JP4402896B2

JP4402896B2 - Aqueous coating lubricant composition for difficult-to-work metals

Info

Publication number: JP4402896B2
Application number: JP2003099804A
Authority: JP
Inventors: 松男阿高; 一磨平目; 英吉鍜冶
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-04-03
Filing date: 2003-04-03
Publication date: 2010-01-20
Anticipated expiration: 2023-04-03
Also published as: JP2004307570A

Description

【０００１】
【産業上の利用分野】
本発明はチタン鋼板、ステンレス鋼板、亜鉛メッキ鋼板、マグネシウム合金鋼板、等特殊合金鋼板の難加工材（強度が高い、スプリングバックが大きい）の傷防止、絞り加工範囲の拡大が可能な難加工金属用の水性被覆潤滑剤組成物に関する。
【０００２】
【発明が解決しようとしている課題】
例えばチタン鋼板、ステンレス鋼板、亜鉛メッキ鋼板、マグネシウム合金鋼板、等特殊合金鋼板の難加工材はすべり面が少なく、表面の酸化皮膜が非常に薄く、活性に富んでいるために金型との間で焼け付きが生じやすく、深絞り成形が困難とされている。現在適切な潤滑剤が存在していない。
【０００３】
チタン鋼板、マグネシウム合金鋼板等特殊合金鋼板の難加工材は現在コイル製品は開発されているが、それを利用してのプレス加工製品は立ち遅れている。
特殊合金鋼板は軽量で高強度、耐蝕性、電磁波遮断性、延性等に優れているが最密六方格子構造ですべり面が少ない。
【０００４】
それがため、従来では、チタン鋼板、ステンレス鋼板、亜鉛メッキ鋼板、マグネシウム合金鋼板、等特殊合金鋼板の難加工材の深絞り成形品を得るためには、その難加工材の溶融金属又は半溶融金属を金型に流し込み必要な形状を得ている、そのような成形方法では、熱エネルギー、製品の歩留まり、剥離材の塗布、その除去に多くのコストを必要とし、又加工工数、中間焼鈍、切削加工等の多くの加工工程を必要とする。
【０００５】
曲げ加工等は行われているが、量産加工を行うと、金属粉（パウダリンギング現象）が発生して、連続生産が困難な状況が起きている。
特殊合金鋼板は種類によって、指紋が付着すると除去するために大変費用が掛かり、他の油類が付着しても商品価値を損ねる。
【０００６】
【課題を解決するための手段】
本発明者は幅広い研究により、特定な水性被覆潤滑剤組成物を使用すると、難加工材を深絞り加工できることを発見して、本発明に至った。すなわち本発明の水性被覆潤滑剤組成物は、水性溶液として金属表面に塗布し、乾燥すると密度が高く硬い皮膜を形成し、同時に高い潤滑性を持つことを発見し、又水性被覆潤滑剤組成物が難加工金属に良好な深絞り効果を発揮することを本発明者は、発見して本発明に至った。
【０００７】
すなわち本発明の第一態様は、（ａ）非反応型、自己乳化型ウレタン樹脂を実質上乳化剤を使用せずに水中に分散させた水系ウレタン樹脂、（ｂ）フッ素樹脂粉末またはあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）メチルセロソルブ（エチレングリコールモノメチルエーテル）、エチルセロソルブ（エチレングリコールモノエチルエーテル）、ブチルセロソルブ（エチレングリコールモノブチルエーテル）、メチルセロソルブアセテート（エチレングリコールモノメチルエーテルアセテート）、エチルセロソルブアセテート（エチレングリコールモノエチルエーテルアセテート）又はブチルセロソルブアセテート（エチレングリコールモノブチルエーテルアセテート）等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｄ）アルコールを含み、樹脂成分が総重量の６〜３５重量％を含む難加工金属用の水性被覆潤滑剤組成物に関する。
【０００８】
本発明の第二態様は、（ａ）非反応型、自己乳化型ウレタン樹脂を実質上乳化剤を使用せずに水中に分散させた水系ウレタン樹脂、（ｂ）フッ素樹脂粉末またはあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）シリカ、（ｄ）シリコーン系非イオン界面活性剤（ｅ）シリコーン系消泡剤及び（ｆ）アルコールを含み、樹脂成分が総重量の６〜３５重量％を含む難加工金属用の水性被覆潤滑剤組成物に関する。
【０００９】
本発明の第三態様は、（ａ）非反応型、自己乳化型であり、異なる粒径からなるウレタン樹脂、そのウレタン樹脂は実質上乳化剤を使用せずに水中に分散させる事ができ、又は前期ウレタン樹脂とウレタン・アクリル複合樹脂との混合物、その混合物は、異なる粒径の粒子からなり、（ｂ）フッ素樹脂粉末またはあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート又はブチルセロソルブアセテート等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｄ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物に関する。
【００１０】
本発明の第四態様は、（ａ）非反応型、自己乳化型であり、異なる粒径からなるウレタン樹脂、そのウレタン樹脂は実質上乳化剤を使用せずに水中に分散させる事ができ、又は前期ウレタン樹脂とウレタン・アクリル複合樹脂との混合物、その混合物は、異なる粒径の粒子からなり、（ｂ）フッ素樹脂粉末又はあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）シリカ（ｄ）シリコーン系消泡剤及び（ｆ）シリコーン系非イオン界面活性剤及（ｅ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物に関する。
【００１１】
本発明の第五態様は、（ａ）非反応型、自己乳化型であり、実質上乳化剤を使用せずに水中に分散させる事ができるウレタン樹脂とウレタン・アクリル複合樹脂との混合物、この場合その混合物は、異なる粒径の粒子からなり、（ｂ）フッ素樹脂粉末又はあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート又はブチルセロソルブアセテート等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｄ）イソプロピルアルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物に関する。
【００１２】
本発明の第六態様は、（ａ）非反応型、自己乳化型であり、実質上乳化剤を使用せずに水中に分散させる事ができるウレタン樹脂とウレタン・アクリル複合樹脂との混合物、この場合その混合物は、異なる粒径の粒子からなり、（ｂ）フッ素樹脂粉末又はあらかじめその微粒子を分散剤によって水分散させたディスパージョン（ｃ）シリカ（ｄ）シリコーン系非イオン界面活性剤，（ｄ）シリコーン系消泡剤及び（ｅ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物に関する。
【００１３】
本発明の第七態様は、（ａ）非反応型、自己乳化型ウレタン樹脂を実質上乳化剤を使用せずに水中に分散させた水系ウレタン樹脂、（ｂ）メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート又はブチルセロソルブアセテート等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｃ）アルコールを含む難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１４】
本発明の第八態様は、（ａ）非反応型、自己乳化型ウレタン樹脂を実質上乳化剤を使用せずに水中に分散させた水系ウレタン樹脂、（ｂ）シリカ、（ｃ）シリコーン系非イオン界面活性剤（ｄ）シリコーン系消泡剤及び（ｅ）アルコールを含む難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１５】
本発明の第九態様は、（ａ）非反応型、自己乳化型であり、異なる粒径からなるウレタン樹脂、そのウレタン樹脂は実質上乳化剤を使用せずに水中に分散させる事ができ、又は前期ウレタン樹脂とウレタン・アクリル複合樹脂との混合物、その混合物は、異なる粒径の粒子からなり、（ｂ）メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート又はブチルセロソルブアセテート等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｃ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１６】
本発明の第十態様は、（ａ）非反応型、自己乳化型であり、異なる粒径からなるウレタン樹脂、そのウレタン樹脂は実質上乳化剤を使用せずに水中に分散させる事ができ、又は前期ウレタン樹脂とウレタン・アクリル複合樹脂との混合物、その混合物は、異なる粒径の粒子からなり、（ｂ）シリカ（ｃ）シリコーン系消泡剤及び（ｄ）シリコーン系非イオン界面活性剤及（ｅ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１７】
本発明の十一態様は、（ａ）非反応型、自己乳化型であり、実質上乳化剤を使用せずに水中に分散させる事ができるウレタン樹脂とウレタン・アクリル複合樹脂との混合物、この場合その混合物は、異なる粒径の粒子からなり、（ｂ）メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート又はブチルセロソルブアセテート等のセロソルブ系化合物又はシリコーン系非イオン界面活性剤及び（ｃ）イソプロピルアルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１８】
本発明の第十二態様は、（ａ）非反応型、自己乳化型であり、実質上乳化剤を使用せずに水中に分散させる事ができるウレタン樹脂とウレタン・アクリル複合樹脂との混合物、この場合その混合物は、異なる粒径の粒子からなり、（ｂ）シリカ（ｃ）シリコーン系非イオン界面活性剤，（ｄ）シリコーン系消泡剤及び（ｅ）アルコールを含み、組成物（ａ）は組成物中エマルジョンとして存在する難加工金属用の水性被覆潤滑剤組成物を難加工金属に塗布し、乾燥してその組成物の塗膜を形成し、その後、その金属の深絞り加工を行なうことを特徴とする金属の加工方法に関する。
【００１９】
総樹脂成分が総重量の６〜３５重量％を含むことが好ましい。
本発明の難加工金属用の水性被覆潤滑剤組成物には金属支持体の表面の耐蝕性を良くするためにクロム酸を加えても良い。
【００２０】
樹脂成分は、水性被覆潤滑剤組成物の６〜３５重量％含まれることが好ましい。
本発明で使用されるウレタン樹脂は、非反応型、自己乳化型ウレタン樹脂であり、それはウレタン樹脂に若干の親水性を、又は親水性セグメントを付与し、水溶性又は自己分散型にしたものであり、乳化剤を使用せずに、水に分散又は溶解できる。
【００２１】
自己乳化型でないウレタン樹脂は乳化させる際に、乳化剤が必要となる。乳化剤を使用して乳化させた自己乳化型でないウレタン樹脂の水性エマルジョンを本発明のように使用するとゲル化し、所望の被覆潤滑剤組成物は得られない。本発明のウレタン樹脂エマルジョンは、ウレタン樹脂を液体中に例えば高速分散させて得られたものである。
【００２２】
ウレタン・アクリル複合樹脂とは、ウレタン樹脂とアクリル樹脂との単なる混合物ではなく、ウレタンポリマーとアクリルポリマー又はアクリル−スチレンコポリマーとを特殊複合化したエマルジョンである。例えば、アクリル樹脂に導入したケト基とウレタン樹脂に導入したヒドラジド基による架橋反応させて、ウレタン・アクリル複合樹脂を製造する。また、水性ウレタン樹脂の存在下、アクリルモノマーを重合することで、ウレタン・アクリル複合樹脂を製造しても良い。
【００２３】
本発明で使用されるフッ素樹脂粉末は潤滑性、離型性、耐熱に優れ、ウレタン樹脂皮膜の耐摩耗性を高め、難加工金属に良好な深絞り効果を発揮することに役に立つ。フッ素樹脂は固体材用の中で最も低い摩擦係数を示し、これを主剤であるウレタン樹脂に添加することにより、より難度の高い加工が可能になる。
そのフッ素樹脂粉末の平均粒径は０．１〜５０μｍのものが好ましい。
【００２４】
フッ素樹脂粉末は比重により液中に沈殿しやすいのであらかじめ水分散処置がとられているディスパージョンタイプの使用が望ましい。
フッ素樹脂粉末は一般に総組成物量に対し５〜１５％が望ましい。
【００２５】
フッ素樹脂の単独使用による難加工適用も考え得るが、この樹脂を金属に密着させるにはいずれにおいても硬化剤の使用、もしくは長時間高温での焼付けが必要であり、工業使用についてはフッ素樹脂そのものの高価格もあいまって非常にコストのかかるものとなる。
【００２６】
本発明で使用されるフッ素樹脂粉末はウレタン樹脂に均一に分散させることが重要であり、この為にあらかじめ分散剤によって水分散されたフッ素樹脂ディスパージョンを使用しても良い。
【００２７】
本発明の第一、第三及び第五の様態に使用されるセルソルブ化合物は、レベリング及び濡れ性の付与に役に立つ、セルソルブ化合物としてブチセルソルブがもっとも好ましい。
一般にセルソルブ化合物は総組成物量の５〜２０％使用することが好ましい。
【００２８】
アルコールとしてイソプロピルアルコールが好ましい。イソプロピルアルコールは、低い温度（１００℃以下の温度）で水と一緒に外気に飛散しやすいので乾燥は速くなる。イソプロピルアルコールは一般に総組成物量に対し８〜２５％使用するのが好ましい。
【００２９】
本発明の第二、第四及び第六の様態においてシリカとしてシリカゾルが好ましい。シリカゾルは、金属支持体の膜の傷防止、硬度を高めかつ耐食性の改良及び付加、白化防止において役に立つ。シリカとセルソルブ化合物を一緒に使用すると樹脂がゲル化する。そのためシリカを使用する時は、セルソルブ化合物の代わりにシリコーン系非イオン界面活性剤及びシリコーン系消泡剤を使用する。
【００３０】
ウレタン樹脂及びウレタン・アクリル樹脂、フッ素樹脂は耐熱、耐久性、可撓性、耐摩耗性に優れ、金属表面に接着硬化、皮膜の分子密度が高く硬度Ｈ以上では難加工材に対し良好な潤滑保護皮膜になる又、加工中及び加工後の傷防止となる。
【００３１】
本発明の第四から第六の態様において異なる粒径からなる樹脂を使用する。難加工材に鏡面加工を施されている場合、密着力を高めるのに役に立つ。ウレタン樹脂のみを使用するときは、異なる粒径からなるウレタン樹脂を使用する。例えば、前記異なる粒径からなるウレタン樹脂は、１０〜４０ｎｍの粒径の粒子と６０〜１００ｎｍの粒径の粒子とからなることが好ましい。
非反応型、自己乳化型ウレタン樹脂を実質上乳化剤を使用せずに水中に分散させたウレタン樹脂とウレタン・アクリル複合樹脂との混合物を使用する場合、その混合物は、１０〜４０ｎｍの粒径の粒子と６０〜１００ｎｍの粒径の粒子とからなることが好ましい。この場合、ウレタン樹脂は、６０〜１００ｎｍの粒径の粒子を使用し、ウレタン・アクリル複合樹脂は、１０〜４０ｎｍの粒径の粒子を使用することが、より好ましい。
即ちこのフッ素樹脂を分散させたウレタン樹脂及び／又はウレタン・アクリル複合樹脂は、通常の水性樹脂皮膜では見られない分子間の密度高くピンホール無く耐熱性があり、温水によって膨張しにくいため塗装に際し高速でシームレス状の皮膜を作るため熱風加熱（前、後）温度７０℃〜１２０℃スプレー塗装、空気冷却１〜３秒で固化するため塗装前後の液の垂れ状態がないため作業環境が良く際しようが出来水溶性のため引火性がないので危険物とならない。
本発明において樹脂成分として、ウレタン樹脂及びウレタン・アクリル複合樹脂を使用する場合、それぞれの樹脂は、２０〜８０重量％使用することが好ましい。
本発明においてフッ素樹脂は総樹脂成分の５〜４５重量％使用することが好ましい。
本発明において、組成分中、樹脂成分は、６〜３０重量％使用することが好ましい。
本発明の各成分は任意の方法で混合して組成物を形成できる。
本発明組成物を金属支持体に適用する方法はまず金属支持体を例えば温度７０℃〜１２０℃で暖めその後本発明組成物をスプレー塗布し乾燥すると共にその樹脂は皮膜化し硬化する。又、室温の金属支持体に組成物をスプレー塗布後、炉内温度７０℃〜１２０℃上昇させてその組成物を乾燥硬化させる。
本発明組成物は本発明はチタン鋼板、ステンレス鋼板、亜鉛メッキ鋼板、マグネシウム合金鋼板、等特殊合金鋼板の難加工材（強度が高い、スプリングバックが大きい）の傷防止、深絞り加工範囲の拡大を可能にする性能を備えている。
【００３２】
本発明組成物においてはフッ素樹脂を分散させたウレタン樹脂、ウレタン・アクリル複合樹脂は水性のため、危険物にならず、引火しない。しかも速乾性、密着硬膜なので金属表面に接着硬化し被膜は光沢があり深絞り加工後、例えば鋼管と鋼管またロールとの物理的接触をしても被膜が剥離しにくい、そして均一被膜（シームレス）により製品表面の向上となる。潤滑性、離型性、耐熱、耐久性、可撓性、耐摩耗性に優れ、難加工材の深絞り加工範囲の拡大、傷防止に最適である。
又、例えば組成物を金属支持体にスプレーした後、下にしたたり落ちた組成物は循環再使用が出来るため経済的である。
【００３３】
【実施例】
以下に本発明をさらに説明のため、実施例を示す。これらの実施例は、本発明を限定するものではない。
以下の実施例及び比較例の成分から水性組成物を調整した。すべての組成物においてウレタン樹脂、ウレタン・アクリル複合樹脂は、エマルジョンとなっている。
【００３４】
実施例１
ウレタン樹脂エマルジョン１８．０ＷＴ％
フッ素樹脂粉末３．０〃
ブチルセロソルブ１６．０〃
イソプロピルアルコール２０．０〃
トリエチルアミン０．２〃
水道水４２．８〃
実施例２
ウレタン樹脂エマルジョン１５．０ＷＴ％
フッ素樹脂粉末１．５〃
ブチルセロソルブ１８．０〃
イソプロピルアルコール２２．０〃
水道水４３．５〃
実施例３
ウレタン樹脂エマルジョン１５．０ＷＴ％
フッ素樹脂ディスパージョン６．５〃
シリカゾル４．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水７３．５〃
実施例４
ウレタン樹脂エマルジョン１０．０ＷＴ％
フッ素樹脂ディスパージョン５．０〃
イソプロピルアルコール２０．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水６４．０〃
実施例５
ウレタン樹脂エマルジョン１５．０ＷＴ％
フッ素樹脂粉末１．５〃
ブチルセロソルブ１８．０〃
イソプロピルアルコール２２．０〃
水道水４３．５〃
ウレタン樹脂の粒径
９０ｎｍ３０ＷＴ％
８０ｎｍ３０ＷＴ％
２０ｎｍ６０ＷＴ％
実施例６
ウレタン樹脂エマルジョン８．０ＷＴ％
ウレタン・アクリル複合樹脂７．０〃
フッ素樹脂ディスパージョン５．０〃
イソプロピルアルコール２０．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水６４．０〃
樹脂の粒径
ウレタン樹脂の粒径９０ｎｍ
ウレタン・アクリル樹脂の粒径３０ｎｍ
実施例７
ウレタン樹脂エマルジョン１５．０ＷＴ％
ブチルセロソルブ１８．０〃
イソプロピルアルコール２２．０〃
水道水４５．０〃
実施例８
ウレタン樹脂エマルジョン１５．０ＷＴ％
ブチルセロソルブ１８．０〃
イソプロピルアルコール２２．０〃
水道水４３．５〃
実施例９
ウレタン樹脂エマルジョン１５．０ＷＴ％
シリカゾル４．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水７３．５〃
実施例１０
ウレタン樹脂エマルジョン１０．０ＷＴ％
イソプロピルアルコール２０．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水６４．０〃
実施例１１
ウレタン樹脂エマルジョン１５．０ＷＴ％
ブチルセロソルブ１８．０〃
イソプロピルアルコール２２．０〃
水道水４３．５〃
ウレタン樹脂の粒径
９０ｎｍ３０ＷＴ％
８０ｎｍ３０ＷＴ％
２０ｎｍ６０ＷＴ％
実施例１２
ウレタン樹脂エマルジョン８．０ＷＴ％
ウレタン・アクリル複合樹脂７．０〃
イソプロピルアルコール２０．０〃
シリコーン系非イオン界面活性剤０．９〃
シリコーン系消泡剤０．１〃
水道水６４．０〃
比較例１
ＰＥフィルム
比較例２
プレス油
実施例８
円筒では東京衡機製ＴＦ−１０２−３０型深絞り試験機を使用し、角筒では日本オートマチック株式会社製ＨＹＰ１０００卓上油圧プレス機を使用した。基本仕様を表１，２に示す。
【００３５】
【表１】

