the initially formed precipitate is completely dissolved, as a complexing agent 5 g of succinimide and 3 g of citric acid monohydrate were dissolved, and then 13 g of glyoxylic acid as a crystal modifier was added and completely dissolved to prepare an electroless silver plating solution.
Next, the divinylbenzene resin particles obtained above were charged into the electroless silver plating solution, and the solution was heated with stirring to keep the temperature at 50 ° C. Thereafter, the resultant was separated by filtration using a Buchner funnel to separate particles, and dried with a vacuum dryer at 80 ° C. for 2 hours to obtain spherical Ag-plated resin particles (conductive particles) having an average particle diameter of 20 μm.
＜示差走査熱量測定（ＤＳＣ測定）＞
以下の条件でＤＳＣ測定を行い、昇温時における溶融開始温度、吸熱ピーク温度、及び吸熱量、並びに降温時における結晶化開始温度、発熱ピーク温度、及び発熱量を求めた。結果を表１−１に示す。
測定装置：Ｑ１００、ティー・エイ・インスツルメント社製
測定試料：５ｍｇ
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間
<Differential Scanning Calorimetry (DSC Measurement)>
DSC measurement was performed under the following conditions to determine the melting start temperature, endothermic peak temperature and heat absorption amount at the time of temperature rise, and the crystallization start temperature, exothermic peak temperature, and calorific value at the time of temperature lowering. The results are shown in Table 1-1.
Measuring device: Q100, manufactured by TA Instruments Measurement sample: 5 mg
Measurement temperature range: 30 ° C to 250 ° C
Heating rate: 10 ° C / min Cooling rate: 20 ° C / min
＜接合体の製造、及び接合体の評価＞
以下の方法により接合体を製造し、以下に示す評価を行った。結果を表１−１に示す。
第２の電子部品として、プリント配線板〔０．４ｍｍピッチ（ライン／スペース＝０．２／０．２）、銅パターン厚み３５μｍ、ニッケル／金めっき処理、基材厚み１．０ｍｍ〕を用いた。
第１の電子部品として、フレキシブルプリント基板〔０．４ｍｍピッチ（ライン／スペース＝０．２／０．２）、ポリイミド厚み２５μｍ、銅パターン厚み１２μｍ、ニッケル／金めっき処理〕を用いた。
前記第２の電子部品の端子上に、上記で得られた異方性導電フィルム（フィルム幅２．０ｍｍ）を配置した。続いて、前記異方性導電フィルム上に、前記第１の電子部品を配置した。続いて、緩衝材（シリコーンラバー、厚み０．２ｍｍ）を介して、加熱ツール（幅２．０ｍｍ）により１２０℃、２ＭＰａ、３秒間の条件で、前記第１の電子部品を加熱及び押圧し、接合体を得た。
<Manufacturing of joined body, and evaluation of joined body>
The bonded body was manufactured by the following method, and evaluation shown below was performed. The results are shown in Table 1-1.
Printed wiring board [0.4 mm pitch (line / space = 0.2 / 0.2), copper pattern thickness 35 μm, nickel / gold plating treatment, substrate thickness 1.0 mm] was used as the second electronic component .
As the first electronic component, a flexible printed board [0.4 mm pitch (line / space = 0.2 / 0.2), polyimide thickness 25 μm, copper pattern thickness 12 μm, nickel / gold plating treatment] was used.
The anisotropic conductive film (film width 2.0 mm) obtained above was disposed on the terminal of the second electronic component. Subsequently, the first electronic component was disposed on the anisotropic conductive film. Subsequently, the first electronic component is heated and pressed through a buffer material (silicone rubber, 0.2 mm thickness) with a heating tool (width 2.0 mm) under conditions of 120 ° C., 2 MPa, 3 seconds, A conjugate was obtained.
＜＜導通抵抗値（接続抵抗）＞＞
得られた接合体の初期抵抗値、及び高温高湿試験（６０℃９５％ＲＨ環境下で５００時間放置）後の抵抗値を以下の方法で測定し、評価を行った。
デジタルマルチメーター（品番：デジタルマルチメーター３４４０１Ａ、アジレント社製）を用いて４端子法にて電流１ｍＡを流したときの抵抗値を測定した。３０チャンネルについて抵抗値を測定し、最大の抵抗値を以下の評価基準で評価した。結果を表１−１に示す。
〔評価基準〕
○：抵抗値が０．１１Ω未満
△：抵抗値が０．１１Ω以上０．１５未満
×：抵抗値が０．１５Ω以上
<< Conduction resistance value (connection resistance) >>
The initial resistance value of the obtained bonded body and the resistance value after the high temperature and high humidity test (left for 500 hours in an environment of 60 ° C. and 95% RH) were measured and evaluated by the following method.
The resistance value when a current of 1 mA was applied was measured by a four-terminal method using a digital multimeter (part number: digital multimeter 34401A, manufactured by Agilent). Resistance values were measured for 30 channels, and the maximum resistance value was evaluated by the following evaluation criteria. The results are shown in Table 1-1.
〔Evaluation criteria〕
○: Resistance value less than 0.11 Ω Δ: Resistance value 0.11 or more and less than 0.15 ×: Resistance value 0.15 or more
＜＜ピール強度＞＞
フレキシブルプリント基板をプリント配線板から９０°方向で剥離する９０°剥離試験（ＪＩＳ Ｋ６８５４−１）を行った。剥離試験には、１ｃｍ幅にカットした試験片を用いた。ピール強度を測定し以下の評価基準で評価した。結果を表１−１に示す。
〔評価基準〕
○：８．０Ｎ／ｃｍ以上
△：６．０Ｎ／ｃｍ以上８．０Ｎ／ｃｍ未満
×：６．０Ｎ／ｃｍ未満
<< Peel strength >>
A 90 ° peeling test (JIS K6854-1) was carried out to peel the flexible printed circuit board from the printed wiring board in the 90 ° direction. For the peeling test, a test piece cut into a width of 1 cm was used. The peel strength was measured and evaluated by the following evaluation criteria. The results are shown in Table 1-1.
〔Evaluation criteria〕
○: 8.0 N / cm or more △: 6.0 N / cm or more and less than 8.0 N / cm ×: less than 6.0 N / cm
（実施例２〜６、比較例１〜２）
実施例１において、結晶性樹脂、非晶性樹脂、及びエラストマーの配合を表１−１に記載の配合に変えた以外は、実施例１と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−１に示す。
(Examples 2 to 6, Comparative Examples 1 to 2)
An anisotropic conductive film and a joined body were prepared in the same manner as in Example 1 except that the composition of the crystalline resin, the amorphous resin, and the elastomer was changed to the composition described in Table 1-1 in Example 1. Made.
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-1.
実施例６で得られた異方性導電フィルムのＤＳＣ測定結果を図１及び図２に示す。図１は、昇温時のＤＳＣチャートである。図２は、降温時のＤＳＣチャートである。図１のＤＳＣチャートでは、７７．０℃に溶融開始温度が観察され、１０７．５℃に吸熱ピークが観察された。また、吸熱ピーク面積から計算した吸熱量は７．３Ｊ／ｇであった。図２のＤＳＣチャートでは、９９．３℃に結晶化開始温度が観察され、９５．３℃に発熱ピークが観察された。また、発熱ピーク面積から計算した発熱量は、３．７Ｊ／ｇであった。 The DSC measurement result of the anisotropic conductive film obtained in Example 6 is shown in FIG. 1 and FIG. FIG. 1 is a DSC chart at the time of temperature rise. FIG. 2 is a DSC chart at the time of temperature decrease. In the DSC chart of FIG. 1, the melting start temperature was observed at 77.0 ° C., and the endothermic peak was observed at 107.5 ° C. Moreover, the endothermic heat calculated from the endothermic peak area was 7.3 J / g. In the DSC chart of FIG. 2, the crystallization start temperature was observed at 99.3 ° C., and an exothermic peak was observed at 95.3 ° C. The calorific value calculated from the exothermic peak area was 3.7 J / g.
