JP3048397B2 - Rust-preventive oil composition for both press working and galvanized steel sheet - Google Patents
Rust-preventive oil composition for both press working and galvanized steel sheetInfo
- Publication number
- JP3048397B2 JP3048397B2 JP3059467A JP5946791A JP3048397B2 JP 3048397 B2 JP3048397 B2 JP 3048397B2 JP 3059467 A JP3059467 A JP 3059467A JP 5946791 A JP5946791 A JP 5946791A JP 3048397 B2 JP3048397 B2 JP 3048397B2
- Authority
- JP
- Japan
- Prior art keywords
- rust
- oil
- galvanized steel
- preventive
- steel sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、亜鉛めっき鋼板用プレ
ス加工兼用防錆油組成物に関し、詳しくは、各種亜鉛め
っき鋼板（電気めっき・溶融めっき・合金化めっき・合
金めっき鋼板等）の保存期間中、特に積層状態における
防錆性、変色防止性、脱脂性と共に、最近、自動車産業
を中心に強い要求性能となっている、プレス加工性を付
与した亜鉛めっき鋼板用防錆油に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust-preventive oil composition for both press working and galvanized steel sheet, and more particularly, to preservation of various types of galvanized steel sheets (electroplating, hot-dip plating, alloyed plating, alloy-plated steel sheets, etc.). The present invention relates to a rust-preventive oil for galvanized steel sheet, which has been given a high demand performance mainly in the automobile industry recently, in addition to rust-preventing property, anti-tarnishing property and degreasing property, especially in a laminated state during the period.
【０００２】[0002]
【従来の技術】これまで鋼板用防錆油は、鉄鋼メーカー
から出荷されるコイル鋼板、切り板鋼板に出荷防錆油と
して塗油され、保管期間及び自動車、家電産業等でプレ
ス加工工程に入るまでの間の防錆性、積層状態における
ステイン防止性、そして、優れた脱脂性と化成・塗装処
理における油のにじみ出し防止、および塗膜のクレータ
ー防止性に重点が置かれている。2. Description of the Related Art Until now, rust-preventive oil for steel sheets has been applied as a rust-preventive oil to coil steel sheets and cut steel sheets shipped from steel manufacturers, and enters the press working process during the storage period and in the automobile and home appliance industries. The emphasis has been placed on the anti-rust properties up to this point, the anti-stain properties in the laminated state, the excellent degreasing properties, the prevention of oil bleeding during chemical conversion and coating treatment, and the anti-crater properties of the coating film.
【０００３】また、油の持出しによる経済性、ハンドリ
ング時における様々な作業性の観点からも、製品粘度と
して、４０℃で３０センチストークス以下が求められて
いる。[0003] Also, from the viewpoints of economy by taking out oil and various workability during handling, a product viscosity of 30 centistokes or less at 40 ° C is required.
【０００４】プレス加工性に関しては、省資源、省エネ
ルギーの見地から、プレス工程での合理化が進み、自動
車産業を中心として、鋼板用防錆油で簡単な加工部品の
プレス加工の機会がより多く求められている。[0004] With regard to press formability, from the viewpoint of resource saving and energy saving, rationalization in the press process has been progressing, and more and more opportunities for press working of simple processed parts with rust preventive oil for steel sheets have been demanded mainly in the automobile industry. Have been.
【０００５】一方、最近の自動車産業の発展に伴い、よ
り複雑な形状をした自動車部品の成形が求められ、防錆
油では対処できず、４０℃粘度で５０〜１００センチス
トークスの高粘度のプレス油が使用される機会も多い。
この高粘度のプレス油が加わると防錆性、経済性、作業
性はもとより、特に、脱脂性や亜鉛めっき鋼板特有の変
色に悪い影響が現れる。On the other hand, with the recent development of the automobile industry, molding of automobile parts having a more complicated shape has been demanded, which cannot be dealt with by rust-preventive oil, and has a high viscosity of 50 to 100 centistokes at a viscosity of 40 ° C. There are many occasions where oil is used.
Addition of this high viscosity press oil has a bad effect on rust prevention, economic efficiency and workability, as well as on degreasing properties and discoloration peculiar to galvanized steel sheets.
【０００６】また、トランスファプレス等大型プレス機
の導入、および車体防錆のための防錆鋼板として、亜鉛
めっき鋼板の導入が進むに従い、現行防錆油の防錆性、
脱脂性、特に加工性に対する従来の技術では立ち行かな
いところまできているのが現状である。[0006] With the introduction of large-sized presses such as transfer presses and the introduction of galvanized steel sheets as rust-preventive steel sheets for body rust prevention, the rust-prevention properties of existing rust-preventive oils have been improved.
At present, degreasing, especially workability, has been out of reach of conventional techniques.
【０００７】これまでの亜鉛めっき鋼板用防錆油の基油
組成、および防錆油添加剤組成では、若干の油性効果だ
けであり、充分な潤滑効果は期待出来ない。そこで、潤
滑性（プレス加工性）を付与するために、先に述べた理
由から、製品粘度を４０℃で３０センチストークス以下
と限定すると、基油、防錆剤等による増粘効果は期待出
来ず、様々な極圧剤ないし極圧添加剤（塩素、りん、硫
黄、有機モリブデン等、以下、極圧剤という。）の添加
効果が考えられる。但し、これらの極圧剤は活性タイプ
が多く、正しい選択と配合組成を持たないと、亜鉛めっ
き鋼板表面でのオイルステイン、変色、そして脱脂性能
を極端に低下させるトラブルのもととなる。[0007] The conventional base oil composition of rust-preventive oil for galvanized steel sheet and the composition of rust-preventive oil additive have only a slight oily effect, and a sufficient lubricating effect cannot be expected. Therefore, if the product viscosity is limited to 30 centistokes or less at 40 ° C. for the reason described above in order to impart lubricity (press workability), the thickening effect of the base oil, rust inhibitor, etc. can be expected. In addition, the effect of adding various extreme pressure agents or extreme pressure additives (chlorine, phosphorus, sulfur, organic molybdenum, etc., hereinafter, referred to as extreme pressure agents) can be considered. However, these extreme pressure agents have many active types, and if they do not have the correct selection and composition, they cause oil stains, discoloration, and troubles that extremely reduce the degreasing performance on the surface of the galvanized steel sheet.
【０００８】現在、市場に現れている亜鉛めっき鋼板用
防錆油で、プレス加工用防錆油として、充分な性能を兼
ね備えた防錆油は見当たらないように思われる。更に、
冷延鋼板用防錆油に比べ、亜鉛めっき鋼板に対するプレ
ス加工性能としては、めっき被膜のやわらかな純めっき
材の凝着摩耗防止性、被膜の固い合金化材のめっき層剥
離（パウダリング、フレーキング）防止性、各種厚めっ
き材によるプレス割れ防止性から、プレス加工時に従来
以上の潤滑性能が防錆油に求められている。なお、、プ
レス加工性能を付与した亜鉛めっき鋼板用防錆油として
は、特開平２−１６７３９７号や特開平２−２５２７９
９号が提案されている。特開平２−１６７３９７号は基
油に防錆添加剤及び不活性タイプの硫黄系極圧剤を配合
するものであり、また、特開平２−２５２７９９号は石
油系基油に超高塩基性スルホネートを配合するものであ
るが、これらはいずれも防錆性、脱脂性に問題がある
（後記比較例１及び２参照）。 At present, it seems that there is no rust preventive oil for galvanized steel sheet that has appeared on the market and has sufficient performance as a rust preventive oil for press working. Furthermore,
Compared to rust-preventive oil for cold-rolled steel sheets, the press working performance of galvanized steel sheets is as follows: anti-adhesion and abrasion resistance of pure plating material with a soft coating film, peeling of plating layer of alloyed material with hard coating (powdering, flaking) King) The anti-rust oil is required to have more lubricating performance during press working because of its prevention and press cracking prevention by various thick plating materials. In addition,
Rust-preventive oil for galvanized steel sheet with less processing performance
Are described in JP-A-2-167397 and JP-A-2-25279.
No. 9 has been proposed. JP-A-2-167397 is based on
Rust preventive additive and inert sulfur type extreme pressure agent mixed with oil
Japanese Patent Laid-Open No. 252799/1989 discloses stones.
An oil-based base oil containing an ultra-basic sulfonate
However, all of these have problems with rust prevention and degreasing
(See Comparative Examples 1 and 2 below).
【０００９】[0009]
【発明が解決しようとする課題】本発明は亜鉛めっき鋼
板用防錆油にプレス加工性能を付与することを目的とす
る。さらに、防錆鋼板として亜鉛めっき鋼板の用途拡
大、生産の増大に伴って、防錆性能、脱脂性能、プレス
加工性能等をバランス良く備えた亜鉛めっき鋼板用プレ
ス加工兼用防錆油組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a rust preventive oil for galvanized steel sheet with press working performance. In addition, with the expanded use of galvanized steel sheets and increased production as rust-preventive steel sheets, we provide a press-workable anti-rust oil composition for galvanized steel sheets that has a good balance of rust-prevention performance, degreasing performance, and press-working performance. Is to do.
【００１０】[0010]
【課題を解決するための手段】そこで、本発明者らは上
記課題の解決を目的として、従来の亜鉛めっき鋼板用防
錆油の知見の上に、不活性タイプ硫黄系極圧剤と高塩基
性スルホネートの選択と組合せの検討を行い、防錆性
能、脱脂性能とプレス加工性能のバランス上、最も良好
な配合量を見出すべく鋭意研究した結果、本発明を完成
させた。In order to solve the above-mentioned problems, the present inventors, based on the knowledge of conventional rust preventive oils for galvanized steel sheets, have developed an inert type sulfur-based extreme pressure agent and a high base. The present invention was completed as a result of intensive studies on the selection and combination of a water-soluble sulfonate, and a intensive study to find the best blending amount in terms of the balance between rust prevention performance, degreasing performance and press working performance.
【００１１】本発明は、４０℃における粘度が１０〜
２０ｃｓｔの潤滑油基油、Ｃ１６以上のアルキルスル
ホン酸のアルカリ土類金属塩、アミン塩、Ｃ１２以上の
カルボン酸、Ｃ１２以上のカルボン酸のアルカリ土類金
属塩、アミン塩から選ばれた防錆添加剤、不活性タイ
プ硫黄系極圧剤、アルカリ土類金属の油溶性スルホン
酸塩に、これらの金属の水酸化物、酸化物、炭酸塩を過
剰に含有させた高塩基性スルホネート、上記６５〜８
５重量％に上記５〜２０重量％を加え、さらに、上記
との混合物１０〜２０重量％を加えてなり、しかも
上記の１〜４容量部に対して、上記は１容量部であ
る防錆油組成物であって、全塩基価が２０ｍｇＫＯＨ／
ｇ以下であり、且つ、上記アルカリ土類金属の高塩基
性、油溶性スルホン酸塩の金属がＭｇ、Ｃａ、Ｂａのう
ち、少なくとも１種以上を含むものであって、全塩基価
が２５０〜５００ｍｇＫＯＨ／ｇの高塩基性スルホネー
トであることを要旨とする。According to the present invention, the viscosity at 40.degree.
20 cst lubricating base oil, selected from alkaline earth metal salts and amine salts of C 16 or higher alkyl sulfonic acids, amine salts, C 12 or higher carboxylic acids, alkaline earth metal salts of C 12 or higher carboxylic acids and amine salts Rust prevention additives, inert type sulfur-based extreme pressure agents, oil-soluble sulfonates of alkaline earth metals, hydroxides, oxides of these metals, high-basic sulfonate excessively containing carbonates, 65-8 above
5 to 20% by weight of 5% by weight, and 10 to 20% by weight of a mixture of the above, and 1 part by volume to 1 to 4 parts by volume of rust prevention An oil composition having a total base number of 20 mg KOH /
g or less, and the metal of the highly basic alkaline earth metal and the oil-soluble sulfonate contains at least one of Mg, Ca and Ba, and has a total base number of 250 to The gist is that it is a highly basic sulfonate of 500 mgKOH / g.
【００１２】本発明の好ましい実施態様は、不活性タイ
プ硫黄系極圧剤は硫黄分１５％以下、活性硫黄分５％以
下である硫化ラード、硫化植物油エステル、合成ポリサ
ルファイドから選ばれた、少なくとも１種以上であるこ
とを特徴とする。In a preferred embodiment of the present invention, the inactive type sulfur-based extreme pressure agent is at least one selected from lard sulfide, sulfurized vegetable oil ester and synthetic polysulfide having a sulfur content of 15% or less and an active sulfur content of 5% or less. It is characterized by more than species.
【００１３】本発明者らは、研究過程で下記に示す新た
な知見を得た。 （１）亜鉛めっき鋼板用プレス加工兼用防錆油に求めら
れる性能を維持するためには、根本的に相反する防錆
性、脱脂性、加工性の三つの基本的な性能を構成する添
加剤組成を、いかにバランス良く配合するかである。The present inventors have obtained the following new findings during the course of the research. (1) In order to maintain the performance required of a rust-preventive oil for both press working and galvanized steel sheet, additives that constitute the three fundamental properties of rust prevention, degreasing, and workability that are fundamentally contradictory. It is how to mix the compositions in a well-balanced manner.
【００１４】主成分としては、基油、防錆添加剤、脱脂
助剤、そして不活性タイプ硫黄系極圧剤と高塩基性スル
ホネートが必要であり、補助成分として酸化防止剤、水
置換剤、流動点降下剤等が考えられる。特に、不活性タ
イプ硫黄系極圧剤は、硫黄結合化合物の種類、活性硫黄
の含有量、また、高塩基性スルホネートは、全塩基価、
アルカリ土類金属の種類等が重要であり、その上で、不
活性タイプ硫黄系極圧剤、高塩基性スルホネートの両者
の配合比、配合量を選択するかによって、上記の性能が
求められることを見出した。 （２）プレス成形時、めっき層のやわらかな純めっき材
の凝着摩耗によるプレス割れ防止性、めっき層の固い合
金化材のめっき層剥離防止性などに対しても、同様に不
活性タイプ硫黄系極圧剤、高塩基性スルホネートの最適
配合比、配合量があることを見出した。As main components, a base oil, a rust preventive additive, a degreasing aid, an inert type sulfur type extreme pressure agent and a highly basic sulfonate are required, and as an auxiliary component, an antioxidant, a water displacement agent, Pour point depressants and the like are conceivable. In particular, the inert type sulfur-based extreme pressure agent is a type of sulfur-binding compound, the content of active sulfur, and a highly basic sulfonate is a total base number,
The type of alkaline earth metal, etc. is important, and on top of that, the above-mentioned performance is required by selecting the mixing ratio and mixing amount of both the inert type sulfur-based extreme pressure agent and the highly basic sulfonate. Was found. (2) In the case of press molding, the inert type sulfur is also used to prevent press cracking due to cohesive abrasion of the soft pure plating material of the plating layer and the peeling of the plating layer of the alloyed material with a hard plating layer. It has been found that there are optimal blending ratios and blending amounts of the system extreme pressure agent and the highly basic sulfonate.
【００１５】深絞り加工における加工速度は、低速ほ
ど、また、合金化材に比べ、純めっき材は凝着摩耗を起
こし易く、プレス割れを起こす。これは低速になればな
るほど、加工面への潤滑剤の引き込み効果が少ないため
と考えられる。The processing speed in the deep drawing process is lower, and the pure plating material is liable to cause adhesive wear and press cracking as compared with the alloyed material. This is probably because the lower the speed, the less the effect of drawing the lubricant into the machined surface.
【００１６】逆に、純めっき材に比べ合金化材は、加工
速度が高速になるほど剥離（パウダリング）を起こす。
これは純めっき材のめっき被膜に比べ、密着性の悪い合
金化材のめっき被膜が、加工速度に追従出来なくなるた
めと考えられる。[0016] Conversely, pure plated alloying material than in the cause peeling higher processing speed increases (Pas c Daringu).
This is considered to be because the plated film of the alloying material having poor adhesion cannot follow the processing speed as compared with the plated film of the pure plated material.
【００１７】この様に、最近の自動車産業を中心とした
高速プレスラインを考えた時、成形性（プレス割れ防止
性）、剥離防止性のバランスの上でも、不活性タイプ硫
黄系極圧剤、高塩基性スルホネートの組合せに最適値が
あることが認められた。 （３）白錆防止性、変色防止性に対して、不活性タイプ
硫黄系極圧剤の添加量の増加は悪い方向に向い、高塩基
性スルホネートは鉄面（片面めっき材）、合金化材、鉄
・亜鉛合金材の耐食性、特に脱脂性に添加量の増加と共
に悪影響が現れる。このことから、亜鉛めっき鋼板用防
錆油の防錆性、脱脂性に与える影響に対しても、不活性
タイプ硫黄系極圧剤と高塩基性スルホネートの配合に最
適バランス点があることを認めた。 （４）本発明に用いられる防錆添加剤のスルホン酸塩と
しては、アルキルベンゼンスルホン酸、アルキルナフタ
レンスルホン酸、石油系スルホン酸のアルカリ土類金属
塩、アミン塩が挙げられ、また、カルボン酸（オレイル
ザルコシン酸等）、カルボン酸塩としては、Ｃ１２以上
のカルボン酸、酸化ワックス、ラノリン脂肪酸のアルカ
リ土類金属塩、アミン塩が挙げられる。また、防錆性と
共に脱脂性の見地からは、ソルビタン脂肪酸エステルの
タイプとして、脂肪酸の種類がオレエート、ステアレー
ト、ラウレートのものが挙げられる。As described above, when considering a recent high-speed press line mainly in the automobile industry, an inert type extreme pressure agent based on an inert type sulfur, It has been found that there is an optimum value for the combination of highly basic sulfonates. (3) With respect to white rust prevention and discoloration prevention, the increase in the amount of the inert type sulfur-based extreme pressure agent tends to be inferior, and the highly basic sulfonate has an iron surface (one-side plating material) and an alloying material. In addition, the corrosion resistance of the iron / zinc alloy material, particularly the degreasing property, has an adverse effect as the amount of addition increases. From this, it was confirmed that there is an optimal balance point between the combination of the inert type sulfur-based extreme pressure agent and the highly basic sulfonate with respect to the effect on the rust prevention and degreasing properties of the rust prevention oil for galvanized steel sheets . Was. (4) As the sulfonate rust-preventive agent used in the present invention, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkaline earth metal salts of petroleum sulfonic acids, include amine salts, also carboxylic acid (such as I sarcosine acid), the carboxylic acid salt, C 12 or higher carboxylic acids, oxidized waxes, alkaline earth metal salts of lanolin fatty acids, amine salts. In addition, from the viewpoint of degreasing as well as rust prevention, the sorbitan fatty acid ester includes fatty acids of oleate, stearate and laurate.
【００１８】通常、これらの１種または２種以上を組合
せて使用することが出来るが、好ましくは上記記載のう
ち、合成スルホネートＢａ塩、酸化ワックスＢａ塩、ソ
ルビタンエステルが挙げられ、他の成分とのバランスを
考えて、使用量は５〜２０重量％となる。防錆添加剤が
５重量％未満の場合、腐食性物質及び腐食性物質を含ん
だ水分等から、金属表面を保護するに充分な防錆添加剤
による緻密な吸着膜が形成されず、防錆性能に悪影響を
およぼす。一方、防錆添加剤が２０重量％を越える場
合、防錆添加剤が保有する防錆性能と脱脂性能とは、添
加剤の吸着能力によって、金属面を保護すると言う性質
からも、相反する関係にあり、必要以上の配合量は脱脂
性に悪影響をおよぼす。また２０重量％を越える場合
は、極圧剤の添加効果を抑制する。 （５）次に、本発明の潤滑性向上剤としては、不活性タ
イプ硫黄系極圧剤と高塩基性スルホネートの最適組合せ
により潤滑効果の上がることを見出した。Usually, one or a combination of two or more of these can be used, but preferably, of the above description, a synthetic sulfonate Ba salt, an oxidized wax Ba salt, and a sorbitan ester are used. In consideration of the balance, the used amount is 5 to 20% by weight. When the content of the rust-preventive additive is less than 5% by weight, a dense adsorption film is not formed by the rust-preventive additive sufficient to protect the metal surface from corrosive substances and moisture containing corrosive substances. Affects performance. On the other hand, when the content of the rust-preventive additive exceeds 20% by weight, the rust-preventive performance and the degreasing performance possessed by the rust-preventive additive are incompatible with each other because of the property that the metal surface is protected by the adsorbing ability of the additive. And an excessive amount of compounding has an adverse effect on degreasing. If it exceeds 20% by weight, the effect of adding the extreme pressure agent is suppressed. (5) Next, as the lubricity improver of the present invention, it has been found that the lubricating effect is improved by an optimal combination of an inert type sulfur-based extreme pressure agent and a highly basic sulfonate.
【００１９】不活性タイプ硫黄系極圧剤は、活性硫黄含
有量が５重量％以下であり、不飽和油脂、不飽和脂肪酸
およびオレフィンからメルカプタン、硫化水素を用い、
硫化して得られる硫黄結合を持つ化合物（極圧剤）であ
る。それぞれ原料に動・植物油を用い、また、製造方法
を選択して得られる硫化ラード、硫化植物油エステル、
合成ポリサルファイドタイプの極圧剤である。The inert type sulfur type extreme pressure agent has an active sulfur content of 5% by weight or less and uses mercaptan and hydrogen sulfide from unsaturated fats and oils, unsaturated fatty acids and olefins,
It is a compound having sulfur bond (extreme pressure agent) obtained by sulfurization. Using animal and vegetable oils as raw materials, and sulphide lard, sulphide vegetable oil esters obtained by selecting the production method,
It is a synthetic polysulfide type extreme pressure agent.
【００２０】高塩基性スルホネートは清浄分散剤として
用いられ、省エネルギーエンジン油の潤滑効果のために
も、広く知られている。その中より、金属塩としてＣ
ａ、Ｂａ、Ｍｇタイプ、全塩基価として２５０〜５００
ｍｇＫＯＨ／ｇ、好ましくは３００ｍｇＫＯＨ／ｇ〜４
００ｍｇＫＯＨ／ｇのものを選択する。Highly basic sulfonates are used as detergents and dispersants and are widely known for their lubricating effect on energy-saving engine oils. Among them, C as a metal salt
a, Ba, Mg type, 250 to 500 as total base number
mgKOH / g, preferably 300 mgKOH / g to 4
Select the one with 00 mg KOH / g.
【００２１】そして、不活性タイプ硫黄系極圧剤と高塩
基性スルホネートの配合割合は、凝着摩耗、腐食摩耗か
らのプレス割れ防止性、めっき被膜の剥離防止性に亜鉛
めっき鋼板用プレス加工兼用防錆油の潤滑成分として、
不活性タイプ硫黄系極圧剤と高塩基性スルホネートの最
適配合比１対１から４対１と両方を合わせた配合量１０
〜２０重量％が選択される。The inert type sulfur-based extreme pressure agent and the highly basic sulfonate are used in combination with a press working for a galvanized steel sheet to prevent press cracking from adhesion wear and corrosion wear and prevent peeling of a plating film. As a lubricating component of rust preventive oil,
Optimal blending ratio of inert type extreme sulfur agent and highly basic sulfonate from 1: 1 to 4: 1 and a combined amount of both 10
-20% by weight is selected.
【００２２】好ましくは、不活性タイプ硫黄系極圧剤の
活性硫黄含有量が３重量％以下の硫化植物油エステル
と、全塩基価が３００ｍｇＫＯＨ／ｇのスルホン酸塩の
金属がＣａの高塩基性スルホネートを用い、配合比１対
１、配合量１０〜１２重量％で、最終製品の全塩基価と
して２０ｍｇＫＯＨ／ｇ以下が望ましい。本発明の組成
物（最終製品）の全塩基価が２０ｍｇＫＯＨ／ｇを越え
る場合、上記の高塩基スルホネート配合量の、防錆性
能、脱脂性能に与える悪影響の上限値となる。（６）本
発明の基油成分としては、鉱油の軽質油炭化水素類と重
質油炭化水素類を、通常２種または３種以上を組合せて
使用することにより、４０℃における粘度を１０〜２０
センチストークス（ｃｓｔ）に調整したものである。潤
滑油基油粘度が１０ｃｓｔ未満の場合、防錆油被膜を形
成する重質油基油（重質油炭化水素）の配合量が少なく
なり、塗油後の油膜が薄膜となり、プレス加工性能では
油膜の油性効果（粘度効果）に悪影響が出る。防錆性能
では、良好な膜厚を持った被膜が得られず、防錆性に悪
影響となる。Preferably, a sulfurized vegetable oil ester having an active sulfur content of 3% by weight or less of the inert type sulfur-based extreme pressure agent, and a highly basic sulfonate having a total base number of 300 mgKOH / g as a metal of a sulfonate of Ca It is desirable that the total base number of the final product be 20 mgKOH / g or less at a compounding ratio of 1 to 1 and a compounding amount of 10 to 12 wt%. When the total base number of the composition (final product) of the present invention exceeds 20 mg KOH / g, the upper limit of the adverse effect on the rust prevention performance and the degreasing performance of the above-mentioned high base sulfonate compounding amount is obtained. (6) As the base oil component of the present invention, a light oil hydrocarbon of mineral oil and a heavy oil hydrocarbon are usually used in combination of two or more kinds, so that the viscosity at 40 ° C. is 10 to 10. 20
It is adjusted to centistokes (cst). When the viscosity of the lubricating base oil is less than 10 cst, the compounding amount of the heavy oil base oil (heavy oil hydrocarbon) forming the rust-preventive oil film decreases, and the oil film after oiling becomes a thin film. The oily effect (viscosity effect) of the oil film is adversely affected. In the rust prevention performance, a film having a good film thickness cannot be obtained, which adversely affects rust prevention.
【００２３】一方、潤滑油基油粘度が２０ｃｓｔを越え
る場合、重質油基油の配合量が多くなるか、更に重質油
基油の高粘度化となり、油膜の膜厚が大きく、高粘度と
なる。従って、塗油鋼板のベタ付き等から作業性に悪影
響をうける。変色防止性も高膜厚油膜の吸水性の増大か
ら悪影響をうける。特に、脱脂性は、高膜厚、高粘度化
によって、物理的にも、油膜の吸着能力の増大からも悪
影響をうける。On the other hand, when the viscosity of the lubricating base oil exceeds 20 cst, the blending amount of the heavy oil base oil increases, or the viscosity of the heavy oil base oil increases, and the oil film thickness increases, Becomes Therefore, the workability is adversely affected due to, for example, stickiness of the oiled steel sheet. The anti-tarnish property is also adversely affected by the increase in water absorption of the high-thickness oil film. In particular, the degreasing property is adversely affected by increasing the film thickness and the viscosity, both physically and by increasing the adsorption capacity of the oil film.
【００２４】軽質油炭化水素類としては、４０℃におけ
る粘度を２〜５センチストークスの軽質油基油、および
５〜１０センチストークスのスピンドル油までとし、引
火点１００℃以上のもので、該組成物の溶解と製品の粘
度調整に役立ち、後工程のプレス加工時には揮発して、
他の成分の働きに悪影響を与えないものとする。The light oil hydrocarbons are those having a viscosity at 40 ° C. of a light oil base oil of 2 to 5 centistokes and a spindle oil of 5 to 10 centistokes having a flash point of 100 ° C. or more, and Useful for dissolving materials and adjusting the viscosity of products.
It shall not adversely affect the function of other components.
【００２５】重質油炭化水素としては、１５０ニュート
ラルから５００ニュートラル留分とし、ナフテン系鉱油
は、さらに良好なものとして、後工程のプレス加工時に
は、潤滑油組成分の基油として充分に働き、防錆油被膜
材として存在しつづけ、防錆性、脱脂性等に悪影響を与
えないものとする。そして、軽質油、重質油炭化水素類
の組合せで、配合比が前者を０〜２５重量％、後者を７
５〜１００重量％とし、亜鉛めっき鋼板用プレス加工兼
用防錆油の製品配合量としては、６５〜８５重量％とす
る。潤滑油基油の重量％が６５％未満の場合、防錆油被
膜を形成する重質油基油（重質油炭化水素）の配合量が
少なくなり、塗油後の油膜が薄膜となり、プレス加工性
能では油膜の油性効果（粘度効果）に悪影響が出る。防
錆性能では、良好な膜厚を持った被膜が得られず、防錆
性に悪影響となる。一方、潤滑油基油の重量％が８５％
を越える場合、重質油基油の配合量が多くなるか、更に
重質油基油の高粘度化となり、油膜の膜厚が大きく、高
粘度となる。従って、塗油鋼板のベタ付き等から作業性
に悪影響をうける。変色防止性も高膜厚油膜の吸水性の
増大から悪影響をうける。特に、脱脂性は、高膜厚、高
粘度化によって、物理的にも、油膜の吸着能力の増大か
らも悪影響をうける。The heavy oil hydrocarbons are from 150 to 500 neutral fractions, and the naphthenic mineral oils are better and work well as a base oil for the lubricating oil composition during the subsequent press working, It shall continue to exist as a rust preventive oil coating material and will not adversely affect rust prevention, degreasing, etc. In the combination of light oil and heavy oil hydrocarbons, the compounding ratio is 0 to 25% by weight for the former and 7 for the latter.
The content of the rust-preventive oil for both press working and galvanized steel sheet is 65 to 85% by weight. When the weight% of the lubricating base oil is less than 65%, the amount of the heavy oil base oil (heavy oil hydrocarbon) forming the rust-preventive oil film is reduced, and the oil film after oiling becomes a thin film, and the press In processing performance, the oily effect (viscosity effect) of the oil film is adversely affected. In the rust prevention performance, a film having a good film thickness cannot be obtained, which adversely affects rust prevention. On the other hand, the weight% of the lubricating base oil is 85%.
When it exceeds, the compounding amount of the heavy oil base oil increases, or the viscosity of the heavy oil base oil further increases, so that the film thickness of the oil film becomes large and the viscosity becomes high. Therefore, the workability is adversely affected due to, for example, stickiness of the oiled steel sheet. The anti-tarnish property is also adversely affected by the increase in water absorption of the high-thickness oil film. In particular, the degreasing property is adversely affected by increasing the film thickness and the viscosity, both physically and by increasing the adsorption capacity of the oil film.
【００２６】より好ましくは、軽質油炭化水素の２種と
重質油炭化水素の１５０ニュートラル留分１種を用い、
基油成分の４０℃の粘度を１５〜２０センチストークス
に調整することが望ましい。More preferably, two types of light oil hydrocarbons and one type of 150 neutral fraction of heavy oil hydrocarbons are used,
It is desirable to adjust the viscosity at 40 ° C. of the base oil component to 15 to 20 centistokes.
【００２７】尚、本発明においては、酸化防止剤、油性
剤、水置換剤等の潤滑油添加剤のうち、少なくとも１種
類以上を配合した亜鉛めっき鋼板用プレス加工兼用防錆
油組成物にしてもよい。In the present invention, a rust-preventive oil composition for both press working and galvanized steel sheet containing at least one or more of lubricating oil additives such as an antioxidant, an oil agent and a water displacing agent. Is also good.
【００２８】[0028]
【実施例】以下に実施例と比較例を挙げて、本発明を例
証する。但し、本発明はこれら実施例に限定されるもの
ではない。The present invention will now be illustrated by way of examples and comparative examples. However, the present invention is not limited to these examples.
【００２９】表１に本発明の実施例および比較例の重量
％による組成を示す。また、比較例３、４は自動車産業
用の薄鋼板に塗油される鋼板用防錆油、プレス加工時に
使用されているプレス油の市販油である。Table 1 shows the compositions of Examples and Comparative Examples of the present invention in terms of% by weight. Further, Comparative Examples 3 and 4 are rust preventive oils for steel sheets which are applied to thin steel sheets for the automobile industry, and commercially available press oils used in press working.
【００３０】表２に評価結果をまとめて示す。なお、評
価方法については、後述の試験法の説明を参照できる。Table 2 summarizes the evaluation results. In addition, for the evaluation method, the description of the test method described below can be referred to.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 本発明の実施例は、比較例に比べ、防錆性、脱脂性、潤
滑性の面でバランス良く優れている。比較油３、比較油
４の鋼板防錆油、プレス油は、それぞれに防錆性、加工
性の分野では優れているが、防錆油は加工性、プレス油
は防錆性、脱脂性に大きな問題がある。[Table 2] The examples of the present invention are superior to the comparative examples in terms of rust prevention, degreasing and lubricity in a well-balanced manner. The steel plate rust preventive oil and press oil of Comparative Oil 3 and Comparative Oil 4 are excellent in the field of rust prevention and workability, respectively, but the rust preventive oil has the workability and the press oil has the rust prevention and degreasing properties. There is a big problem.
【００３３】また、比較油１、比較油２に示すように、
硫黄系極圧剤の高配合油の比較油１は、防錆性、脱脂性
に悪影響を与えている。また、潤滑性の評価でプレス加
工時の成形性（プレス割れ防止性）には大きな効果を示
すものの、剥離性防止には、逆のマイナス効果が現れて
いる。As shown in Comparative Oil 1 and Comparative Oil 2,
Comparative oil 1, which is a highly blended oil containing a sulfur-based extreme pressure agent, has an adverse effect on rust prevention and degreasing. In the evaluation of the lubricity, the moldability during press working (prevention of press cracking) shows a great effect, but the prevention of peelability has the opposite negative effect.
【００３４】比較油２の高塩基性スルホネートの高配合
油は、防錆性、特に脱脂性に悪影響を示す。潤滑性は特
徴的な剥離防止性への効果と共に、合金化材に比べて、
純亜鉛めっき材の成形性に効果が認められる。[0034] The highly blended oil of the highly basic sulfonate of Comparative Oil 2 has an adverse effect on rust prevention, especially on degreasing. Lubricity has a characteristic effect on anti-peeling, and compared to alloyed materials,
An effect is recognized on the formability of the pure galvanized material.
【００３５】従って、硫黄系極圧剤、高塩基性スルホネ
ートの高配合は、必ずしも全てに、良好な結果とはなら
ず、実施例１、実施例２のような悪影響の見られる場合
は、防錆添加剤も高配合が必要となる。実施例３、４、
５、６、７の供試油は亜鉛めっき鋼板用プレス加工兼用
防錆油として、添加剤配合のバランスの良さが、防錆
性、脱脂性、加工性の良い評価結果に示されている。 試験法の説明 供試亜鉛めっき鋼板 電気亜鉛めっき鋼板 ＥＧ材 ２０／２０、
０．７ｔｍｍ 合金化溶融亜鉛めっき鋼板 ＧＡ材 ６０／６０、
０．７５ｔｍｍ 試験油の塗油はゴムロール法で、１．５±０．２ｇに定
量塗油して試験に供した。 １．防錆性試験 １）湿潤試験 ａ試験鋼板 ＧＡ材 ６０／６０、１５０×７０、０．
７５ｔｍｍ ｂ試験条件 ＪＩＳ Ｋ ２２４６に準拠 ｃ判定 ２４０時間後の白錆、赤錆の発生度を測定
する。Therefore, a high blending of a sulfur-based extreme pressure agent and a highly basic sulfonate does not always give good results. In cases where adverse effects such as those in Examples 1 and 2 are observed, prevention is required. Rust additives also require high loadings. Examples 3, 4,
The test oils of Nos. 5, 6, and 7 are rust preventive oils for both press working and galvanized steel sheet, and the good balance of additives is shown in the evaluation results of good rust prevention, degreasing, and workability. Description of test method Test galvanized steel sheet Electrogalvanized steel sheet EG material 20/20,
0.7tmm alloyed hot-dip galvanized steel sheet GA material 60/60,
0.75 tmm The test oil was applied to the test by applying a fixed amount of 1.5 ± 0.2 g by a rubber roll method. 1. Rust prevention test 1) Wet test a Test steel plate GA material 60/60, 150 × 70, 0.
75 tmm b Test condition According to JIS K 2246 c determination The degree of white rust and red rust occurrence after 240 hours is measured.
【００３６】Ａ級；０〜１％未満 Ｂ級；１％以上〜１０％未満 Ｃ級；１０％以上〜２５％未満 Ｄ級；２５％以上〜５０％未満 Ｅ級；５０％以上 ２）湿潤パック・スペーサー試験（Ｖスタック試験） ａ試験鋼板 ＥＧ材 ２０／２０、１５０×７０、０．
７ｔｍｍ ＧＡ材 ６０／６０、１５０×７０、０．７５ｔｍｍ ｂ試験方法 １０枚スタック後ダブルクリップ止め テフロンスペーサー（０．０５ｍｍ） ｃ試験条件 温度；５０℃ 湿度；９５％ 日数；１０日間 ｄ判定 錆発生度 ○；なし、△；０〜１０％未
満、×；１０％以上 変色度 ○；なし、△；少し変色、×；著しい変色 ２．アルカリ脱脂試験 ａ試験鋼板 ＥＧ材 ２０／２０、１５０×７０、０．
７ｔｍｍ ＧＡ材 ６０／６０、１５０×７０、０．７５ｔｍｍ ｂ試験方法 １０枚スタック後ダブルクリップ止め ・室内放置 １週間後に試験に供する。Class A: 0 to less than 1% Class B: 1% to less than 10% Class C: 10% to less than 25% Class D: 25% to less than 50% Class E: 50% or more 2) Wet Pack spacer test (V-stack test) a Test steel sheet EG material 20/20, 150 × 70, 0.
7tmm GA material 60/60, 150 × 70, 0.75tmm b Test method Double clip fastening after stacking 10 sheets Teflon spacer (0.05mm) c Test conditions Temperature; 50 ° C Humidity; 95% days; 10 days d judgment Rust generation Degree ○: None, Δ: 0 to less than 10%, ×: 10% or more Discoloration degree ○: None, Δ: Slight discoloration, ×: Remarkable discoloration Alkaline degreasing test a Test steel sheet EG material 20/20, 150 × 70, 0.
7 tmm GA material 60/60, 150 × 70, 0.75 tmm b Test method Double clip fastening after stacking 10 sheets ・ Leaving indoors One week later, test.
【００３７】・Ｖスタック試験（スペーサーはなし）条
件に１週間格納したものを試験に供する。A V-stack test (without spacers) stored for one week under the conditions is subjected to the test.
【００３８】ｃ試験条件 低温アルカリ脱脂剤ＦＣ−Ｌ
４４８０を用い、浸漬脱脂（軽流動層）を行う。Test conditions c Low temperature alkaline degreasing agent FC-L
Using 4480, immersion degreasing (light fluidized bed) is performed.
【００３９】温度；４５℃ 濃度；２０ｇ／ｌ 時間；３０，６０，９０，１２０秒 ｄ判定 脱脂後水洗を３０秒、６０°にたてかけ３
０秒後の水ぬれ面積を目視より求める。○；３０秒で９
８％以上水ぬれする。Temperature: 45 ° C. Concentration: 20 g / l Time: 30, 60, 90, 120 seconds d-judgment After degreasing, wash with water for 30 seconds at 60 ° 3
The water wet area after 0 seconds is determined visually. ○; 9 in 30 seconds
Wet 8% or more.
【００４０】△；６０〜１２０秒未満で９８％以上水ぬ
れする。Δ: 98% or more of water is wet in less than 60 to 120 seconds.
【００４１】×；１２０秒で９８％以下水ぬれする。 ３．潤滑性試験（プレス加工性試験） １）ＳＲＶ摩擦摩耗試験 ａ試験機 ＳＲＶ（振動摩擦摩耗）試験機は種々の金
属の組合せと潤滑剤の条件下で摩擦摩耗の状況を荷重の
振動すべり運動によって再現する。X: Water wetting of 98% or less in 120 seconds. 3. Lubricity test (press workability test) 1) SRV friction and wear test a tester SRV (vibration friction and wear) tester measures friction and wear conditions under various metal combinations and lubricant conditions by vibrating sliding motion of load. Reproduce.
【００４２】ｂ試験片 試験片の片方のボール、シリ
ンダーにベアリング鋼（ＳＵＪ−２）、一方にベアリン
グ鋼、純亜鉛材（ＺＡＰ）を選択する。B Test piece A bearing steel (SUJ-2) is selected for one ball and cylinder of the test piece, and a bearing steel and pure zinc material (ZAP) are selected for one of them.
【００４３】[0043]
【表３】 ｄ判定 摩擦特性は一定の試験状態で試験片の組合
せを変え、摩擦係数の変化、および純亜鉛材時の摩擦特
性の不安定現象を測定する。また、剥離防止性は試験片
の一方、ステージに純亜鉛材を用い、試験前後のステー
ジ重量を測定し、重量差を摩耗量（ｍｇ）とする。摩耗
量により試料油の剥離防止性を評価する。[Table 3] d Judgment The friction characteristics are measured by changing the combination of test pieces in a certain test state, and measuring the change in friction coefficient and the unstable phenomenon of the friction characteristics when pure zinc is used. Further, for the anti-peeling property, a pure zinc material is used for one stage of the test piece, the stage weight before and after the test is measured, and the difference in weight is defined as a wear amount (mg). The peeling resistance of the sample oil is evaluated based on the wear amount.
【００４４】摩擦特性 ○；不安定現象 小 △； 〃 中 ×； 〃 大 ２）高速深絞り試験 ａ試験鋼板 ＥＧ材 ２０／２０、８４φ、０．７ｔｍ
ｍ ＧＡ材 ６０／６０、８４φ、０．７５ｔｍｍ ｂ試験機 高速円筒深絞り試験機（東京試験機） ｃ試験条件 治具 ポンチ径 ４０ｍｍ ダイス径 ４２ｍｍ ダイス肩径 ８ｍｍ 絞り比 ２．１ 絞り速度 破断限界 １．８ｍ／Ｍ 剥離防止性 ０．５ｍｍ／ｓｅｃ しわ押え力 破断限界 １．０〜１２．０Ｔ 剥離防止性 １．０Ｔ 温度 室温 ｄ判定 破断限界；しわ押え荷重０．５ｔ単位で増加し、１回で
も破断を起こさない最大しわ押え力（Ｔ）を破断限界と
する。Friction characteristics ；: unstable phenomenon small △; 〃 medium ×; 〃 large 2) High speed deep drawing test a Test steel sheet EG material 20/20, 84φ, 0.7 tm
m GA material 60/60, 84φ, 0.75 tmm b Testing machine High-speed cylindrical deep drawing tester (Tokyo Testing Machine) c Test condition Jig Punch diameter 40 mm Die diameter 42 mm Die shoulder diameter 8 mm Drawing ratio 2.1 Drawing speed Breaking limit 1.8m / M Anti-peeling property 0.5mm / sec Wrinkle holding force Break limit 1.0-12.0T Anti-peeling property 1.0T Temperature Room temperature d judgment Break limit; The maximum wrinkle holding force (T) that does not cause breakage even once is defined as the breakage limit.
【００４５】剥離防止性；しわ押え荷重を一定にして、
絞り抜け（完全成形）時の成形品を用い、試験前後の試
験片、成形品の重量から剥離量を測定する。Anti-peeling property;
Using the molded product at the time of drawing-out (complete molding), the peeling amount is measured from the weight of the test piece and the molded product before and after the test.
【００４６】重量法による剥離量の測定は、石油系溶剤
の超音波洗浄３０分後に乾燥して秤量する。In the measurement of the amount of peeling by the gravimetric method, 30 minutes after ultrasonic cleaning of a petroleum-based solvent, the film is dried and weighed.
【００４７】[0047]
【発明の効果】本発明に係る亜鉛めっき鋼板用プレス加
工兼用防錆油組成物は、特定粘度範囲の潤滑油基油に、
防錆添加剤、不活性タイプの硫黄系極圧剤と、高塩基性
スルホネートの最適組合せの添加剤を主とし、脱脂助
剤、補助成分等がバランス良く加えられているので、優
れた防錆性、変色防止性、脱脂性、プレス加工性が得ら
れる。The rust-preventive oil composition for both press working and galvanized steel sheet according to the present invention can be used in a lubricating base oil having a specific viscosity range.
Rust additive, a sulfur-based extreme pressure inert type, an optimum combination of additives of the high salt group of sulfonates and primary, degreasing aid, the auxiliary components and the like is added well-balanced, excellent anti Rust, discoloration prevention, degreasing, and press workability are obtained.
【００４８】特にプレス加工性については、プレス割れ
防止性能、及び剥離防止性能が付与されたので、亜鉛め
っき鋼板の防錆、変色防止とプレス加工を一種類の潤滑
油組成物で行うことが出来るようになり、仕上がりの良
い鋼板が得られるほかに、工程の簡略化、合理化、生産
性の向上、プレス部品の品質向上、省資源、作業環境の
改善等に資するところが大きい。In particular, with regard to the press workability, the anti-press cracking property and the anti-peeling property are provided, so that the rust prevention, discoloration prevention and press working of the galvanized steel sheet can be performed with one kind of lubricating oil composition. As a result, in addition to obtaining a steel plate with a good finish, it greatly contributes to simplifying the process, streamlining, improving productivity, improving the quality of pressed parts, saving resources, and improving the working environment.
Claims (2)
の潤滑油基油、 Ｃ１６以上のアルキルスルホン酸のアルカリ土類金属
塩、アミン塩、Ｃ１２以上のカルボン酸、Ｃ１２以上の
カルボン酸のアルカリ土類金属塩、アミン塩から選ばれ
た防錆添加剤、 不活性タイプ硫黄系極圧剤、 アルカリ土類金属の油溶性スルホン酸塩に、これらの
金属の水酸化物、酸化物、炭酸塩を過剰に含有させた高
塩基性スルホネート、 上記６５〜８５重量％に上記５〜２０重量％を加
え、さらに、上記との混合物１０〜２０重量％を加
えてなり、しかも上記の１〜４容量部に対して、上記
は１容量部である防錆油組成物であって、全塩基価が
２０ｍｇＫＯＨ／ｇ以下であり、 且つ、上記アルカリ土類金属の高塩基性、油溶性スルホ
ン酸塩の金属がＭｇ、Ｃａ、Ｂａのうち、少なくとも１
種以上を含むものであって、全塩基価が２５０〜５００
ｍｇＫＯＨ／ｇの高塩基性スルホネートであることを特
徴とする亜鉛めっき鋼板用プレス加工兼用防錆油組成
物。1. A viscosity at 40 ° C. of 10 to 20 cst.
Of the lubricating base oil, C 16 or more alkaline earth metal salts of alkyl sulfonic acids, amine salts, C 12 or higher carboxylic acids, alkaline earth metal salts of C 12 or higher carboxylic acids, anti selected from amine salts Rust additive, inert type sulfur-based extreme pressure agent, oil-soluble sulfonate of alkaline earth metal, high basic sulfonate containing excess of hydroxide, oxide and carbonate of these metals, 5 to 20% by weight is added to 65 to 85% by weight, and 10 to 20% by weight of a mixture with the above is added, and the above is 1 part by volume with respect to the above 1 to 4 parts by volume. A rust-preventive oil composition, wherein the total base number is 20 mgKOH / g or less, and at least one of Mg, Ca, and Ba is selected from the group consisting of a highly basic alkaline earth metal and an oil-soluble sulfonate metal.
A total base number of 250 to 500
A rust-preventive oil composition for both press working and galvanized steel sheet, which is a highly basic sulfonate of mgKOH / g.
以下、活性硫黄分５％以下である硫化ラード、硫化植物
油エステル、合成ポリサルファイドから選ばれた、少な
くとも１種以上であることを特徴とする請求項１記載の
亜鉛めっき鋼板用プレス加工兼用防錆油組成物。2. The inert type sulfur type extreme pressure agent has a sulfur content of 15%.
The rust-preventive oil for galvanized steel sheets according to claim 1, wherein the rust-preventive oil is at least one member selected from the group consisting of sulfurized lard, sulfurized vegetable oil ester and synthetic polysulfide having an active sulfur content of 5% or less. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3059467A JP3048397B2 (en) | 1991-02-28 | 1991-02-28 | Rust-preventive oil composition for both press working and galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3059467A JP3048397B2 (en) | 1991-02-28 | 1991-02-28 | Rust-preventive oil composition for both press working and galvanized steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04275399A JPH04275399A (en) | 1992-09-30 |
| JP3048397B2 true JP3048397B2 (en) | 2000-06-05 |
Family
ID=13114146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3059467A Expired - Lifetime JP3048397B2 (en) | 1991-02-28 | 1991-02-28 | Rust-preventive oil composition for both press working and galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3048397B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3500237B2 (en) * | 1995-09-22 | 2004-02-23 | 新日本石油株式会社 | Pressing and cleaning rust preventive oil composition for cold rolled steel sheet and galvanized steel sheet |
| JPH1190323A (en) * | 1997-09-24 | 1999-04-06 | Nisshin Steel Co Ltd | Metal material subjected to rust preventing treatment and its production |
| JP5570683B2 (en) * | 2007-02-09 | 2014-08-13 | トヨタ紡織株式会社 | Lubricating oil for metal material press working and metal material press working method using the same |
| CN109504843A (en) * | 2018-12-06 | 2019-03-22 | 汎宇化学（昆山）有限公司 | Vacuum quenching oil and preparation method thereof |
| WO2023085386A1 (en) * | 2021-11-11 | 2023-05-19 | 株式会社ハイレックスコーポレーション | Lubricant composition with anti-rust properties |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0742470B2 (en) * | 1989-11-20 | 1995-05-10 | 日本パーカライジング株式会社 | Anti-rust press working oil for galvanized steel sheet |
-
1991
- 1991-02-28 JP JP3059467A patent/JP3048397B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04275399A (en) | 1992-09-30 |
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