JP4060019B2 - Paste composition for aluminum brazing, coating film thereof, and brazing method - Google Patents
Paste composition for aluminum brazing, coating film thereof, and brazing method Download PDFInfo
- Publication number
- JP4060019B2 JP4060019B2 JP2000039923A JP2000039923A JP4060019B2 JP 4060019 B2 JP4060019 B2 JP 4060019B2 JP 2000039923 A JP2000039923 A JP 2000039923A JP 2000039923 A JP2000039923 A JP 2000039923A JP 4060019 B2 JP4060019 B2 JP 4060019B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- mass
- brazing
- aluminum
- resin
- 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
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する分野】
本発明は、アルミニウム部材同士をろう付接合する際のろう付用合金粉末（ろう材粉末ともいう）を含有するペースト状組成物に関する。尚、本明細書においては、アルミニウムとは、断わりのない限り純アルミニウムおよびアルミニウム合金を含む。
【０００２】
【従来の技術とその問題点】
従来アルミニウムのろう付には、ブレージングシートが多用されており、これは例えば、３００３合金（以下４ケタの番号・記号はＪＩＳで定められているものである）や３Ｎ０３合金等の心材の片面あるいは両面に４３４３合金や４０４５合金等のろう材をクラッドさせたものが用いられている。これらはろう付する部分以外にもクラッドされたろう材が使われていることになるため、最終製品のコストが高くなる。また、製造上厚みの制限があり、６０μｍ程度のクラッド材が限度であり、これより薄いクラッド材の製造は、工業上極めて困難であり、出来たとしても皮材の厚みが不均一となり、安定した品質や性能は得られない。
【０００３】
また、従来ブレージングシートのろう付にはフラックスが必要で、ろう付の直前にろう付部に塗布するタイプのものがあるが、その組成上完全な乾燥が困難なものが多く、乾燥できたとしても容易にフラックスが剥離、脱落するためろう付前の長時間の保存や運搬、および加工・組立等が不可能であった。また、加えてフラックス等が粉塵となり作業環境・衛生面ですこぶる好ましいものではなかった。さらに、フラックスと特開平６−２８５６８２等で開示されている樹脂とでは、ろう付の際に反応が起こり、ろう付部が黒変化する等意匠的に製品価値がすこぶる低いものであった。
【０００４】
近年においてはブレージングシートを使用せず、アルミニウム−けい素系のろう材粉末とフラックスを混合したものをアルミニウム部材のろう付部に塗布してろう付する方法も報告されているが、コストの面以外では前記の問題点は解決されていなかった。
【０００５】
【課題を解決するための手段】
本発明者らは鋭意創意工夫を重ねた結果、本発明を完成するに至った。すなわち本発明は、次の組成物、塗膜および方法からなる。
【０００６】
１．
（ａ）ろう付用合金粉末１０質量％〜７０質量％
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物。
【０００７】
２．ろう付用合金粉末が平均粒径２〜１００μｍのアルミニウム−けい素系の合金粉末である前記1記載のアルミニウムろう付用ペースト状組成物。
【０００８】
３．ろう付用合金粉末が平均粒径２〜１００μｍのアルミニウム−けい素―亜鉛系の合金粉末である前記1記載のアルミニウムろう付用ペースト状組成物。
【０００９】
４．
（ａ）平均粒径２〜１００μｍのアルミニウム−けい素系の合金粉末と亜鉛粉末の混合粉末１０質量％〜７０質量％
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物。
【００１０】
５．カップリング剤を含有する前記1〜４いずれか記載のアルミニウムろう付用ペースト状組成物。
【００１１】
６．前記１〜５いずれか記載のペースト状組成物をアルミニウム部材の表面の少なくとも１部以上に塗布後乾燥して得られる塗膜。
【００１２】
７．前記１〜５いずれか記載のペースト状組成物をアルミニウム部材の表面の少なくとも１部以上に塗布後乾燥したアルミニウム部材。
【００１３】
８．
（ａ）ろう付用合金粉末、またはろう付用合金粉末と亜鉛粉末の混合粉末１０質量％〜７０質量％
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物をアルミニウム部材の表面の少なくとも１部以上に塗布、乾燥後、他のアルミニウム部材とろう付を行うことを特徴とするアルミニウム部材のろう付方法。
【００１４】
以下、さらに本発明の実施の形態を詳述する。
【００１５】
本発明に使用する弗化物系フラックスは、ＡｌＦ３−ＫＦ、ＫＡｌＦ４−Ｋ３ＡｌＦ６、Ｋ３ＡｌＦ６およびＫＡｌＦ４等の弗化物系フラックスが例示されるが、Ｋ３ＡｌＦ６とＫＡｌＦ４を主成分とする市販品の「ノコロック（商品名）」（アルキャン社製）が特に好適である。前記フラックスのペースト状組成物への配合量は２〜５０質量％、好ましくは５〜３０質量％程度である。フラックスの配合量が２質量％未満の場合には、十分なフラックス作用が得がたく、５０質量％を超えても過剰であり、コストアップとなる。
【００１６】
ペースト状組成物中で、バインダーの作用を担う樹脂／ゴムとしては、アルキッド樹脂，アルキッド樹脂とブチルゴムの混合物，アルキッド樹脂と石油樹脂の混合物，アルキッド樹脂とブチルゴムと石油樹脂の混合物，アクリル樹脂とブチルゴムの混合物，アクリル樹脂と石油樹脂の混合物，アクリル樹脂とブチルゴムと石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダーが使用できる。ブチルゴムは、イソブチレンとイソプレンの共重合体であるブチルゴムで、分子量２５万〜５５万のものが好ましい。石油樹脂は、Ｃ５系石油樹脂、Ｃ９系石油樹脂およびＣ５Ｃ９共重合石油樹脂の１種以上が使用でき、好ましい分子量は６００〜２０００程度である。アクリル樹脂は、分子量１００〜１００００００のものが好適である。該バインダーの配合量は１質量％〜１５質量％が適当で、より好ましくは２質量％〜１０質量％である。１質量％未満では、フラックス組成物の粘度が低く、アルミニウム部材に塗布した際にダレが生じ、アルミニウム部材との密着性が悪くなるので好ましくない。一方１５質量％を超えても過剰で、コストアップになる恐れがある。
【００１７】
本発明で用いる有機溶剤は、前記バインダーが可溶であれば、特に限定されず、トルエン、ヘキサン、オクタン、シクロヘキサン等を単独、あるいは２種以上を混合して用いることができる。有機溶剤の配合量は、ペースト状組成物の粘度等を調整するために適宜加えればよいが、具体的には０．１〜８７質量％好ましくは５〜７０質量％の範囲内で調整すればよい。
【００１８】
本発明で用いるろう付用合金粉末は、アルミニウムを主体とする合金粉末を使用する事が出来る。例えば、アルミニウム−けい素系合金粉末、アルミニウム−けい素−亜鉛系合金紛、アルミニウム−亜鉛系合金粉末、アルミニウムーけい素―Ｘ（Ｃｕ，Ｂｉ、Ｍｇ，Ｓｂ、Ｂａ等）等の三元系以上の合金粉末等が使用できる。これらの粉末は主に、アトマイズ法・粉砕法・回転円盤法・キャビテーション法・メルトスピニング法等あるいはこれらの組合せによって得ることができる。もちろんこれらの粉末は市販品をそのまま使用することもできる。合金粉末の形状は球状、偏平状、板状、涙滴状、針状、回転楕円体状、不定形状等のいずれであっても差し支えない。該合金粉末はアルゴンガスあるいは窒素ガスアトマイズによって得られる粉末が好ましく使用できる。該合金粉末に含まれる酸素量は、粒度や形状にもよるが、１．５質量％以下が好ましく、これを超える場合には、酸化皮膜が強固となり、十分に溶融しなかったり、流動性が低下する恐れがある。該合金粉末の大きさは平均粒径（本明細書においてはレーザー回折式粒度分布測定法による）で２〜１００μｍ望ましくは５〜５０μｍの範囲内が適当で、平均粒径２μｍ未満の粉末は、酸素含有量が多くなる可能性が高く、またコストが高いものであるので好ましくない。一方１００μｍを超える場合には、塗布後の塗膜厚みが必要以上に厚くなったり、組成物中での均一性が損なわれる恐れがある。
【００１９】
ろう付用合金粉末に含まれるけい素の量は３〜１７質量％、亜鉛の量は０〜３０質量％（両方とも金属成分１００％に対し）の範囲内が適当でる。これはその範囲内の組成でろう付時の融点が低く、溶融状態での流動性が良好なことによる。特にけい素の共晶点以上（平衡状態図ではけい素約１２質量％）の場合は、アルミニウム部材と合金化することにより、ろう付温度で溶融してより流動化が増長される。ろう付用合金粉末中の不可避不純物元素は特に制限されるものではなく、Ｆｅ，Ｍｎ，Ｔｉ，Ｎｉ，Ｃｒ等の元素が数ｐｐｍ〜約１質量％程度混入していてもさしたる支障はないが、不純物であるＦｅは、ろう付後の耐食性を低下させるのでなるべく低い方がよい。
【００２０】
前記合金粉末中の亜鉛は必ずしも合金の状態である必要はなく、亜鉛粉単体で前記合金粉末に添加することもでき、犠牲防食効果を得るために亜鉛粉を０〜３０質量％（金属成分１００％に対し）、好ましくは３〜２５質量％添加混合することができる。亜鉛粉末の平均粒径は、平均粒子径０．１〜１００μｍ、望ましくは１〜３０μｍの範囲が適当で、平均粒子径が０．１μｍ未満の粉末では、酸素量やその他の不純物が多くなり好ましくない。また、１００μｍを超えても組成物中で均一な分散が出来なくなり好ましくない。亜鉛粉単体を用いる場合は、純度９０．０質量％以上、望ましくは９７．０質量％以上の亜鉛粉を使用すればよい。純度９０質量％未満の粉末では、不純物であるＰｂ（鉛）の含有量が多くなり、ろう付後の耐食性が低下するので好ましくない。
【００２１】
また、その他の適当な添加元素を添加しても差し支えなく、必要に応じてＣｕ、Ｍｇ、Ｂｉ、Ｓｂ、Ｂａ等の１種以上を約５質量％以下（金属成分１００％に対し）添加することも可能である。これらの添加元素は合金の状態、単体の粉末の状態のいずれであってもよい。
【００２２】
ろう付用合金粉末、またはろう付用合金粉末と亜鉛粉末の混合粉末の配合量はペースト状組成物全体を１００質量％としたとき１０質量％〜７０質量％が適当で、好ましくは２０質量％〜６０質量％である。１０質量％未満では、ろう材としての効果に乏しく、７０質量％を超えると必要なフラックス量が多くなるためコストアップとなる。
【００２３】
本発明に用いるペースト状組成物には、公知の添加物を添加しても差し支えなく、例えば、酸化防止剤、腐食抑制剤、消泡剤、増粘剤、可塑剤、分散剤、タックファイヤー、カップリング剤等を必要に応じて添加できる。特にカップリング剤は、塗膜の付着性を向上させるために有効であり、０．００１〜１．０質量％程度の添加が有効である。中でもチタネート系カップリング剤は、特に有効である。
【００２４】
本発明のペースト状組成物は、アルミニウム部材の表面の少なくとも一部以上、すなわちろう付しようとする部分に必要量塗布して使用することができ、乾燥後の平均膜厚は好ましくは３〜５００μｍ、より好ましくは１０〜１５０μｍである。平均膜厚が３μｍ未満でもろう付は可能ではあるが、ろう付強度が不足する恐れがある。一方５００μｍを超えても過剰で、コストアップになる恐れがある。しかしながら、穴を塞ぐためや隙間を埋めるために本発明のペースト状組成物を使用する場合は、厚み５００μｍに限定されることはなく、これを超えても使用することができる。