比較例２で得られた異方性導電フィルムのＤＳＣ測定結果を図３及び図４に示す。図３は、昇温時のＤＳＣチャートである。図４は、降温時のＤＳＣチャートである。図３のＤＳＣチャートでは、吸熱ピークは観察されなかった。図４のＤＳＣチャートでは、発熱ピークは観察されなかった。 The DSC measurement result of the anisotropic conductive film obtained by the comparative example 2 is shown in FIG.3 and FIG.4. FIG. 3 is a DSC chart at the time of temperature rise. FIG. 4 is a DSC chart at the time of temperature decrease. No endothermic peak was observed in the DSC chart of FIG. No exothermic peak was observed in the DSC chart of FIG.
（実施例７〜１０）
実施例１において、結晶性樹脂、非晶性樹脂、及びエラストマーの配合を表１−２に記載の配合に変えた以外は、実施例１と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−２に示す。
(Examples 7 to 10)
An anisotropic conductive film and a joined body were prepared in the same manner as in Example 1 except that the composition of the crystalline resin, the amorphous resin, and the elastomer was changed to the composition described in Table 1-2 in Example 1. Made.
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-2.
（実施例１１）
実施例５において、結晶性樹脂をバイロンＧＡ−６４００（東洋紡株式会社製、結晶性ポリエステル樹脂）に代え、非晶性樹脂をエリーテルＵＥ３６００（ユニチカ株式会社製、非晶性ポリエステル樹脂）に代えた以外は、実施例５と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−２に示す。
(Example 11)
In Example 5, except that the crystalline resin was replaced by Byron GA-6400 (manufactured by Toyobo Co., Ltd., crystalline polyester resin) and the non-crystalline resin was replaced by Elytel UE 3600 (manufactured by Unitika Co., Ltd., non-crystalline polyester resin) In the same manner as in Example 5, an anisotropic conductive film and a bonded body were produced.
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-2.
（実施例１２）
実施例５において、エラストマーをテイサンレジンＳＧ−８０Ｈ（ナガセケムテックス株式会社製、アクリルゴム系エラストマー）に代えた以外は、実施例５と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−２に示す。
(Example 12)
An anisotropic conductive film and a composite were produced in the same manner as in Example 5 except that the elastomer was replaced with Teisan resin SG-80H (manufactured by Nagase ChemteX Co., Ltd., acrylic rubber-based elastomer) in Example 5. .
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-2.
（実施例１３）
実施例６において、導電性粒子を平均粒子径１０μｍの球状Ａｇめっき樹脂粒子に代えた以外は、実施例６と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−２に示す。
(Example 13)
An anisotropic conductive film and a joined body were produced in the same manner as in Example 6, except that the conductive particles in Example 6 were replaced by spherical Ag-plated resin particles having an average particle diameter of 10 μm.
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-2.
（比較例３）
実施例５において、非晶性樹脂（非晶性ポリエステル樹脂）をＹＰ−５０（新日鐵化学株式会社製、非晶性フェノキシ樹脂）に代えた以外は、実施例５と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−３に示す。
(Comparative example 3)
Example 5 is the same as Example 5, except that the amorphous resin (amorphous polyester resin) is replaced by YP-50 (amorphous phenoxy resin manufactured by Nippon Steel Chemical Co., Ltd.). The anisotropic conductive film and the junction were produced.
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-3.
（比較例４〜５）
実施例１において、結晶性樹脂、及び非晶性樹脂の配合を表１−３に記載の配合に変えた以外は、実施例１と同様にして、異方性導電フィルム及び接合体を作製した。
得られた異方性導電フィルム及び接合体について、実施例１と同様の評価を行った。結果を表１−３に示す。
(Comparative Examples 4 to 5)
An anisotropic conductive film and a bonded body were produced in the same manner as in Example 1 except that the composition of the crystalline resin and the amorphous resin was changed to the composition described in Table 1-3 in Example 1. .
Evaluation similar to Example 1 was performed about the obtained anisotropic conductive film and a conjugate | zygote. The results are shown in Table 1-3.
