JP4272915B2 - Highly lubricated rust-proof metal plate - Google Patents

Description

【化２】

（式（１）及び（２）中、Ｒ¹及びＲ²は炭素数４〜３０のアルキル基、アルケニル基、アルキルアリール基及びアリールアルキル基を示し、同一でも異なっていてもよい。）
【化３】

（式（３）中、Ｒ³及びＲ⁴は炭素数４〜３０のアルキル基、アルケニル基、アルキルアリール基及びアリールアルキル基を示し、同一でも異なっていてもよい。）
【００５１】
正リン酸エステルは上記一般式（１）のジエステルと一般式（２）のモノエステルの混合物である。具体的には、例えば、２−エチルヘキシルアシッドホスフェート、エチルアシッドホスフェート、ブチルアシッドホスフェート、オレイルアシッドホスフェート、テトラコシルアシッドホスフェート、イソデシルアシッドホスフェート、ラウリルアシッドホスフェート、トリデシルアシッドホスフェート、ステアリルアシッドホスフェート、イソステアリルアシッドホスフェート、オレイルアシッドホスフェートなどを挙げることができる。
【００５２】
亜リン酸エステルとしては、具体的には例えばジブチルハイドロゲンホスファイト、ジラウリルハイドロゲンホスファイト、ジオレイルハイドロゲンホスファイト、ジステアリルハイドロゲンホスファイト、ジフェニルハイドロゲンホスファイトなどを挙げることができる。
【００５３】
以上の酸性リン酸エステル類の中で、例えば２−エチルヘキシルアシッドホスフェート、ステアリルアシッドホスフェート、オレイルアシッドホスフェートなどを好ましいものとして挙げることができる。
【００５４】
また、以上の酸性エステル類の好ましい金属塩として、Ｃａセッケンなどを挙げることができる。
【００５５】
さらに、これらとアミン塩を形成するアミン類としては、例えば、下記一般式（４）で表されるモノ置換アミン、ジ置換アミン又はトリ置換アミンが挙げられる。
Ｒ_n ＮＨ_3-n ・ ・ ・（４）
（式（４）中、Ｒは炭素数３〜３０のアルキル基もしくはアルケニル基、炭素数６〜３０のアリール基もしくはアリールアルキル基又は炭素数２〜３０のヒドロキシアルキル基を示し、ｎは１、２又は３を示す。また、Ｒが複数ある場合、複数のＲは同一でも異なっていてもよい。）上記一般式（４）におけるＲのうちの炭素数３〜３０のアルキル基もしくはアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。
【００５６】
ここで、モノ置換アミンの例としては、ブチルアミン、ペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、オクチルアミン、ラウリルアミン、ステアリルアミン、オレイルアミン、ベンジルアミンなどを挙げることができ、ジ置換アミンの例としては、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジシクロヘキシルアミン、ジオクチルアミン、ジラウリルアミン、ジステアリルアミン、ジオレイルアミン、ジベンジルアミン、ステアリル・モノエタノールアミン、デシル・モノエタノールアミン、ヘキシル・モノプロパノールアミン、ベンジル・モノエタノールアミン、フェニル・モノエタノールアミン、トリル・モノプロパノールなどを挙げることができる。また、トリ置換アミンの例としては、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリシクロヘキシルアミン、トリオクチルアミン、トリラウリルアミン、トリステアリルアミン、トリオレイルアミン、トリベンジルアミン、ジオレイル・モノエタノールアミン、ジラウリル・モノプロパノールアミン、ジオクチル・モノエタノールアミン、ジヘキシル・モノプロパノールアミン、ジブチル・モノプロパノールアミン、オレイル・ジエタノールアミン、ステアリル・ジプロパノールアミン、ラウリル・ジエタノールアミン、オクチル・ジプロパノールアミン、ブチル・ジエタノールアミン、ベンジル・ジエタノールアミン、フェニル・ジエタノールアミン、トリル・ジプロパノールアミン、キシリル・ジエタノールアミン、トリエタノールアミン、トリプロパノールアミンなどを挙げることができる。
【００５７】
上記の（Ｅ）成分は一種でもよく、二種以上を組み合わせて使用してもよい。その配合量は、組成物全量基準で、リン分として、０．０１〜５質量％であり、０．０１質量％未満であると、潤滑性の効果は出ず、５質量％を超えても、量に見合った効果は出ず経済的でない。好ましくは０．０１〜０．５質量％である。
【００５８】
なお、（Ａ）、（Ｄ）及び（Ｅ）成分中の硫黄分は純亜鉛メッキ面での硫化亜鉛の形成によるめっき剥離防止と金型への凝着による摩擦係数増大の点で１００ｐｐｍ以下であることが望ましい。また、本発明の組成物は潤滑油基油に、上記の（Ａ）〜（Ｅ）成分を配合して調製することができるが、その際に組成物の４０℃における動粘度が４〜１００ｍｍ²／ｓ、特に５〜２０ｍｍ²／ｓとなるように、各成分の種類、性状、配合割合を選択することが有効である。本発明の組成物においては、所望に応じ、本発明の目的を損なわない範囲で、酸化防止剤、金属不活性化剤、腐食防止剤、消泡剤などの公知の添加剤を添加することができる。本発明の組成物を、浸漬法、シャワー法、静電塗装法などの一般的な手法により金属材料の表面に塗布すればよい。
【００５９】
防錆兼プレス加工油の塗油量は、０．２〜１０ｇ／ｍ²であり、０．２ｇ／ｍ²未満であると、潤滑性の効果は出ず、１０ｇ／ｍ²を超えても、量に見合った効果は出ず経済的でない。好ましくは０．４〜５ｇ／ｍ²である。
【００６０】
本発明の下地金属板としては、特に限定されるものではなく、鋼板、アルミニウム板、銅板、チタン板等成形加工して使用されるあらゆる金属板、合金板が使用できる。下地金属板として鋼板を使用する場合、熱延鋼板、冷延鋼板共に使用でき、鋼種もＡｌキルド鋼、Ｔｉ、Ｎｂ等を添加した極低炭素鋼板、およびこれらにＰ、Ｓｉ、Ｍｎ等の強化元素を添加した高強度鋼、ステンレス鋼等種々のものが適用できる。
【００６１】
また、これら金属板の上に亜鉛や亜鉛系合金めっき、アルミニウム系めっきを行っためっき金属板も下地金属板として適用できる。代表的なめっき金属板としては、Ａｌ：０．０５〜１．０質量％、Ｆｅ：５〜１５質量％を含有し、残部がＺｎおよび不可避的不純物からなる合金化溶融亜鉛めっき層を有するめっき鋼板、Ａｌ、Ｍｇのいずれかまたは両方を０．２〜１０質量％含有し、残部がＺｎおよび不可避的不純物からなる溶融亜鉛めっき層を有するめっき鋼板、Ａｌ：４〜２２質量％、Ｍｇ：１〜１０質量％、Ｓｉ：０．５質量％以下を含有し、残部がＺｎおよび不可避的不純物からなる溶融亜鉛めっき層を有するめっき鋼板、Ａｌ：４〜７０質量％、Ｓｉ：３質量％以下を含有し、残部がＺｎおよび不可避的不純物からなる溶融亜鉛めっき層を有するめっき鋼板、Ｓｉ：２〜１５質量％含有し、残部がＡｌおよび不可避的不純物からなる溶融アルミニウムめっき層を有するめっき鋼板、Ｚｎおよび不可避的不純物からなる電気亜鉛めっき鋼板、Ｎｉ：４〜１５質量％含有し、残部がＺｎおよび不可避的不純物からなる電気亜鉛めっき鋼板等が挙げられる。
【００６２】
本発明において合金化溶融亜鉛めっき層のＡｌ組成を０．０５〜１．０質量％に限定した理由は、０．０５質量％未満では合金化処理時においてＺｎ−Ｆｅ合金化が進みすぎ、地鉄界面に脆い合金層が発達しすぎてめっき密着性が劣化するためであり、１．０質量％を超えるとＦｅ−Ａｌ−Ｚｎ系バリア層が厚く形成され過ぎ合金化処理時において合金化が進まないため目的とする鉄含有量のめっきが得られないためである。
【００６３】
また、Ｆｅ組成を５〜１５質量％に限定した理由は、５質量％未満だとめっき表面に柔らかいＺｎ−Ｆｅ合金が形成されプレス成形性を劣化させるためであり、１５質量％を超えると地鉄界面に脆い合金層が発達し過ぎてめっき密着性が劣化するためである。
【００６４】
本発明においてＡｌ、Ｍｇのいずれかまたは両方を含有するめっき層のＡｌ組成を０．２〜１０質量％に限定した理由は、０．２質量％未満のＡｌ量で通常の溶融めっき処理を行うと、めっき処理時においてＺｎ−Ｆｅ合金化反応が起こり、地鉄界面に脆い合金層が発達し、めっき密着性が劣化するためであり、１０質量％を超えるとＦｅ−Ａｌ合金層の成長が顕著となりめっき密着性を阻害するためである。
【００６５】
また、Ｍｇ組成を０．２〜１０質量％に限定した理由は、０．２質量％未満では耐食性を向上させる効果が不十分であるためであり、１０質量％を超えるとめっき浴が酸化しやすくなり、浴表面にＭｇの酸化物が多量に発生しめっきが困難となるためである。
【００６６】
さらに耐食性の良いめっき鋼板を得るためにはＺｎ−Ａｌめっき層のＡｌ組成を増加させると効果的であるが、前述したようにＡｌ組成が１０質量％を超えるとＦｅ−Ａｌ合金層の成長が顕著となりめっき密着性を阻害する。従って、Ｚｎ−Ａｌめっき層のＡｌ組成を増加させるためには、Ｆｅ−Ａｌ合金層の成長を抑制させるためにＳｉを添加させる必要がある。
【００６７】
本発明においてＺｎ−Ａｌ−Ｓｉめっき層のＡｌ組成を４〜７０質量％に限定した理由は、４質量％未満のＡｌ量ではＳｉを添加しなくても密着性が十分であるためであり、７０質量％を超えると耐食性を向上させる効果が飽和するためである。
【００６８】
Ｓｉの含有量を３質量％以下（０質量％を除く）に限定した理由は、ＳｉはＦｅ−Ａｌ合金層の成長を抑制し密着性を向上させる効果があるが、３質量％を超えると密着性を向上させる効果が飽和するためである。望ましくは０．０１〜３質量％である。さらに望ましくはＡｌ含有量の１％以上である。Ｓｉの添加はＡｌの含有量が１０質量％を超えるめっき層には必須であるが、Ａｌの含有量が１０％以下のめっき層においてもめっき密着性向上に効果が大きいため、加工が厳しい部材に使用する等、高いめっき密着性を必要とする場合にはＳｉを添加する必要がある。
【００６９】
さらに、Ｚｎ−Ａｌ−Ｍｇめっき層においてもめっき層のＡｌ組成を増加させると耐食性向上に効果的であるが、前述したようにＡｌ組成が１０質量％を超えるとＦｅ−Ａｌ合金層の成長が顕著となりめっき密着性を阻害する。従って、Ｚｎ−Ａｌめっき層のＡｌ組成を増加させるためには、Ｆｅ−Ａｌ合金層の成長を抑制させるためにＳｉを添加させる必要がある。
【００７０】
本発明においてＺｎ−Ａｌ−Ｍｇ−Ｓｉめっき層のＡｌ組成を４〜２２質量％に限定した理由は、４質量％未満のＡｌ量ではＳｉを添加しなくても十分な密着性が得られるためであり、２２質量％を超えると耐食性を向上させる効果が飽和するためである。
【００７１】
Ｍｇ組成を１〜１０質量％に限定した理由は、１質量％未満では耐食性を向上させる効果が不十分であるためであり、１０質量％を超えるとめっき浴が酸化しやすくなり、浴表面にＭｇの酸化物が多量に発生しめっきが困難となるためである。
【００７２】
Ｓｉの含有量を０．５質量％以下（０質量％を除く）に限定した理由は、Ｓｉは密着性を向上させる効果があるが、０．５質量％を超えると密着性を向上させる効果が飽和するためである。望ましくは０．００００１〜０．５質量％である。さらに望ましくは０．０００１〜０．５質量％である。Ｓｉの添加はＡｌの含有量が１０質量％を超えるめっき層には必須であるが、Ａｌの含有量が１０％以下のめっき層においてもめっき密着性向上に効果が大きいため、加工が厳しい部材に使用する等、高いめっき密着性を必要とする場合にはＳｉを添加する必要がある。
【００７３】
Ｓｉ：２〜１５質量％、残部がＡｌおよび不可避的不純物からなるめっき層においてＳｉ組成を２〜１５質量％に限定した理由は、２質量％未満及び１５質量％を超えたＳｉ量ではめっき浴の融点が十分低下しないためにめっきが困難となるためである。
【００７４】
Ｎｉ：４〜１５質量％含有し、残部がＺｎおよび不可避的不純物からなる電気亜鉛めっき層においてＮｉ組成を４〜１５質量％に限定した理由は、４質量％未満では耐食性を向上させる効果が不十分であるためであり、１５質量％を超えると耐食性が低下するためである。
【００７５】
めっき金属板めっきの付着量については特に制約は設けないが、耐食性の観点から１０ｇ／ｍ²以上、加工性の観点から３５０ｇ／ｍ²以下で有ることが望ましい。
【００７６】
また、上記めっき金属板のうち、めっき層中にＡｌを含有し、初晶としてＡｌ相が晶出するものは、このＡｌ相が大きく成長することによってめっき表面に凸凹が形成され、表面平滑性が低下することがある。この凸凹抑制にはめっきへのＴｉ添加が有効である。
【００７７】
Ｔｉの含有量を０．１質量％以下（０質量％は除く）に限定した理由は、ＴｉはＴｉ−Ａｌ系金属間化合物を晶出させ、表面平滑性を向上させる効果があるが、０．１質量％を超えるとめっき後の外観が粗雑になり、外観不良が発生するためである。また、Ｔｉ−Ａｌ系金属間化合物はＴｉ含有量で０．１質量％を超えるとめっき表面に濃化し表面平滑性を低下させる。望ましくは０．００００１〜０．１質量％である。さらに望ましくは０．００００１〜０．０１質量％未満である。
【００７８】
亜鉛めっき層中には、これ以外にＦｅ、Ｓｂ、Ｐｂ、Ｓｎを単独あるいは複合で０．５質量％以内含有してもよい。また、Ｃａ、Ｂｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒ、Ｍｎ、Ｐ、Ｂ、Ｎｂ、Ｂｉ、Ｖ、Ｎｂやランタノイド系のような３族元素を合計で０．５質量％以下含有しても本発明の効果を損なわず、その量によってはさらに耐食性が改善される等好ましい場合もある。
【００７９】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００８０】
（実施例１）
４０℃における動粘度が５ｍｍ²／ｓ（基油Ａ）と３０ｍｍ²／ｓ（基油Ｂ）のパラフィン系鉱油を混合した基油に、表１に示す所定の化合物を所定の割合（質量％）で配合した高潤滑防錆油を調製した。多価アルコール脂肪酸フルエステルにはトリメチロールプロパントリパルミテートを使用した。過塩基性スルホネートには、全塩基価４００ｍｇＫＯＨ／ｇのＣａスルホネート（金属分４０％）を使用した。中性スルホネートには、全塩基価１ｍｇＫＯＨ／ｇ以下のＣａスルホネート（金属分４０％）を使用した。動植物油脂には、精製やし油を使用した。酸性リン酸エステルのＣａ塩は、２−エチルヘキシルアシッドホスフェートのＣａ塩を使用した。リン分は１０％である。硫化植物油エステルは硫黄分を１０％含有する物を使用した。４０℃における各高潤滑防錆油の動粘度は表１に示す。
【００８１】
めっき鋼板は、溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、Ｚｎ−Ａｌ−Ｍｇめっき鋼板を使用した。溶融亜鉛めっき鋼板の組成は、Ａｌ：０．４質量％、残Ｚｎ、合金化溶融亜鉛めっき鋼板の組成は、Ａｌ：０．４質量％、Ｆｅ：１０質量％、残Ｚｎ、Ｚｎ−Ａｌ−Ｍｇめっき鋼板の組成は、Ａｌ：１１質量％、Ｍｇ：３質量％、Ｓｉ：０．２質量％、残Ｚｎであった。板厚はいずれも０．７ｍｍを使用した。
【００８２】
【表１】

【００８３】
これらの高潤滑防錆油を表２に示す塗油量でめっき鋼板に塗油し、成形性、脱脂性、防錆性について評価した。
【００８４】
成形性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、円筒深絞り試験を行って評価した。絞り比２．２、しわ押さえ荷重を変化させ、以下に示す評点づけで判定した。評点は◎と○、△を合格とした。
◎：４０００ｋｇ／ｃｍ²以上で絞り抜け
○：１５００ｋｇ／ｃｍ²以上４０００ｋｇ／ｃｍ²未満で絞り抜け
△：５００ｋｇ／ｃｍ²以上１５００ｋｇ／ｃｍ²未満で絞り抜け
×：５００ｋｇ／ｃｍ²で破断
【００８５】
脱脂性は、日本パーカライジング製ＦＣ−Ｌ４４６０に各防錆油を５ｇ／ｌ添加した脱脂液に試験片を４３℃で６０秒浸漬揺動し、３０秒水道水スプレー水洗後、３０秒放置し水濡れ面積を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：水塗れ面積１００％
△：水塗れ面積８０％以上１００％未満
×：水塗れ面積８０％未満
【００８６】
防錆性は、ＳＳＴ６ｈｒ後の白錆発生有無を評価した。評価は、白錆が発生していないものを合格、白錆が発生していたものを不合格とした。
【００８７】
長期防錆性は、厚さ０．０５ｍｍポリテトラフルオロエチレンシートを間に挟んだ試験片をろ紙で梱包し、５０℃、ＲＨ９５％の環境で試験し、さび、ステインの有無を評価した。評価は、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：３０日間さび、ステイン発生無し
△：１０日間さび、ステイン発生無し
×：１０日間でさび、ステイン発生
【００８８】
評価結果を表２に示す。比較にはＢａスルホネートと酸化ワックスエステルを添加した市販の一般防錆油を使用した。番号２、２４、４６は多価アルコール脂肪酸フルエステルの添加量が本発明の範囲外であるため、防錆性が不合格となった。番号５、２７、４９は過塩基性スルホネートの添加量が本発明の範囲外であるため、長期防錆性が不合格となった。番号９、３１、５３は中性スルホネートの添加量が本発明の範囲外であるため、脱脂性、防錆性が不合格となった。番号１６、３８、６０は油脂の添加量が本発明の範囲外であるため、脱脂性が不合格となった。番号２２、４４、６６は一般防錆油を使用したため成形性が不合格となった。表１の防錆兼プレス加工油２０は硫化植物油エステルの添加により、番号４２の合金化溶融亜鉛めっき鋼板の成形性は合格となったが、番号２０、６４は硫黄分とめっきが反応し成形性が不合格となった。これら以外はいずれも良好な成形性、脱脂性、防錆性を示した。
【００８９】
【表２】

【００９０】
（実施例２）
４０℃における動粘度が５ｍｍ²／ｓ（基油Ａ）と３０ｍｍ²／ｓ（基油Ｂ）のパラフィン系鉱油を混合した基油に、表３に示す所定の化合物を所定の割合（質量％）で配合した高潤滑防錆油を調製した。多価アルコール脂肪酸フルエステルにはトリメチロールプロパントリパルミテートを使用した。過塩基性スルホネートには、全塩基価４００ｍｇＫＯＨ／ｇのＣａスルホネート（金属分４０％）を使用した。中性スルホネートには、全塩基価１ｍｇＫＯＨ／ｇ以下のＣａスルホネート（金属分４０％）を使用した。動植物油脂には、精製やし油、米糠油、大豆を使用した。酸性リン酸エステルのＣａ塩、アミン塩は、２−エチルヘキシルアシッドホスフェートのＣａ塩、ステアリルアシッドホスフェートのＣａ塩、オレイルアシッドホスフェートのアミン塩を使用した。リン分はいずれも１０％である。４０℃における各高潤滑防錆油の動粘度はいずれも１５ｍｍ²／ｓとした。
【００９１】
めっき鋼板は、溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、Ｚｎ−Ａｌ−Ｍｇめっき鋼板を使用した。溶融亜鉛めっき鋼板の組成は、Ａｌ：０．４質量％、残Ｚｎ、合金化溶融亜鉛めっき鋼板の組成は、Ａｌ：０．４質量％、Ｆｅ：１０質量％、残Ｚｎ、Ｚｎ−Ａｌ−Ｍｇめっき鋼板の組成は、Ａｌ：１１質量％、Ｍｇ：３質量％、Ｓｉ：０．２質量％、残Ｚｎであった。板厚はいずれも０．７ｍｍを使用した。
【００９２】
【表３】

【００９３】
これらの高潤滑防錆油を表４に示す塗油量でめっき鋼板に塗油し、成形性、脱脂性、防錆性について評価した。
【００９４】
成形性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、円筒深絞り試験を行って評価した。絞り比２．２、しわ押さえ荷重を変化させ、以下に示す評点づけで判定した。評点は◎と○、△を合格とした。
◎：４０００ｋｇ／ｃｍ²以上で絞り抜け
○：１５００ｋｇ／ｃｍ²以上４０００ｋｇ／ｃｍ²未満で絞り抜け
△：５００ｋｇ／ｃｍ²以上１５００ｋｇ／ｃｍ²未満で絞り抜け
×：５００ｋｇ／ｃｍ²で破断
【００９５】
脱脂性は、日本パーカライジング製ＦＣ−Ｌ４４６０に各防錆油を５ｇ／ｌ添加した脱脂液に試験片を４３℃で６０秒浸漬揺動し、３０秒水道水スプレー水洗後、３０秒放置し水濡れ面積を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：水塗れ面積１００％
△：水塗れ面積８０％以上１００％未満
×：水塗れ面積８０％未満
【００９６】
防錆性は、ＳＳＴ６ｈｒ後の白錆発生有無を評価した。評価は、白錆が発生していないものを合格、白錆が発生していたものを不合格とした。
【００９７】
長期防錆性は、厚さ０．０５ｍｍポリテトラフルオロエチレンシートを間に挟んだ試験片をろ紙で梱包し、５０℃、ＲＨ９５％の環境で試験し、さび、ステインの有無を評価した。評価は、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：３０日間さび、ステイン発生無し
△：１０日間さび、ステイン発生無し
×：１０日間でさび、ステイン発生
評価結果を表４に示す。比較にはＢａスルホネートと酸化ワックスエステルを添加した市販の一般防錆油を使用した。番号１、２２、４３は塗油量が本発明の範囲外であるため、成形性、防錆性が不合格となった。番号２１、４２、６３は一般防錆油を使用したため成形性が不合格となった。これら以外はいずれも良好な成形性、脱脂性、防錆性を示した。
【００９８】
【表４】

【００９９】
（実施例３）
亜鉛以外の添加元素が表５に示す組成で板厚０．７ｍｍの溶融亜鉛系めっき鋼板を準備し、これらに表３に示す所定の化合物を所定の割合（質量％）で配合した高潤滑防錆油を表５に示す塗油量で塗油し、成形性、脱脂性、防錆性について評価した。
【０１００】
【表５】

【０１０１】
また、表６に示す溶融アルミニウムめっき鋼板、電気亜鉛めっき鋼板、電気Ｚｎ−Ｎｉめっき鋼板を準備し、これらに表３に示す所定の化合物を所定の割合（質量％）で配合した高潤滑防錆油を表６に示す塗油量で塗油し、成形性、脱脂性、防錆性について評価した。溶融アルミニウムめっき鋼板の組成は、Ｓｉ：１０質量％、残Ａｌ、電気亜鉛めっき鋼板はＺｎのみ、電気Ｚｎ−Ｎｉめっき鋼板の組成は、Ｎｉ：１０質量％、残Ｚｎであった。板厚はいずれも０．７ｍｍを使用した。
【０１０２】
深絞り性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、円筒深絞り試験を行って評価した。絞り比２．２、しわ押さえ荷重を変化させ、以下に示す評点づけで判定した。評点は◎と○、△を合格とした。
◎：４０００ｋｇ／ｃｍ²以上で絞り抜け
○：１５００ｋｇ／ｃｍ²以上４０００ｋｇ／ｃｍ²未満で絞り抜け
△：５００ｋｇ／ｃｍ²以上１５００ｋｇ／ｃｍ²未満で絞り抜け
×：５００ｋｇ／ｃｍ²で破断
【０１０３】
パウダリング性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、絞り比１．８、しわ押さえ加重２５００ｋｇ／ｃｍ²、成形速度２００ｍｍ／ｍｉｎで成形深さ２５ｍｍ成形させた試料のたて壁直壁部のめっき剥離を評価した。評価は、成形試験後の試料のたて壁直壁部にセロハンテープを貼り付け、剥離しためっきをテープに付着させた後、テープの黒化率を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：黒化率３０％未満
△：黒化率３０％以上５０％未満
×：黒化率５０％以上
【０１０４】
フレーキング性は、肩Ｒが１ｍｍＲの角ビード（凸部は４×４ｍｍ）を使用して引き抜き試験を行い、ビード通過部のめっき剥離を評価した。引き抜き試験は、幅３０ｍｍ長さ３００ｍｍのサンプルをビード金型で挟んだ後、１０００ｋｇｆの押し付け加重で引き抜きいた。評価は、引き抜き後の試料のビード通過部にセロハンテープを貼り付け、剥離しためっきをテープに付着させた後、テープの黒化率を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。○：黒化率３０％未満
△：黒化率３０％以上５０％未満
×：黒化率５０％以上
【０１０５】
脱脂性は、日本パーカライジング製ＦＣ−Ｌ４４６０に各防錆油を５ｇ／ｌ添加した脱脂液に試験片を４３℃で６０秒浸漬揺動し、３０秒水道水スプレー水洗後、３０秒放置し水濡れ面積を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：水塗れ面積１００％
△：水塗れ面積８０％以上１００％未満
×：水塗れ面積８０％未満
【０１０６】
防錆性は、ＳＳＴ６ｈｒ後の白錆発生有無を評価した。評価は、白錆が発生していないものを合格、白錆が発生していたものを不合格とした。
【０１０７】
長期防錆性は、厚さ０．０５ｍｍポリテトラフルオロエチレンシートを間に挟んだ試験片をろ紙で梱包し、５０℃、ＲＨ９５％の環境で試験し、さび、ステインの有無を評価した。評価は、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：３０日間さび、ステイン発生無し
△：１０日間さび、ステイン発生無し
×：１０日間でさび、ステイン発生
【０１０８】
評価結果を表５、６に示す。比較にはＢａスルホネートと酸化ワックスエステルを添加した市販の一般防錆油を使用した。番号１はめっき中のＡｌ含有率が本発明の範囲外であるため、成形性が不合格となった。番号３、８は一般防錆油を使用したため、成形性が不合格となった。番号９はめっき中のＡｌ含有率が本発明の範囲外であるため、成形性が不合格となった。これら以外はいずれも良好な成形性、脱脂性、防錆性を示した。
【０１０９】
【表６】

【０１１０】
（実施例４）
亜鉛以外の元素が表７に示す組成で板厚０．７ｍｍの合金化溶融亜鉛めっき鋼板を準備し、これらに表３に示す所定の化合物を所定の割合（質量％）で配合した高潤滑防錆油を表７に示す塗油量で塗油し、成形性、脱脂性、防錆性について評価した。
【０１１１】
深絞り性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、円筒深絞り試験を行って評価した。絞り比２．２、しわ押さえ荷重を変化させ、以下に示す評点づけで判定した。評点は◎と○、△を合格とした。
◎：４０００ｋｇ／ｃｍ²以上で絞り抜け
○：１５００ｋｇ／ｃｍ²以上４０００ｋｇ／ｃｍ²未満で絞り抜け
△：５００ｋｇ／ｃｍ²以上１５００ｋｇ／ｃｍ²未満で絞り抜け
×：５００ｋｇ／ｃｍ²で破断
【０１１２】
パウダリング性は、ポンチ径：５０ｍｍφ、ダイス径：５１．９５ｍｍφ、肩Ｒ：５Ｒの金型を使用し、絞り比１．８、しわ押さえ加重２５００ｋｇ／ｃｍ²、成形速度２００ｍｍ／ｍｉｎで成形深さ２５ｍｍ成形させた試料のたて壁直壁部のめっき剥離を評価した。評価は、成形試験後の試料のたて壁直壁部にセロハンテープを貼り付け、剥離しためっきをテープに付着させた後、テープの黒化率を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：黒化率３０％未満
△：黒化率３０％以上５０％未満
×：黒化率５０％以上
【０１１３】
フレーキング性は、肩Ｒが１ｍｍＲの角ビード（凸部は４×４ｍｍ）を使用して引き抜き試験を行い、ビード通過部のめっき剥離を評価した。引き抜き試験は、幅３０ｍｍ長さ３００ｍｍのサンプルをビード金型で挟んだ後、１０００ｋｇｆの押し付け加重で引き抜きいた。評価は、引き抜き後の試料のビード通過部にセロハンテープを貼り付け、剥離しためっきをテープに付着させた後、テープの黒化率を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。○：黒化率３０％未満
△：黒化率３０％以上５０％未満
×：黒化率５０％以上
【０１１４】
脱脂性は、日本パーカライジング製ＦＣ−Ｌ４４６０に各防錆油を５ｇ／ｌ添加した脱脂液に試験片を４３℃で６０秒浸漬揺動し、３０秒水道水スプレー水洗後、３０秒放置し水濡れ面積を測定し、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：水塗れ面積１００％
△：水塗れ面積８０％以上１００％未満
×：水塗れ面積８０％未満
【０１１５】
防錆性は、ＳＳＴ６ｈｒ後の白錆発生有無を評価した。評価は、白錆が発生していないものを合格、白錆が発生していたものを不合格とした。
【０１１６】
長期防錆性は、厚さ０．０５ｍｍポリテトラフルオロエチレンシートを間に挟んだ試験片をろ紙で梱包し、５０℃、ＲＨ９５％の環境で試験し、さび、ステインの有無を評価した。評価は、以下に示す評点づけで判定した。評点は○と△を合格とした。
○：３０日間さび、ステイン発生無し
△：１０日間さび、ステイン発生無し
×：１０日間でさび、ステイン発生
【０１１７】
評価結果を表７に示す。比較にはＢａスルホネートと酸化ワックスエステルを添加した市販の一般防錆油を使用した。番号６はめっき中のＡｌ含有率とＦｅ含有率が本発明の範囲外であるため、成形性が不合格となった。番号１０はめっき中のＦｅ含有率が本発明の範囲外であるため、成形性が不合格となった。番号１１、１２は一般防錆油を使用したため、成形性が不合格となった。これら以外はいずれも良好な成形性、脱脂性、防錆性を示した。
【０１１８】
【表７】

【０１１９】
【発明の効果】
以上述べてきたように、本発明により、成形性、脱脂性、防錆性に優れた高潤滑防性処理金属板を製造することが可能となり、工業上極めて優れた効果を奏することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal plate such as a steel plate, and more particularly to a highly lubricated and rust-proof metal plate having good anti-rust properties and good lubricity and degreasing properties during subsequent press working.
[0002]
[Prior art]
In general, steel makers generally apply rust-preventive oil to steel sheets to prevent rust and discoloration during storage of steel sheets. We are supplying coated steel sheets.
[0003]
The rust preventive oil used for such purposes has the function of preventing rust and discoloration during storage of steel sheets in steel manufacturers, but it is necessary to prevent rust of steel sheets on the user side of steel sheets, In order to perform functions such as degreasing, chemical conversion, oil surface adhesion, weldability, and handling properties, mineral oil is used as a base oil and the minimum rust preventive additive is added to it, and the kinematic viscosity at 40 ° C. Is 25mm ² Generally, those prepared to have a low viscosity of / s or less are employed.
[0004]
On the other hand, for steel plate users, the steel plate that has been coated with anti-corrosion oil at the steel manufacturer is either used as it is, or a lubricant such as high-viscosity press working oil is applied according to the desired processing mode. In fact, it is used for processing. In addition, some steel manufacturers apply a wax-based lubricant coating or a resin-based lubricant coating to the steel plate in advance in order to abolish the lubricant application work prior to steel plate processing by the user of the steel plate. The means to deliver to the user is also taken.
[0005]
In recent years, it has been decided to omit press oil for the purpose of reducing steel plate manufacturing costs and steel plate processing costs, downgrade steel plates, and increase the strength of steel plates for the purpose of reducing the weight and increasing strength of processed steel products such as automobiles. For example, the processing conditions of the steel sheet are becoming strict. For this reason, in the case of subjecting the steel sheet just coated with rust preventive oil to processing, due to insufficient lubrication, cracks and galling occur in the processed steel sheet, reducing the quality of the processed product, In the mold, there is a problem that wear is increased and the service life is reduced.
[0006]
In addition, when applying a wax-based lubricant film or a resin-based lubricant film to the steel sheet in order to improve the workability of the steel sheet, these lubricants are more expensive than rust preventive oils, Since a special coating process must be provided, the cost of the steel sheet and the manufacturing cost of the steel sheet are increased, and the steel sheet becomes expensive.
[0007]
In order to address these problems, attempts have been made to develop rust preventive oils that can impart lubricity during pressing of steel sheets. And a rust-preventing oil composition for galvanized steel sheets to which a highly basic sulfonate is added (for example, see Patent Document 1). In addition, a rust preventive oil for press working in which a low-viscosity solvent is added with a sulfonate, a carboxylate, a phosphate ester derivative, or the like, an ultrabasic sulfonate, and potassium borate (for example, see Patent Document 2), There is a rust preventive and press working oil composition to which a rust preventive agent, superbasic Ca sulfonate, a sulfur-based extreme pressure agent and potassium borate are added (for example, see Patent Document 3).
[0008]
[Patent Document 1]
JP-A-4-275399
[Patent Document 2]
JP-A-5-339589
[Patent Document 3]
Japanese Patent Application Laid-Open No. 10-279979
[0009]
[Problems to be solved by the invention]
However, in the above-mentioned and other previously disclosed rust preventive oils and steel plates coated with the rust preventive oil, formability and rust preventive properties are not sufficiently ensured.
[0010]
In Patent Document 1 and Patent Document 3, lubricity is imparted by a sulfur-based extreme pressure agent, but the sulfur-based extreme pressure agent improves the formability of a metal plate having a hard surface such as a steel plate or a galvannealed steel plate. It is effective for the purpose, but a metal plate with a soft surface such as a galvanized steel sheet, a zinc-aluminum-based steel sheet, or an aluminum plate accelerates the peeling of zinc or aluminum, increases the friction coefficient, and deteriorates the formability. .
[0011]
Moreover, in patent document 2 and patent document 3, although lubricity is provided with potassium borate, potassium borate produces boric acid by hydrolysis and degrades rust prevention.
[0012]
Then, this invention is made | formed in view of the said problem, and it aims at providing the highly lubricated rust prevention metal plate excellent in a moldability and rust prevention property, without degreasing and adhesiveness falling. Yes.
[0013]
[Means for Solving the Problems]
As a result of intensive research on the development of a highly lubricated and rust preventive metal excellent in moldability and rust preventive properties, the inventors of the present invention have found that a lubricant base oil contains a fatty acid full ester of a polyhydric alcohol, an overbased metal sulfonate. ,During Metal sulfonate And acidic phosphoric acid esters or metal salts or amine salts thereof The present invention was completed by finding that a highly lubricated and rust-prevented metal excellent in formability and rust-preventing property can be obtained by applying a rust-preventing and pressing oil containing bismuth to the surface of a metal plate.
[0014]
That is, the gist of the present invention is as follows.
[0015]
(1) One or more of mineral oil and synthetic oil are mixed, and the kinematic viscosity at 40 ° C. is 4 to 100 mm. ² / A base oil with (s) fatty acid having 12 or more carbon atoms The sulfur content is 100 ppm or less 1 to 10% by mass of a fatty acid full ester of a polyhydric alcohol, (B) 0.2 to 10% by mass of an overbased metal sulfonate as a metal, and (C) 0.2 to 10 by mass of a neutral metal sulfonate as a metal. mass%, (D) 1 to 10% by mass of animal and vegetable fats and oils having a sulfur content of 100 ppm or less, (E) Sulfur content is 100ppm or less Contains 0.01 to 5% by mass of phosphoric acid acid esters or metal salts or amine salts thereof And the mass ratio of the (A) component and the [(B) + (C)] component is 1: 1 to 1: 2. 0.2-10 g / m of anti-rust and press working oil on the entire surface or part of the surface ² A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, characterized by having.
[0019]
( 2 The total base number of component (B) is 400 mgKOH / g or more, (1) A highly lubricated and rust-proof metal plate with excellent formability and rust-proofing properties as described in 1.
[0020]
( 3 (B) and (C) are sulfonates of Ba, Ca, Na, Mg or Zn, respectively (1) Or (2 A highly lubricated and rust-proof metal plate excellent in formability and rust-prevention property as described in any of the above.
[0023]
( 4 ) (1) to ( 3 ) Has a galvannealed alloy layer containing Al: 0.05 to 1.0 mass%, Fe: 5 to 15 mass%, and the balance consisting of Zn and inevitable impurities. A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, characterized by being a plated steel sheet.
[0024]
( 5 ) (1) to ( 3 ) Is a plated steel sheet having a hot-dip galvanized layer containing 0.2 to 10% by mass of Al or Mg, and the balance being Zn and inevitable impurities. Highly lubricated and rust-proof metal plate with excellent moldability and rust prevention.
[0025]
( 6 ) (1) to ( 3 ) Hot-dip galvanized metal plate containing Al: 4 to 22% by mass, Mg: 1 to 10% by mass, Si: 0.5% by mass or less, with the balance being Zn and inevitable impurities A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, characterized by being a plated steel sheet having a layer.
[0026]
( 7 ) (1) to ( 3 ) Is a plated steel sheet having a hot dip galvanized layer composed of Zn and unavoidable impurities. A highly lubricated and rust-proof metal plate with excellent formability and rust prevention characteristics.
[0027]
( 8 ) (1) to ( 3 ) Is a plated steel sheet having a molten aluminum plating layer containing Si: 2 to 15% by mass and the balance being Al and inevitable impurities. Highly lubricated and rust-proof metal plate.
[0028]
( 9 ) Said ( 5 ) To ( 8 A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, characterized in that the plated steel sheet according to any one of 1) contains 0.1% by mass or less of Ti in the plating layer.
[0029]
( 10 ) (1) to ( 3 The metal plate according to any one of 1) is a plated steel plate having an electrogalvanized layer made of Zn and inevitable impurities.
[0030]
( 11 ) (1) to ( 3 The metal plate according to any one of (1) and (2) above is Ni: 4 to 15% by mass, and the balance is a plated steel sheet having an electrogalvanized layer composed of Zn and inevitable impurities. Highly lubricated and rust-proof metal plate.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0032]
In the present invention, the highly lubricated and rust-proof metal plate is a metal plate coated with rust-proofing and pressing oil.
[0033]
The kinematic viscosity at 40 ° C. of the lubricating base oil of the antirust and press working oil is 4 to 100 mm. ² / S. Kinematic viscosity at 40 ° C is 4 to 100 mm ² The reason for limiting to / s is 4mm ² If it is less than / s, it will evaporate and volatilize when applied to a steel sheet and stored for a long period of time, resulting in a decrease in rust prevention. ² This is because, if it exceeds / s, the degreasing property after the molding process is lowered. Preferably 5-20mm ² / S.
[0034]
To adjust the kinematic viscosity of the lubricating base oil to the above range, the kinematic viscosity at 40 ° C. is 2 to 500 mm. ² / S in two or more types may be mixed. Specifically, the kinematic viscosity at 40 ° C. is 4 to 10 mm. ² / S and 10-120mm ² / S can be mixed at a mass ratio of 1: 2 to 1: 5.
[0035]
The type of the lubricating base oil is not particularly limited, and can be used regardless of whether it is a mineral oil or a synthetic system as long as it is normally used as a base oil for a lubricating oil. As the mineral oil base oil, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or by distilling the residual oil of atmospheric distillation under reduced pressure, Or refined oil obtained by refine | purifying this according to a conventional method, for example, solvent refined oil, hydrogenated refined oil, dewaxing process oil, clay-treated oil, etc. can be mentioned. Synthetic lubricant base oils include, for example, poly α-olefin, α-olefin copolymer, polybutene, alkylbenzene, polyol ester, dibasic acid ester, polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol. Examples include ether, hindered ester, and silicone oil. These lubricating base oils may be used alone or in combination of two or more kinds, and a mineral oil and a synthetic oil may be combined.
[0036]
Next, the components (A) to (E) blended in the lubricating base oil will be described.
[0037]
(A) component
The component (A) is a fatty acid full ester of a polyhydric alcohol, and the polyhydric alcohol preferably has 3 to 6 valences. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, arabitol, sorbitol and the like.
[0038]
As a fatty acid, a C12 or more thing is preferable and a thing of 12-24 is more preferable.
[0039]
The fatty acid having 12 to 24 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specific examples of the linear saturated fatty acid include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, and lignoceric acid. it can. Specific examples of linear unsaturated fatty acids include Linderic acid, 5-Lauroleic acid, Tuzic acid, Myristoleic acid, Zomalinic acid, Petroceric acid, Oleic acid, Elaidic acid, Codoic acid, Erucic acid, Seracoleic acid And so on.
[0040]
Specific examples of branched saturated fatty acids include various methylundecanoic acids, various propylnonanoic acids, various methyldodecanoic acids, various propyldecanoic acids, various methyltridecanoic acids, various methyltetradecanoic acids, various methylpentadecanoic acids, various Ethyltetradecanoic acid, various methylhexadecanoic acids, various propyltetradecanoic acids, various ethylhexadecanoic acids, various methylheptadecanoic acids, various butyltetradecanoic acids, various methyloctadecanoic acids, various ethyloctadecanoic acids, various methylnonadecanoic acids, various ethyloctadecanoic acids, various Methyl eicosanoic acid, various propyl octadecanoic acids, various butyl octadecanoic acids, various methyl docosanoic acids, various pentyl octadecanoic acids, various methyl tricosanoic acids, various ethyl docosanoic acids, various propyl hexaeicosas Acid, various hexyl octadecanoic acids; 4,4-dimethyldecanoic acid; 2-ethyl-3-methylnonanoic acid; 2,2-dimethyl-4-ethyloctanoic acid; 2-propyl-3-methylnonanoic acid; 2,3-dimethyl Dodecanoic acid; 2-butyl-3-methylnonanoic acid; 3,7,11-trimethyldodecanoic acid; 4,4-dimethyltetradecanoic acid; 2-butyl-2-pentylheptanoic acid; 2,3-dimethyltetradecanoic acid; 8,12-trimethyltridecanoic acid; 14,14-dimethylpentadecanoic acid; 3-methyl-2-heptylnonanoic acid; 2,2-dipentylheptanoic acid; 2,2-dimethylhexadecanoic acid; 2-octyl-3-methylnonanoic acid 2,3-dimethylheptadecanoic acid; 2,4-dimethyloctadecanoic acid; 2-butyl-2-heptylnonanoic acid; 2 , And the like 20-dimethyl hen eicosanoic acid.
[0041]
Examples of branched unsaturated fatty acids include 5-methyl-2-undecenoic acid, 2-methyl-2-dodecenoic acid, 5-methyl-2-tridecenoic acid, 2-methyl-9-octadecenoic acid, 2-ethyl-9 -Octadecenoic acid, 2-propyl-9-octadecenoic acid, 2-methyl-2-eicosenoic acid, etc. can be mentioned. Among the above fatty acids having 12 to 24 carbon atoms, stearic acid, oleic acid, 16-methylheptadecanoic acid (isostearic acid) and the like are preferable.
[0042]
The component (A) may be used alone or in combination of two or more. The blending amount is 1 to 10% by mass based on the total amount of the composition, and if it is less than 1% by mass, the effect of rust prevention does not come out, and even if it exceeds 10% by mass, the effect commensurate with the amount is It is not economical. Preferably it is 3-7 mass%.
[0043]
(B) component
The overbased metal sulfonate of component (B) is a metal salt of various sulfonic acids, and examples of the sulfonic acid include aromatic petroleum sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid, and alkyl aryl sulfonic acid. Include dodecylbenzenesulfonic acid, dilaurylcetylbenzenesulfonic acid, paraffin wax-substituted benzenesulfonic acid, polyolefin-substituted benzenesulfonic acid, polyisobutylene-substituted benzenesulfonic acid, naphthalenesulfonic acid, and the like. As the metal, Ba, Ca, Mg or Zn is preferable. Moreover, it is preferable that the total base number is 400 mgKOH / g or more (JIS K2501; perchloric acid method) from the point of addition amount.
[0044]
Said (B) component may be 1 type, and may be used in combination of 2 or more type. The compounding quantity is 0.2-10 mass% as a metal content on the composition whole quantity basis. When the blending amount of the component (B) is less than 0.2% by mass, the long-term rust prevention property is lowered, and when the blending amount exceeds 10% by mass, an improvement in the long-term rust prevention property corresponding to the amount is not recognized. . Preferably it is 0.4-2 mass%.
[0045]
(C) component
The neutral metal sulfonate of component (C) is a metal salt of various sulfonic acids, and has a total base number of almost 0 mg KOH / g (JIS K 2501; perchloric acid method). Examples of the sulfonic acid include the same as the component (B). As the metal, Ba, Ca, Mg or Zn is preferable.
[0046]
Said (C) component may be 1 type, and may be used in combination of 2 or more type. The compounding quantity is 0.2-10 mass% as a metal content on the composition whole quantity basis. When the blending amount of the component (C) is less than 0.2% by mass, the degreasing property and the rust preventive property are deteriorated. . Preferably it is 0.2-2 mass%. In addition, regarding the relationship between the amounts of the components (A), (B), and (C), the mass ratio of the component (A) and the component ((B) + (C)] is preferably 1: 1 to 1: 2. In this ratio, the most excellent degreasing property is exhibited.
[0047]
(D) component
(D) The animal and vegetable fats and oils of component are mainly composed of glycerin fatty acid ester, and the fatty acid is 37-50 mass% oleic acid, 35-48 mass% palmitic acid, and myristic acid, stearic acid, linoleic acid. It is desirable to include.
[0048]
Said (D) component may be 1 type, and may be used in combination of 2 or more type. The blending amount is 1 to 10% by mass on the basis of the total amount of the composition, and if it is less than 1% by mass, the effect of lubricity does not come out, and if it exceeds 10% by mass, the solubility decreases and the degreasing property also increases. descend. Moreover, the effect corresponding to the amount does not appear and it is not economical. Preferably it is 3-7 mass%.
[0049]
(E) component
Among the components (E), as acidic esters, the following general formulas (1) and (2)
There is a normal phosphoric acid ester represented by the following general formula (3).
[0050]
[Chemical 1]

[Chemical formula 2]

(In the formulas (1) and (2), R ¹ And R ² Represents an alkyl group having 4 to 30 carbon atoms, an alkenyl group, an alkylaryl group and an arylalkyl group, which may be the same or different. )
[Chemical 3]

(In formula (3), R ^Three And R ^Four Represents an alkyl group having 4 to 30 carbon atoms, an alkenyl group, an alkylaryl group and an arylalkyl group, which may be the same or different. )
[0051]
The orthophosphate ester is a mixture of the diester of the above general formula (1) and the monoester of the general formula (2). Specifically, for example, 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, iso Examples include stearyl acid phosphate and oleyl acid phosphate.
[0052]
Specific examples of the phosphite include dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, and diphenyl hydrogen phosphite.
[0053]
Among the above acidic phosphate esters, for example, 2-ethylhexyl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, and the like can be mentioned as preferable ones.
[0054]
Moreover, Ca soap etc. can be mentioned as a preferable metal salt of the above acidic esters.
[0055]
Furthermore, examples of amines that form amine salts with these include mono-substituted amines, di-substituted amines, and tri-substituted amines represented by the following general formula (4).
R _n NH _3-n (4)
(In the formula (4), R represents an alkyl group or alkenyl group having 3 to 30 carbon atoms, an aryl group or arylalkyl group having 6 to 30 carbon atoms, or a hydroxyalkyl group having 2 to 30 carbon atoms, and n is 1, 2 or 3. In addition, when there are a plurality of R, the plurality of R may be the same or different.) The alkyl group or alkenyl group having 3 to 30 carbon atoms of R in the general formula (4) is , Any of linear, branched and cyclic.
[0056]
Here, examples of the mono-substituted amine include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, and benzylamine. Examples of the disubstituted amine include Dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl Examples include monoethanolamine, phenyl monoethanolamine, and tolyl monopropanol. Examples of tri-substituted amines are tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl. Monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine , Phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine It may be mentioned triethanolamine, tripropanolamine and the like.
[0057]
Said (E) component may be 1 type, and may be used in combination of 2 or more type. The blending amount is 0.01 to 5% by mass as the phosphorus content on the basis of the total amount of the composition, and if it is less than 0.01% by mass, the effect of lubricity does not appear and even if it exceeds 5% by mass. However, it is not economical as the effect is not commensurate with the amount. Preferably it is 0.01-0.5 mass%.
[0058]
In addition, the sulfur content in the components (A), (D) and (E) is 100 ppm or less in terms of prevention of plating peeling due to the formation of zinc sulfide on the pure zinc plating surface and an increase in the coefficient of friction due to adhesion to the mold. It is desirable to be. In addition, the composition of the present invention can be prepared by blending the above-mentioned components (A) to (E) with a lubricating base oil. In this case, the kinematic viscosity at 40 ° C. of the composition is 4 to 100 mm. ² / S, especially 5-20mm ² It is effective to select the type, properties and blending ratio of each component so as to be / s. In the composition of the present invention, a known additive such as an antioxidant, a metal deactivator, a corrosion inhibitor, and an antifoaming agent may be added as desired within a range that does not impair the purpose of the present invention. it can. What is necessary is just to apply | coat the composition of this invention to the surface of a metal material by general methods, such as a dipping method, a shower method, and an electrostatic coating method.
[0059]
The amount of rust prevention and press working oil applied is 0.2 to 10 g / m. ² 0.2 g / m ² If it is less than 10 g / m, the lubricity effect does not appear. ² Exceeding the value is not economical because the effect is not commensurate with the amount. Preferably 0.4 to 5 g / m ² It is.
[0060]
The base metal plate of the present invention is not particularly limited, and any metal plate or alloy plate that is used after being molded, such as a steel plate, an aluminum plate, a copper plate, or a titanium plate, can be used. When using steel plates as the base metal plate, both hot-rolled and cold-rolled steel plates can be used, and the steel grades are ultra-low-carbon steel plates to which Al killed steel, Ti, Nb, etc. are added, and reinforced with P, Si, Mn, etc. Various materials such as high-strength steel and stainless steel to which elements are added can be applied.
[0061]
A plated metal plate obtained by performing zinc, zinc-based alloy plating, or aluminum-based plating on these metal plates can also be applied as the base metal plate. As a typical plated metal plate, plating having Al: 0.05 to 1.0% by mass, Fe: 5 to 15% by mass, the balance being an alloyed hot dip galvanized layer composed of Zn and inevitable impurities Steel sheet, plated steel sheet having a hot-dip galvanized layer containing either 0.2 or 10% by mass of Al or Mg and the balance being Zn and inevitable impurities, Al: 4 to 22% by mass, Mg: 1 10% by mass, Si: 0.5% by mass or less, a plated steel sheet having a hot-dip galvanized layer consisting of Zn and inevitable impurities, Al: 4-70% by mass, Si: 3% by mass or less A plated steel sheet having a galvanized layer containing Zn and the inevitable impurities in the balance, Si: 2 to 15% by mass, and a molten aluminum plating layer having the balance consisting of Al and the inevitable impurities Electro-galvanized steel sheet comprising a plated steel sheet, Zn and unavoidable impurities having, Ni: 4 to 15 containing wt%, the balance include electro-galvanized steel sheet or the like made of Zn and unavoidable impurities.
[0062]
In the present invention, the reason why the Al composition of the alloyed hot-dip galvanized layer is limited to 0.05 to 1.0% by mass is that if it is less than 0.05% by mass, Zn-Fe alloying proceeds too much during the alloying treatment. This is because a brittle alloy layer develops too much at the iron interface and the plating adhesion deteriorates. If it exceeds 1.0% by mass, the Fe—Al—Zn-based barrier layer is formed too thick and alloying occurs during the alloying treatment. This is because the desired iron content plating cannot be obtained because it does not progress.
[0063]
The reason why the Fe composition is limited to 5 to 15% by mass is that if it is less than 5% by mass, a soft Zn—Fe alloy is formed on the plating surface and press formability is deteriorated. This is because a brittle alloy layer develops too much at the iron interface and the plating adhesion deteriorates.
[0064]
In the present invention, the reason why the Al composition of the plating layer containing either or both of Al and Mg is limited to 0.2 to 10% by mass is that a normal hot dipping process is performed with an Al amount of less than 0.2% by mass. And a Zn-Fe alloying reaction takes place during the plating process, and a brittle alloy layer develops at the interface between the steel and the adhesion of the plating deteriorates. If it exceeds 10% by mass, the growth of the Fe-Al alloy layer will occur. This is because it becomes prominent and obstructs plating adhesion.
[0065]
The reason why the Mg composition is limited to 0.2 to 10% by mass is that if it is less than 0.2% by mass, the effect of improving the corrosion resistance is insufficient, and if it exceeds 10% by mass, the plating bath is oxidized. This is because a large amount of Mg oxide is generated on the bath surface and plating becomes difficult.
[0066]
Furthermore, it is effective to increase the Al composition of the Zn-Al plating layer in order to obtain a corrosion-resistant plated steel sheet. However, as described above, when the Al composition exceeds 10% by mass, the growth of the Fe-Al alloy layer is caused. It becomes noticeable and inhibits plating adhesion. Therefore, in order to increase the Al composition of the Zn—Al plating layer, it is necessary to add Si in order to suppress the growth of the Fe—Al alloy layer.
[0067]
In the present invention, the reason why the Al composition of the Zn-Al-Si plating layer is limited to 4 to 70% by mass is that, with an Al amount of less than 4% by mass, adhesion is sufficient without adding Si, It is because the effect which improves corrosion resistance will be saturated when it exceeds 70 mass%.
[0068]
The reason for limiting the Si content to 3% by mass or less (excluding 0% by mass) is that Si has the effect of suppressing the growth of the Fe—Al alloy layer and improving the adhesion, but if it exceeds 3% by mass This is because the effect of improving the adhesion is saturated. Desirably, it is 0.01-3 mass%. More desirably, it is 1% or more of the Al content. The addition of Si is essential for plating layers with an Al content of more than 10% by mass. However, even in plating layers with an Al content of 10% or less, the effect of improving plating adhesion is great, so the parts are severely processed. When high plating adhesion is required, such as for use in Si, it is necessary to add Si.
[0069]
Furthermore, in the Zn-Al-Mg plating layer, increasing the Al composition of the plating layer is effective in improving the corrosion resistance. However, as described above, when the Al composition exceeds 10% by mass, the growth of the Fe-Al alloy layer is caused. It becomes noticeable and inhibits plating adhesion. Therefore, in order to increase the Al composition of the Zn—Al plating layer, it is necessary to add Si in order to suppress the growth of the Fe—Al alloy layer.
[0070]
In the present invention, the reason why the Al composition of the Zn—Al—Mg—Si plating layer is limited to 4 to 22 mass% is that sufficient adhesion can be obtained without adding Si with an Al amount of less than 4 mass%. This is because the effect of improving the corrosion resistance is saturated when it exceeds 22% by mass.
[0071]
The reason why the Mg composition is limited to 1 to 10% by mass is that if it is less than 1% by mass, the effect of improving the corrosion resistance is insufficient, and if it exceeds 10% by mass, the plating bath tends to be oxidized, This is because a large amount of Mg oxide is generated and plating becomes difficult.
[0072]
The reason why the content of Si is limited to 0.5% by mass or less (excluding 0% by mass) is that Si has an effect of improving adhesiveness, but if it exceeds 0.5% by mass, an effect of improving adhesiveness. This is because is saturated. Desirably, it is 0.00001-0.5 mass%. More desirably, the content is 0.0001 to 0.5% by mass. The addition of Si is essential for plating layers with an Al content of more than 10% by mass. However, even in plating layers with an Al content of 10% or less, the effect of improving plating adhesion is great, so the parts are severely processed. When high plating adhesion is required, such as for use in Si, it is necessary to add Si.
[0073]
The reason why the Si composition was limited to 2 to 15% by mass in the plating layer consisting of Si: 2 to 15% by mass and the balance being Al and inevitable impurities is that the plating bath is less than 2% by mass and exceeds 15% by mass. This is because the melting point of the metal does not sufficiently decrease, so that plating becomes difficult.
[0074]
Ni: The content of Ni is 4 to 15% by mass, and the balance is limited to 4 to 15% by mass in the electrogalvanized layer consisting of Zn and inevitable impurities. The reason why the corrosion resistance is not improved is less than 4% by mass. This is because it is sufficient, and if it exceeds 15% by mass, the corrosion resistance is lowered.
[0075]
There are no particular restrictions on the amount of metal plating plated, but 10 g / m from the viewpoint of corrosion resistance. ² From the viewpoint of workability, 350 g / m ² It is desirable that
[0076]
Also, among the above plated metal plates, those in which the plating layer contains Al, and the Al phase is crystallized as the primary crystal, the surface of the plated surface is uneven due to the growth of the Al phase, resulting in surface smoothness. May decrease. Addition of Ti to the plating is effective for suppressing the unevenness.
[0077]
The reason why the content of Ti is limited to 0.1% by mass or less (excluding 0% by mass) is that Ti has the effect of crystallizing a Ti—Al intermetallic compound and improving surface smoothness. This is because when the amount exceeds 1% by mass, the appearance after plating becomes rough and appearance defects occur. Moreover, when Ti-Al type intermetallic compound exceeds 0.1 mass% by Ti content, it will concentrate on the plating surface and will reduce surface smoothness. Desirably, it is 0.00001-0.1 mass%. More desirably, it is 0.00001-0.01 mass%.
[0078]
In addition to this, the galvanized layer may contain Fe, Sb, Pb, and Sn alone or in combination within 0.5% by mass. Moreover, even if it contains a total of 0.5% by mass or less of group III elements such as Ca, Be, Cu, Ni, Co, Cr, Mn, P, B, Nb, Bi, V, Nb and lanthanoids The effect of the invention is not impaired, and depending on the amount, the corrosion resistance may be further improved.
[0079]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
[0080]
(Example 1)
Kinematic viscosity at 40 ° C is 5mm ² / S (Base oil A) and 30mm ² A highly-lubricated rust preventive oil was prepared by blending a predetermined compound shown in Table 1 at a predetermined ratio (mass%) with a base oil obtained by mixing / s (base oil B) paraffinic mineral oil. Trimethylolpropane tripalmitate was used as the polyhydric alcohol fatty acid full ester. As the overbased sulfonate, Ca sulfonate (metal content 40%) having a total base number of 400 mgKOH / g was used. As the neutral sulfonate, Ca sulfonate (40% metal content) having a total base number of 1 mgKOH / g or less was used. Refined coconut oil was used for animal and vegetable fats and oils. As the Ca salt of the acidic phosphate ester, the Ca salt of 2-ethylhexyl acid phosphate was used. The phosphorus content is 10%. The sulfurized vegetable oil ester used contained 10% sulfur. Table 1 shows the kinematic viscosity of each highly lubricated rust preventive oil at 40 ° C.
[0081]
As the plated steel sheet, a hot dip galvanized steel sheet, an alloyed hot dip galvanized steel sheet, or a Zn—Al—Mg plated steel sheet was used. The composition of the hot dip galvanized steel sheet is Al: 0.4% by mass, remaining Zn, and the composition of the galvannealed steel sheet is Al: 0.4% by weight, Fe: 10% by weight, remaining Zn, Zn—Al— The composition of the Mg-plated steel sheet was Al: 11% by mass, Mg: 3% by mass, Si: 0.2% by mass, and the remaining Zn. The plate thickness was 0.7 mm in all cases.
[0082]
[Table 1]

[0083]
These high-lubricating rust preventive oils were applied to plated steel sheets in the amounts shown in Table 2 and evaluated for formability, degreasing properties, and rust prevention properties.
[0084]
The moldability was evaluated by performing a cylindrical deep drawing test using a mold having a punch diameter: 50 mmφ, a die diameter: 51.95 mmφ, and a shoulder R: 5R. The squeezing ratio was 2.2 and the wrinkle holding load was changed, and the following scoring was used. The grades are ◎, ○, and △.
A: 4000 kg / cm ² With this
○: 1500kg / cm ² 4000kg / cm ² Less than
Δ: 500 kg / cm ² 1500 kg / cm ² Less than
X: 500 kg / cm ² Break at
[0085]
The degreasing property is determined by immersing and shaking the test piece at 43 ° C. for 60 seconds in a degreasing solution obtained by adding 5 g / l of each rust preventive oil to FC-L4460 manufactured by Nihon Parkerizing. The wet area was measured and judged by the following rating. The grades were ○ and △.
○: Water coverage area 100%
Δ: Water coverage 80% or more and less than 100%
×: Less than 80% wet area
[0086]
The antirust property evaluated the presence or absence of white rust generation after SST6hr. In the evaluation, a case where white rust was not generated passed, and a case where white rust was generated was rejected.
[0087]
For long-term rust prevention, a test piece sandwiched between 0.05 mm thick polytetrafluoroethylene sheets was packed with filter paper and tested in an environment of 50 ° C. and RH 95% to evaluate the presence or absence of rust and stain. Evaluation was determined by the following scoring. The grades were ○ and △.
○: Rust for 30 days, no stain
Δ: Rust for 10 days, no stain
×: Rust and stain occurred in 10 days
[0088]
The evaluation results are shown in Table 2. For comparison, a commercially available general antirust oil to which Ba sulfonate and oxidized wax ester were added was used. In Nos. 2, 24, and 46, the addition amount of the polyhydric alcohol fatty acid full ester was outside the range of the present invention, so the rust prevention property was rejected. In Nos. 5, 27, and 49, the addition amount of the overbased sulfonate was outside the range of the present invention, so the long-term rust prevention property was rejected. In Nos. 9, 31, and 53, the addition amount of neutral sulfonate was out of the scope of the present invention, so that the degreasing and rust preventive properties were rejected. In Nos. 16, 38 and 60, the addition amount of fats and oils was out of the range of the present invention, so that the degreasing property was rejected. Nos. 22, 44, and 66 used general rust preventive oil, so the moldability was not acceptable. The antirust and press working oil 20 in Table 1 has passed the formability of the alloyed hot dip galvanized steel sheet No. 42 due to the addition of the sulfurized vegetable oil ester, but Nos. 20 and 64 are formed by reacting the sulfur content with the plating. Sex was rejected. Except for these, all exhibited good moldability, degreasing properties, and rust prevention properties.
[0089]
[Table 2]

[0090]
(Example 2)
Kinematic viscosity at 40 ° C is 5mm ² / S (Base oil A) and 30mm ² A highly-lubricated rust-preventing oil was prepared by blending a predetermined compound shown in Table 3 in a predetermined ratio (mass%) with a base oil obtained by mixing / s (base oil B) paraffinic mineral oil. Trimethylolpropane tripalmitate was used as the polyhydric alcohol fatty acid full ester. As the overbased sulfonate, Ca sulfonate (metal content 40%) having a total base number of 400 mgKOH / g was used. As the neutral sulfonate, Ca sulfonate (40% metal content) having a total base number of 1 mgKOH / g or less was used. Refined coconut oil, rice bran oil, and soybean were used for the animal and vegetable oils and fats. As the Ca salt and amine salt of acidic phosphoric acid ester, Ca salt of 2-ethylhexyl acid phosphate, Ca salt of stearyl acid phosphate, and amine salt of oleyl acid phosphate were used. The phosphorus content is 10% in all cases. The kinematic viscosity of each highly lubricated rust preventive oil at 40 ° C is 15 mm ² / S.
[0091]
As the plated steel sheet, a hot dip galvanized steel sheet, an alloyed hot dip galvanized steel sheet, or a Zn—Al—Mg plated steel sheet was used. The composition of the hot dip galvanized steel sheet is Al: 0.4% by mass, remaining Zn, and the composition of the galvannealed steel sheet is Al: 0.4% by weight, Fe: 10% by weight, remaining Zn, Zn—Al— The composition of the Mg-plated steel sheet was Al: 11% by mass, Mg: 3% by mass, Si: 0.2% by mass, and the remaining Zn. The plate thickness was 0.7 mm in all cases.
[0092]
[Table 3]

[0093]
These high-lubricating rust preventive oils were applied to plated steel sheets in the amounts shown in Table 4, and evaluated for formability, degreasing properties, and rust preventive properties.
[0094]
The moldability was evaluated by performing a cylindrical deep drawing test using a mold having a punch diameter: 50 mmφ, a die diameter: 51.95 mmφ, and a shoulder R: 5R. The squeezing ratio was 2.2 and the wrinkle holding load was changed, and the following scoring was used. The grades are ◎, ○, and △.
A: 4000 kg / cm ² With this
○: 1500kg / cm ² 4000kg / cm ² Less than
Δ: 500 kg / cm ² 1500 kg / cm ² Less than
X: 500 kg / cm ² Break at
[0095]
The degreasing property is determined by immersing and shaking the test piece at 43 ° C. for 60 seconds in a degreasing solution obtained by adding 5 g / l of each rust preventive oil to FC-L4460 manufactured by Nihon Parkerizing. The wet area was measured and judged by the following rating. The grades were ○ and △.
○: Water coverage area 100%
Δ: Water coverage 80% or more and less than 100%
×: Less than 80% wet area
[0096]
The antirust property evaluated the presence or absence of white rust generation after SST6hr. In the evaluation, a case where white rust was not generated passed, and a case where white rust was generated was rejected.
[0097]
For long-term rust prevention, a test piece sandwiched between 0.05 mm thick polytetrafluoroethylene sheets was packed with filter paper and tested in an environment of 50 ° C. and RH 95% to evaluate the presence or absence of rust and stain. Evaluation was determined by the following scoring. The grades were ○ and △.
○: Rust for 30 days, no stain
Δ: Rust for 10 days, no stain
×: Rust and stain occurred in 10 days
The evaluation results are shown in Table 4. For comparison, a commercially available general antirust oil to which Ba sulfonate and oxidized wax ester were added was used. Nos. 1, 22, and 43 were unsatisfactory in moldability and rust prevention because the amount of oil coating was outside the scope of the present invention. Nos. 21, 42 and 63 used general rust preventive oil, so the moldability was rejected. Except for these, all exhibited good moldability, degreasing properties, and rust prevention properties.
[0098]
[Table 4]

[0099]
(Example 3)
Prepared hot dip galvanized steel sheet having a thickness of 0.7 mm with additive elements other than zinc as shown in Table 5, and formulated with a predetermined ratio (mass%) of a predetermined compound shown in Table 3 in a high lubricity prevention Rust oil was applied in the amount shown in Table 5 and evaluated for moldability, degreasing properties, and rust prevention properties.
[0100]
[Table 5]

[0101]
Moreover, the hot-lubrication rust prevention steel which prepared the hot dip galvanized steel plate shown in Table 6, the electrogalvanized steel plate, and the electro Zn-Ni galvanized steel plate, and mix | blended the predetermined compound shown in Table 3 by the predetermined | prescribed ratio (mass%). The oil was applied in the amount shown in Table 6 and evaluated for moldability, degreasing properties, and rust prevention properties. The composition of the hot-dip aluminum-plated steel sheet was Si: 10% by mass, the remaining Al and the electrogalvanized steel sheet were only Zn, and the composition of the electro-Zn—Ni-plated steel sheet was Ni: 10% by mass and the remaining Zn. The plate thickness was 0.7 mm in all cases.
[0102]
The deep drawability was evaluated by performing a cylindrical deep draw test using a mold having a punch diameter: 50 mmφ, a die diameter: 51.95 mmφ, and a shoulder R: 5R. The squeezing ratio was 2.2 and the wrinkle holding load was changed, and the following scoring was used. The grades are ◎, ○, and △.
A: 4000 kg / cm ² With this
○: 1500kg / cm ² 4000kg / cm ² Less than
Δ: 500 kg / cm ² 1500 kg / cm ² Less than
X: 500 kg / cm ² Break at
[0103]
The powdering property uses a die having a punch diameter of 50 mmφ, a die diameter of 51.95 mmφ, and a shoulder R of 5R, a drawing ratio of 1.8, and a wrinkle holding load of 2500 kg / cm. ² Then, plating peeling of the vertical wall portion of the sample molded at a molding speed of 200 mm / min and a molding depth of 25 mm was evaluated. The evaluation was made by pasting the cellophane tape on the vertical wall of the sample after the molding test, attaching the peeled plating to the tape, measuring the blackening rate of the tape, and judging by the following ratings. . The grades were ○ and △.
○: Blackening rate of less than 30%
Δ: Blackening rate of 30% or more and less than 50%
×: Blackening rate of 50% or more
[0104]
For the flaking property, a pull-out test was performed using a square bead having a shoulder R of 1 mmR (the convex portion is 4 × 4 mm), and plating peeling at the bead passage portion was evaluated. In the pull-out test, a sample having a width of 30 mm and a length of 300 mm was sandwiched between bead molds, and then pulled out with a pressing load of 1000 kgf. The evaluation was made by attaching a cellophane tape to the bead passing part of the sample after drawing, attaching the peeled plating to the tape, measuring the blackening rate of the tape, and judging by the following rating. The grades were ○ and △. ○: Blackening rate of less than 30%
Δ: Blackening rate of 30% or more and less than 50%
×: Blackening rate of 50% or more
[0105]
The degreasing property is determined by immersing and shaking the test piece at 43 ° C. for 60 seconds in a degreasing solution obtained by adding 5 g / l of each rust preventive oil to FC-L4460 manufactured by Nihon Parkerizing. The wet area was measured and judged by the following rating. The grades were ○ and △.
○: Water coverage area 100%
Δ: Water coverage 80% or more and less than 100%
×: Less than 80% wet area
[0106]
The antirust property evaluated the presence or absence of white rust generation after SST6hr. In the evaluation, a case where white rust was not generated passed, and a case where white rust was generated was rejected.
[0107]
For long-term rust prevention, a test piece sandwiched between 0.05 mm thick polytetrafluoroethylene sheets was packed with filter paper and tested in an environment of 50 ° C. and RH 95% to evaluate the presence or absence of rust and stain. Evaluation was determined by the following scoring. The grades were ○ and △.
○: Rust for 30 days, no stain
Δ: Rust for 10 days, no stain
×: Rust and stain occurred in 10 days
[0108]
The evaluation results are shown in Tables 5 and 6. For comparison, a commercially available general antirust oil to which Ba sulfonate and oxidized wax ester were added was used. In No. 1, since the Al content during plating was outside the range of the present invention, the formability was rejected. Nos. 3 and 8 used general rust preventive oil, so the moldability was rejected. In No. 9, since the Al content during plating was outside the range of the present invention, the formability was rejected. Except for these, all exhibited good moldability, degreasing properties, and rust prevention properties.
[0109]
[Table 6]

[0110]
(Example 4)
An alloyed hot-dip galvanized steel sheet having a composition shown in Table 7 and elements other than zinc prepared in a thickness of 0.7 mm, and a high-prevention lubricant in which a predetermined compound shown in Table 3 is blended at a predetermined ratio (mass%) Rust oil was applied in the amount shown in Table 7 and evaluated for moldability, degreasing properties, and rust prevention properties.
[0111]
The deep drawability was evaluated by performing a cylindrical deep draw test using a mold having a punch diameter: 50 mmφ, a die diameter: 51.95 mmφ, and a shoulder R: 5R. The squeezing ratio was 2.2 and the wrinkle holding load was changed, and the following scoring was used. The grades are ◎, ○, and △.
A: 4000 kg / cm ² With this
○: 1500kg / cm ² 4000kg / cm ² Less than
Δ: 500 kg / cm ² 1500 kg / cm ² Less than
X: 500 kg / cm ² Break at
[0112]
The powdering property uses a die having a punch diameter of 50 mmφ, a die diameter of 51.95 mmφ, and a shoulder R of 5R, a drawing ratio of 1.8, and a wrinkle holding load of 2500 kg / cm. ² Then, plating peeling of the vertical wall portion of the sample molded at a molding speed of 200 mm / min and a molding depth of 25 mm was evaluated. The evaluation was made by pasting the cellophane tape on the vertical wall of the sample after the molding test, attaching the peeled plating to the tape, measuring the blackening rate of the tape, and judging by the following ratings. . The grades were ○ and △.
○: Blackening rate of less than 30%
Δ: Blackening rate of 30% or more and less than 50%
×: Blackening rate of 50% or more
[0113]
For the flaking property, a pull-out test was performed using a square bead having a shoulder R of 1 mmR (the convex portion is 4 × 4 mm), and plating peeling at the bead passage portion was evaluated. In the pull-out test, a sample having a width of 30 mm and a length of 300 mm was sandwiched between bead molds, and then pulled out with a pressing load of 1000 kgf. The evaluation was made by attaching a cellophane tape to the bead passing part of the sample after drawing, attaching the peeled plating to the tape, measuring the blackening rate of the tape, and judging by the following rating. The grades were ○ and △. ○: Blackening rate of less than 30%
Δ: Blackening rate of 30% or more and less than 50%
×: Blackening rate of 50% or more
[0114]
The degreasing property is determined by immersing and shaking the test piece at 43 ° C. for 60 seconds in a degreasing solution obtained by adding 5 g / l of each rust preventive oil to FC-L4460 manufactured by Nihon Parkerizing. The wet area was measured and judged by the following rating. The grades were ○ and △.
○: Water coverage area 100%
Δ: Water coverage 80% or more and less than 100%
×: Less than 80% wet area
[0115]
The antirust property evaluated the presence or absence of white rust generation after SST6hr. In the evaluation, a case where white rust was not generated passed, and a case where white rust was generated was rejected.
[0116]
For long-term rust prevention, a test piece sandwiched between 0.05 mm thick polytetrafluoroethylene sheets was packed with filter paper and tested in an environment of 50 ° C. and RH 95% to evaluate the presence or absence of rust and stain. Evaluation was determined by the following scoring. The grades were ○ and △.
○: Rust for 30 days, no stain
Δ: Rust for 10 days, no stain
×: Rust and stain occurred in 10 days
[0117]
Table 7 shows the evaluation results. For comparison, a commercially available general antirust oil to which Ba sulfonate and oxidized wax ester were added was used. In No. 6, since the Al content and the Fe content in the plating were outside the scope of the present invention, the formability was rejected. In No. 10, since the Fe content during plating was outside the range of the present invention, the moldability was rejected. Nos. 11 and 12 used general rust preventive oil, so that the moldability was rejected. Except for these, all exhibited good moldability, degreasing properties, and rust prevention properties.
[0118]
[Table 7]

[0119]
【The invention's effect】
As described above, according to the present invention, it is possible to produce a highly lubrication-proof metal plate excellent in formability, degreasing properties, and rust-proofing properties, and it is possible to achieve extremely excellent effects in industry.

Claims (11)

Mineral oil, one or more synthetic oils are mixed, the base oil kinematic viscosity was 4~100mm ² / s at 40 ° C., (A) Ri der 12 or more carbon atoms of the fatty acid, sulfur content 1 to 10% by mass of fatty acid full ester of polyhydric alcohol having a concentration of 100 ppm or less , (B) 0.2 to 10% by mass of overbased metal sulfonate as a metal component, and (C) 0 as neutral metal sulfonate as a metal component. 2 to 10% by mass, (D) 1 to 10% by mass of animal and vegetable oils and fats having a sulfur content of 100 ppm or less , (E) acidic phosphate esters having a sulfur content of 100 ppm or less, or a metal salt or amine salt thereof 0.01 to 5% by mass in minutes, and a rust preventive and press working oil having a mass ratio of (A) component and [(B) + (C)] component of 1: 1 to 1: 2 on the surface It has 0.2-10 g / m < ² > in the whole surface or a part. Highly lubricated and rust-proof metal plate with excellent formability and rust prevention. (B) The total base number of a component is 400 mgKOH / g or more, The highly lubricated rust prevention metal plate excellent in the moldability and rust prevention property of Claim 1 . (B), (C) component is the sulfonate of Ba, Ca, Na, Mg, or Zn, respectively, The highly lubricious rust prevention excellent in the moldability and rust prevention property of Claim 1 or 2 characterized by the above-mentioned Processing metal plate. The alloyed molten zinc in which the metal plate according to any one of claims 1 to 3 contains Al: 0.05 to 1.0 mass%, Fe: 5 to 15 mass%, with the balance being Zn and inevitable impurities. A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, which is a plated steel sheet having a plating layer. A plated steel sheet having a hot-dip galvanized layer in which the metal plate according to any one of claims 1 to 3 contains 0.2 to 10% by mass of Al or Mg, and the balance is Zn and inevitable impurities. A highly-lubricated and rust-proof metal plate with excellent formability and rust-proofing characteristics. The metal plate according to any one of claims 1 to 3 contains Al: 4 to 22% by mass, Mg: 1 to 10% by mass, Si: 0.5% by mass or less, and the balance is made of Zn and inevitable impurities. A highly lubricated and rust-proof metal plate excellent in formability and rust-proofing properties, characterized by being a plated steel plate having a hot-dip galvanized layer. Plating which has the hot dip galvanized layer which the metal plate in any one of Claims 1 thru | or 3 contains Al: 4-70 mass%, Si: 0.01-3 mass%, and remainder consists of Zn and an unavoidable impurity A highly lubricated and rust-proof metal plate excellent in formability and rust prevention, characterized by being a steel plate. Formability characterized in that the metal plate according to any one of claims 1 to 3 is a plated steel plate having a molten aluminum plating layer containing Si: 2 to 15% by mass and the balance being Al and inevitable impurities. Highly lubricated and rust-proof metal plate with excellent rust resistance. The plated steel sheet according to any one of claims 5 to 8 , wherein Ti: 0.1% by mass or less is contained in the plating layer, and a highly lubricated and rust-proof metal plate excellent in formability and rust prevention . A highly lubricated rust preventive treatment excellent in formability and rust preventive property, wherein the metal plate according to any one of claims 1 to 3 is a plated steel plate having an electrogalvanized layer made of Zn and inevitable impurities. Metal plate. Formability characterized in that the metal plate according to any one of claims 1 to 3 is a plated steel plate having an electrogalvanized layer containing Ni: 4 to 15% by mass and the balance being Zn and inevitable impurities. Highly lubricated and rust-proof metal plate with excellent rust resistance.