JP4144998B2 - Material for heat dissipation - Google Patents
Material for heat dissipation Download PDFInfo
- Publication number
- JP4144998B2 JP4144998B2 JP2000190875A JP2000190875A JP4144998B2 JP 4144998 B2 JP4144998 B2 JP 4144998B2 JP 2000190875 A JP2000190875 A JP 2000190875A JP 2000190875 A JP2000190875 A JP 2000190875A JP 4144998 B2 JP4144998 B2 JP 4144998B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- weight
- organopolysiloxane
- parts
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、発熱性部品に発生した熱を放熱するために使用される放熱用シート等の放熱用部材に関する。
【０００２】
【従来の技術】
従来、パワートランジスタ、サイリスタ等の発熱性部品は、発生する熱により特性が低下するので、その対策として、該部品を機器に設置する際、ヒートシンクを取り付けて熱を放散させたり、機器の金属製シャーシに熱を逃がすなどの方法が採られている。これらの方法のうち、ヒートシンクを取り付けて熱を放散させる方法では、発熱性部品の電気絶縁性と熱伝導性を向上させるため、発熱性部品とヒートシンクの間に、放熱用部材として、放熱絶縁性材料からなる放熱絶縁性シートが挿填される。
この放熱絶縁性材料としては、シリコーンゴム等に熱伝導性充填剤を配合したものが使用され、例えば、シリコーンゴム等の合成ゴム１００重量部に、酸化ベリリウム、酸化アルミニウム、水和酸化アルミニウム、酸化マグネシウム、酸化亜鉛から選ばれる少なくとも１種以上の金属酸化物を１００〜８００重量部配合した絶縁性組成物が開示されている（特開昭４７−３２４００号公報参照）。
また、電気絶縁性を必要としない場所に用いられる放熱用部材の場合、それを構成する放熱材料としては、付加硬化型シリコーンゴム１００重量部に、シリカ及び銀、金、ケイ素等の熱伝導性粉末を６０〜５００重量部配合した組成物が開示されている（特開昭５６−１００８４９号公報参照）。
しかしながら、これらの放熱材料は、いずれも熱伝導率が１．５Ｗ／ｍ・Ｋより低く、熱伝導性を向上させるために熱伝導性充填剤を多量に配合すると、液状シリコーンゴム組成物の場合は流動性が低下し、ミラブルタイプのシリコーンゴム組成物の場合は可塑度が増加して、いずれも成形加工性が非常に悪くなるという問題があった。
そこで、この問題を解決する方法として、平均粒径５μｍ以下のアルミナ粒子１０〜３０重量%と、残部が平均粒径１０μｍ以上の単一粒子であり、かつ、カッティングエッジを有しない形状である球状コランダム粒子からなるアルミナを配合した高熱伝導性ゴム・プラスチック組成物が開示されている（特開平１−６９６６１号公報参照）。また、平均重合度６，０００〜１２，０００のガム状のオルガノポリシロキサンと平均重合度２００〜２，０００のオイル状のオルガノポリシロキサンを併用したベースと、球状酸化アルミニウム粉末５００〜１，２００重量部からなる熱伝導性シリコーンゴム組成物が開示されている（特開平４−３２８１６３号公報）。
【０００３】
【発明が解決しようとする課題】
しかしながら、これらの組成物を用いても、熱伝導性が不十分であり、また、得られる放熱用部材が硬すぎて熱抵抗が大きくなるため、実際の放熱性は不十分であった。
一方、パーソナルコンピューター、ワードプロセッサ、ＣＤ−ＲＯＭドライブ等の電子機器では、高集積化が進み、該電子機器内にあるＬＳＩ、ＣＰＵ等の集積回路素子の発熱量が増加したため、従来の冷却方法では不十分な場合がある。特に、携帯用のノート型パーソナルコンピューターの場合、その内部空間が狭いため、大きなヒートシンクや冷却ファンを取り付けることができない。
また、上記した電子機器では、プリント基板上に集積回路素子が搭載されているが、該基板の材質には、熱伝導性の悪いガラス補強エポキシ樹脂やポリイミド樹脂が用いられているので、従来のように放熱絶縁シートを介して該基板から熱を逃がすことができない。
そこで、これらを解決する方法として、集積回路素子の近傍に自然冷却タイプ或いは強制冷却タイプの放熱用部材を設置して、集積回路素子で発生した熱を放熱用部材に伝えて放熱する方法が採られている。しかし、この方法により集積回路素子と放熱用部材を直接接触させると、該素子の表面に凹凸があり、放熱用部材の柔軟性に欠けるため、接触が不十分となり、熱の伝導性が悪い。
また、放熱絶縁シートを介して集積回路素子をプリント基板に取り付けても、放熱絶縁シートの柔軟性がやや劣るため、熱膨張により該素子とプリント基板との間に応力がかかり、これらを破損する恐れがある。
一方、各集積回路素子ごとに放熱用部材を取り付けようとすると、余分なスペースが必要となり、機器の小型化が難しくなるので、いくつかの集積回路素子を１つの放熱用部材に組み合わせて冷却する方法が採られることもある。
特にノート型のパーソナルコンピューターで用いられているＢＧＡタイプのＣＰＵは、高さが他の集積回路素子に比べて低く、発熱量が大きいため、冷却方法を十分考慮する必要がある。この場合、集積回路素子ごとに高さが異なることによって生じる種々の隙間を埋めることができる低硬度の放熱用部材が必要になる。
すなわち、このような状況に対して、熱伝導性に優れ、柔軟性があり、種々の隙間に対応することができる低硬度の放熱用部材、特に放熱用シートが要望される。
また、年々、駆動周波数の高周波化に伴い、ＣＰＵの性能が向上して発熱量が増大しているため、より高熱伝導性の放熱用部材が求められている。
そこで、本発明は、熱伝導性に非常に優れると共に、柔軟性を有するため、優れた放熱性を与える放熱用部材を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、オルガノポリシロキサンに対して熱伝導性充填剤を所定量配合したオルガノポリシロキサン組成物の硬化物が、熱伝導性に非常に優れると共に、柔軟性を有し、実用上優れた放熱性を示すことを見出し、かかる知見に基づき、本発明を完成するに至った。
すなわち、本発明は、オルガノポリシロキサン１００重量部に対して、熱伝導性充填剤を少なくとも１，０００重量部配合したオルガノポリシロキサン組成物の硬化物であって、熱伝導率が５Ｗ／ｍ・Ｋ以上であり、デュロメータＡによる硬度が８０以下であることを特徴とする放熱用部材である。
【０００５】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の放熱用部材は、前記したように、オルガノポリシロキサン１００重量部に対して、熱伝導性充填剤を少なくとも１，０００重量部充填したオルガノポリシロキサン組成物の硬化物であって、該硬化物の熱伝導率が５Ｗ／ｍ・Ｋ以上であり、デュロメータＡによる硬度が８０以下であることを特徴とする。かかる特徴を有することにより、熱伝導性が非常に優れると共に柔軟性を有する放熱用部材が得られるという優れた効果を奏する。
本発明の放熱用部材を構成するオルガノポリシロキサン組成物は、オルガノポリシロキサン１００重量部に対して、熱伝導性充填剤を少なくとも１，０００重量部、好ましくは１，０００〜３，０００重量部、特に好ましくは１，３００〜２，５００重量部配合したものである。熱伝導性充填剤が１，０００重量部より少ないと、良好な熱伝導性を得ることができない。また、熱伝導性充填剤が３，０００重量部を超えると配合が困難となることがある。
オルガノポリシロキサンは、上記組成物として硬化性を有するものであれば、オイル状、ガム状のいずれでもよく、また、構造や重合度の異なる２種以上を組み合わせてもよい。市販のシリコーンゲルや低硬度タイプのシリコーンゴム組成物から選択してもよい。
【０００６】
熱伝導性充填剤としては、熱伝導性を有する各種充填剤を使用することができ、無機粉末、金属粉末等が好適である。具体的には、酸化アルミニウム、酸化亜鉛、酸化ケイ素、炭化ケイ素、窒化ケイ素、酸化マグネシウム、窒化アルミニウム、窒化ホウ素、グラファイト等の無機粉末、アルミニウム、銅、銀、ニッケル、鉄、ステンレス等の金属粉末などが例示される。これらの中でも、特には酸化アルミニウム、酸化亜鉛、酸化ケイ素、炭化ケイ素、窒化ケイ素、酸化マグネシウム及びグラファイトから選ばれる無機粉末、アルミニウム、銅、銀、ニッケル、鉄及びステンレスから選ばれる金属粉末が好適に使用される。なお、熱伝導性充填剤としては、上記無機粉末又は金属粉末の１種又は２種以上を組み合わせて用いてもよい。
【０００７】
熱伝導性充填剤は、平均粒径が５０μｍ以下、好ましくは０．１〜４０μｍ、特に好ましくは０．５〜３０μｍである。平均粒径が５０μｍよりも大きいと分散性が悪くなり、液状シリコーンゴムの場合、放置しておくと熱伝導性充填剤が沈降してしまう場合がある。
本発明の放熱用部材は、平均粒径の異なる２種以上の熱伝導性充填剤を使用することが好ましい。特に平均粒径５〜４０μｍである熱伝導性充填剤と平均粒径０．１〜３μｍである熱伝導性充填剤を組み合わせることが好ましい。これにより充填効率が向上し、より高充填が可能となり、より高熱伝導化することができる。
また、上記と同様の効果を得るために、球状の熱伝導性充填剤を配合することが好ましい。具体的な球状の熱伝導性充填剤としては、球状アルミナＡＳシリーズ（昭和電工社製、商品名）、高純度球状アルミナＡＯシリーズ（アドマテックス社製、商品名）等が挙げられる。
【０００８】
本発明の放熱用部材には、必要に応じて、カーボンブラック補強性シリカ、着色剤、酸化鉄、酸化セリウム等の耐熱性向上剤、白金化合物、酸化チタン、ベンゾトリアゾール等の難燃性向上剤、分散剤、接着助剤等の任意成分を配合してもよい。
【０００９】
本発明の放熱用部材は、デュロメータＡにより測定される硬度が８０以下であることが必要である。そのため、熱伝導性充填剤の種類や配合量等を適宜調節することにより、デュロメータＡによる硬度が８０以下、好ましくは５０以下となるように、架橋密度を選択する必要がある。デュロメータＡによる硬度が８０を超えると、本発明の放熱用部材が目的とする柔軟性を得ることができない。硬度の下限は、特に制限されないが、アスカーＣ硬度計により測定されるアスカーＣ硬度が１０以上であることが好ましい。アスカーＣ硬度が１０より小さいと放熱用部材の強度が弱くなることがある。特に低硬度が必要な場合はアスカーＣ硬度が１０〜９０、特には２０〜８０であることが好ましい。
また、本発明の放熱用部材は、熱伝導率が５Ｗ／ｍ・Ｋ以上であり、特には７Ｗ／ｍ・Ｋ以上であることが好ましい。熱伝導率が５Ｗ／ｍ・Ｋ未満であると放熱性が不十分となることがある。なお、熱伝導率の測定は、熱伝導率計（例えば、商品名：Ｓｈｏｔｈｅｒｍ ＱＴＭ迅速熱伝導率計、昭和電工社製）を使用して行えばよい。
【００１０】
次に、本発明の放熱用部材の製造方法について述べる。
まず、前記した所定量のオルガノポリシロキサンと熱伝導性充填剤を、二本ロール、ニーダー、バンバリーミキサー等の混合機を用いて混合し、オルガノポリシロキサン組成物を調製する。前記したように、オルガノポリシロキサン組成物には、必要に応じてカーボンブラック補強性シリカ、着色剤、酸化鉄、酸化セリウム等の耐熱性向上剤、白金化合物、酸化チタン、ベンゾトリアゾール等の難燃性向上剤、接着助剤等の任意成分を配合する。なお、これら任意成分の配合量は、本発明の効果を妨げない範囲であればよい。また、オルガノポリシロキサン組成物は必要に応じて、熱処理をしてもよい。
【００１１】
オルガノポリシロキサン組成物を調製した後、これを硬化、成形することにより、本発明の放熱用部材が得られる。
オルガノポリシロキサン組成物の硬化は、付加反応による硬化、縮合反応による硬化、有機過酸化物による硬化、光による硬化等、特に制限されないが、付加反応による硬化、有機過酸化物による硬化が好ましく、特に、架橋密度のコントロールが容易で、低硬度化しやすい点から、付加反応による硬化が好ましい。
付加反応による硬化は、オルガノポリシロキサンがアルケニル基を２個以上有する場合に適用され、硬化剤としてはケイ素原子に結合した水素原子を１分子中に２個以上含有するオルガノハイドロジェンポリシロキサンと白金族系触媒からなる付加反応型硬化剤が挙げられる。この場合、架橋剤であるオルガノハイドロジェンポリシロキサンは、１分子中にケイ素原子に直接結合している水素原子を２個以上含んでいる直鎖状、分岐状又は環状の分子からなるものであり、２５℃における粘度が１〜１，０００ｍｍ2／ｓの範囲であることが好ましい。オルガノハイドロジェンポリシロキサンの添加量は、オルガノポリシロキサンのアルケニル基１個に対して、オルガノハイドロジェンポリシロキサン中のＳｉＨ基が通常０．０５〜３当量、特に０．１〜２当量となる範囲が好適である。この添加量が０．０５当量より少ない場合は、架橋密度が低くなりすぎて、硬化したオルガノポリシロキサン組成物の硬度が低下し、成形及び取扱いが難しくなる。一方、３当量より多い場合は、硬化したオルガノポリシロキサン組成物の硬度が高くなりすぎることがある。
また、白金族系触媒としては、公知の白金金属又は白金化合物が好ましく、その添加量は、白金族金属として０．１〜１，０００ｐｐｍ、好ましくは１〜５００ｐｐｍである。更に制御剤を用いてもよい。
【００１２】
有機過酸化物による硬化の場合は、有機過酸化物として、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ジクミルパーオキサイド等のラジカル反応に使用される有機過酸化物が例示される。有機過酸化物の添加量は、オルガノポリシロキサン１００重量部に対して、０．１〜１０重量部、特に０．２〜５重量部である。
【００１３】
上記オルガノポリシロキサン組成物の硬化、成形方法は、オルガノポリシロキサンが液状タイプであるか、又はミラブルタイプであるかに応じて、下記方法より適宜選択する。具体的には、▲１▼金型中に未硬化のオルガノポリシロキサン組成物を仕込み、金型を締めてから熱プレス機により圧力と熱をかけ、該組成物を硬化させるモールド成形、▲２▼射出成形機上の加熱した金型の中に、ノズルから未硬化のオルガノポリシロキサン組成物を射出して金型のキャビティ内に充填し、硬化後金型を開け、成形品を取り出す射出成形、▲３▼コーティング装置に連続的にフィルム（例えば、ポリエチレンテレフタレート）を供給し、この上に未硬化の液状オルガノポリシロキサン組成物を、ナイフコータ等により一定の厚さに塗布してから、加熱炉を通して該液状組成物を硬化させるコーティング成形、▲４▼押出機のダイスとニップルの組み合わせにより、未硬化のミラブルタイプのオルガノポリシロキサン組成物を任意のチューブ形状に成形してから、加熱炉を通して該組成物を硬化させる押出成形、▲５▼カレンダーロールにより未硬化のオルガノポリシロキサン組成物を一定の厚さに分出しし、フィルム上に該組成物を転写してから加熱炉を通して組成物を硬化させるカレンダー成形が挙げられる。
硬化条件は、成形方法に応じて適宜調整することが好ましいが、１００〜４００℃で２秒〜３０分が好適である。
【００１４】
本発明の放熱用部材の態様として、放熱用シリコーンゴムシートが挙げられる。放熱用シリコーンゴムシートを作製する場合、その内部にガラスクロス、ポリエステル、ナイロン等からなるクロス或いは不織布、ポリイミド、ナイロン、ポリエステル等からなる樹脂フィルム等を入れて補強してもよい。これにより該シートの強度が向上すると共に、伸びが抑制されるので、取扱いやすくなり作業性が向上する。
【００１５】
【実施例】
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００１６】
（実施例１）
２５℃における粘度が３０，０００ｃｓで両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン１５重量部、２５℃における粘度が６００ｃｓで両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン５０重量部、２５℃における粘度が３００ｃｓで両末端がトリメチルシロキシ基で封鎖されたジメチルポリシロキサン１５重量部、片末端がトリメトキシ基で封鎖され、他方の片末端がトリメチルシロキシ基で封鎖された重合度が３１であるジメチルポリシロキサン３０重量部に、平均粒径１０μｍの球状アルミナＡＯ−４１Ｒ（アドマテックス社製、商品名）１，２００重量部、平均粒径０．７μｍの球状アルミナＡＯ−５０Ｚ（アドマテックス社製、商品名）２００重量部を配合し、オルガノポリシロキサン組成物を得た。
次に、触媒として塩化白金酸のビニルシロキサン錯体（白金含有量１％）０．３５重量部、硬化剤として２５℃における粘度が１８ｃｓのメチルハイドロジェンポリシロキサン（ＳｉＨ０．００３１モル／ｇ）３．６重量部を均一に混合した。
そして、得られた混合物をモールド成形により１５０℃で１０分間加熱して、厚さ６ｍｍのシートを作製し、アスカーＣ硬度計で硬度を測定した。また、厚さ２０ｍｍのブロック体をモールド成形で作製し、熱伝導率計（商品名：Ｓｈｏｔｈｅｒｍ ＱＴＭ迅速熱伝導率計、昭和電工社製）を使用して熱伝導率を測定した。その結果、アスカーＣ硬度は２５であり、熱伝導率は５．５Ｗ／ｍ・Ｋであった。実施例１の放熱用部材は、このように熱伝導性に優れ、非常に低硬度であるため、電子部品との密着性も良好であり、優れた放熱性を有する。
【００１７】
（実施例２）
２５℃における粘度が３０，０００ｃｓで両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン３０重量部、２５℃における粘度が６００ｃｓで両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン４０重量部、片末端がトリメトキシシロキシ基で封鎖され、他方の片末端がトリメチルシロキシ基で封鎖された重合度が３１であるジメチルポリシロキサン６０重量部に、ＡＯ−４１Ｒ（前出）２，０００重量部、ＡＯ−５０Ｚ（前出）５００重量部を配合し、オルガノポリシロキサン組成物を得た。そして、実施例１と同様の方法、条件でアスカーＣ硬度と熱伝導率を測定した。その結果、アスカーＣ硬度は５５であり、熱伝導率は１０Ｗ／ｍ・Ｋであった。実施例２の放熱用部材は、このように熱伝導性に優れ、非常に低硬度であるため、電子部品との密着性も良好であり、優れた放熱性を有する。
【００１８】
【発明の効果】
本発明によれば、熱伝導性に非常に優れると共に、柔軟性を有する実用上優れた放熱性をもつ放熱用部材が得られる。また、アスカーＣ硬度で測定できるような低硬度化も可能であり、電子部品との密着性もよく、効率よく放熱することができる。
本発明の放熱用部材は、一般の電源、電子機器等に用いられる放熱用部材、特に放熱シート及びパーソナルコンピューター、ワードプロセッサ、ＣＤ−ＲＯＭドライブ等の電子機器のＬＳＩ、ＣＰＵ等の集積回路素子の放熱に用いる低硬度放熱性シリコーンゴムシート等として最適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat dissipation member such as a heat dissipation sheet used to dissipate heat generated in a heat-generating component.
[0002]
[Prior art]
Conventionally, the characteristics of heat-generating parts such as power transistors and thyristors deteriorate due to the generated heat. As a countermeasure, heat sinks can be attached to dissipate heat when the parts are installed in equipment. Methods such as releasing heat to the chassis are used. Of these methods, the method of dissipating heat by attaching a heat sink improves the electrical insulation and thermal conductivity of the heat-generating component. A heat dissipation insulating sheet made of material is inserted.
As this heat insulating insulating material, a silicone rubber or the like blended with a heat conductive filler is used. For example, 100 parts by weight of a synthetic rubber such as silicone rubber is mixed with beryllium oxide, aluminum oxide, hydrated aluminum oxide, oxidized An insulating composition containing 100 to 800 parts by weight of at least one metal oxide selected from magnesium and zinc oxide is disclosed (see JP-A-47-32400).
In addition, in the case of a heat radiating member used in a place that does not require electrical insulation, the heat radiating material constituting the heat radiating material includes 100 parts by weight of addition-curable silicone rubber, heat conductivity of silica, silver, gold, silicon, or the like. A composition containing 60 to 500 parts by weight of powder is disclosed (see JP-A-56-100849).
However, all of these heat dissipation materials have a thermal conductivity lower than 1.5 W / m · K, and in the case of a liquid silicone rubber composition when a large amount of a thermally conductive filler is blended in order to improve thermal conductivity. In the case of a millable type silicone rubber composition, there is a problem that the plasticity increases and the moldability becomes very poor.
Therefore, as a method for solving this problem, 10 to 30% by weight of alumina particles having an average particle diameter of 5 μm or less, and the remaining spherical particles having a shape having no cutting edge and a single particle having an average particle diameter of 10 μm or more. A highly heat-conductive rubber / plastic composition containing alumina composed of corundum particles is disclosed (see JP-A-1-69661). Further, a base in which a gum-like organopolysiloxane having an average degree of polymerization of 6,000 to 12,000 and an oily organopolysiloxane having an average degree of polymerization of 200 to 2,000 are used together, and spherical aluminum oxide powders 500 to 1,200. A thermally conductive silicone rubber composition comprising parts by weight is disclosed (Japanese Patent Laid-Open No. 4-328163).
[0003]
[Problems to be solved by the invention]
However, even when these compositions are used, the thermal conductivity is insufficient, and the obtained heat radiating member is too hard to increase the thermal resistance, so that the actual heat radiating property is insufficient.
On the other hand, electronic devices such as personal computers, word processors, and CD-ROM drives have been highly integrated, and the amount of heat generated by integrated circuit elements such as LSIs and CPUs in the electronic devices has increased. It may be enough. In particular, in the case of a portable notebook personal computer, a large heat sink or cooling fan cannot be attached because its internal space is narrow.
Further, in the above-described electronic device, an integrated circuit element is mounted on a printed circuit board, but a glass-reinforced epoxy resin or polyimide resin having poor thermal conductivity is used as the material of the circuit board. Thus, heat cannot be released from the substrate via the heat dissipation insulating sheet.
Therefore, as a method for solving these problems, a natural cooling type or forced cooling type heat radiation member is installed in the vicinity of the integrated circuit element, and the heat generated in the integrated circuit element is transmitted to the heat radiation member to dissipate the heat. It has been. However, when the integrated circuit element and the heat radiating member are brought into direct contact by this method, the surface of the element has irregularities and the heat radiating member lacks flexibility, so that the contact becomes insufficient and the heat conductivity is poor.
In addition, even if the integrated circuit element is attached to the printed circuit board through the heat insulating sheet, the heat insulating sheet is slightly inflexible, so that stress is applied between the element and the printed circuit board due to thermal expansion, and these elements are damaged. There is a fear.
On the other hand, if an attempt is made to attach a heat dissipation member for each integrated circuit element, extra space is required and it becomes difficult to reduce the size of the device. Therefore, several integrated circuit elements are combined into one heat dissipation member for cooling. A method may be taken.
In particular, a BGA type CPU used in a notebook personal computer has a height lower than that of other integrated circuit elements and a large amount of heat generation, so that a cooling method needs to be sufficiently considered. In this case, a low-heat-dissipating member that can fill various gaps caused by different heights for each integrated circuit element is required.
That is, for such a situation, there is a demand for a low-heat radiation member, particularly a heat radiation sheet, which has excellent thermal conductivity and flexibility and can cope with various gaps.
In addition, with the increase in driving frequency year by year, the CPU performance is improved and the amount of heat generation is increased, so that a heat radiating member with higher thermal conductivity is required.
Accordingly, an object of the present invention is to provide a heat dissipating member that provides excellent heat dissipation because it has excellent thermal conductivity and flexibility.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor has found that a cured product of an organopolysiloxane composition in which a predetermined amount of a thermally conductive filler is blended with an organopolysiloxane has a very high thermal conductivity. The present inventors have found that it has excellent flexibility and practically excellent heat dissipation, and has completed the present invention based on such knowledge.
That is, the present invention is a cured product of an organopolysiloxane composition in which at least 1,000 parts by weight of a thermally conductive filler is blended with 100 parts by weight of an organopolysiloxane, and has a thermal conductivity of 5 W / m · The heat dissipating member is characterized by having a hardness of K or higher and a durometer A hardness of 80 or lower.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
As described above, the heat dissipating member of the present invention is a cured product of an organopolysiloxane composition in which at least 1,000 parts by weight of a heat conductive filler is filled with respect to 100 parts by weight of organopolysiloxane, The cured product has a thermal conductivity of 5 W / m · K or more and a durometer A hardness of 80 or less. By having such a feature, there is an excellent effect that a heat radiating member having excellent heat conductivity and flexibility can be obtained.
The organopolysiloxane composition constituting the heat dissipating member of the present invention is at least 1,000 parts by weight, preferably 1,000 to 3,000 parts by weight of the thermally conductive filler with respect to 100 parts by weight of the organopolysiloxane. Particularly preferred is a blend of 1,300 to 2,500 parts by weight. When the heat conductive filler is less than 1,000 parts by weight, good heat conductivity cannot be obtained. Moreover, when the heat conductive filler exceeds 3,000 parts by weight, blending may be difficult.
The organopolysiloxane may be in the form of an oil or a gum as long as it has curability as the above composition, and may be a combination of two or more different structures and polymerization degrees. You may select from a commercially available silicone gel or a low hardness type silicone rubber composition.
[0006]
As the thermally conductive filler, various fillers having thermal conductivity can be used, and inorganic powder, metal powder, and the like are preferable. Specifically, inorganic powders such as aluminum oxide, zinc oxide, silicon oxide, silicon carbide, silicon nitride, magnesium oxide, aluminum nitride, boron nitride and graphite, metal powders such as aluminum, copper, silver, nickel, iron and stainless steel Etc. are exemplified. Among these, in particular, an inorganic powder selected from aluminum oxide, zinc oxide, silicon oxide, silicon carbide, silicon nitride, magnesium oxide and graphite, and a metal powder selected from aluminum, copper, silver, nickel, iron and stainless steel are preferable. used. In addition, as a heat conductive filler, you may use 1 type or 2 types or more in combination of the said inorganic powder or metal powder.
[0007]
The heat conductive filler has an average particle size of 50 μm or less, preferably 0.1 to 40 μm, particularly preferably 0.5 to 30 μm. When the average particle size is larger than 50 μm, the dispersibility is deteriorated. In the case of a liquid silicone rubber, the heat conductive filler may settle if left untreated.
The heat radiating member of the present invention preferably uses two or more kinds of thermally conductive fillers having different average particle diameters. It is particularly preferable to combine a thermally conductive filler having an average particle diameter of 5 to 40 μm with a thermally conductive filler having an average particle diameter of 0.1 to 3 μm. Thereby, the filling efficiency is improved, higher filling is possible, and higher thermal conductivity can be achieved.
Moreover, in order to acquire the effect similar to the above, it is preferable to mix | blend a spherical heat conductive filler. Specific spherical heat conductive fillers include spherical alumina AS series (made by Showa Denko, trade name), high-purity spherical alumina AO series (made by Admatechs, trade name), and the like.
[0008]
In the heat radiating member of the present invention, if necessary, heat resistance improver such as carbon black reinforcing silica, colorant, iron oxide, cerium oxide, and flame retardant improver such as platinum compound, titanium oxide, benzotriazole Further, optional components such as a dispersant and an adhesion aid may be blended.
[0009]
The heat radiating member of the present invention is required to have a hardness measured by durometer A of 80 or less. Therefore, it is necessary to select a crosslinking density so that the hardness by durometer A is 80 or less, preferably 50 or less, by appropriately adjusting the type and blending amount of the heat conductive filler. When the hardness by durometer A exceeds 80, the intended flexibility of the heat radiating member of the present invention cannot be obtained. The lower limit of the hardness is not particularly limited, but the Asker C hardness measured by an Asker C hardness meter is preferably 10 or more. If the Asker C hardness is less than 10, the strength of the heat radiating member may be weakened. In particular, when low hardness is required, the Asker C hardness is preferably 10 to 90, particularly 20 to 80.
The heat radiating member of the present invention has a thermal conductivity of 5 W / m · K or more, and particularly preferably 7 W / m · K or more. If the thermal conductivity is less than 5 W / m · K, the heat dissipation may be insufficient. The thermal conductivity may be measured using a thermal conductivity meter (for example, trade name: Shotherm QTM rapid thermal conductivity meter, manufactured by Showa Denko KK).
[0010]
Next, the manufacturing method of the member for heat dissipation of this invention is described.
First, the above-mentioned predetermined amount of organopolysiloxane and a thermally conductive filler are mixed using a mixer such as a two-roll, kneader or Banbury mixer to prepare an organopolysiloxane composition. As described above, the organopolysiloxane composition includes a carbon black reinforcing silica, a colorant, a heat resistance improver such as iron oxide and cerium oxide, a flame retardant such as a platinum compound, titanium oxide, and benzotriazole as necessary. An optional component such as a property improver and an adhesion aid is blended. In addition, the compounding quantity of these arbitrary components should just be a range which does not prevent the effect of this invention. Moreover, the organopolysiloxane composition may be heat-treated as necessary.
[0011]
After preparing the organopolysiloxane composition, it is cured and molded to obtain the heat radiating member of the present invention.
Curing of the organopolysiloxane composition is not particularly limited, such as curing by addition reaction, curing by condensation reaction, curing by organic peroxide, curing by light, etc., but curing by addition reaction, curing by organic peroxide is preferable, In particular, curing by addition reaction is preferable because the crosslinking density can be easily controlled and the hardness can be easily reduced.
Curing by addition reaction is applied when the organopolysiloxane has two or more alkenyl groups. As the curing agent, organohydrogenpolysiloxane and platinum containing two or more hydrogen atoms bonded to silicon atoms in one molecule. An addition reaction type curing agent comprising a group catalyst. In this case, the organohydrogenpolysiloxane as a cross-linking agent is composed of linear, branched or cyclic molecules containing two or more hydrogen atoms directly bonded to silicon atoms in one molecule. The viscosity at 25 ° C. is preferably in the range of 1 to 1,000 mm 2 / s. The addition amount of the organohydrogenpolysiloxane is usually within a range of 0.05 to 3 equivalents, particularly 0.1 to 2 equivalents of SiH groups in the organohydrogenpolysiloxane with respect to one alkenyl group of the organopolysiloxane. Is preferred. When this addition amount is less than 0.05 equivalent, the crosslinking density becomes too low, the hardness of the cured organopolysiloxane composition is lowered, and molding and handling become difficult. On the other hand, when it exceeds 3 equivalents, the hardness of the cured organopolysiloxane composition may be too high.
Moreover, as a platinum group-type catalyst, a well-known platinum metal or a platinum compound is preferable, and the addition amount is 0.1-1,000 ppm as a platinum group metal, Preferably it is 1-500 ppm. Further, a control agent may be used.
[0012]
In the case of curing with an organic peroxide, examples of the organic peroxide include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and dicumyl peroxide. Illustrative are organic peroxides used in radical reactions. The addition amount of the organic peroxide is 0.1 to 10 parts by weight, particularly 0.2 to 5 parts by weight with respect to 100 parts by weight of the organopolysiloxane.
[0013]
The method for curing and molding the organopolysiloxane composition is appropriately selected from the following methods depending on whether the organopolysiloxane is a liquid type or a millable type. Specifically, (1) Mold molding in which an uncured organopolysiloxane composition is charged into a mold, the mold is tightened, and pressure and heat are applied by a hot press to cure the composition. (2) ▼ Injection molding in which the uncured organopolysiloxane composition is injected from a nozzle into a heated mold on an injection molding machine, filled into the mold cavity, the mold is opened after curing, and the molded product is removed. (3) A film (for example, polyethylene terephthalate) is continuously supplied to the coating apparatus, and an uncured liquid organopolysiloxane composition is applied to the coating apparatus to a certain thickness with a knife coater or the like. (4) An uncured millable type organopolysiloxane composition by a combination of an extrusion die and a nipple. After forming into an arbitrary tube shape, extrusion molding in which the composition is cured through a heating furnace, (5) uncured organopolysiloxane composition is dispensed to a certain thickness by a calender roll, Examples include calendar molding in which the composition is transferred and then cured through a heating furnace.
The curing conditions are preferably adjusted as appropriate according to the molding method, but are preferably 100 to 400 ° C. and 2 seconds to 30 minutes.
[0014]
Examples of the heat dissipation member of the present invention include a heat dissipation silicone rubber sheet. When producing a heat-dissipating silicone rubber sheet, a cloth made of glass cloth, polyester, nylon or the like, or a non-woven cloth, a resin film made of polyimide, nylon, polyester, or the like may be put inside the sheet to be reinforced. As a result, the strength of the sheet is improved and the elongation is suppressed, so that handling becomes easier and workability is improved.
[0015]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0016]
(Example 1)
15 parts by weight of dimethylpolysiloxane having a viscosity at 25 ° C. of 30,000 cs and both ends blocked with dimethylvinylsiloxy groups, 50 weight of dimethylpolysiloxane having a viscosity at 25 ° C. of 600 cs and both ends blocked with dimethylvinylsiloxy groups 15 parts by weight of dimethylpolysiloxane having a viscosity at 25 ° C. of 300 cs and blocked at both ends with a trimethylsiloxy group, a degree of polymerization in which one end is blocked with a trimethoxy group and the other end is blocked with a trimethylsiloxy group 31 parts by weight of dimethylpolysiloxane 31 and 1,200 parts by weight of spherical alumina AO-41R (trade name, manufactured by Admatex Co., Ltd.) having an average particle diameter of 10 μm and spherical alumina AO-50Z having an average particle diameter of 0.7 μm Mattex Co., Ltd., trade name) 200 parts by weight, organopolysil A xanthan composition was obtained.
Next, 0.35 parts by weight of a vinyl siloxane complex of chloroplatinic acid (platinum content 1%) as a catalyst and methyl hydrogen polysiloxane (SiH 0.0031 mol / g) having a viscosity at 25 ° C. of 18 cs as a curing agent 6 parts by weight were mixed uniformly.
The obtained mixture was heated at 150 ° C. for 10 minutes by molding to produce a sheet having a thickness of 6 mm, and the hardness was measured with an Asker C hardness meter. Further, a block body having a thickness of 20 mm was produced by molding, and the thermal conductivity was measured using a thermal conductivity meter (trade name: Shotherm QTM rapid thermal conductivity meter, manufactured by Showa Denko KK). As a result, the Asker C hardness was 25, and the thermal conductivity was 5.5 W / m · K. The heat dissipating member of Example 1 is excellent in thermal conductivity and has a very low hardness as described above, and thus has good adhesion to an electronic component and has excellent heat dissipation.
[0017]
(Example 2)
30 parts by weight of dimethylpolysiloxane having a viscosity of 30,000 cs at 25 ° C. and both ends blocked with dimethylvinylsiloxy groups, 40 weight of dimethylpolysiloxane having a viscosity of 600 cs at 25 ° C. and both ends blocked with dimethylvinylsiloxy groups Part, 60 parts by weight of dimethylpolysiloxane having a degree of polymerization of 31 blocked at one end with a trimethoxysiloxy group and blocked at the other end with a trimethylsiloxy group, AO-41R (supra) 2,000 weight Part, AO-50Z (supra) 500 parts by weight was blended to obtain an organopolysiloxane composition. The Asker C hardness and thermal conductivity were measured under the same method and conditions as in Example 1. As a result, the Asker C hardness was 55, and the thermal conductivity was 10 W / m · K. Since the heat radiating member of Example 2 is excellent in thermal conductivity and extremely low in hardness as described above, it has good adhesion to electronic components and has excellent heat dissipation.
[0018]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, while being excellent in thermal conductivity, the heat radiating member which has the soft heat | fever property excellent in practical use which has a softness | flexibility is obtained. Further, it is possible to reduce the hardness so that it can be measured by Asker C hardness, good adhesion to electronic components, and efficient heat dissipation.
The heat dissipating member of the present invention is a heat dissipating member used in general power supplies, electronic devices, etc., especially heat dissipating sheets and integrated circuit elements such as LSIs and CPUs of electronic devices such as personal computers, word processors and CD-ROM drives. It is optimal as a low-hardness heat-dissipating silicone rubber sheet used in
Claims (6)
の硬化物であって、熱伝導率が５Ｗ／ｍ・Ｋ以上であり、デュロメータＡによる硬度が８０以下であることを特徴とする放熱用部材。For 100 parts by weight of organopolysiloxane, as a spherical thermal conductive filler, aluminum oxide, zinc oxide, silicon oxide, silicon carbide, silicon nitride, magnesium oxide, aluminum nitride, boron nitride, graphite, aluminum, copper, silver, One or more selected from the group consisting of nickel, iron and stainless steel, and a spherical heat conductive filler having an average particle diameter of 5 to 10 μm and a spherical heat conduction having an average particle diameter of 0.1 to 3 μm Organopolysiloxane composition cured by addition reaction or organic peroxide, in which 1,300 to 3,000 parts by weight of a spherical thermal conductive filler composed only of a conductive filler is blended (however, (A) viscosity at 25 ° C. Having an average of 0.1 or more silicon-bonded alkenyl groups in one molecule Loxane 100 parts by weight, (B) an organopolysiloxane having a viscosity of 1 to 100,000 mPa · s at 25 ° C. and containing an average of 2 or more silicon-bonded hydrogen atoms in one molecule {in component (A) Amount of silicon atom-bonded hydrogen atom in this component to be 0.1 to 1.5 mol per mole of silicon atom-bonded alkenyl group}, (C) 500 to 2,500 parts by weight of thermally conductive filler, And (D) a platinum-based catalyst {a thermally conductive silicone comprising an amount of 0.01 to 1,000 ppm by weight of platinum metal in this component with respect to the total weight of components (A) and (B)} It is a rubber composition, and the surface of the component (C) is (E) general formula: R 1 R 2 a Si (OR 3 ) (3-a) (wherein R 1 has 4 to 20 carbon atoms ) alkyl group, R 2 is a phenyl group or an alkyl group having 1 to 3 carbon atoms, R 3 is carbon A heat-conductive silicone rubber composition characterized by being treated with an alkylalkoxysilane represented by formula (1) to (3), a being an integer of 0 to 2), or a partial hydrolyzate thereof. Excluding things.)
A heat-dissipating member having a thermal conductivity of 5 W / m · K or more and a durometer A hardness of 80 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000190875A JP4144998B2 (en) | 2000-06-26 | 2000-06-26 | Material for heat dissipation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000190875A JP4144998B2 (en) | 2000-06-26 | 2000-06-26 | Material for heat dissipation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002003831A JP2002003831A (en) | 2002-01-09 |
| JP4144998B2 true JP4144998B2 (en) | 2008-09-03 |
Family
ID=18690273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000190875A Expired - Fee Related JP4144998B2 (en) | 2000-06-26 | 2000-06-26 | Material for heat dissipation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4144998B2 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4255287B2 (en) * | 2001-05-14 | 2009-04-15 | 東レ・ダウコーニング株式会社 | Thermally conductive silicone composition |
| JP2008120969A (en) * | 2006-11-15 | 2008-05-29 | Momentive Performance Materials Japan Kk | Silicone rubber composition and fixing member |
| JP5290539B2 (en) * | 2007-06-08 | 2013-09-18 | バンドー化学株式会社 | RUBBER COMPOSITION, RUBBER MOLDED BODY, HEAT-RELEASING SHEET AND METHOD FOR PRODUCING THE SAME |
| JP5155033B2 (en) * | 2008-06-26 | 2013-02-27 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally conductive silicone composition |
| JP2012102301A (en) * | 2010-11-13 | 2012-05-31 | Nitto Denko Corp | Bubble-containing thermally conductive resin composition layer, method for manufacturing the same, and pressure-sensitive adhesive tape or sheet using the same |
| JP6050207B2 (en) * | 2013-09-25 | 2016-12-21 | 信越化学工業株式会社 | Heat dissipation sheet, high heat dissipation sheet-like cured product, and method of using heat dissipation sheet |
| EP3135783B1 (en) * | 2014-04-25 | 2021-06-09 | Denka Company Limited | Aluminum-diamond composite, and heat dissipating component using same |
| JP2015218086A (en) * | 2014-05-16 | 2015-12-07 | トヨタ自動車株式会社 | Graphite sheet |
| JP6214094B2 (en) * | 2014-06-10 | 2017-10-18 | 信越化学工業株式会社 | Thermally conductive sheet |
| JP2016111045A (en) * | 2014-12-02 | 2016-06-20 | 北川工業株式会社 | Heat conductive sheet |
| US11254849B2 (en) | 2015-11-05 | 2022-02-22 | Momentive Performance Materials Japan Llc | Method for producing a thermally conductive polysiloxane composition |
| TWI769994B (en) | 2015-11-05 | 2022-07-11 | 日商邁圖高新材料日本合同公司 | Method for producing thermoconductive polysiloxane composition |
| US11118056B2 (en) | 2016-07-22 | 2021-09-14 | Momentive Performance Materials Japan Llc | Thermally conductive polysiloxane composition |
| CN109415564B (en) | 2016-07-22 | 2021-12-21 | 迈图高新材料日本合同公司 | Thermally conductive silicone composition |
| KR102334773B1 (en) | 2016-07-22 | 2021-12-03 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Thermally conductive polyorganosiloxane composition |
| JP6363301B2 (en) | 2016-07-22 | 2018-07-25 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Surface treatment agent for thermally conductive polyorganosiloxane composition |
| WO2018139506A1 (en) | 2017-01-27 | 2018-08-02 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally conductive polyorganosiloxane composition |
| JP6383885B2 (en) | 2017-01-27 | 2018-08-29 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally conductive polyorganosiloxane composition |
| EP3636715A4 (en) | 2017-05-31 | 2021-03-10 | Momentive Performance Materials Japan LLC | Heat-conductive polyorganosiloxane composition |
| US11359124B2 (en) | 2017-05-31 | 2022-06-14 | Momentive Performance Materials Japan Llc | Thermally conductive polysiloxane composition |
| JP7122528B2 (en) * | 2017-08-09 | 2022-08-22 | パナソニックＩｐマネジメント株式会社 | THERMALLY CONDUCTIVE COMPOSITION AND SEMICONDUCTOR DEVICE |
| WO2020262449A1 (en) | 2019-06-26 | 2020-12-30 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally conductive polysiloxane composition |
| TW202227588A (en) | 2020-10-09 | 2022-07-16 | 日商陶氏東麗股份有限公司 | Thermally conductive silicone composition and thermally conductive member |
| EP4357419A1 (en) | 2021-06-16 | 2024-04-24 | Momentive Performance Materials Japan LLC | Thermally-conductive polysiloxane composition |
| WO2022264715A1 (en) | 2021-06-16 | 2022-12-22 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally-conductive polysiloxane composition |
-
2000
- 2000-06-26 JP JP2000190875A patent/JP4144998B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002003831A (en) | 2002-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4144998B2 (en) | Material for heat dissipation | |
| JP3543663B2 (en) | Thermal conductive silicone rubber composition and method for producing the same | |
| JP3444199B2 (en) | Thermal conductive silicone rubber composition and method for producing the same | |
| JP5015436B2 (en) | Thermally conductive silicone elastomer, thermal conductive medium and thermally conductive silicone elastomer composition | |
| JP5154010B2 (en) | Thermally conductive silicone rubber composition | |
| JP6136952B2 (en) | Thermally conductive composite silicone rubber sheet | |
| KR101224371B1 (en) | Thermoconductive silicone elastomer, thermoconductive silicone elastomer composition and thermoconductive medium | |
| TWI822954B (en) | Thermal conductive silicone composition and manufacturing method thereof, and thermally conductive silicone hardened material | |
| JP6202475B2 (en) | Thermally conductive composite silicone rubber sheet | |
| JPWO2015087620A1 (en) | Thermal storage composition | |
| KR20150043545A (en) | Thermal interface materials | |
| JPH11209618A (en) | Heat-conductive silicone rubber composition | |
| JP2002294269A (en) | Extrusible crosslinked grease-like radiation material, container in which the material is filled and enclosed, manufacturing method of the container and radiation method using these | |
| JP2009203373A (en) | Thermoconductive silicone composition | |
| KR20150056477A (en) | Thermal conductive composite sheet | |
| JP7285231B2 (en) | Thermally conductive silicone composition and cured product thereof | |
| JP2021534262A (en) | Its application to thermal gap fillers and battery management systems | |
| JP2006089675A (en) | Thermally-conductive silicone elastomer and thermally-conductive silicone elastomer composition | |
| JP3521781B2 (en) | Heat dissipation member | |
| TW201943768A (en) | Heat-conductive silicone composition and cured product thereof | |
| TW200536896A (en) | Composition for heat conductive siloxanes heat release and its using method | |
| CN112714784B (en) | Heat-conductive silicone composition and cured product thereof | |
| JP3493258B2 (en) | Flame-retardant silicone rubber composition and flame-retardant silicone rubber molded article using the same | |
| CN112074572A (en) | Thermally conductive silicone rubber composition, sheet thereof, and method for producing same | |
| JP2005042096A (en) | Thermally conductive composition, and putty-like heat radiating sheet and heat radiating structure using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061011 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061016 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061215 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070129 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070330 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080331 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080521 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080611 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080617 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110627 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110627 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140627 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |