JP4967276B2 - Circuit connection material, circuit terminal connection structure and connection method - Google Patents
Circuit connection material, circuit terminal connection structure and connection method Download PDFInfo
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本発明は、相対向する回路電極間に介在され、相対向する回路電極を加圧し加圧方向の電極間のみを電気的に接続する回路接続材料と、回路端子の接続構造体及び接続方法とに関する。 The present invention relates to a circuit connection material that is interposed between circuit electrodes facing each other, pressurizes the circuit electrodes facing each other, and electrically connects only the electrodes in the pressing direction, a circuit terminal connection structure, and a connection method About.
エポキシ樹脂系接着剤は、高い接着強度が得られ、耐水性や耐熱性に優れること等から、電気・電子・建築・自動車・航空機等の各種用途に多用されている。
中でも一液型エポキシ樹脂系接着剤は、主剤と硬化剤との混合が不必要であり使用が簡便なことから、フィルム状、ペースト状、粉体状の形態で使用されている。この場合、エポキシ樹脂と硬化剤及び変性剤との多様な組合せにより、特定の性能を得ることが一般的である。しかしながら、このようなエポキシ樹脂系のフィルム状接着剤は、作業性に優れるものの、低温速硬化性の点で不十分であった。
Epoxy resin adhesives are widely used in various applications such as electricity, electronics, architecture, automobiles and airplanes because of their high adhesive strength and excellent water resistance and heat resistance.
Among them, the one-pack type epoxy resin adhesive is used in the form of a film, a paste, or a powder because it is not necessary to mix the main agent and the curing agent and is easy to use. In this case, it is common to obtain specific performance by various combinations of epoxy resins, curing agents and modifiers. However, such an epoxy resin film adhesive is excellent in workability, but is insufficient in terms of low temperature fast curing.
低温速硬化性の接着剤として、ラジカル重合性接着剤が知られている（例えば、特許文献１）が、低温硬化性を重視した場合、分解温度(半減期温度)の低い硬化剤(過酸化物)が使用されるため、貯蔵安定性が低下する問題があった。また、エポキシ樹脂と光照射により塩基を発生するアミンイミド化合物を含む接着剤も、低温速硬化性の接着剤として提案されている（例えば特許文献２、３）。尚、この接着剤ではアミンイミド化合物はエポキシ樹脂に対する硬化剤として配合されている。
他に光照射と低温加熱による硬化方法として光カチオン硬化が提案されているが（例えば特許文献４）、金属部材への腐食及び触媒の毒性等で問題があった。
In addition, although photocationic curing has been proposed as a curing method by light irradiation and low-temperature heating (for example, Patent Document 4), there are problems with corrosion to metal members and toxicity of the catalyst.
本発明の目的は、低温速硬化性と貯蔵安定性に優れた回路接続材料を提供することである。 An object of the present invention is to provide a circuit connecting material excellent in low-temperature fast curing property and storage stability.
本発明者らは、上記課題に鑑み、鋭意研究した結果、ラジカル重合性接着剤に、ラジカル重合開始剤と共に、光照射によって塩基を発生する光塩基発生剤を組み合わせることで、光塩基発生剤由来の塩基がラジカル重合開始剤の分解を促すことにより、接着剤の低温速硬化が向上し、かつ光を遮断した場合には貯蔵安定性に優れることを見出し、本発明を完成させた。
本発明によれば、以下の回路接続材料等が提供される。
１．相対向する回路電極間に介在され、相対向する回路電極を加圧し、加圧方向の電極間のみを電気的に接続する回路接続材料であって、下記（１）〜（３）の成分を含有する回路接続材料。
（１）ラジカル重合性物質
（２）ラジカル重合開始剤
（３）光照射によって塩基を発生する光塩基発生剤
２．前記光塩基発生剤がカルバミン酸エステル誘導体、オキシムエステル誘導体、アミンイミド誘導体、イミダゾリウム塩誘導体、４級アンモニウム塩誘導体、α-アミノケトン誘導体、ニフェジピン誘導体からなる群より選ばれる一以上の化合物である１記載の回路接続材料。
３．さらに、熱可塑性樹脂を含有する１または２記載の回路接続材料。
４．前記熱可塑性樹脂がフェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアクリル樹脂から選ばれる３記載の回路接続材料。
５．さらに、導電性粒子を含有する１〜４のいずれか一項記載の回路接続材料。
６．第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とが、第一の接続端子と第二の接続端子を対向して配置されており、前記対向配置した第一の接続端子と第二の接続端子の間に１〜５のいずれか記載の回路接続材料が介在されており、前記対向配置した第一の接続端子と第二の接続端子のみが電気的に接続されている回路端子の接続構造体。
７．第一の接続端子を有する第一の回路部材上に前記１〜５のいずれかに記載の回路接続材料を配置させ、回路接続材料の上方から光照射を行った後、第二の接続端子を有する第二の回路部材を対向して配置し、加熱しながら加圧して対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。
８．第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に前記１〜５のいずれかに記載の回路接続材料を介在させ、光照射と同時に加熱しながら加圧して前記対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。
As a result of diligent research in view of the above problems, the present inventors derived from a photobase generator by combining a radical polymerizable adhesive and a photobase generator that generates a base by light irradiation together with a radical polymerization initiator. It was found that this base promotes the decomposition of the radical polymerization initiator, thereby improving the low-temperature rapid curing of the adhesive and excellent storage stability when light is blocked. Thus, the present invention has been completed.
According to the present invention, the following circuit connection materials and the like are provided.
1. A circuit connecting material that is interposed between opposing circuit electrodes, pressurizes the opposing circuit electrodes, and electrically connects only the electrodes in the pressurizing direction, and includes the following components (1) to (3): Contains circuit connection material.
(1) radical polymerizable substance (2) radical polymerization initiator (3) photobase generator that generates a base by light irradiation 1 wherein the photobase generator is one or more compounds selected from the group consisting of carbamic acid ester derivatives, oxime ester derivatives, amine imide derivatives, imidazolium salt derivatives, quaternary ammonium salt derivatives, α-aminoketone derivatives, and nifedipine derivatives. Circuit connection material.
3. Furthermore, the circuit connection material of 1 or 2 containing a thermoplastic resin.
4). 4. The circuit connecting material according to 3, wherein the thermoplastic resin is selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyimide resin, and polyacrylic resin.