【００２５】
塗布の方法は、公知の方法が採用でき、はけ塗り、スプレー塗装、ロールコーター、バーコーター、ドクターブレード等で塗布することができる。これらの方法以外にも単にペースト状組成物にアルミニウム部材を浸漬する等の方法でもよい。
【００２６】
ペースト状組成物の塗布後の乾燥は、通常室温乾燥、必要に応じて３０〜１５０℃程度の温度で乾燥させればよい。ろう付の方法は、特に限定されず、公知の方法が採用できるが、炉中ろう付による方法が特に好ましい。炉中ろう付によれば、人手をかけずに一度に大量にろう付でき、工業生産に適している。ろう付の温度は組成にもよるが、通常４５０℃〜６３０℃程度である。雰囲気については、真空、Ａｒ、窒素等の非酸化性雰囲気が好ましい。雰囲気中の酸素濃度については２００ｐｐｍ以下、好ましくは１００ｐｐｍ以下が望ましく、２００ｐｐｍを超える場合にはフラックス作用の低下、前記合金粉末の酸化等のためろう付け不良が発生する恐れがある。
【００２７】
本発明のペースト状組成物は、ろう付可能なアルミニウム部材に適用することができ、例えばヒーターコア、エバポレータ、コンデンサ等の熱交換器を構成するフィン・ピン・パイプ・チューブ・プレート等のろう付接合に使用することができる。また、熱交換器に限定されることはなく、各種機械部品、車両部品、構造部品、スポーツ用品、ＯＡ機器、日用品等に適用可能である。
【００２８】
【効果】
１．本発明のペースト状組成物は、アルミニウム部材への密着性が良好で、乾燥後の塗膜は容易に剥離・脱落が起こらないので、該ペースト状組成物の塗布後に容易に塗布物の取扱を行うことが出来る。さらに、ブチルゴム配合系の該ペースト状組成物を使用する場合には、塗布後により容易に塗布物の塑性加工を行うことが出来る。
【００２９】
２．本発明のペースト状組成物に用いる特定のバインダーは、ろう付を行う際の昇温中に熱分解するため、ろう付後のろう付部（フィレット）の外観が良好であり、黒変化や白色残さを生じない。
【００３０】
３．本発明のペースト状組成物は、適切な有機溶剤の選定により室温でも乾燥させることができ、余分なコストがかからず、乾燥後も良好な塗膜状態であるので、粉塵等が発生せず、作業環境が良好である。
【００３１】
４．本発明のペースト状組成物は、溶剤の配合量等により適度な粘度に調整できるので、複雑形状の部品や凹凸屈曲等のある部材へも塗布可能である。
【００３２】
５．本発明のろう付方法は、特別な装置や機器が不要であるので、既存の設備で実施可能である。
【００３３】
【実施例】
実施例および比較例
表１および表２の配合にて混合し、ペースト状組成物を作製した。作製したペースト状組成物を刷毛で、３００３アルミニウム板（６０×５０×２ｍｍ）の片面に（乾燥後平均膜厚４０μｍ）塗布後、希釈用有機溶剤（トルエン）を完全に蒸発させるために、１０５℃×５分加熱した。得られた塗板を下記の評価に供した。
【００３４】
・成膜性：○→指触硬化している。
×→指触硬化していない。
・付着性：Ａ→強く指でこすっても塗膜ははがれない。
Ｂ→軽く指でこすっても塗膜ははがれない。
Ｃ→指でこすれば塗膜ははがれるが、たたいてもはがれない。
Ｄ→たたくと塗膜ははがれ落ちる。
Ｅ→評価外（成膜できず）
【００３５】
・折曲性：○→直径１０ｍｍの丸棒で塗板を１８０°折り曲げて塗膜のはく離や亀裂なし
△→直径１０ｍｍの丸棒で塗板を１８０°折り曲げて塗膜の亀裂はあるが、剥離なし
×→直径１０ｍｍの丸棒で塗板を１８０°折り曲げて塗膜の亀裂および剥離あり
【００３６】
前記で作製した各塗板を加熱あるいはろう付を行い次の評価を行った。
・臭気：下記ろう付（６００℃）の加熱中に炉から出てくるガスの臭いをかいで評価した。
Ａ→ほとんど臭わない、気にならない。
Ｂ→臭いが認識できるが、作業には影響しない。
Ｃ→異様な臭気があり、やや気になる。
Ｄ→不快臭であり、作業しにくい。
Ｅ→悪臭で、作業できない。
【００３７】
・フィレット形成（外観）：前記で作製した塗板の塗布面中央に３００３アルミニウム板を垂直に立て、ステンレスワイヤーで仮留めした後、窒素ガス雰囲気（窒素ガスフロー４Ｎｍ３／ｈ）の炉にて６００℃で３分間保持してろう付を行った。冷却した後、炉から取り出しろう付部のフィレットの形成状況を目視にて観察を行った。
【００３８】
Ａ→フィレットの形成具合良好（ろう付部周辺に均一にフィレットが形成されている。）
Ｂ→フィレットは形成されているが、やや不均一である。
Ｃ→フィレットは形成されているが、かなり不均一である。
Ｄ→フィレットが十分に形成されておらず、切れがある。
Ｅ→ろう付できていない。
【００３９】
以上の結果より、本発明のペースト状組成物を使用したろう付は、上記の評価に満足するものである。
【００４０】
【表１】
【表２】
[Field of the Invention]
The present invention relates to a paste-like composition containing a brazing alloy powder (also referred to as a brazing material powder) when brazing and joining aluminum members. In this specification, aluminum includes pure aluminum and aluminum alloys unless otherwise specified.
[0002]
[Prior art and its problems]
Conventionally, brazing sheets are often used for brazing aluminum, such as one side of a core material such as 3003 alloy (hereinafter, 4 digit number / symbol is defined by JIS) or 3N03 alloy. What clad with brazing materials, such as 4343 alloy and 4045 alloy, is used for both surfaces. Since these use brazed brazing material in addition to the brazing part, the cost of the final product increases. In addition, there is a limitation on the thickness in production, and a clad material of about 60 μm is the limit. Production of a clad material thinner than this is extremely difficult industrially, and even if possible, the thickness of the skin material becomes uneven and stable. Quality and performance is not obtained.
[0003]
Also, brazing of conventional brazing sheets requires a flux, and there is a type that is applied to the brazed part immediately before brazing, but it is difficult to completely dry due to its composition, and it can be dried However, since the flux easily peels off, it cannot be stored and transported for a long period of time before brazing, and processing / assembly is not possible. In addition, the flux and the like become dust, which is not preferable in terms of working environment and hygiene. Further, the flux and the resin disclosed in JP-A-6-285682 have a very low product value in terms of design, for example, a reaction occurs during brazing and the brazed portion changes to black.
[0004]
In recent years, a method has been reported in which a brazing sheet is not used but a mixture of an aluminum-silicon brazing powder and a flux is applied to a brazing portion of an aluminum member and brazed. Other than the above, the above problems were not solved.
[0005]
[Means for Solving the Problems]
As a result of repeated ingenuity, the present inventors have completed the present invention. That is, this invention consists of the following composition, coating film, and method.
[0006]
1.
(A) Brazing alloy powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
A paste-like composition for aluminum brazing comprising (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ).
[0007]
2. 2. The paste composition for aluminum brazing according to 1, wherein the brazing alloy powder is an aluminum-silicon alloy powder having an average particle diameter of 2 to 100 μm.
[0008]
3. 2. The paste composition for aluminum brazing as described in 1 above, wherein the brazing alloy powder is an aluminum-silicon-zinc alloy powder having an average particle diameter of 2 to 100 μm.
[0009]
4).
(A) Mixed powder of aluminum-silicon alloy powder having an average particle diameter of 2 to 100 μm and zinc powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
A paste-like composition for aluminum brazing comprising (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ).