表１−１〜表１−３における各組成の配合量（含有量と同じ）の単位は質量部である。
表１−１〜表１−３におけるΔＴ１は、示差走査熱量測定における昇温時の溶融開始温度と吸熱ピーク温度との差の絶対値であり、ΔＴ２は、示差走査熱量測定における降温時の結晶化開始温度と発熱ピーク温度との差の絶対値である。
The unit of the compounding amount (the same as the content) of each composition in Tables 1-1 to 1-3 is a part by mass.
ΔT1 in Tables 1-1 to 1-3 is an absolute value of the difference between the melting start temperature and the endothermic peak temperature at the time of temperature increase in differential scanning calorimetry, and ΔT2 is the crystal at the time of temperature decrease in differential scanning calorimetry It is an absolute value of the difference between the crystallization start temperature and the exothermic peak temperature.
実施例１〜１３から、本発明の異方性導電フィルムが、十分な接続抵抗を維持しつつ、低温（１２０℃）、低圧力（２ＭＰａ）、及び短時間（３秒間）での接続が可能であることが確認できた。また、ピール強度についても優れていることが確認できた。
実施例１〜３及び実施例９〜１０の結果から、結晶性樹脂と非晶性樹脂との質量比（結晶性樹脂：非晶性樹脂）が、２５：７５〜７５：２５であると、導通抵抗値及びピール強度の接続特性がより優れることが確認できた。
実施例４〜６、及び８の結果から、結晶性樹脂の含有量及び非晶性樹脂の含有量の和（Ｘ）と、エラストマーの含有量（Ｙ）との質量比（Ｘ：Ｙ）が、１６０：４０〜６０：１４０であると、高温高湿試験後でも接続抵抗値がより優れることが確認できた。
比較例１は、非晶性樹脂を含まないために、平滑な異方性導電フィルムが得られず、その結果、高温高湿試験後の導通抵抗値が不十分となった。
比較例２及び５は、結晶性樹脂を含まないために、異方性導電フィルムの凝集力が低く、その結果、高温高湿試験後の導通抵抗値が不十分となった。
比較例３は、結晶性樹脂と非晶性樹脂との種類が異なる（樹脂を特徴づける結合が異なる）ために、平滑な異方性導電フィルムが得られず、その結果、高温高湿試験後の導通抵抗値が不十分となった。
比較例４は、非晶性樹脂を含まないために、平滑な異方性導電フィルムが得られず、その結果、高温高湿試験後の導通抵抗値が不十分となった。また、結晶性樹脂の含有量が多く、エラストマーに均一に分散していない為、局所的に硬い部分が生じたことで、ピール強度が不十分となった。
From Examples 1 to 13, the anisotropic conductive film of the present invention can be connected at low temperature (120 ° C.), low pressure (2 MPa), and short time (3 seconds) while maintaining sufficient connection resistance. Was confirmed. It was also confirmed that the peel strength was excellent.
From the results of Examples 1 to 3 and Examples 9 to 10, the mass ratio of the crystalline resin to the amorphous resin (crystalline resin: amorphous resin) is 25: 75 to 75: 25. It was confirmed that the connection characteristics of the conduction resistance value and the peel strength were more excellent.
From the results of Examples 4 to 6 and 8, the mass ratio (X: Y) of the sum (X) of the content of the crystalline resin and the content of the amorphous resin and the content (Y) of the elastomer is It can be confirmed that the connection resistance value is more excellent even after the high temperature and high humidity test if 160: 40 to 60: 140.
In Comparative Example 1, a smooth anisotropic conductive film was not obtained because it did not contain an amorphous resin, and as a result, the conduction resistance value after the high temperature and high humidity test became insufficient.
In Comparative Examples 2 and 5, since the crystalline resin was not contained, the cohesive force of the anisotropic conductive film was low, and as a result, the conduction resistance value after the high temperature and high humidity test became insufficient.
In Comparative Example 3, a smooth anisotropic conductive film can not be obtained because the types of the crystalline resin and the non-crystalline resin are different (the bond characterizing the resin is different). As a result, after the high temperature high humidity test The conduction resistance value of the
In Comparative Example 4, a smooth anisotropic conductive film was not obtained because it did not contain the amorphous resin, and as a result, the conduction resistance value after the high temperature and high humidity test became insufficient. In addition, since the content of the crystalline resin is large and the resin is not uniformly dispersed in the elastomer, the peel strength is insufficient because a hard portion locally occurs.
本発明の異方性導電フィルムは、十分な接続抵抗を維持しつつ、低温、低圧力、及び短時間での接続が可能であるため、基板の端子と電子部品の端子とを異方性導電接続させて接合体を製造する際の接続材料として好適に用いることができる。
The anisotropic conductive film of the present invention enables connection at low temperature, low pressure, and short time while maintaining sufficient connection resistance, so anisotropic conduction of the terminal of the substrate and the terminal of the electronic component is possible. It can use suitably as a connection material at the time of making it connect and manufacturing a joined object.
Claims (10)
結晶性樹脂と、非晶性樹脂と、導電性粒子と、エラストマー（ただし、前記エラストマーは、前記結晶性樹脂及び前記非晶性樹脂とは異なる。）とを含有し、
前記結晶性樹脂が、前記非晶性樹脂が有する樹脂を特徴づける結合と同じ、樹脂を特徴づける結合を有する結晶性樹脂を含有し、
下記の測定温度範囲、昇温速度、及び降温速度での示差走査熱量測定において、昇温時に吸熱ピークを示し、かつ降温時に発熱ピークを示すことを特徴とする異方性導電フィルム。
測定温度範囲：３０℃〜２５０℃
昇温速度：１０℃／分間
降温速度：２０℃／分間 An anisotropic conductive film for anisotropically conductively connecting a terminal of a first electronic component and a terminal of a second electronic component,
A crystalline resin, an amorphous resin, conductive particles, and an elastomer (wherein the elastomer is different from the crystalline resin and the amorphous resin),
The crystalline resin contains a crystalline resin having a bond characterizing the resin, which is the same as the bond characterizing the resin possessed by the amorphous resin,
What is claimed is: 1. An anisotropic conductive film which exhibits an endothermic peak at the time of temperature rise and an exothermic peak at the time of temperature drop in differential scanning calorimetry at the following measurement temperature range, temperature rising rate and temperature lowering rate.
Measurement temperature range: 30 ° C to 250 ° C
Heating rate: 10 ° C / min Cooling rate: 20 ° C / min
非晶性樹脂が、非晶性ポリエステル樹脂を含有する請求項１から２のいずれかに記載の異方性導電フィルム。 The crystalline resin contains a crystalline polyester resin,
The anisotropic conductive film according to any one of claims 1 to 2, wherein the amorphous resin contains an amorphous polyester resin.
前記第２の電子部品の端子上に請求項１から７のいずれかに記載の異方性導電フィルムを配置する第１の配置工程と、
前記異方性導電フィルム上に前記第１の電子部品を、前記第１の電子部品の端子が前記異方性導電フィルムと接するように配置する第２の配置工程と、
前記第１の電子部品を加熱押圧部材により加熱及び押圧する加熱押圧工程とを含むことを特徴とする接続方法。 A connection method for anisotropically conductively connecting a terminal of a first electronic component and a terminal of a second electronic component,
A first arrangement step of arranging the anisotropic conductive film according to any one of claims 1 to 7 on a terminal of the second electronic component;
A second disposing step of disposing the first electronic component on the anisotropic conductive film such that a terminal of the first electronic component is in contact with the anisotropic conductive film;
And a heating and pressing step of heating and pressing the first electronic component with a heating and pressing member.
前記異方性導電フィルムが、請求項１から７のいずれかに記載の異方性導電フィルムであることを特徴とする接合体。 A first electronic component having a terminal, a second electronic component having a terminal, and a terminal of the first electronic component interposed between the first electronic component and the second electronic component And an anisotropic conductive film for electrically connecting to the terminal of the second electronic component,
The bonded body characterized in that the anisotropic conductive film is the anisotropic conductive film according to any one of claims 1 to 7.
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