5. Furthermore, the circuit connection material as described in any one of 1-4 containing electroconductive particle.
6). The first circuit member having the first connection terminal and the second circuit member having the second connection terminal are arranged to face the first connection terminal and the second connection terminal, and The circuit connection material according to any one of 1 to 5 is interposed between the first connection terminal and the second connection terminal that are arranged to face each other, and only the first connection terminal and the second connection terminal that are arranged to face each other. A circuit terminal connection structure in which is electrically connected.
7). The circuit connection material according to any one of the above 1 to 5 is disposed on a first circuit member having a first connection terminal, and after irradiating light from above the circuit connection material, the second connection terminal is A circuit terminal connection method in which a second connection member having a first connection terminal and a second connection terminal, which are arranged to face each other and are heated and pressurized to face each other, are electrically connected.
8). A first circuit member having a first connection terminal and a second circuit member having a second connection terminal are disposed so that the first connection terminal and the second connection terminal are opposed to each other, and the opposed arrangement is performed. The circuit connection material according to any one of 1 to 5 described above is interposed between the first connection terminal and the second connection terminal, and the first connection is disposed opposite to the substrate by applying pressure while heating simultaneously with light irradiation. A circuit terminal connection method for electrically connecting only the terminal and the second connection terminal.
本発明によれば、低温速硬化性と貯蔵安定性に優れた回路接続材料を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the circuit connection material excellent in low-temperature quick curing property and storage stability can be provided.
本発明において用いる（１）ラジカル重合性物質としては、スチレン化合物に代表されるようなラジカルによって重合する化合物であれば、特に制限無く公知のものを使用することができるが、分子内にアクリロイル基またはメタクリロイル基 （以後、（メタ）アクリロイル基と呼ぶ）を分子内に２つ以上有する化合物やマレイミド化合物が、より好ましい。 As the radically polymerizable substance (1) used in the present invention, a known substance can be used without particular limitation as long as it is a compound that is polymerized by a radical represented by a styrene compound, but an acryloyl group in the molecule. Alternatively, a compound having two or more methacryloyl groups (hereinafter referred to as (meth) acryloyl groups) in the molecule or a maleimide compound is more preferable.
具体的には、エポキシ（メタ）アクリレートオリゴマー、ウレタン（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー等のオリゴマー、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、イソシアヌル酸変性２官能（メタ）アクリレート、イソシアヌル酸変性３官能（メタ）アクリレート、２，２’-ジ（メタ）アクリロイロキシジエチルホスフェート、２−（メタ）アクリロイロキシエチルアシッドホスフェート等の多官能（メタ）アクリレート化合物が挙げられる。
これらは単独又は併用して用いることができ、必要によっては、ハイドロキノン、メチルエーテルハイドロキノン類等の重合禁止剤を適宜用いてもよい。
また、ジシクロペンテニル基及び／又はトリシクロデカニル基及び／又はトリアジン環を有する場合は、耐熱性が向上するので好ましい。
Specifically, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, oligomer such as polyester (meth) acrylate oligomer, trimethylolpropane tri (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate Polyfunctional (meth) acrylate compounds such as 2- (meth) acryloyloxyethyl acid phosphate.
These can be used alone or in combination. If necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be appropriately used.
Moreover, when it has a dicyclopentenyl group and / or a tricyclodecanyl group and / or a triazine ring, since heat resistance improves, it is preferable.
マレイミド化合物としては、分子中にマレイミド基を少なくとも２個以上含有するもので、例えば、１−メチル−２，４−ビスマレイミドベンゼン、Ｎ，Ｎ’−ｍ−フェニレンビスマレイミド、Ｎ，Ｎ’−ｐ−フェニレンビスマレイミド、Ｎ，Ｎ’−ｍ−トルイレンビスマレイミド、Ｎ，Ｎ’−４，４−ビフェニレンビスマレイミド、Ｎ，Ｎ’−４，４−（３，３’−ジメチル−ビフェニレン）ビスマレイミド、Ｎ，Ｎ’−４，４−（３，３’−ジメチルジフェニルメタン）ビスマレイミド、Ｎ，Ｎ’−４，４−（３，３’−ジエチルジフェニルメタン）ビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルプロパンビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’−３，３’−ジフェニルスルホンビスマレイミド、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ｓ−ブチル−４−８（４−マレイミドフェノキシ）フェニル）プロパン、１，１−ビス（４−（４−マレイミドフェノキシ）フェニル）デカン、４，４’−シクロヘキシリデン−ビス（１−（４マレイミドフェノキシ）−２−シクロヘキシルベンゼン、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）ヘキサフルオロプロパン等を挙げることができる。これらは単独でもまた組み合わせても使用できる。 The maleimide compound contains at least two maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′— p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, N, N′-4,4- (3,3′-dimethyl-biphenylene) Bismaleimide, N, N′-4,4- (3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3′-diethyldiphenylmethane) bismaleimide, N, N′- 4,4-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-4,4-diphenyl ether bismaleimide N, N′-3,3′-diphenylsulfone bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4-8 (4 -Maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4'-cyclohexylidene-bis (1- (4maleimidophenoxy) -2-cyclohexylbenzene, Examples include 2,2-bis (4- (4-maleimidophenoxy) phenyl) hexafluoropropane, etc. These can be used alone or in combination.