[0010]
5. The paste composition for aluminum brazing according to any one of the above 1 to 4, which contains a coupling agent.
[0011]
6). The coating film obtained by apply | coating the pasty composition in any one of said 1-5 to at least 1 part or more of the surface of an aluminum member, and drying.
[0012]
7). The aluminum member which dried after apply | coating the pasty composition in any one of said 1-5 to at least 1 part or more of the surface of an aluminum member.
[0013]
8).
(A) Brazing alloy powder, or mixed powder of brazing alloy powder and zinc powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
An aluminum brazing paste-like composition containing (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ) is applied to at least one part of the surface of the aluminum member. A method of brazing an aluminum member, characterized by performing brazing with another aluminum member after drying.
[0014]
Hereinafter, the embodiment of the present invention will be described in detail.
[0015]
Fluoride-based flux used in the present invention, AlF 3 -KF, KAlF 4 -K 3 AlF 6, K 3 is AlF 6 and KAlF 4 such fluoride-based flux is illustrated, K 3 AlF 6 and KAlF 4 A commercially available “Nocolok (trade name)” (manufactured by Alcan) is particularly suitable. The blending amount of the flux in the paste-like composition is about 2 to 50% by mass , preferably about 5 to 30% by mass . When the blending amount of the flux is less than 2% by mass , a sufficient flux effect is difficult to obtain, and even if it exceeds 50% by mass , it is excessive and the cost is increased.
[0016]
Resins / rubbers that act as binders in paste-like compositions include alkyd resins, mixtures of alkyd resins and butyl rubber, mixtures of alkyd resins and petroleum resins, mixtures of alkyd resins, butyl rubber and petroleum resins, acrylic resins and butyl rubber. At least one binder selected from the group consisting of: a mixture of acrylic resin and petroleum resin; and a mixture of acrylic resin, butyl rubber and petroleum resin. The butyl rubber is butyl rubber which is a copolymer of isobutylene and isoprene, and preferably has a molecular weight of 250,000 to 550,000. Petroleum resins, C 5 petroleum resins, can be used one or more C 9 petroleum resins and C 5 C 9 copolymer petroleum resin, the preferred molecular weight is about 600 to 2000. The acrylic resin preferably has a molecular weight of 100 to 1,000,000. 1 mass %-15 mass % is suitable for the compounding quantity of this binder, More preferably, it is 2 mass %-10 mass %. If it is less than 1% by mass , the viscosity of the flux composition is low, sagging occurs when applied to an aluminum member, and the adhesion to the aluminum member is deteriorated, which is not preferable. On the other hand, even if it exceeds 15 mass %, it is excessive and there is a risk that the cost will increase.
[0017]
The organic solvent used in the present invention is not particularly limited as long as the binder is soluble, and toluene, hexane, octane, cyclohexane and the like can be used alone or in admixture of two or more. The blending amount of the organic solvent may be appropriately added in order to adjust the viscosity and the like of the paste-like composition. Specifically, it is 0.1 to 87% by mass, preferably 5 to 70% by mass. Good.
[0018]
As the brazing alloy powder used in the present invention, an alloy powder mainly composed of aluminum can be used. For example, ternary system such as aluminum-silicon alloy powder, aluminum-silicon-zinc alloy powder, aluminum-zinc alloy powder, aluminum-silicon-X (Cu, Bi, Mg, Sb, Ba, etc.) The above alloy powders can be used. These powders can be obtained mainly by an atomizing method, a pulverizing method, a rotating disk method, a cavitation method, a melt spinning method, or a combination thereof. Of course, these powders can be used as they are. The shape of the alloy powder may be any of a spherical shape, a flat shape, a plate shape, a teardrop shape, a needle shape, a spheroid shape, an indefinite shape, and the like. The alloy powder is preferably a powder obtained by argon gas or nitrogen gas atomization. The amount of oxygen contained in the alloy powder is preferably 1.5% by mass or less, although it depends on the particle size and shape, and if it exceeds this, the oxide film becomes strong and does not melt sufficiently or has fluidity. May fall. The size of the alloy powder is 2-100 μm, preferably 5-50 μm in terms of average particle size (in this specification, by laser diffraction particle size distribution measurement method), and the powder having an average particle size of less than 2 μm is This is not preferable because the oxygen content is likely to increase and the cost is high. On the other hand, if it exceeds 100 μm, the coating thickness after coating may become unnecessarily thick, or the uniformity in the composition may be impaired.
[0019]
The amount of silicon contained in the brazing alloy powder is suitably in the range of 3 to 17% by mass and the amount of zinc in the range of 0 to 30% by mass (both with respect to 100% of the metal component). This is because the composition within that range has a low melting point during brazing and good fluidity in the molten state. In particular, when the eutectic point is higher than the eutectic point of silicon (about 12% by mass of silicon in the equilibrium diagram), alloying with an aluminum member melts at the brazing temperature and further enhances fluidization. The inevitable impurity elements in the brazing alloy powder are not particularly limited, and there is no problem even if elements such as Fe, Mn, Ti, Ni, and Cr are mixed in about several ppm to about 1% by mass. Further, Fe, which is an impurity, is preferably as low as possible because it reduces the corrosion resistance after brazing.