【００３６】
【表２】

【００３７】
金型
パンチとダイス寸法を表３に示し、そのクリアランスは、一般的に最適条件とされている範囲内で片側０．５８ｍｍとした。パンチ、ダイス、しわ抑え板の材質は工具鋼（ＳＫＤ１１）を使用した。
【００３８】
【表３】

【００３９】
実験材料
本試験に使用した供試材は、板厚ｔ＝０．５ｍｍの冷間圧延純チタン板一種（ＴＰ２７０Ｃ）で表４にその機械的性質を示す。尚、供試材の圧延方向をＬ方向、圧延に直角方向をＴ方向とする。但し、ＰＳは耐力、ＴＳは引張強さ、ＥＬは全伸びを示す。
【００４０】
【表４】

【００４１】
潤滑剤
潤滑剤はＰＥフィルム、プレス油、ＤＱ−３３１Ｓ（実施例７）、ＤＱ−３３１ＳＴ（実施例１）を使用した。潤滑剤の性状を表５に示す。
【００４２】
【表５】

【００４３】
ＤＱ−３３１ＳＴは、ＤＱ−３３１Ｓにポリフルオロカーボンを加えたものである。
ＤＱ−３３１Ｓ及びＤＱ−３３１ＳＴは、予めチタン板に塗布し、乾燥して、チタン板の表面に塗膜を形成した。
【００４４】
ＰＥフィルム２枚の間にチタン板を挟んで実験を行なった。
プレス油は、予め型に塗布した。
板厚ひずみ測定位置
円筒絞りにおいて板厚ひずみの測定位置を図１に示す。
円筒実験
実験方法
ＰＥフィルム二枚の間には供試材を挟んで絞り加工する。ＤＱ−３３１Ｓ、ＤＱ−３３１ＳＴは片面に吹きかけ、遠赤外線コンベアを使用し乾燥させる。裏面の同様に行う。しわ抑え力は、ＰＥフィルムの場合３．０ｔ、ＤＱ−３３１Ｓ、ＤＱ−３３１ＳＴの場合０．３ｔとする。
【００４５】
限界絞り比（ＬＤＲ）は、供試材径Ｄとポンチ径ｄを用いて次式で表される。
ＬＤＲ＝Ｄ／ｄ（１）
実験結果及び考察
図２よりＬＤＲはＤＱ−３３１ＳＴとＰＥフィルムが大きいことがわかる。ＳＱ３３１Ｓに比べＤＱ−３３１ＳＴの方のＬＤＲが大きいのは、ＤＱ−３３１ＳＴに含まれるポリフロロカーボンの影響だと考える。ポリフロロカーボンの特性として低摩擦力であり、事故潤滑性に優れているという事が挙げられる。よって、ＤＱ−３３１ＳよりＤＱ−３３１ＳＴの方が優れた潤滑剤であることが分かった。昨年度の研究で固形潤滑剤のＰＥフィルムが一番だと考えられていた。しかし、図３及び４の板厚ひずみのグラフにより、ＰＥフィルムに比べ、全般的にＤＱ−３３１ＳＴの方の板厚ひずみが抑えられている。測定位置９，１０で板厚ひずみが増加するのは、しわの影響である。今後もＤＱ−３３１ＳＴについて考えていかなければならないだろう。
【００４６】
実施例２〜６及び実施例８〜１２の組成物を使用して同様な実験を行なった。図１に示す９及び１０の測定位置の板厚ひずみ（％）は、以下の表６に示される。
【００４７】
【表６】

【図面の簡単な説明】
【図１】測定装置の概略図
【図２】テストサンプルの限界絞り比を示すグラフ
【図３】板厚ひずみ方向と板厚ひずみとの関係を示すグラフ
【図４】板厚ひずみ方向と板厚ひずみとの関係を示すグラフ[0001]
[Industrial application fields]
The present invention is a difficult-to-work metal capable of preventing scratches on specially-made steel plates such as titanium steel plates, stainless steel plates, galvanized steel plates, magnesium alloy steel plates, etc. (high strength, large springback) and expanding the drawing range. The present invention relates to an aqueous coating lubricant composition.
[0002]
[Problems to be solved by the invention]
For example, difficult-to-process materials such as titanium steel plate, stainless steel plate, galvanized steel plate, magnesium alloy steel plate, etc. have few sliding surfaces, and the surface oxide film is very thin and rich in activity. In this case, seizure is likely to occur and deep drawing is difficult. There is currently no suitable lubricant.
[0003]
Coil products are currently being developed for difficult-to-process materials of special alloy steel plates such as titanium steel plates and magnesium alloy steel plates, but press-processed products using them are behind.
Special alloy steel plate is lightweight and has high strength, corrosion resistance, electromagnetic wave shielding, ductility, etc., but it has a close-packed hexagonal lattice structure and few sliding surfaces.
[0004]
Therefore, conventionally, in order to obtain deep-drawn products of difficult-to-work materials such as titanium steel plates, stainless steel plates, galvanized steel plates, magnesium alloy steel plates, etc. In such a molding method in which a metal is poured into a mold to obtain a necessary shape, a lot of cost is required for heat energy, product yield, application of a release material, removal thereof, processing man-hours, intermediate annealing, Many processing steps such as cutting are required.
[0005]
Bending is carried out, but when mass production is carried out, metal powder (powder ringing phenomenon) is generated, and continuous production is difficult.
Depending on the type of special alloy steel plate, it will be very expensive to remove when fingerprints are attached, and even if other oils are attached, the commercial value will be lost.
[0006]
[Means for Solving the Problems]
Through extensive research, the present inventor has found that when a specific aqueous coating lubricant composition is used, it is possible to deep-draw a difficult-to-process material, leading to the present invention. That is, the aqueous coating lubricant composition of the present invention was found to form a hard film with high density when applied to a metal surface as an aqueous solution and dried, and at the same time has high lubricity, and the aqueous coating lubricant composition The present inventor has found that a good deep drawing effect is exerted on difficult-to-work metals, and has led to the present invention.
[0007]
That is, the first aspect of the present invention comprises (a) a water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, (b) a fluororesin powder or fine particles thereof in advance. Dispersion dispersed in water with a dispersant (c) methyl cellosolve (ethylene glycol monomethyl ether) , ethyl cellosolve (ethylene glycol monoethyl ether) , butyl cellosolve ( ethylene glycol monobutyl ether) , methyl cellosolve acetate ( ethylene glycol monomethyl ether acetate) , Cellosolve compounds such as ethyl cellosolve acetate ( ethylene glycol monoethyl ether acetate) or butyl cellosolve acetate (ethylene glycol monobutyl ether acetate) or silico The present invention relates to an aqueous coating lubricant composition for difficult-to-work metals containing a nonionic surfactant and (d) an alcohol, wherein the resin component comprises 6 to 35% by weight of the total weight.
[0008]
The second aspect of the present invention is: (a) a water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier; (b) a fluororesin powder or its fine particles are dispersed in advance. Dispersion dispersed in water with an agent (c) silica, (d) silicone-based nonionic surfactant (e) silicone-based antifoaming agent and (f) alcohol, the resin component being 6 to 35% by weight of the total weight The present invention relates to an aqueous coating lubricant composition for difficult-to-work metals.
[0009]
The third aspect of the present invention is (a) a non-reactive type, a self-emulsifying type, a urethane resin having a different particle size, the urethane resin can be dispersed in water substantially without using an emulsifier, or Mixture of urethane resin and urethane / acrylic composite resin in the previous period, and the mixture consists of particles of different particle diameters, (b) Dispersion in which fluororesin powder or its fine particles are dispersed in water with a dispersant (c) Methyl cellosolve , Ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, cellosolve compound such as ethyl cellosolve acetate or butyl cellosolve acetate, or a silicone-based nonionic surfactant and (d) an alcohol, and composition (a) exists as an emulsion in the composition The present invention relates to an aqueous coating lubricant composition for difficult-to-work metals.
[0010]
The fourth aspect of the present invention is (a) a non-reactive type, a self-emulsifying type, a urethane resin having a different particle size, the urethane resin can be dispersed in water substantially without using an emulsifier, or A mixture of urethane resin and urethane / acrylic composite resin in the previous period, and the mixture is composed of particles having different particle diameters. (B) Dispersion (c) Silica (c) d) An aqueous coated lubricant composition for difficult-to-work metals comprising a silicone-based antifoam and (f) a silicone-based nonionic surfactant and (e) an alcohol, wherein the composition (a) is present as an emulsion in the composition. About.
[0011]
The fifth aspect of the present invention is (a) a non-reactive, self-emulsifying type, which is a mixture of a urethane resin and a urethane / acrylic composite resin that can be dispersed in water substantially without using an emulsifier, in this case The mixture is composed of particles having different particle diameters, and (b) a dispersion in which fluororesin powder or fine particles thereof are dispersed in water with a dispersant in advance (c) methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Or a cellosolve compound such as butyl cellosolve acetate or a silicone-based nonionic surfactant and (d) isopropyl alcohol, wherein the composition (a) relates to an aqueous coating lubricant composition for difficult-to-work metals present as an emulsion in the composition. .
[0012]
The sixth aspect of the present invention is (a) a non-reactive type, self-emulsifying type, which is a mixture of a urethane resin and a urethane-acrylic composite resin that can be dispersed in water substantially without using an emulsifier, in this case The mixture is composed of particles having different particle diameters, (b) a dispersion in which fluororesin powder or fine particles thereof are dispersed in water with a dispersant in advance (c) silica (d) silicone-based nonionic surfactant, (d) Composition (a) relates to an aqueous coated lubricant composition for difficult-to-work metals present as an emulsion in the composition, comprising a silicone antifoam and (e) an alcohol.
[0013]
The seventh aspect of the present invention comprises (a) a water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, (b) methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl An aqueous coating lubricant composition for difficult-to-work metal containing cellosolve compound such as cellosolve acetate, ethyl cellosolve acetate or butyl cellosolve acetate or silicone nonionic surfactant and alcohol is applied to the difficult-to-work metal and dried. The present invention relates to a method for processing a metal, characterized in that a coating film of the composition is formed, and then deep drawing of the metal is performed.
[0014]
The eighth aspect of the present invention is: (a) a non-reactive, self-emulsifying urethane resin dispersed in water substantially without using an emulsifier, (b) silica, (c) silicone-based nonionic the surfactant (d) silicone antifoaming agent and (e) an aqueous coating lubricant composition for flame processing metal containing alcohol was applied to the hard-to-work metals, and dried to form a coating film of the composition, Then, it is related with the metal processing method characterized by performing deep drawing of the metal.
[0015]
The ninth aspect of the present invention is (a) a non-reactive type, a self-emulsifying type, a urethane resin having a different particle size, the urethane resin can be dispersed in water substantially without using an emulsifier, or Mixture of urethane resin and urethane / acrylic composite resin, the mixture consists of particles of different particle size, and (b) cellosolv type such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate or butyl cellosolve acetate compound or comprises a silicone-based non-ionic surfactant and (c) an alcohol, the composition (a) is coated with an aqueous coating lubricant composition for flame working metal present as an emulsion in the composition in hard-to-work metals, dried to form a coating film of the composition, then, characterized by performing the deep drawing of the metal Processing method of the metal to be about.
[0016]
The tenth aspect of the present invention is (a) a non-reactive type, a self-emulsifying type, a urethane resin having a different particle size, the urethane resin can be dispersed in water substantially without using an emulsifier, or The mixture of urethane resin and urethane / acrylic composite resin in the previous period, and the mixture is composed of particles having different particle diameters, and includes (b) silica (c) silicone-based antifoaming agent and (d) silicone-based nonionic surfactant ( e) An alcohol-containing composition (a) is formed by applying an aqueous coated lubricant composition for difficult-to-work metals present as an emulsion in the composition to the difficult-to-work metal and drying to form a coating film of the composition. Then, the present invention relates to a metal processing method characterized by performing deep drawing of the metal.
[0017]
The eleventh aspect of the present invention is (a) a non-reactive type, self-emulsifying type, which is a mixture of a urethane resin and a urethane-acrylic composite resin that can be dispersed in water substantially without using an emulsifier, in this case The mixture consists of particles of different particle sizes, (b) a cellosolve compound such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate or butyl cellosolve acetate, or a silicone nonionic surfactant and (c) The composition (a) comprises an aqueous coating lubricant composition for difficult-to-work metals present as an emulsion in the composition, applied to the difficult-to-work metal and dried to form a coating film of the composition; Then, it is related with the metal processing method characterized by performing deep drawing of the metal.
[0018]
A twelfth aspect of the present invention is (a) a non-reactive type, self-emulsifying type, which is a mixture of a urethane resin and a urethane / acrylic composite resin that can be dispersed in water substantially without using an emulsifier, The mixture comprises particles of different particle sizes, comprising (b) silica (c) silicone-based nonionic surfactant, (d) silicone-based antifoaming agent and (e) alcohol, wherein composition (a) comprises An aqueous coating lubricant composition for difficult-to-work metals present as an emulsion in the composition is applied to the difficult-to-work metal and dried to form a coating film of the composition, followed by deep drawing of the metal The present invention relates to a method for processing metal.
[0019]
It is preferred that the total resin component comprises 6 to 35% by weight of the total weight.
In order to improve the corrosion resistance of the surface of the metal support, chromic acid may be added to the aqueous coating lubricant composition for difficult-to-work metals of the present invention.
[0020]
The resin component is preferably contained in an amount of 6 to 35% by weight of the aqueous coating lubricant composition.
The urethane resin used in the present invention is a non-reactive type, self-emulsifying type urethane resin, which imparts some hydrophilicity or hydrophilic segment to the urethane resin to make it water-soluble or self-dispersible. Yes, it can be dispersed or dissolved in water without using an emulsifier.
[0021]
When the urethane resin that is not self-emulsifying is emulsified, an emulsifier is required. When an aqueous emulsion of a urethane resin that is not self-emulsified and emulsified using an emulsifier is used as in the present invention, it gels and a desired coated lubricant composition cannot be obtained. The urethane resin emulsion of the present invention is obtained by, for example, dispersing a urethane resin in a liquid at high speed.
[0022]
The urethane / acrylic composite resin is not a simple mixture of a urethane resin and an acrylic resin, but an emulsion in which a urethane polymer and an acrylic polymer or an acrylic-styrene copolymer are specially combined. For example, a urethane-acrylic composite resin is produced by a cross-linking reaction between a keto group introduced into an acrylic resin and a hydrazide group introduced into a urethane resin. Alternatively, a urethane / acrylic composite resin may be produced by polymerizing an acrylic monomer in the presence of an aqueous urethane resin.
[0023]
The fluororesin powder used in the present invention is excellent in lubricity, releasability, and heat resistance, enhances the wear resistance of the urethane resin film, and is useful for exhibiting a good deep drawing effect on difficult-to-work metals. A fluororesin exhibits the lowest coefficient of friction among solid materials, and by adding this to the urethane resin as the main agent, processing with a higher degree of difficulty becomes possible.
The fluororesin powder preferably has an average particle size of 0.1 to 50 μm.
[0024]
Since the fluororesin powder is likely to precipitate in the liquid due to its specific gravity, it is desirable to use a dispersion type in which a water dispersion treatment has been taken in advance.
In general, the fluororesin powder is desirably 5 to 15% based on the total amount of the composition.
[0025]
Although it is possible to apply difficult processing by using a fluororesin alone, it is necessary to use a curing agent or baking at a high temperature for a long time in order to adhere this resin to a metal. For industrial use, the fluororesin itself Combined with the high price, it can be very expensive.
[0026]
It is important to uniformly disperse the fluororesin powder used in the present invention in the urethane resin. For this purpose, a fluororesin dispersion previously dispersed in water with a dispersant may be used.
[0027]
The cellosolve compound used in the first, third and fifth modes of the present invention is most preferably butycelsolve as the cellosolve compound, which is useful for imparting leveling and wettability.
In general, the cellosolve compound is preferably used in an amount of 5 to 20% of the total composition.
[0028]
Isopropyl alcohol is preferred as the alcohol. Since isopropyl alcohol is likely to be scattered to the outside air together with water at a low temperature (temperature of 100 ° C. or lower), drying is quick. In general, isopropyl alcohol is preferably used in an amount of 8 to 25% based on the total amount of the composition.
[0029]
In the second, fourth and sixth aspects of the present invention, silica sol is preferred as the silica. Silica sol is useful in preventing scratches on the metal support film, increasing hardness and improving and adding corrosion resistance, and preventing whitening. When silica and a cellsolve compound are used together, the resin gels. Therefore, when using silica, a silicone-based nonionic surfactant and a silicone-based antifoaming agent are used in place of the cellsolve compound.
[0030]
Urethane resin, urethane / acrylic resin, and fluororesin have excellent heat resistance, durability, flexibility, and wear resistance. Adhesion and curing on metal surface, high molecular density of film, and good lubrication for difficult-to-work materials when hardness is H or higher. It also becomes a protective film and prevents scratches during and after processing.
[0031]
In the fourth to sixth embodiments of the present invention, resins having different particle sizes are used. Useful for enhancing adhesion when difficult-to-process materials are mirror-finished. When only urethane resin is used, urethane resin having different particle diameters is used. For example, the urethane resin having different particle diameters is preferably composed of particles having a particle diameter of 10 to 40 nm and particles having a particle diameter of 60 to 100 nm.
When using a mixture of a urethane resin and a urethane-acrylic composite resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, the mixture has a particle size of 10 to 40 nm. The particles are preferably composed of particles and particles having a particle diameter of 60 to 100 nm. In this case, it is more preferable that the urethane resin uses particles having a particle diameter of 60 to 100 nm, and the urethane / acrylic composite resin uses particles having a particle diameter of 10 to 40 nm.
In other words, the urethane resin and / or urethane / acrylic composite resin in which this fluororesin is dispersed has a high intermolecular density and heat resistance without pinholes that cannot be seen in a normal aqueous resin film, and is difficult to expand by warm water. Hot air heating (before and after) temperature 70 ° C-120 ° C spray coating to create a high-speed seamless film, air cooling solidifies in 1 to 3 seconds, so there is no dripping state before and after coating, and the working environment is good Because it is water-soluble and has no flammability, it is not dangerous.
In the present invention, when a urethane resin and a urethane / acrylic composite resin are used as the resin component, each resin is preferably used in an amount of 20 to 80% by weight.
In the present invention, the fluororesin is preferably used in an amount of 5 to 45% by weight based on the total resin components.
In the present invention, the resin component is preferably used in an amount of 6 to 30% by weight in the composition.
The components of the present invention can be mixed by any method to form a composition.
In the method of applying the composition of the present invention to a metal support, the metal support is first warmed at a temperature of, for example, 70 ° C. to 120 ° C., and then the composition of the present invention is spray-coated and dried, and the resin is filmed and cured. Moreover, after spray-coating the composition on a metal support at room temperature, the temperature in the furnace is increased from 70 ° C. to 120 ° C., and the composition is dried and cured.
The composition of the present invention is a titanium steel plate, a stainless steel plate, a galvanized steel plate, a magnesium alloy steel plate, a special alloy steel plate such as a difficult-to-process material (high strength, large spring back), and a deep drawing process range expansion. It has the performance that makes it possible.
[0032]
In the composition of the present invention, the urethane resin in which the fluororesin is dispersed and the urethane / acrylic composite resin are water-based, so that they are not dangerous and do not ignite. Moreover, since it is a quick-drying and adhesive hard film, it adheres and hardens on the metal surface, the film is glossy, and after deep drawing, for example, the film does not peel easily even if physical contact is made between the steel pipe and the steel pipe or roll. ) Improves the product surface. It has excellent lubricity, releasability, heat resistance, durability, flexibility, and wear resistance, and is ideal for expanding the deep drawing range of difficult-to-process materials and preventing scratches.
Further, for example, a composition dropped or dropped after spraying the composition on a metal support is economical because it can be recycled.
[0033]
【Example】
The following examples are provided to further illustrate the present invention. These examples do not limit the invention.
Aqueous compositions were prepared from the components of the following Examples and Comparative Examples. In all the compositions, the urethane resin and the urethane / acrylic composite resin are emulsions.
[0034]
Example 1
Urethane resin emulsion 18.0WT%
Fluororesin powder 3.0 〃
Butyl cellosolve 16.0 〃
Isopropyl alcohol 20.0 〃
Triethylamine 0.2 〃
Tap water 42.8 〃
Example 2
Urethane resin emulsion 15.0WT%
Fluorine resin powder 1.5 〃
Butyl cellosolve 18.0 〃
Isopropyl alcohol 22.0 〃
Tap water 43.5 〃
Example 3
Urethane resin emulsion 15.0WT%
Fluorine resin dispersion 6.5 〃
Silica sol 4.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 73.5 〃
Example 4
Urethane resin emulsion 10.0WT%
Fluorine resin dispersion 5.0 〃
Isopropyl alcohol 20.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 64.0 〃
Example 5
Urethane resin emulsion 15.0WT%
Fluorine resin powder 1.5 〃
Butyl cellosolve 18.0 〃
Isopropyl alcohol 22.0 〃
Tap water 43.5 〃
Urethane resin particle size 90nm 30WT%
80nm 30WT%
20nm 60WT%
Example 6
Urethane resin emulsion 8.0WT%
Urethane / acrylic composite resin 7.0 〃
Fluorine resin dispersion 5.0 〃
Isopropyl alcohol 20.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 64.0 〃
Resin particle size Urethane resin particle size 90nm
Particle size of urethane / acrylic resin 30nm
Example 7
Urethane resin emulsion 15.0WT%
Butyl cellosolve 18.0 〃
Isopropyl alcohol 22.0 〃
Tap water 45.0 〃
Example 8
Urethane resin emulsion 15.0WT%
Butyl cellosolve 18.0 〃
Isopropyl alcohol 22.0 〃
Tap water 43.5 〃
Example 9
Urethane resin emulsion 15.0WT%
Silica sol 4.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 73.5 〃
Example 10
Urethane resin emulsion 10.0WT%
Isopropyl alcohol 20.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 64.0 〃
Example 11
Urethane resin emulsion 15.0WT%
Butyl cellosolve 18.0 〃
Isopropyl alcohol 22.0 〃
Tap water 43.5 〃
Urethane resin particle size 90nm 30WT%
80nm 30WT%
20nm 60WT%
Example 12
Urethane resin emulsion 8.0WT%
Urethane / acrylic composite resin 7.0 〃
Isopropyl alcohol 20.0 〃
Silicone nonionic surfactant 0.9 〃
Silicone defoamer 0.1 〃
Tap water 64.0 〃
Comparative Example 1
PE film comparative example 2
Press oil Example 8
A TF-102-30 deep drawing tester manufactured by Tokyo Henki was used for the cylinder, and a HYP1000 desktop hydraulic press machine manufactured by Nippon Automatic Co., Ltd. was used for the square tube. Tables 1 and 2 show the basic specifications.
[0035]
[Table 1]

[0036]
[Table 2]

[0037]
The die punch and die dimensions are shown in Table 3, and the clearance is set to 0.58 mm on one side within a range generally considered as an optimum condition. Tool steel (SKD11) was used as the material for the punch, die and wrinkle restraining plate.
[0038]
[Table 3]

[0039]
Experimental material The test material used in this test is a kind of cold-rolled pure titanium plate (TP270C) having a thickness t = 0.5 mm, and its mechanical properties are shown in Table 4. In addition, let the rolling direction of a test material be an L direction, and let a perpendicular direction to rolling be a T direction. However, PS is the yield strength, TS is the tensile strength, and EL is the total elongation.
[0040]
[Table 4]

[0041]
As the lubricant, PE film, press oil, DQ-331S (Example 7), and DQ-331ST (Example 1) were used. Table 5 shows the properties of the lubricant.
[0042]
[Table 5]

[0043]
DQ-331ST is obtained by adding polyfluorocarbon to DQ-331S.
DQ-331S and DQ-331ST were previously applied to a titanium plate and dried to form a coating film on the surface of the titanium plate.
[0044]
The experiment was conducted with a titanium plate sandwiched between two PE films.
The press oil was previously applied to the mold.
Plate thickness strain measurement position Fig. 1 shows the plate thickness strain measurement position in the cylindrical diaphragm.
Cylindrical experiment test method A drawing material is drawn between two PE films. DQ-331S and DQ-331ST are sprayed on one side and dried using a far-infrared conveyor. Do the same for the back side. The wrinkle restraining force is 3.0 t for PE film, and 0.3 t for DQ-331S and DQ-331ST.
[0045]
The limit drawing ratio (LDR) is expressed by the following equation using the specimen diameter D and punch diameter d.
LDR = D / d (1)
Experimental Results and Discussion From FIG. 2, it can be seen that LDR is larger in DQ-331ST and PE film. It is considered that the LDR of DQ-331ST is larger than that of SQ331S because of the influence of polyfluorocarbon contained in DQ-331ST. A characteristic of polyfluorocarbon is low frictional force and excellent accident lubricity. Therefore, it was found that DQ-331ST is a better lubricant than DQ-331S. In the last year's research, solid lubricant PE film was considered the best. However, the thickness strain graphs of FIGS. 3 and 4 generally suppress the thickness strain of DQ-331ST as compared to the PE film. The increase in plate thickness distortion at the measurement positions 9 and 10 is due to wrinkles. I will have to think about DQ-331ST in the future.
[0046]
Similar experiments were performed using the compositions of Examples 2-6 and Examples 8-12. The thickness strain (%) at the measurement positions 9 and 10 shown in FIG. 1 is shown in Table 6 below.
[0047]
[Table 6]

[Brief description of the drawings]
FIG. 1 is a schematic diagram of a measuring apparatus. FIG. 2 is a graph showing a limit drawing ratio of a test sample. FIG. 3 is a graph showing a relation between a plate thickness strain direction and a plate thickness strain. Graph showing the relationship with thickness strain

Claims

(A) A water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, and the urethane resin has a particle size of 10 to 40 nm and a particle size of 60 to 100 nm. (B) a dispersion in which a fluororesin powder or its fine particles are dispersed in water with a dispersant , (c) ethylene glycol monomethyl ether , ethylene glycol monoethyl ether , ethylene glycol monobutyl ether , ethylene glycol monomethyl ether acetate, A compound selected from ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate or a silicone-based nonionic surfactant , and (d) an alcohol,
An aqueous coating lubricant composition for difficult-to-work metals.

(A) A water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, and the urethane resin has a particle size of 10 to 40 nm and a particle size of 60 to 100 nm. (B) a dispersion in which a fluororesin powder or its fine particles are dispersed in water with a dispersant , (c) silica, (d) a silicone-based nonionic surfactant , (e) a silicone-based antifoaming agent , And (f) including alcohol,
An aqueous coating lubricant composition for difficult-to-work metals.

(A) Non-reactive, self-emulsifying urethane resin, the urethane resin can be dispersed in water substantially without using an emulsifier, or a mixture of the urethane resin and urethane / acrylic composite resin, the urethane resin Or the mixture consists of particles with a particle size of 10-40 nm and particles with a particle size of 60-100 nm,
(B) a dispersion in which a fluororesin powder or its fine particles are dispersed in water with a dispersant in advance ; (c) ethylene glycol monomethyl ether , ethylene glycol monoethyl ether , ethylene glycol monobutyl ether , ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl A compound selected from ether acetate or ethylene glycol monobutyl ether acetate or a silicone-based nonionic surfactant , and (d) an alcohol, wherein composition (a) is present as an emulsion in the composition;
An aqueous coating lubricant composition for difficult-to-work metals.

(A) Non-reactive, self-emulsifying urethane resin, the urethane resin can be dispersed in water substantially without using an emulsifier, or a mixture of the urethane resin and urethane / acrylic composite resin, the urethane resin Alternatively, the mixture is composed of particles having a particle size of 10 to 40 nm and particles having a particle size of 60 to 100 nm, and (b) a dispersion in which the fluororesin powder or the fine particles thereof are dispersed in water with a dispersant , (c) silica , (D) a silicone-based antifoaming agent , (e) a silicone-based nonionic surfactant , and (f) an alcohol, wherein the composition (a) is present as an emulsion in the composition,
An aqueous coating lubricant composition for difficult-to-work metals.

(A) A mixture of a urethane resin and a urethane-acrylic composite resin that is non-reactive and self-emulsifying and can be dispersed in water substantially without using an emulsifier, in which case the mixture is 10 to 40 nm (B) a dispersion in which a fluororesin powder or its fine particles are dispersed in water with a dispersant in advance , (c) ethylene glycol monomethyl ether , ethylene glycol monoethyl ether A compound selected from ethylene glycol monobutyl ether , ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate, or a silicone-based nonionic surfactant , and (d) isopropyl alcohol The composition (a) is present as an emulsion in the composition,
An aqueous coating lubricant composition for difficult-to-work metals.

(A) A mixture of a urethane resin and a urethane-acrylic composite resin that is non-reactive and self-emulsifying and can be dispersed in water substantially without using an emulsifier, in which case the mixture is 10 to 40 nm (B) a dispersion in which a fluororesin powder or its fine particles are dispersed in water with a dispersant in advance , (c) silica , (d) a silicone-based nonionic interface An active agent , (e) a silicone-based antifoam agent , and (f) an alcohol, wherein the composition (a) is present as an emulsion in the composition,
An aqueous coating lubricant composition for difficult-to-work metals.

The aqueous coating lubricant composition for difficult-to-work metal according to claim 5 or 6, wherein the urethane resin is composed of particles having a particle diameter of 60 to 100 nm, and the urethane / acrylic composite resin is composed of particles having a particle diameter of 10 to 40 nm. object.

The aqueous coating lubricant composition according to any one of claims 1 to 7, wherein the total resin component is contained in an amount of 6 to 35% by weight of the total weight.

The aqueous coating lubricant composition according to claim 1, wherein the difficult-to-work metal is titanium steel or magnesium alloy steel.

The aqueous coating lubricant composition according to any one of claims 1 to 6 is applied to a difficult-to-work metal, dried to form a coating film of the composition, and then deep drawing of the metal is performed. A metal processing method characterized by the above.

(A) A water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, and the urethane resin has a particle size of 10 to 40 nm and a particle size of 60 to 100 nm. (B) a compound selected from ethylene glycol monomethyl ether , ethylene glycol monoethyl ether , ethylene glycol monobutyl ether , ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate ionic surfactant, and an aqueous coating lubricant composition is applied to difficult-to-work metal containing (c) an alcohol and dried to form a coating film of the composition, then performing the deep drawing of the metal Metal processing characterized by Law.

(A) A water-based urethane resin in which a non-reactive, self-emulsifying urethane resin is dispersed in water substantially without using an emulsifier, and the urethane resin has a particle size of 10 to 40 nm and a particle size of 60 to 100 nm. An aqueous coating lubricant composition comprising particles, comprising (b) silica, (c) a silicone-based nonionic surfactant , (d) a silicone-based antifoaming agent , and (e) an alcohol. A metal processing method comprising: drying to form a coating film of the composition, followed by deep drawing of the metal.

(A) Non-reactive type, self-emulsifying type urethane resin having different particle diameters, the urethane resin can be dispersed in water substantially without using an emulsifier, or the urethane resin and urethane / acrylic composite The mixture with the resin, the urethane resin or the mixture is composed of particles having a particle size of 10 to 40 nm and particles having a particle size of 60 to 100 nm, and (b) ethylene glycol monomethyl ether , ethylene glycol monoethyl ether , ethylene glycol monobutyl ether A compound selected from ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate or a silicone-based nonionic surfactant , and (c) an alcohol, wherein the composition (a) is in the composition Emma The aqueous coating lubricant composition present as John applied to hard-to-work metals, and dried to form a coating film of the composition, then the processing method of the metal, characterized in that to perform deep drawing of the metal .

(A) Non-reactive type, self-emulsifying type urethane resin having different particle diameters, the urethane resin can be dispersed in water substantially without using an emulsifier, or the urethane resin and urethane / acrylic composite The mixture with the resin, the urethane resin or the mixture is composed of particles having a particle diameter of 10 to 40 nm and particles having a particle diameter of 60 to 100 nm , and (b) silica , (c) silicone-based antifoaming agent (d) silicone-based An aqueous coating lubricant composition comprising a nonionic surfactant and (e) an alcohol, wherein the composition (a) is present as an emulsion in the composition is applied to a difficult-to-work metal and dried to form a coating film of the composition Is formed, and then deep drawing of the metal is performed.

(A) A mixture of a urethane resin and a urethane-acrylic composite resin that is non-reactive and self-emulsifying and can be dispersed in water substantially without using an emulsifier, in which case the mixture is 10 to 40 nm (B) ethylene glycol monomethyl ether , ethylene glycol monoethyl ether , ethylene glycol monobutyl ether , ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol compound selected from monobutyl ether acetate or silicone based nonionic surfactants, and include (c) of isopropyl alcohol, the composition (a) is an aqueous coating lubricant composition present as an emulsion in the composition in flame processing metal Cloth, and dried to form a coating film of the composition, then the processing method of the metal, characterized in that to perform deep drawing of the metal.

(A) A mixture of a urethane resin and a urethane-acrylic composite resin that is non-reactive and self-emulsifying and can be dispersed in water substantially without using an emulsifier, in which case the mixture is 10 to 40 nm A composition comprising particles having a particle size and particles having a particle size of 60 to 100 nm, comprising (b) silica , (c) a silicone-based nonionic surfactant , (d) a silicone-based antifoaming agent , and (e) an alcohol. For the product (a), an aqueous coating lubricant composition existing as an emulsion in the composition is applied to a difficult-to-work metal, dried to form a coating film of the composition, and then deep drawing of the metal is performed. A metal processing method characterized by the above.

The processing method according to claim 10, wherein the difficult-to-process metal is titanium steel or magnesium alloy steel.