本発明において用いる（２）ラジカル重合開始剤としては、従来から知られている過酸化物やアゾ化合物等公知の化合物を用いることができるが、安定性、反応性、相溶性の観点から、１分間半減期温度が９０〜１７５℃で、かつ分子量が１８０〜１,０００の過酸化物が好ましい。
具体的には、クミルパーオキシネオデカノエート、１,１,３,３−テトラメチルブチルパーオキシネオデカノエート、1−シクロヘキシル−１−メチルエチルパーオキシノエデカノエート、ｔ−ヘキシルパーオキシネオデカノエート、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーオキシピバレート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、２，５−ジメチル−２，５−ジ（２−エチルヘキサノイルパーオキシ）ヘキサン、t−ヘキシルパーオキシ−２−エチルヘキサノエート、t−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシネオヘプタノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサヒドロテレフタレート、ｔ−アミルパーオキシ−３，５，５−トリメチルヘキサノエート、３−ヒドロキシ−１，１−ジメチルブチルパーオキシネオデカノエート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、ｔ−アミルパーオキシネオデカノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、２，２’−アゾビス−２，４−ジメチルバレロニトリル、１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチロニトリル、４，４’−アゾビス（４−シアノバレリン酸）、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシマレイン酸、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシラウレート、２，５−ジメチル−２,５−ジ（３−メチルベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、ｔ−ヘキシルパーオキシベンゾエート、２，５−ジメチル−２,５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシベンゾエート、ジブチルパーオキシトリメチルアジペート、ｔ−アミルパーオキシノルマルオクトエート、ｔ−アミルパーオキシイソノナノエート、ｔ−アミルパーオキシベンゾエート、ベンゾイルパーオキサイド、ジ-（３-メチルベンゾイル）パーオキサイド等が挙げられる。
これらの化合物は、単独で用いる他に、２種以上の化合物を混合して用いても良い。
As the radical polymerization initiator (2) used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint of stability, reactivity, and compatibility, 1 Peroxides with a minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred.
Specifically, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylper Oxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneohepta Noate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amino Peroxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate , T-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy- 1-phenylethane), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4 '-Azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate, t- Tilperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) Hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyl Examples include adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate, benzoyl peroxide, and di- (3-methylbenzoyl) peroxide.
These compounds may be used alone or as a mixture of two or more compounds.
（２）ラジカル重合開始剤の添加量は、（１）ラジカル重合性物質１００部に対して、ラジカル重合開始剤０.０５〜３０質量部であり、好ましくは０．１〜２０質量部である。添加量が０．０５質量部未満の場合、硬化不足が懸念され、また、３０質量部を超える場合には、放置安定性が低下する恐れがある。 (2) The addition amount of the radical polymerization initiator is 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to (1) 100 parts of the radical polymerizable substance. . When the addition amount is less than 0.05 parts by mass, there is a concern about insufficient curing, and when it exceeds 30 parts by mass, the standing stability may be lowered.
本発明に用いる（３）光塩基発生剤は、光照射によって、塩基を発生する化合物であれば特に制限は受けないが、カルバミン酸エステル誘導体、オキシムエステル誘導体、アミンイミド誘導体、イミダゾリウム塩誘導体、４級アンモニウム塩誘導体、α-アミノケトン誘導体、ニフェジピン誘導体が、光照射に対して効率よく塩基を発生する観点から、より好ましい。
例えば、Ｃｈｅｍｉｓｔｒｙ ＆ Ｔｅｃｈｎｏｌｏｇｙ ｏｆ ＵＶ ＆ ＥＢ Ｆｏｒｍｕｌａｔｉｏｎ ｆｏｒ Ｃｏａｔｉｎｇｓ， Ｉｎｋｓ ＆ Ｐａｉｎｔｓ，Ｅｄ．ｂｙ Ｇ． Ｂｒａｄｌｅｙ，Ｊｏｈｎ Ｗｉｌｅｙ ａｎｄ Ｓｏｎｓ Ｌｔｄ．（１９９８年）、ｐ４７９〜ｐ５４５に記載されているカルバミン酸エステル誘導体やオキシムエステル誘導体、４級アンモニウム塩誘導体が挙げられる。また、特開平１１-７１４５０号に記載されているα-アミノアセトフェノン誘導体やＷＯ２００２／０５１９０５号に記載されているアミンイミド誘導体、特開２００３−２１２８５６号に記載されているイミダゾリウム塩誘導体、特公平１−５３７７１号に記載されているジヒドロピリジン誘導体(以下ニフェジピン誘導体と呼ぶ)が挙げられる。
The (3) photobase generator used in the present invention is not particularly limited as long as it is a compound that generates a base by light irradiation. However, the carbamic acid ester derivative, oxime ester derivative, amine imide derivative, imidazolium salt derivative, 4 A quaternary ammonium salt derivative, α-aminoketone derivative, and nifedipine derivative are more preferable from the viewpoint of efficiently generating a base with respect to light irradiation.
See, for example, Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Ed. by G. Bradley, John Wiley and Sons Ltd. (1998), carbamic acid ester derivatives, oxime ester derivatives, and quaternary ammonium salt derivatives described in p479 to p545. Further, α-aminoacetophenone derivatives described in JP-A-11-71450, amine imide derivatives described in WO2002 / 051905, imidazolium salt derivatives described in JP2003-212856, and JP 1 And dihydropyridine derivatives described in No. -53771 (hereinafter referred to as nifedipine derivatives).
本発明の（３）光塩基発生剤の添加量は、（１）ラジカル重合性物質１００重量部に対して０．０１〜２００重量部が好ましく、０．０２〜１５０重量部がさらに好ましい。光塩基発生剤が０．０１重量部未満では耐熱性が低下する傾向があり、２００重量部を超える場合には、フィルム物性が低下する傾向がある。 The addition amount of the (3) photobase generator of the present invention is preferably 0.01 to 200 parts by weight, more preferably 0.02 to 150 parts by weight with respect to 100 parts by weight of the (1) radical polymerizable substance. When the photobase generator is less than 0.01 parts by weight, the heat resistance tends to be lowered, and when it exceeds 200 parts by weight, the film physical properties tend to be lowered.
本発明の回路接続材料は、さらに熱可塑性樹脂を含むことができる。熱可塑性樹脂としては、特に制限は受けないが、樹脂の主鎖骨格あるいは側鎖に水酸基、エーテル基、エステル基、ウレタン基、アミド基、イミド基、カルボンキシル基、等の極性基を含有する樹脂が接着性の観点から好ましい。具体的には、フェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアクリル樹脂、等が使用できる。また前記ポリマーをラジカル重合性の官能基で変性したものは耐熱性が向上するためより好ましい。
これらのポリマーの分子量は特に制限を受けるものではないが、一般的な重量平均分子量としては５，０００〜１５０，０００が好ましく、１０，０００〜８０，０００が特に好ましい。この値が、５，０００未満ではフィルム形成性が劣る傾向があり、また１５０，０００を超えると他の成分との相溶性が悪くなる傾向がある。使用量としては（１）ラジカル重合性化合物１００重量部に対して２０〜３２０重量部とすることが好ましい。
The circuit connection material of the present invention can further contain a thermoplastic resin. The thermoplastic resin is not particularly limited, but the main chain skeleton or side chain of the resin contains a polar group such as a hydroxyl group, an ether group, an ester group, a urethane group, an amide group, an imide group, or a carboxyxyl group. Resins are preferred from the viewpoint of adhesiveness. Specifically, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyimide resin, polyacrylic resin, and the like can be used. Further, a polymer obtained by modifying the polymer with a radical polymerizable functional group is more preferable because heat resistance is improved.
The molecular weight of these polymers is not particularly limited, but the general weight average molecular weight is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to deteriorate. The amount used is preferably (1) 20 to 320 parts by weight per 100 parts by weight of the radically polymerizable compound.
本発明の回路接続材料は導電性粒子がなくても、接続時に相対向する回路電極の直接接触により接続が得られるが、導電性粒子を含有した場合、より安定した接続が得られる。
導電性粒子としては、Ａｕ、Ａｇ、Ｎｉ、Ｃｕ、はんだ等の金属粒子やカーボン等があり、十分なポットライフを得るためには、表層はＡｕ、Ａｇ、白金族の貴金属類が好ましくＡｕがより好ましい。
また、Ｎｉ等の遷移金属類の表面をＡｕ等の貴金属類で被覆したものでもよい。また、非導電性のガラス、セラミック、プラスチック（ポリスチレン等）等に前記した導通層を被覆等により形成し、最外層を貴金属類、核をプラスチックとした場合や、熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。
導電性粒子の使用量は、回路接続材料１００体積に対して０．１〜３０体積％とすることが好ましく、０．１〜１０体積％とすることがより好ましい。この値が、０．１体積％未満であると導電性が劣る傾向があり、３０体積％を超えると回路の短絡が起こる傾向がある。尚、体積％は２３℃の硬化前の各成分の体積をもとに決定されるが、各成分の体積は、比重を利用して重量から体積に換算することができる。
Even if the circuit connection material of the present invention does not have conductive particles, connection can be obtained by direct contact of circuit electrodes facing each other at the time of connection. However, when conductive particles are contained, more stable connection can be obtained.
Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, carbon, and the like. In order to obtain a sufficient pot life, the surface layer is preferably Au, Ag, or a platinum group noble metal, preferably Au. More preferred.
Further, the surface of a transition metal such as Ni may be coated with a noble metal such as Au. In addition, the conductive layer described above is formed by coating or the like on non-conductive glass, ceramic, plastic (polystyrene, etc.), the outermost layer is precious metal, the core is plastic, and in the case of hot-melt metal particles, heating Since it has deformability by pressurization, it is preferable because the contact area with the electrode is increased at the time of connection and the reliability is improved.
The amount of the conductive particles used is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume with respect to 100 volumes of the circuit connecting material. If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur. The volume% is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can be converted from weight to volume using specific gravity.
さらに、充填材、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤、アミノキシル誘導体や及びフェノール誘導体に代表される重合禁止剤を含有することもできる。 Furthermore, it can contain a polymerization inhibitor represented by fillers, softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, coupling agents, aminoxyl derivatives and phenol derivatives. .
本発明の回路接続材料は、（３）光塩基発生剤の塩基発生効率を向上させることを目的に、増感剤を併用してもよい。使用する増感剤としては、硬化性組成物に悪影響を及ぼさない限り、公知の一重項増感剤、三重項増感剤を用いることができる。例えば、ナフタレン、アントラセン、ピレン等の芳香族化合物誘導体、カルバゾール誘導体、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体等が好適に用いられる。増感剤の使用量は、増感剤の吸収波長及びモル吸光係数を参考にする必要があるが、一般的に（３）光塩基発生剤１重量部に対して０．０１〜５重量部であり、０.１〜２重量部が特に好ましい。増感剤が０.０１重量部未満になると光吸収の効率が低くなり、５重量部を超えると硬化性組成物全体に光が届かない恐れがある。 In the circuit connection material of the present invention, (3) a sensitizer may be used in combination for the purpose of improving the base generation efficiency of the photobase generator. As a sensitizer to be used, a known singlet sensitizer and triplet sensitizer can be used as long as they do not adversely affect the curable composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. The amount of the sensitizer used should refer to the absorption wavelength and molar extinction coefficient of the sensitizer, but generally (3) 0.01 to 5 parts by weight with respect to 1 part by weight of the photobase generator. 0.1 to 2 parts by weight is particularly preferable. When the sensitizer is less than 0.01 parts by weight, the light absorption efficiency is low, and when it exceeds 5 parts by weight, there is a possibility that light does not reach the entire curable composition.
本発明の回路接続材料では、（３）光塩基発生剤が硬化剤として機能するよりむしろ（２）ラジカル重合開始剤の分解を促進することにより、回路接続材料全体の反応を進め、その結果、低温速硬化性が向上する。通常、ラジカル重合開始剤の分解は、塩基性化合物によって促進されるものの、塩基性化合物そのものを添加した場合、保存安定性が低下する。そこで、本発明では、光照射によって塩基性化合物を発生させることによって、保存安定性と低温速硬化が可能となる。 In the circuit connection material of the present invention, (3) rather than the photobase generator functioning as a curing agent, (2) by promoting the decomposition of the radical polymerization initiator, the reaction of the entire circuit connection material is promoted. Low temperature fast curability is improved. Usually, the decomposition of the radical polymerization initiator is promoted by the basic compound, but when the basic compound itself is added, the storage stability is lowered. Therefore, in the present invention, storage stability and low-temperature rapid curing are possible by generating a basic compound by light irradiation.
本発明の接続方法は、第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に本発明の回路接続材料を介在させ、前記対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる。
このような回路部材としては半導体チップ、抵抗体チップ、コンデンサチップ等のチップ部品、プリント基板等の基板等が用いられる。回路部材には接続端子が通常は多数（場合によっては単数でもよい）設けられている。
In the connection method of the present invention, a first circuit member having a first connection terminal and a second circuit member having a second connection terminal are arranged so that the first connection terminal and the second connection terminal are opposed to each other. The circuit connection material of the present invention is interposed between the first connection terminal and the second connection terminal arranged opposite to each other, and only the first connection terminal and the second connection terminal arranged opposite to each other are electrically connected. Connect.
As such a circuit member, a chip component such as a semiconductor chip, a resistor chip or a capacitor chip, a substrate such as a printed circuit board, or the like is used. The circuit member is usually provided with a large number of connection terminals (or a single connection terminal in some cases).
より良好な電気的接続を得るためには、回路電極（接続端子）の少なくとも一方の表面を、金、銀、錫及び白金族から選ばれる金属にすることが好ましい。表面層は金、銀、白金族、又は錫のいずれかから選択され、これらを組み合わせて用いてもよい。また、銅／ニッケル／金のように複数の金属を組み合わせて多層構成としてもよい。 In order to obtain better electrical connection, it is preferable that at least one surface of the circuit electrode (connection terminal) is made of a metal selected from gold, silver, tin, and a platinum group. The surface layer is selected from gold, silver, platinum group, or tin, and these may be used in combination. Moreover, it is good also as a multilayer structure combining several metals like copper / nickel / gold.
接続方法としては、第一の接続端子を有する第一の回路部材上に回路接続材料を仮圧着にて配置させた後、回路接続材料の上方から光照射を行った後、第二の接続端子を有する第二の回路部材を対向して配置し、加熱しながら加圧して接着させることができる。
また、第一の回路部材が紫外域から可視域にかけて透明な基材の場合には、第一の接続端子を有する第一の回路部材上に回路接続材料を仮圧着にて配置させた後、第二の接続端子を有する第二の回路部材を対向して配置し、第二の回路部材上から加熱、加圧すると共に第一の回路部材下方から光照射を行って接着させることができる。
硬化条件は、通常、加熱の場合、０．１〜１０ＭＰａの加圧下で、１００〜２００℃で１秒〜１２０秒であるが、これに限定されるものでない。光照射は、１５０〜７５０ｎｍの波長域の照射光が好ましく、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプを使用することができ、光照射量としては３６５ｎｍ照度換算で０．０１〜１０Ｊ/ｃｍ２であるが、これに限定されるものでない。
As a connection method, after arranging the circuit connection material on the first circuit member having the first connection terminal by temporary pressure bonding, after irradiating light from above the circuit connection material, the second connection terminal The 2nd circuit member which has can be arrange | positioned facing and can be made to adhere | attach by pressurizing, heating.
In addition, in the case where the first circuit member is a transparent base material from the ultraviolet region to the visible region, after placing the circuit connection material on the first circuit member having the first connection terminal by provisional pressure bonding, A second circuit member having a second connection terminal can be disposed oppositely, heated and pressurized from above the second circuit member, and irradiated with light from below the first circuit member for bonding.
The curing condition is usually 1 to 120 seconds at 100 to 200 ° C. under a pressure of 0.1 to 10 MPa in the case of heating, but is not limited thereto. The light irradiation is preferably in the wavelength range of 150 to 750 nm, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or a metal halide lamp can be used. 0.01 to 10 J / cm 2 , but is not limited thereto.
本発明の回路接続材料は、常温（２５℃）で液状である場合にはペースト状で使用することができる。室温で固体の場合には、加熱して使用する他、溶剤を使用してペースト化してもよい。使用できる溶剤としては、硬化性に悪影響を及ぼさず、かつ十分な溶解性を示すものであれば、特に制限は受けないが、常圧での沸点が５０〜１５０℃であるものが好ましい。沸点が５０℃未満の場合、室温で放置すると揮発する恐れがあり、開放系での使用が制限される。また、沸点が１５０℃を超えると、溶剤の除去が難しくなる恐れがある。 The circuit connection material of the present invention can be used in the form of a paste when it is liquid at room temperature (25 ° C.). In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the curability and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. at normal pressure is preferable. If the boiling point is less than 50 ° C., it may volatilize if left at room temperature, which limits the use in an open system. Moreover, when a boiling point exceeds 150 degreeC, there exists a possibility that removal of a solvent may become difficult.
本発明の回路接続材料はフィルム状にして用いることもできる。接着材組成物に必要により溶剤等を加えるなどした溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離形紙等の剥離性基材上に塗布し、あるいは不織布等の基材に前記溶液を含浸させて剥離性基材上に載置し、溶剤等を除去してフィルムとして使用することができる。フィルムの形状で使用すると取扱性等の点から一層便利である。 The circuit connection material of the present invention can be used in the form of a film. A solution prepared by adding a solvent or the like to the adhesive composition as necessary is applied onto a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Can be used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
＜カルバミン酸エステルの合成＞
２，４−ジニトロベンジルアルコール (２.００ｇ、１０ｍｍｏｌ)および１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７(０．１０ｇ、０．６ｍｍｏｌ)をテトラヒドロフラン２０g中に溶解し、シクロヘキシルイソシアネート
(１．２７g、１０ｍｍｏｌ)を室温で滴下した。滴下終了後室温で４８時間攪拌したところ、白色沈殿が生成した。これを濾別した後、酢酸エチルで再結晶を行い、真空乾燥機で乾燥させてカルバミン酸エステル化合物を得た。収量２．２３ｇ、収率６８％であった。
<Synthesis of carbamic acid ester>
2,4-Dinitrobenzyl alcohol (2.00 g, 10 mmol) and 1,8-diaza-bicyclo (5,4,0) undecene-7 (0.10 g, 0.6 mmol) were dissolved in 20 g of tetrahydrofuran to obtain cyclohexyl. Isocyanate
(1.27 g, 10 mmol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 48 hours, and a white precipitate was formed. This was filtered off, recrystallized with ethyl acetate, and dried with a vacuum dryer to obtain a carbamate compound. The yield was 2.23 g and the yield was 68%.
＜オキシムエステルの合成＞
９−フルオレノンオキシム (２.００ｇ、１０ｍｍｏｌ)およびピリジン (０．８０ｇ、１０ｍｍｏｌ)をテトラヒドロフラン２０g中に溶解し、ジエチルカルバモイルクロリド
(１．３６g、１０ｍｍｏｌ)を氷浴で冷却しながらで滴下した。滴下終了後室温で２４時間攪拌したところ、白色沈殿が生成した。これに水を２００g加えると淡黄色沈殿が析出した。これを濾別した後、アセトンで再結晶を行い、真空乾燥機で乾燥させてオキシムエステル化合物を得た。収量２．５８ｇ、収率８８％であった。
<Synthesis of oxime ester>
9-Fluorenone oxime (2.00 g, 10 mmol) and pyridine (0.80 g, 10 mmol) were dissolved in 20 g of tetrahydrofuran and diethylcarbamoyl chloride was dissolved.
(1.36 g, 10 mmol) was added dropwise while cooling in an ice bath. After completion of the dropwise addition, the mixture was stirred at room temperature for 24 hours, and a white precipitate was formed. When 200 g of water was added thereto, a pale yellow precipitate was deposited. This was filtered off, recrystallized with acetone, and dried with a vacuum dryer to obtain an oxime ester compound. The yield was 2.58 g and the yield was 88%.
＜アミンイミドの合成＞
ｐ-ニトロ安息香酸メチルエステル(２.００ｇ、１１ｍｍｏｌ)、Ｎ，Ｎ−ジメチルヒドラジン(０.６６g、１１ｍｍｏｌ)、フェニルグリシジルエーテル（１.６６ｇ、１１ｍｍｏｌ）をｔｅｒｔ−ブタノール（１５.０ｇ）に添加し、５０℃で１０時間攪拌した後、さらに室温（２５℃）で４８時間攪拌したところ、白色沈殿が生成した。これを濾別した後、酢酸エチルで２度洗浄し、真空乾燥機で乾燥させてアミンイミド化合物を得た。収量３.６７ｇ、収率８５％であった。
<Synthesis of amine imide>
Add p-nitrobenzoic acid methyl ester (2.00 g, 11 mmol), N, N-dimethylhydrazine (0.66 g, 11 mmol), phenylglycidyl ether (1.66 g, 11 mmol) to tert-butanol (15.0 g). After stirring at 50 ° C. for 10 hours and further stirring at room temperature (25 ° C.) for 48 hours, a white precipitate was formed. This was filtered off, washed twice with ethyl acetate, and dried in a vacuum dryer to obtain an amine imide compound. The yield was 3.67 g, and the yield was 85%.
＜イミダゾリウム塩の合成＞
ｐ−ニトロフェナシルブロマイド (２.００ｇ、８．２ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させた１，２−ジメチルイミダゾール(０．７９ｇ、８．２ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温で２時間攪拌したところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、イミダゾリウム・ブロマイド塩を得た（収量２．６２ｇ）。
上記イミダゾール・ブロマイド塩（２．００ｇ、５．８ｍｍｏｌ）を、メタノール/水（１５ｇ/１５ｇ）溶液に溶解させ、これに水（５．０ｇ）に溶解させたテトラフェニルほう酸ナトリウム塩（２．０１ｇ、５．８ｍｍｏｌ）の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温で５時間攪拌した。これをろ過し、アセトン（２０ｇ）に溶解させて再結晶を行い、目的のイミダゾリウム・テトラフェニルほう酸塩（イミダゾリウム塩）を得た（収量３．２３ｇ）。
<Synthesis of imidazolium salt>
p-Nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g) and 1,2-dimethylimidazole (0.79 g, 8.2 mmol) dissolved in acetone (5 g) was dissolved therein. The solution was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain an imidazolium bromide salt (yield 2.62 g).
The above-mentioned imidazole bromide salt (2.00 g, 5.8 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and tetraphenylborate sodium salt (2.01 g) dissolved in water (5.0 g). 5.8 mmol) solution was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired imidazolium tetraphenylborate (imidazolium salt) (yield 3.23 g).
＜４級アンモニウム塩の合成＞
ｐ−ニトロフェナシルブロマイド (２.００ｇ、８．２ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させたＮ，Ｎ-ジメチルベンジルアミン(１．１０ｇ、８．２ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温で２時間攪拌したところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、アンモニウム・ブロマイド塩を得た（収量２．７３ｇ）。
上記アンモニウム・ブロマイド塩（２．００ｇ、５．３ｍｍｏｌ）を、メタノール/水（１５ｇ/１５ｇ）溶液に溶解させ、これに水（５．０ｇ）に溶解させたテトラフェニルほう酸ナトリウム塩（１．８４ｇ、５．３ｍｍｏｌ）の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温で５時間攪拌した。これをろ過し、アセトン（２０ｇ）に溶解させて再結晶を行い、目的の４級アンモニウム塩を得た（収量２．９８ｇ）。
<Synthesis of quaternary ammonium salt>
p-Nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g), and N, N-dimethylbenzylamine (1.10 g, 8.2 mmol) dissolved in acetone (5 g) was dissolved therein. The solution was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain an ammonium bromide salt (yield 2.73 g).
Ammonium bromide salt (2.00 g, 5.3 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and tetraphenylborate sodium salt (1.84 g) dissolved in water (5.0 g). 5.3 mmol) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired quaternary ammonium salt (yield 2.98 g).
（実施例１〜７、比較例１〜２）
熱可塑性樹脂として、フェノキシ樹脂及びウレタン樹脂を使用した。フェノキシ樹脂（ＰＫＨＣ、ユニオンカーバイト社製商品名、平均分子量４５，０００）４０ｇを、メチルエチルケトン６０ｇに溶解して、固形分４０重量％の溶液とした。また、ウレタン樹脂は、平均分子量２０００のポリブチレンアジペートジオール４５０重量部と平均分子量２０００のポリオキシテトラメチレングリコール４５０重量部、１，４−ブチレングリコール１００重量部をメチルエチルケトン４０００重量部中で均一に混合し、ジフェニルメタンジイソシアネート３９０重量部を加えて７０℃にて反応させて得られた重量平均分子量１５万のウレタン樹脂を使用した。（１）ラジカル重合性物質として、イソシアヌル酸ＥＯ変性ジアクリレート（Ｍ−２１５、東亜合成株式会社製商品名）、ウレタンアクリレート（ＡＴ−６００、共栄社化学株式会社製商品名）及び２-（メタ）アクリロイロキシエチルホスフェート（ライトエステルＰ-２Ｍ、共栄社株式会社製商品名）、（２）ラジカル重合開始剤として１０時間半減期温度が７３．１℃であるジ-（３−メチルベンゾイル）パーオキサイド（ナイパーＢＭＴ、日本油脂株式会社製商品名）、（３）光塩基発生剤として表１に示す化合物を用いた。またポリスチレンを核とする粒子の表面に、厚み０．２μｍのニッケル層を設け、このニッケル層の外側に、厚み０．０２μｍの金層を設け、平均粒径４μｍ、比重２．５の導電性粒子を作製した。
固形重量比で表１に示すように配合し、さらに導電性粒子を１．５体積％配合分散させ、厚み８０μｍのフッ素樹脂フィルムに塗工装置を用いて塗布し、７０℃、１０分の熱風乾燥によって接着剤層の厚みが２０μｍのフィルム状接着剤を得た。
(Examples 1-7, Comparative Examples 1-2)
As the thermoplastic resin, a phenoxy resin and a urethane resin were used. 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) was dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight. The urethane resin is uniformly mixed with 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone. Then, a urethane resin having a weight average molecular weight of 150,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used. (1) As radical polymerizable substances, isocyanuric acid EO-modified diacrylate (M-215, trade name manufactured by Toa Gosei Co., Ltd.), urethane acrylate (AT-600, trade name manufactured by Kyoeisha Chemical Co., Ltd.) and 2- (meth) Acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Co., Ltd.), (2) di- (3-methylbenzoyl) peroxide having a 10-hour half-life temperature of 73.1 ° C. as a radical polymerization initiator (Nyper BMT, Nippon Oil & Fats Co., Ltd. trade name), (3) The compounds shown in Table 1 were used as photobase generators. Further, a nickel layer having a thickness of 0.2 μm is provided on the surface of a particle having polystyrene as a nucleus, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer, and the conductive material has an average particle diameter of 4 μm and a specific gravity of 2.5. Particles were made.
It mix | blends as shown in Table 1 by solid weight ratio, Furthermore, 1.5 volume% of electroconductive particles are mix | blended and disperse | distributed, and it apply | coats to a 80-micrometer-thick fluororesin film using a coating device, 70 degreeC, hot air for 10 minutes A film adhesive having an adhesive layer thickness of 20 μm was obtained by drying.
ニフェジピン：ジメチル ２,６−ジメチル−４−（ｏ-ニトロフェニル）-１,４−ジヒドロ−３,５−ピリジンジカルボキシレート
Nifedipine: Dimethyl 2,6-dimethyl-4- (o-nitrophenyl) -1,4-dihydro-3,5-pyridinedicarboxylate
〔接着強度、接続抵抗の測定〕
上記製法によって得たフィルム状接着剤を用いて、ライン幅２５μｍ、ピッチ５０μｍ、厚み１８μｍの銅回路を５００本有するフレキシブル回路板（ＴＣＰ）と、０．２μｍの酸化インジウム（ＩＴＯ）の薄層を形成したガラス（厚み１．１ｍｍ、表面抵抗２０Ω／□）とを、熱圧着装置（加熱方式：コンスタントヒート型、東レエンジニアリング株式会社製）を用いて１３０℃の温度で３ＭＰａで１０秒間の加熱加圧を行って幅２ｍｍにわたり接続し、接続体を作製した。この時、あらかじめＩＴＯガラス上に、フィルム状回路接続材料の接着面を７０℃、１ＭＰａで３秒間加熱加圧して仮接続した後、フッ素樹脂フィルムを剥離し、回路接続用組成物からなるフィルム面に、高圧水銀ランプを有する紫外線照射装置（ウシオ電機株式会社製）を用いて１．０Ｊ／ｃｍ２の紫外線を照射した。その後、もう一方の被着体であるＦＰＣと接続し接続体を作製した。この接続体の隣接回路間の抵抗値を、接着直後と、８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した後にマルチメータで測定した。抵抗値は隣接回路間の抵抗３７点の平均で示した。
[Measurement of adhesive strength and connection resistance]
Using the film-like adhesive obtained by the above manufacturing method, a flexible circuit board (TCP) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a thin layer of indium oxide (ITO) of 0.2 μm The formed glass (thickness 1.1 mm, surface resistance 20 Ω / □) is heated with a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) at a temperature of 130 ° C. and 3 MPa for 10 seconds. The connection was made by applying pressure and connecting over a width of 2 mm. At this time, the adhesive surface of the film-like circuit connecting material is preliminarily connected to the ITO glass by heating and pressurizing at 70 ° C. and 1 MPa for 3 seconds, and then the fluororesin film is peeled off to form a film surface comprising the circuit connecting composition. The sample was irradiated with 1.0 J / cm 2 of ultraviolet rays using an ultraviolet irradiation device (manufactured by USHIO INC.) Having a high-pressure mercury lamp. Then, it connected with FPC which is another to-be-adhered body, and produced the connection body. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 168 hours. The resistance value was shown as an average of 37 resistances between adjacent circuits.
また、この接続体の接着強度をＪＩＳ−Ｚ０２３７に準じて９０度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンＵＴＭ−４（剥離速度５０ｍｍ／ｍｉｎ、２５℃）を使用した。 Moreover, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength.
以上のようにして行った接続体の接着強度、接続抵抗の測定の結果を表２に示した。 Table 2 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.
実施例１〜７で得られた接着剤組成物は、加熱温度１３０℃において、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した後で、良好な接続抵抗及び接着強度を示し、良好な特性を示すことが分かった。本発明における光塩基は発生剤を使用しない比較例１では、接着直後の接続抵抗値が高く、８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した場合には、急激な接続抵抗の上昇がみられた。また、接着力についても実施例１〜７と比較して低下し、本発明の光塩基発剤を用いることで、低温硬化性と高い信頼性を確保できることが明らかになった。 The adhesive compositions obtained in Examples 1-7 had good connection resistance and adhesion at a heating temperature of 130 ° C. immediately after adhesion and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 168 hours. It was found to show strength and good properties. In Comparative Example 1 in which the photobase in the present invention does not use a generator, the connection resistance value immediately after bonding is high. The rise of was seen. Moreover, it became clear that adhesive force also fell compared with Examples 1-7, and low temperature curability and high reliability are securable by using the photobase generator of this invention.
（比較例２）
実施例４で得られたフィルム状接着剤の接続体作製の際に、紫外線照射を省略した以外は実施例４と同様にＴＣＰとＩＴＯとを１３０℃、３ＭＰa、１０sで加熱圧着した。以上のようにして得られた接続体の接着強度、接続抵抗を測定したところ、接続抵抗は４．６Ω、接着強度は１５０Ｎ/ｍを示し、接続抵抗、接着強度とも紫外線照射を行った実施例４と比較して悪化した。
(Comparative Example 2)
TCP and ITO were thermocompression bonded at 130 ° C., 3 MPa, and 10 s in the same manner as in Example 4 except that ultraviolet irradiation was omitted when the film adhesive obtained in Example 4 was produced. The connection strength and connection resistance of the connection body obtained as described above were measured. The connection resistance was 4.6Ω and the bond strength was 150 N / m. Both the connection resistance and the bond strength were irradiated with ultraviolet rays. Compared to 4, it worsened.
（実施例８）
実施例１で得られたフィルム状接着剤を、真空包装を施して、４０℃で３日間放置した後、実施例１と同様にＴＣＰとＩＴＯとを１３０℃、３ＭＰa、１０sで加熱圧着を行った。以上のようにして行った接続体の接着強度、接続抵抗を測定したところ、接着強度は７８０Ｎ/ｍ、接続抵抗は１.５Ωを示し、放置安定性に優れることが分かった。
(Example 8)
The film adhesive obtained in Example 1 was vacuum packaged and allowed to stand at 40 ° C. for 3 days, and then TCP and ITO were thermocompression bonded at 130 ° C., 3 MPa, and 10 s as in Example 1. It was. When the adhesion strength and connection resistance of the connection body as described above were measured, it was found that the adhesion strength was 780 N / m, the connection resistance was 1.5Ω, and the storage stability was excellent.
（比較例３）
比較例１のラジカル重合開始剤を１０時間半減期温度が４０．３℃であるジ-ｎ-プロピルパーオキシジカーボネート（パーロイルＮＰＰ、日本油脂株式会社製商品名）に変更した以外は、比較例１と同様にフィルム状接着剤を作成し、真空包装を施して、４０℃で３日間放置した後、放置前後のフィルム状接着剤を実施例１と同様にＴＣＰとＩＴＯとを１３０℃、３ＭＰa、１０sで加熱圧着を行った。以上のようにして行った接続体の接着強度、接続抵抗の測定の結果を表３に示した。
(Comparative Example 3)
Comparative Example 1 except that the radical polymerization initiator of Comparative Example 1 was changed to di-n-propyl peroxydicarbonate (Perroyl NPP, product name manufactured by NOF Corporation) having a 10-hour half-life temperature of 40.3 ° C. A film-like adhesive was prepared in the same manner as in No. 1, vacuum-packed, and allowed to stand at 40 ° C. for 3 days. Then, the film-like adhesive before and after being left was treated with TCP and ITO at 130 ° C. and 3 MPa as in Example 1. Thermocompression bonding was performed in 10 seconds. Table 3 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.
比較例３のフィルム状接着剤は、放置前は接続抵抗、接着強度とも良好な特性を示したものの、４０℃で３日放置後は抵抗が上昇し、かつ接着強度は低下した。この結果から、４０℃放置中に硬化が進行し、放置安定性に劣ることが分かった。 Although the film-like adhesive of Comparative Example 3 exhibited good characteristics in both connection resistance and adhesive strength before standing, the resistance increased and the adhesive strength decreased after standing at 40 ° C. for 3 days. From this result, it was found that the curing progressed during standing at 40 ° C., and the standing stability was poor.
本発明の回路接続材料は、電気・電子用の異方性接着剤等として、幅広く使用できる
The circuit connection material of the present invention can be widely used as an anisotropic adhesive for electrical and electronic use.
Claims (5)
（１）アクリロイル基またはメタクリロイル基を分子内に２つ以上有する化合物であるラジカル重合性物質
（２）過酸化物またはアゾ化合物であるラジカル重合開始剤
（３）光照射によって塩基を発生する光塩基発生剤
を含有する回路接続材料であって、
前記光塩基発生剤がカルバミン酸エステル誘導体、オキシムエステル誘導体、アミンイミド誘導体、イミダゾリウム塩誘導体、４級アンモニウム塩誘導体、α−アミノケトン誘導体、ニフェジピン誘導体からなる群より選ばれる一以上の化合物であり、
さらに、前記回路接続材料が熱可塑性樹脂を含有し、
前記熱可塑性樹脂がフェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂から選ばれる前記回路接続材料。 A circuit connection material that is interposed between circuit electrodes facing each other, pressurizes the circuit electrodes facing each other, and electrically connects only the electrodes in the pressurizing direction, and includes the following components (1) to (3) :
(1) Radical polymerizable substance that is a compound having two or more acryloyl groups or methacryloyl groups in the molecule (2) Radical polymerization initiator that is a peroxide or azo compound (3) A photobase that generates a base by light irradiation Generating agent
A circuit connection material containing
The photobase generator is one or more compounds selected from the group consisting of carbamic acid ester derivatives, oxime ester derivatives, amine imide derivatives, imidazolium salt derivatives, quaternary ammonium salt derivatives, α-aminoketone derivatives, nifedipine derivatives,
Furthermore, the circuit connecting material contains a thermoplastic resin,
The circuit connecting material, wherein the thermoplastic resin is selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, and acrylic resin.
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| CN107078071A (en) * | 2015-01-20 | 2017-08-18 | 迪睿合株式会社 | The manufacture method of connector, the connection method of electronic unit, connector |
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| US20080292801A1 (en) * | 2007-05-23 | 2008-11-27 | National Starch And Chemical Investment Holding Corporation | Corrosion-Preventive Adhesive Compositions |
| JP5428860B2 (en) * | 2007-09-25 | 2014-02-26 | 株式会社スリーボンド | Anaerobic curable composition |
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| JP2002167569A (en) * | 2000-11-29 | 2002-06-11 | Hitachi Chem Co Ltd | Adhesive composition, adhesive composition for connecting circuit, connected unit and semiconductor device |
| JP3728752B2 (en) * | 2003-03-19 | 2005-12-21 | 荒川化学工業株式会社 | Curable composition and cured product thereof |
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| CN107078071A (en) * | 2015-01-20 | 2017-08-18 | 迪睿合株式会社 | The manufacture method of connector, the connection method of electronic unit, connector |
| CN107078071B (en) * | 2015-01-20 | 2020-03-03 | 迪睿合株式会社 | Method for manufacturing connected body, method for connecting electronic component, and connected body |
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