[0020]
Zinc in the alloy powder does not necessarily need to be in an alloy state, and zinc powder alone can be added to the alloy powder. To obtain a sacrificial anticorrosive effect, 0 to 30% by mass of zinc powder (metal component 100) %), Preferably 3 to 25% by mass can be added and mixed. The average particle size of the zinc powder is preferably in the range of average particle size of 0.1 to 100 μm, desirably 1 to 30 μm, and the powder having an average particle size of less than 0.1 μm is preferable because the oxygen amount and other impurities increase. Absent. Moreover, even if it exceeds 100 micrometers, uniform dispersion | distribution in a composition cannot be performed and it is unpreferable. In the case of using zinc powder alone, zinc powder having a purity of 90.0% by mass or more, desirably 97.0% by mass or more may be used. A powder having a purity of less than 90% by mass is not preferable because the content of Pb (lead) as an impurity increases and the corrosion resistance after brazing decreases.
[0021]
Further, other suitable additive elements may be added, and if necessary, one or more of Cu, Mg, Bi, Sb, Ba, etc. are added in an amount of about 5% by mass or less (based on 100% of the metal component). It is also possible. These additive elements may be in an alloy state or a simple powder state.
[0022]
Alloy powder for brazing or amount of the mixed powder of the alloy powder and zinc powder for brazing is suitably 10 to 70% by mass when the total paste composition is 100 mass%, preferably 20 wt% -60 mass %. If it is less than 10% by mass , the effect as a brazing material is poor, and if it exceeds 70% by mass , the required amount of flux increases, resulting in an increase in cost.
[0023]
A known additive may be added to the paste-like composition used in the present invention, for example, an antioxidant, a corrosion inhibitor, an antifoaming agent, a thickener, a plasticizer, a dispersant, a tack fire, A coupling agent or the like can be added as necessary. In particular, the coupling agent is effective for improving the adhesion of the coating film, and the addition of about 0.001 to 1.0% by mass is effective. Of these, titanate coupling agents are particularly effective.
[0024]
The paste-like composition of the present invention can be used by applying a necessary amount to at least a part of the surface of the aluminum member, that is, the part to be brazed, and the average film thickness after drying is preferably 3 to 500 μm. More preferably, it is 10-150 micrometers. Brazing is possible even with an average film thickness of less than 3 μm, but brazing strength may be insufficient. On the other hand, even if it exceeds 500 μm, it is excessive, and there is a risk of increasing the cost. However, when using the paste-like composition of the present invention to close a hole or fill a gap, the thickness is not limited to 500 μm and can be used beyond this.
[0025]
As a coating method, a known method can be adopted, and it can be applied by brush coating, spray coating, roll coater, bar coater, doctor blade or the like. In addition to these methods, a method such as simply immersing an aluminum member in a paste-like composition may be used.
[0026]
The drying after the application of the paste-like composition is usually performed at room temperature, and may be performed at a temperature of about 30 to 150 ° C. as necessary. The method of brazing is not particularly limited, and a known method can be adopted, but a method by brazing in a furnace is particularly preferable. In-furnace brazing is suitable for industrial production because it can be brazed in large quantities at the same time without human intervention. The brazing temperature depends on the composition, but is usually about 450 ° C to 630 ° C. The atmosphere is preferably a non-oxidizing atmosphere such as vacuum, Ar, or nitrogen. The oxygen concentration in the atmosphere is desirably 200 ppm or less, preferably 100 ppm or less. If it exceeds 200 ppm, there is a possibility that poor brazing may occur due to a decrease in flux action or oxidation of the alloy powder.
[0027]
The paste-like composition of the present invention can be applied to brazing aluminum members, for example, brazing of fins, pins, pipes, tubes, plates, etc. constituting heat exchangers such as heater cores, evaporators and condensers. Can be used for bonding. Moreover, it is not limited to a heat exchanger, but can be applied to various machine parts, vehicle parts, structural parts, sports equipment, OA equipment, daily necessities, and the like.
[0028]
【effect】
1. The paste-like composition of the present invention has good adhesion to an aluminum member, and the coated film after drying does not easily peel off or fall off. Therefore, the coated material can be easily handled after application of the paste-like composition. Can be done. Furthermore, when the butyl rubber compounded paste-like composition is used, it is possible to easily perform plastic working of the coated material after coating.
[0029]
2. The specific binder used in the paste-like composition of the present invention is thermally decomposed during the temperature rise during brazing, so that the appearance of the brazed part (fillet) after brazing is good, black change and white There is no residue.
[0030]
3. The paste-like composition of the present invention can be dried at room temperature by selecting an appropriate organic solvent, does not incur extra costs, and is in a good coating state even after drying, so dust and the like are not generated. The working environment is good.
[0031]
4). Since the paste-like composition of the present invention can be adjusted to an appropriate viscosity by the blending amount of the solvent and the like, it can be applied to parts having complicated shapes and uneven bending.
[0032]
5. The brazing method of the present invention does not require a special device or equipment, and can be implemented with existing equipment.
[0033]
【Example】
Examples and Comparative Examples A paste-like composition was prepared by mixing in the formulations shown in Tables 1 and 2. In order to completely evaporate the organic solvent for dilution (toluene) after applying the prepared paste-like composition with a brush to one side of a 3003 aluminum plate (60 × 50 × 2 mm) (average film thickness after drying 40 μm), 105 Heated at 5 ° C. for 5 minutes. The obtained coated plate was subjected to the following evaluation.
[0034]
・ Film formability: ○ → Touch cured.
× → Finger touch is not cured.
-Adhesiveness: A-> Even if it is rubbed strongly with a finger, the coating film does not peel off.
B-> Even if it rubs lightly with a finger, a coating film does not peel off.
C → If you rub with your finger, the coating will peel off, but it will not peel off.
D-> Tap to peel off the coating.
E → not evaluated (film formation not possible)
[0035]
・ Bendability: ○ → The coated plate is bent 180 ° with a round bar with a diameter of 10 mm, and there is no peeling or cracking of the coating film.
Δ → The coated plate is bent 180 ° with a round bar with a diameter of 10 mm, and there is a crack in the coating film, but there is no peeling.
× → Coating plate is bent 180 ° with a round bar with a diameter of 10 mm to cause cracks and peeling of the coating film.
Each coated plate produced as described above was heated or brazed to perform the following evaluation.
-Odor: The odor of gas coming out of the furnace during the following brazing (600 ° C) heating was evaluated.
A → It doesn't bother you.
B → Smell can be recognized, but it does not affect the work.
C → There is a strange odor and it is a little worrisome.
D → Unpleasant odor, difficult to work with.
E → Can't work because of bad odor.
[0037]
Fillet formation (appearance): A 3003 aluminum plate is set up vertically in the center of the coated surface of the coated plate prepared above, temporarily attached with a stainless steel wire, and then 600 in a furnace with a nitrogen gas atmosphere (nitrogen gas flow 4 Nm 3 / h). Brazing was carried out by holding at 3 ° C. for 3 minutes. After cooling, the formation state of the fillet of the brazing part was taken out from the furnace and visually observed.
[0038]
A → Fillet formation is good (fillets are uniformly formed around the brazed part)
B → fillet is formed, but slightly non-uniform.
C → fillet is formed, but it is quite uneven.
D → The fillet is not sufficiently formed and there is a cut.
E → Not brazed.
[0039]
From the above results, brazing using the paste-like composition of the present invention satisfies the above evaluation.
[0040]
[Table 1]
[Table 2]
Claims (8)
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物。(A) Brazing alloy powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
A paste-like composition for aluminum brazing comprising (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ).
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物。(A) Mixed powder of aluminum-silicon alloy powder having an average particle diameter of 2 to 100 μm and zinc powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
A paste-like composition for aluminum brazing comprising (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ).
（ｂ）弗化物系フラックス２質量％〜５０質量％
（ｃ）アルキッド樹脂と分子量２５万〜５５万のブチルゴムの混合物，アルキッド樹脂と分子量６００〜２０００の石油樹脂の混合物，アルキッド樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムの混合物，分子量１００〜１００００００のアクリル樹脂と分子量２５万〜５５万のブチルゴムと分子量６００〜２０００の石油樹脂の混合物，の群から選ばれる少なくとも１つのバインダー１質量％〜１５質量％
前記（ａ）〜（ｃ）を含みさらに残部に有機溶剤を含む（ただし、合計量は１００質量％を超えない）アルミニウムろう付用ペースト状組成物をアルミニウム部材の表面の少なくとも１部以上に塗布、乾燥後、他のアルミニウム部材とろう付を行うことを特徴とするアルミニウム部材のろう付方法。(A) Brazing alloy powder, or mixed powder of brazing alloy powder and zinc powder 10 mass % to 70 mass %
(B) fluoride-based flux 2% by mass to 50%
(C) A Rukiddo resin having a molecular weight from 250000 to 550000 of a mixture of butyl rubber, a mixture of petroleum resin alkyd resin having a molecular weight 600 to 2000, an alkyd resin having a molecular weight from 250000 to 550000 of butyl rubber and petroleum resins having a molecular weight of 600 to 2000 A mixture of an acrylic resin having a molecular weight of 100 to 1000000 and a butyl rubber having a molecular weight of 250,000 to 550,000 , a mixture of an acrylic resin having a molecular weight of 100 to 150,000, a butyl rubber having a molecular weight of 250,000 to 550,000, and a petroleum resin having a molecular weight of 600 to 2000 . 1% by mass to 15% by mass of at least one binder selected from the group
An aluminum brazing paste-like composition containing (a) to (c) and further containing an organic solvent (the total amount does not exceed 100% by mass ) is applied to at least one part of the surface of the aluminum member. A method of brazing an aluminum member, characterized by performing brazing with another aluminum member after drying.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000039923A JP4060019B2 (en) | 2000-02-17 | 2000-02-17 | Paste composition for aluminum brazing, coating film thereof, and brazing method |
| US09/783,123 US6497770B2 (en) | 2000-02-17 | 2001-02-15 | Flux-containing compositions for brazing aluminum, films and brazing method thereby |
| DE60120250T DE60120250T2 (en) | 2000-02-17 | 2001-02-16 | Compositions, in particular in the form of a coating, and methods for brazing aluminum |
| EP01301391A EP1127653B1 (en) | 2000-02-17 | 2001-02-16 | Flux-containing compositions for brazing aluminum, films and brazing method thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000039923A JP4060019B2 (en) | 2000-02-17 | 2000-02-17 | Paste composition for aluminum brazing, coating film thereof, and brazing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001225185A JP2001225185A (en) | 2001-08-21 |
| JP4060019B2 true JP4060019B2 (en) | 2008-03-12 |
Family
ID=18563411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000039923A Expired - Fee Related JP4060019B2 (en) | 2000-02-17 | 2000-02-17 | Paste composition for aluminum brazing, coating film thereof, and brazing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4060019B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20121992U1 (en) * | 2001-08-28 | 2003-10-23 | Behr GmbH & Co. KG, 70469 Stuttgart | Flux composition used for hard-soldering parts made of aluminum or its alloys, especially motor vehicle radiators contains flux, solvent and binder |
| JP5026726B2 (en) * | 2006-04-03 | 2012-09-19 | 東洋アルミニウム株式会社 | Paste composition for aluminum brazing, aluminum-containing member coated with the same, and method for brazing aluminum-containing member using the same |
| JP5041286B2 (en) * | 2007-05-11 | 2012-10-03 | 荒川化学工業株式会社 | Binder for aluminum brazing paste |
| JP4980787B2 (en) * | 2007-05-16 | 2012-07-18 | 三菱アルミニウム株式会社 | Aluminum alloy brazing paint excellent in peeling resistance of coating film, brazing aluminum alloy plate, aluminum alloy member for automobile heat exchanger using the same, and method for producing automobile heat exchanger |
| JP5152727B2 (en) | 2007-12-21 | 2013-02-27 | ハリマ化成株式会社 | Aluminum brazing paste composition |
-
2000
- 2000-02-17 JP JP2000039923A patent/JP4060019B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001225185A (en) | 2001-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1127653B1 (en) | Flux-containing compositions for brazing aluminum, films and brazing method thereby | |
| EP0980738B1 (en) | Flux compositions for brazing aluminium, their films and brazing methods | |
| CN1655903B (en) | Brazing flux mixture, method of manufacturing brazing flux mixture and brazing flux coated sheet | |
| KR101274122B1 (en) | Pasty composition for aluminum brazing, aluminum-containing member coated with the same, and method of brazing aluminum-containing member with the same | |
| JP2016533267A5 (en) | ||
| JP3224440B2 (en) | Aluminum alloy brazing material for heat exchanger brazing and aluminum alloy brazing sheet for heat exchanger | |
| JP4347489B2 (en) | Paste composition for aluminum brazing, coating film thereof, and brazing method | |
| JP4060019B2 (en) | Paste composition for aluminum brazing, coating film thereof, and brazing method | |
| JP3705939B2 (en) | Paste composition for aluminum brazing, coating film thereof, and brazing method | |
| JPH081373A (en) | Sn base brazing filler metal of low melting point | |
| JP2001520940A (en) | Hard solder paste without flux | |
| JP7659441B2 (en) | Nickel brazing material with excellent wettability | |
| JP2003275895A (en) | Pasty composition for brazing and brazing method using the same | |
| JP2001226541A (en) | Undried coating film for soldering and soldering method | |
| JP3337417B2 (en) | Aluminum brazing method | |
| JP5041619B2 (en) | Aluminum brazing flux composition, coating film thereof, and brazing method | |
| JP3434997B2 (en) | Aluminum alloy powder brazing material with excellent brazing properties | |
| JP4150130B2 (en) | Aluminum brazing flux composition, coating film thereof and brazing method | |
| JP4692088B2 (en) | Brazing method of aluminum alloy | |
| JPH09174277A (en) | Composition for brazing aluminum material, aluminum material for brazing, and brazing method for aluminum material | |
| JPH06142977A (en) | Aluminum material for brazing | |
| JPH0825079A (en) | Composition for brazing, aluminum base material which consists by making composition for brazing and heat exchanger | |
| JPH06179094A (en) | Aluminum brazing filler metal | |
| JP3120977B2 (en) | Covered arc welding rod | |
| JPS63160796A (en) | Binder for paste solder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060825 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070724 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070731 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070928 |
|
| 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: 20071211 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20071219 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4060019 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131228 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |