JPH03106993A

JPH03106993A - Composition serving as rustproofing oil and also as press working oil

Info

Publication number: JPH03106993A
Application number: JP24354889A
Authority: JP
Inventors: Kei Sasaoka; 笹岡　勁; Hideo Ide; 井出　英夫
Original assignee: Mitsubishi Oil Co Ltd
Current assignee: Eneos Corp
Priority date: 1989-09-21
Filing date: 1989-09-21
Publication date: 1991-05-07

Abstract

PURPOSE:To obtain the title composition for a galvanized steel sheet by mixing a lube base oil with a fine powder of an alkaline earth metal carbonate and an alkaline earth metal sulfonate so as to provide a total base number in a specified range. CONSTITUTION:A lube base oil is mixed with at least one alkaline earth metal carbonate (e.g. calcium carbonate) having a particle diameter of 100-10,000Angstrom and at least one oil-soluble, alkaline earth metal sulfonate (e.g. calcium sulfo nate) so as to provide a total base number of 5-100mg KOH/g, thus giving the title composition. It is used as an oil to coat a galvanized steel sheet and is excellent in press working properties, rustproofness, discoloration freeness, and degreasing ability. The use of this composition serves to accomplish rustproofing, prevention of discoloration, and press working of a galvanized steel sheet with one lubricating oil composition. It can also prevent powdering which may be caused by the reaction between a galvanized surface and an active extreme-pressure additive in the composition for the conventional press oil.

Description

【発明の詳細な説明】［産業上の利用分野］本発明は自動車産業、家電産業を中心に使用されている
亜鉛めっき鋼板の被覆油として、プレス加工性・防錆性
・変色防止性・脱脂性に優れたプレス加工油兼用防錆油
に関する。更に詳しくは、溶融めっき法又は電気めっき
法等によって製造される純亜鉛めっき、亜鉛一鉄、亜鉛
一ニッケル、亜鉛−アルミニウム等の合金めっき、また
亜鉛一鉄の合金化めっきや複合めっきなどの亜鉛系表面
処理鋼板の貯蔵・保管・輸送中の防錆ならびに変色防止
のために用いる防錆油機能、プレス加工時のプレス油機
能、ならびにプレス加工後のプレス製品の一時貯蔵、保
管中の防錆や変色防止のために用いる工程間防錆油機能
を一種類の潤滑油で処理することを可能とし、プレス加
工時に、従来のプレス油ではその配合組成中の活性な極
圧剤と亜鉛めっき面との反応により生じるバウタリング
（粉化）を防止することを特徴とする亜鉛めっき鋼板用
のプレス加工油兼用防錆油組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a coating oil for galvanized steel sheets mainly used in the automobile industry and the home appliance industry, which has properties such as press workability, rust prevention, discoloration prevention, and degreasing. This product relates to a rust-preventing oil that can also be used as a press processing oil and has excellent properties. More specifically, pure zinc plating manufactured by hot-dip plating or electroplating, alloy plating such as zinc-iron, zinc-nickel, zinc-aluminum, etc., zinc-iron alloy plating, composite plating, etc. Antirust oil function used to prevent rust and discoloration during storage, storage, and transportation of surface-treated steel sheets, press oil function during press processing, and rust prevention during temporary storage and storage of pressed products after press processing. This makes it possible to use a single type of lubricant to perform the rust-preventive oil function used during the process to prevent discoloration and discoloration. The present invention relates to a rust-preventing oil composition that can also be used as a press working oil for galvanized steel sheets, and is characterized by preventing buttering (powdery) caused by reaction with galvanized steel sheets.

［従来の技術と課８］自動車や家電製品は長期間にわたって使用されるので、
その機能と美観を維持するように防錆防食対策を強化す
ることが望まれている。これに対処するため、最近は従
来の冷間圧延鋼板に代って冷間圧延鋼板の片面又は両面
に純亜鉛、亜鉛一鉄・亜鉛一ニッケル、亜鉛−アルミニ
ウム等の合金めっき、亜鉛一鉄などの合金化めっきや複
合めっきなどを施した亜鉛系表面処理鋼板が多く用いら
れるようになった。しかし、これらの亜鉛めっき鋼板は
化成処理や塗装等の防錆処理を施さない限り、冷間圧延
鋼板とは形態が異なるものの錆や変色を生じる。したが
って、製鉄メーカーで製造されてから需要家で自動車や
家電製品にプレス加工されるまでの貯蔵・保管・輸送・
仕掛り期間中での発錆や変色を防ぐことが品質管理上重
要な事柄である。これに対処するため製銑メーカーでは
亜鉛めっき鋼板をコイル状に巻き取る直前、又はシート
状に裁断する直前に防錆油を適量塗布し、ポリエチレン
ラミネートクラフト紙や気化性防錆紙などで厳重に梱包
し出荷する。特に海外へ船舶輸送する場合は船倉の気象
条件が結露や雨だれ現象などによって苛酷であるためコ
イル又はシート製品の積層面に白錆や黒変を生じ易い。[Conventional technology and lesson 8] Since automobiles and home appliances are used for long periods of time,
It is desired to strengthen anti-rust and anti-corrosion measures to maintain its functionality and beauty. To deal with this, recently, instead of conventional cold-rolled steel sheets, pure zinc, alloy plating such as zinc-iron, zinc-nickel, zinc-aluminum, zinc-iron, etc. are used on one or both sides of cold-rolled steel sheets. Zinc-based surface-treated steel sheets with alloy plating or composite plating have come into widespread use. However, unless these galvanized steel sheets are subjected to anti-rust treatment such as chemical conversion treatment or painting, they will rust and discolor, although the form is different from that of cold-rolled steel sheets. Therefore, the storage, storage, transportation, and
Preventing rust and discoloration during the work-in-process period is an important matter for quality control. To deal with this, pig iron manufacturers apply an appropriate amount of anti-rust oil to galvanized steel sheets just before winding them into coils or cutting them into sheets, and then carefully sealing them with polyethylene laminated kraft paper or vaporizable anti-corrosion paper. Pack and ship. Particularly when shipped overseas, the weather conditions in the ship's hold are severe due to dew condensation and rain dripping, so white rust and black discoloration are likely to occur on the laminated surface of the coil or sheet product.

このような条件下では１冷間圧延鋼板に用いられている
防錆油は亜鉛めっき面の防錆や黒変防止に十分な性能が
なく、また防錆油中の添加剤が亜鉛と反応して変質し脱
脂性能も低下させることがある。したがって、一般には
亜鉛めっき専用の防錆油が用いられている。Under these conditions, the rust preventive oil used in 1 cold rolled steel sheets does not have sufficient performance to prevent rust and blackening of the galvanized surface, and the additives in the rust preventive oil may react with the zinc. This may cause deterioration and degreasing performance. Therefore, a rust preventive oil specifically designed for galvanizing is generally used.

一方、亜鉛めっき鋼板は出荷後需要家で一定の形状にプ
レス加工される。プレス加工は張り出し、引っぱり、絞
り加工などの成形が複雑に組み合わされ、高速でプレス
加工できることが要求されている。潤滑性が不足すると
プレス割れ、しわ、傷等が発生する。さらに亜鉛めっき
層のパウダリング現象を生じ、これらの摩耗粉が治具や
ダイスに推積し凹状の押し傷を発生する。これらの現象
を防ぐためにプレス加工直前にプレス油を塗布している
。最近では、プレス機械の改善により潤滑箇所へプレス
油をスプレー塗布している。これらのプレス油は潤滑油
基油に塩素化ノくラフィン、硫化油脂、チオリン酸亜鉛
などの活性な極圧剤や油性剤が配合されている。また最
近では、これらのプレス油組成に乳化剤などの界面活性
剤や水を加えたエマルジョンタイプのプレス油も使用さ
れている。このようなプレス油は冷間圧延鋼板などの鉄
面の加工用に使用されてきたが、亜鉛めっきに対しては
プレス加工時や後工程で極圧剤の熱分解・光分解・加水
分解などによって生じる腐蝕性の塩素イオンや硫黄イオ
ンと反応し、発錆や変色を生じ、また脱脂性能を低下さ
せることがある。したがって、亜鉛めっき鋼板には、こ
れらの問題を生じない専用のプレス油を選定する必要が
あるが、満足すべき亜鉛めっき鋼板用プレス油組成物は
まだ見い出されていない。また、プレス加工は塗布量の
管理が難しく、持ち出しによる浪費が多いため作業環境
を悪化させている。On the other hand, galvanized steel sheets are pressed into a certain shape at the customer after shipment. Pressing involves a complex combination of forming processes such as stretching, pulling, and drawing, and requires high-speed press processing. Insufficient lubricity causes press cracks, wrinkles, scratches, etc. Furthermore, powdering of the galvanized layer occurs, and these abrasion powders accumulate on jigs and dies, causing concave scratches. To prevent these phenomena, press oil is applied immediately before pressing. Recently, improvements in press machines have allowed press oil to be sprayed onto lubricated areas. These press oils contain active extreme pressure agents and oily agents such as chlorinated oil, sulfurized oil, and zinc thiophosphate in the lubricating base oil. Recently, emulsion type press oils have also been used, in which surfactants such as emulsifiers and water are added to these press oil compositions. Such press oils have been used for processing iron surfaces such as cold-rolled steel plates, but for galvanizing, they are used for thermal decomposition, photolysis, hydrolysis, etc. of extreme pressure agents during press processing and post-processing. Reacts with the corrosive chlorine and sulfur ions produced by the process, causing rust and discoloration, and may also reduce degreasing performance. Therefore, it is necessary to select a special press oil for galvanized steel sheets that does not cause these problems, but a satisfactory press oil composition for galvanized steel sheets has not yet been found. Additionally, in press processing, it is difficult to control the amount of application, and there is a lot of waste due to carrying away materials, which worsens the working environment.

一方、活性な極圧添加剤を配合している冷間圧延鋼板の
プレス油を用いて亜鉛めっき鋼板をブレス加工した場合
、そのプレス製品は工程間の仕掛り期間中に錆や変色を
生じ易いので、亜鉛めっき鋼板専用の工程間防錆油を上
塗りして、これらのプレス油を洗い落して防錆と変色防
止を行なっている。しかし、このような処理は防錆油や
プレス油が作業場に流下、飛散するので、作業環境を著
しく悪化させているほか、必要量以上の油量消費を招い
ている。そして、何よりの欠点は、何種類もの油種を使
い分けなければならない煩雑さにある。On the other hand, if galvanized steel sheets are pressed using press oil for cold-rolled steel sheets that contains active extreme pressure additives, the pressed products are susceptible to rust and discoloration during the preparation period between processes. Therefore, during the process, we apply a top coat of anti-corrosion oil specifically designed for galvanized steel sheets, and wash away the press oil to prevent rust and discoloration. However, this type of treatment causes rust preventive oil and press oil to flow down and scatter into the workplace, which not only significantly worsens the working environment but also causes oil consumption to exceed the required amount. The biggest drawback is the complexity of having to use different types of oil.

［発明が解決しようとする課題］上記したように、従来の方法で亜鉛めっき鋼板のプレス
加工と防錆を行なうには、発錆や変色をさせないような
極圧添加剤入りの油を選定するか、または、工程間防錆
油を用いて、プレス油の洗い落としを行ったあと、同防
錆油によって防錆と変色防止を行うなど油種の選定や、
塗布量、洗い落としに用いる量などの油量管理等々に手
間と時間がかかる欠点がある。[Problem to be solved by the invention] As mentioned above, in order to press and rust prevent galvanized steel sheets using the conventional method, it is necessary to select an oil containing extreme pressure additives that will not cause rust or discoloration. Or, after washing off the press oil using rust preventive oil during the process, use the same rust preventive oil to prevent rust and discoloration.
It has the disadvantage that it takes time and effort to control the amount of oil applied, the amount used for washing off, etc.

本発明は、このような従来技術の欠点を解消するために
行なったものであり、一種類の潤滑油で、プレス加工性
・防錆性・変色防止性・脱脂性を兼ね備えたプレス加工
油兼用防錆油組成物を提供することを目的とする。The present invention was made to eliminate these drawbacks of the conventional technology, and is a single type of lubricating oil that can be used as a press working oil that has press workability, rust prevention, discoloration prevention, and degreasing properties. The purpose of the present invention is to provide a rust-preventing oil composition.

［課題を解決するための手段］本発明のプレス加工油兼用防鎖油組成物は、従来の活性
な極圧剤を用いずに潤滑油基油中に１００〜１０，００
０大のアルカリ土類金属の炭酸塩を分散することにより
、プレス加工時に滑剤として作用して、優れたプレス加
工性能を示し、かつ、活性な極圧剤と異なり亜鉛めっき
面と反応しないので、バウダリング現象を生じることな
く、また炭酸塩を潤滑油基油中に分散させるために用い
る界面活性剤としてのアルカリ土類金属の油溶性スルホ
ン酸塩が、炭酸塩と相乗して優れた防錆性・変色防止性
・脱脂性を発揮するようにした。[Means for Solving the Problems] The press processing oil and chain-preventing oil composition of the present invention can be used in a lubricating oil base oil without using a conventional active extreme pressure agent.
By dispersing carbonates of alkaline earth metals in the size 0, it acts as a lubricant during press processing, exhibiting excellent press processing performance, and unlike active extreme pressure agents, it does not react with galvanized surfaces. The alkaline earth metal oil-soluble sulfonate used as a surfactant to disperse the carbonate in the lubricant base oil synergizes with the carbonate to provide excellent rust prevention without causing the bordering phenomenon. - Provides anti-discoloration and degreasing properties.

すなわち、本発明のプレス加工油兼用防錆油組成物は、
１００〜１０．ｏｏｏ大の粒径のアルカリ土類金属の炭
酸塩の群から選ばれた少なくとも１種と、アルカリ土類
金属の油溶性スルホン酸塩の群から選ばれた１種を配合
し、全塩基価を５〜１　０　０　ｍｇＫＯＨ／ｇになる
ように調合してなる。That is, the rust preventive oil composition for press working oil of the present invention is
100-10. At least one selected from the group of carbonates of alkaline earth metals with a particle size of ooo large and one selected from the group of oil-soluble sulfonates of alkaline earth metals are blended to reduce the total base number. It is blended to have a concentration of 5 to 100 mgKOH/g.

潤滑油基油としては、硫酸精製・溶剤精製・水素化精製
などの精製法により製造されるナフテン系、バラフィン
系、または、その混合系のいづれの潤滑浦基油であって
も良い。また、粘度の異なる潤滑油基油を混合しても良
い。潤滑泊基油の粘度は、４０℃の動粘度で５〜５００
ｃＳｔの範囲に調整したものを用いる。５　ｃｓｔ以下
では、アルカリ土類金属の炭酸塩が沈でんしやすくなる
ので好ましくなく、また５　０　０　ｃｓｔ以上では、
粘性が大きくなり流動しにくくなるので好ましくない。The lubricating oil base oil may be a naphthenic base oil, a paraffin base oil, or a mixture thereof, which is produced by a refining method such as sulfuric acid refining, solvent refining, or hydrotreating. Furthermore, lubricant base oils having different viscosities may be mixed. The viscosity of the lubricating base oil is 5 to 500 at kinematic viscosity at 40°C.
Use one adjusted to the range of cSt. Below 5 cst, carbonates of alkaline earth metals tend to precipitate, which is undesirable, and above 500 cst,
This is not preferable because it increases viscosity and becomes difficult to flow.

粘度を調整するために、引火点が７０℃以上の石油系溶
剤、または精製軽油を配合しても良い。７０℃以下の溶
剤の使用は亜鉛めっき鋼板に塗油する際、火災の危険性
があるので好ましくない。In order to adjust the viscosity, a petroleum solvent with a flash point of 70° C. or higher or refined light oil may be blended. The use of solvents at temperatures below 70°C is not preferable when applying oil to galvanized steel sheets, as there is a risk of fire.

アルカリ土類金属の炭酸塩の金属の種類としては、カル
シウム、亜鉛、バリウムがあるが、安全性、入手性など
の理由からカルシウムが良い。粒径は、１００〜１０．
０００大のものを用いる。Types of alkaline earth metal carbonates include calcium, zinc, and barium, but calcium is preferred for reasons of safety and availability. The particle size is 100 to 10.
000 large one is used.

１００大以下では滑剤としての効果に乏しく、１ｏ，ｏ
ｏｏ大以上では、潤滑油基油に安定な分散がしにくくな
るので好ましくない。If it is less than 100, the effect as a lubricant is poor;
If the amount is 0 or more, stable dispersion in the lubricant base oil becomes difficult, which is not preferable.

アルカリ土類金属の油溶性スルホン酸塩の金属の種類と
してはカルシウム、亜鉛、バリウムがあるが、安全性や
価格の点でカルシウムが良く、また、積層亜鉛めっき鋼
板面の湿性オイルスティンや防鯖性、腐蝕性などの点か
ら、油溶性スルホン酸塩の分子量は８５０以上が好まし
い。Calcium, zinc, and barium are the metal types of oil-soluble sulfonates of alkaline earth metals, but calcium is preferable in terms of safety and price, and it is also suitable for wet oil stains on the surface of laminated galvanized steel sheets and for mackerel prevention. From the viewpoint of corrosion resistance, corrosion resistance, etc., the molecular weight of the oil-soluble sulfonate is preferably 850 or more.

また、炭酸カルシウムとカルシウムスルホネートは、炭
酸カルシウムを潤滑油中に均一に分散しやすくするため
に、１００〜１０，０００六の粒径の炭酸カルシウムを
分子量は８５０以上のカルシウムスルホネートと、カル
シウムスルホネートの０．１〜１０倍量の潤滑油基浦の
混合物に分散してなる全塩基価１　０　０　ｌＩｇＫＯ
Ｈ／ｇ以上の超塩基性カルシウムスルホネートであって
も良く、これを潤滑油基油に全塩基価を５〜Ｉ　Ｏ　Ｏ
　ＩＩｌｇＫＯＩＩ／ｇになるように加えて調合しても
良い．なお、上記のようにしてなった組成物に、酸化防止剤、
油性剤、極圧剤、防錆剤、水置換剤等の潤滑油添加剤を
配合しても良い。In addition, calcium carbonate and calcium sulfonate are prepared by mixing calcium carbonate with a particle size of 100 to 10,000 to make it easier to disperse calcium carbonate uniformly in lubricating oil. Total base number 100 lIgKO dispersed in a mixture of 0.1 to 10 times the amount of lubricating oil Motoura
It may be an ultrabasic calcium sulfonate with a total base number of 5 to I O O in lubricating oil base oil.
It may be added and blended so that it becomes IIlgKOII/g. In addition, an antioxidant,
Lubricating oil additives such as oil agents, extreme pressure agents, rust preventive agents, and water displacement agents may also be blended.

［実施例］以下に本発明に基づく実施例を説明するが、本発明はこ
れらの実施例に限定されるものではない。[Examples] Examples based on the present invention will be described below, but the present invention is not limited to these Examples.

実施例　１１８０　　ＶＧ１５のバラフィン系潤滑油基油７８０ｇ
に１００〜５０００六の粒径の炭酸カルシウムを分散し
た超塩基性カルシウムスルホネート［全塩基価３　７　
０ｍｇＫＯＨ／ｇ　］　　１　０　０　ｇを加え、６０
℃で１時間加熱混合し、淡黄色の不透明液体８８０ｇを
得た。油中に分散している炭酸カルシウムは２５℃およ
び−５℃で１０日間放置しても沈でんを生じなかった。Example 1 180 VG15 paraffin based lubricating base oil 780g
Ultrabasic calcium sulfonate in which calcium carbonate with a particle size of 100 to 50006 is dispersed [total base number 37
0mgKOH/g] Add 100g and 60
The mixture was heated and mixed at ℃ for 1 hour to obtain 880 g of a pale yellow opaque liquid. Calcium carbonate dispersed in oil did not precipitate even when left at 25°C and -5°C for 10 days.

これを実施油Ａとする。This is designated as working oil A.

実施油Ａは表１に示すように亜鉛めっき鋼板用防錆剤と
同等以上の防錆性能、変色防止性能、および脱脂性能を
示すとともに、比較油２、及び比較油４のようなプレス
油に比べて、亜鉛の比摩耗量が著しく小さく耐バウダリ
ング性能が優れていると考えられ、同時にプレス油と同
等のプレス性能を示した。As shown in Table 1, the test oil A exhibits rust prevention performance, discoloration prevention performance, and degreasing performance equivalent to or better than the rust preventive agent for galvanized steel sheets, and is also superior to press oils such as Comparative Oil 2 and Comparative Oil 4. In comparison, zinc has a significantly smaller specific wear amount and is thought to have superior bordering resistance, and at the same time showed press performance equivalent to that of press oil.

実施例　２ＩＳＯ　　ＶＧ３２のパラフィン系潤滑油基油７４１ｇ
に１００〜１０，０００大の粒径の炭酸カルシウムを分
散した超塩基性カルシウムスルホネート［全塩基価３　
７　０　ｍｇＫＯＨ／ｇ　］を１　０　０　ｇ，ナフテ
ン酸亜鉛［亜鉛含有量５ｗｔ％］を３０ｇ１ブチルセロ
ソルブを１０ｇ，ジｔ−ブチルパラクレゾールを５ｇ加
え、６０℃で１時間加熱混合し、淡黄色不透明の液体８
８６ｇを得た。油中に分散している炭酸カルシウムは２
５℃、および−５℃で１０日間放置しても沈でんを生じ
なかった。これを実施油Ｂとする。実施油Ｂは表１に示
すように、実施油Ａと同様すぐれた防錆性能、変色防止
性能、脱脂性能、耐バウダリング性能、プレス加工性能
を示した。Example 2 741 g of paraffinic lubricating base oil of ISO VG32
Ultrabasic calcium sulfonate in which calcium carbonate with a particle size of 100 to 10,000 particles is dispersed [total base number 3]
70 mgKOH/g], 30 g of zinc naphthenate [zinc content 5 wt%], 10 g of butyl cellosolve, and 5 g of di-t-butyl para-cresol were added, and the mixture was heated and mixed at 60°C for 1 hour to give a pale yellow opaque color. liquid 8
86g was obtained. Calcium carbonate dispersed in oil is 2
No precipitation occurred even after being left at 5°C and -5°C for 10 days. This was designated as working oil B. As shown in Table 1, Example Oil B exhibited excellent rust prevention performance, discoloration prevention performance, degreasing performance, bordering resistance performance, and press processing performance similar to Example Oil A.

実施例　３ＩＳＯ　　ＶＧ６ｇのパラフィン系潤滑油基油７３４ｇ
に１００〜１０，０００六の粒径の炭酸カルシウムスル
ホネート［全塩基価３７０■ｇＫＯＨ／ｇ］１００ｇ，
ジノニルナフタレンバリウムスルホネート［全塩基価０
　．　　１　ｍｇＫＯＨ／ｇ　］　５　０　ｇ，ジｔ−
ブチルパラクレゾールを３ｇ加え、６０℃で１時間加熱
混合し、淡黄色不透明の液体８８７ｇを得た。油中に分
散している炭酸カルシウムは２５℃、および−５℃で１
０日間放置しても沈でんを生じなかった。これを実施油
Ｃとする。実施油Ｃは表１に示すように、実施油Ａと同
様すぐれた防錆性能、変色防止性能、脱脂性能、耐バウ
ダリング性能、プレス加工性能を示した。Example 3 734g of paraffinic lubricant base oil of ISO VG6g
100 g of calcium carbonate sulfonate with a particle size of 100 to 10,000 [total base number 370 gKOH/g],
Dinonylnaphthalene barium sulfonate [total base number 0
．． 1 mgKOH/g ] 50 g, di-t-
3 g of butyl para-cresol was added and mixed under heating at 60° C. for 1 hour to obtain 887 g of a pale yellow opaque liquid. Calcium carbonate dispersed in oil has a temperature of 1 at 25°C and -5°C.
No sedimentation occurred even after being left for 0 days. This was designated as working oil C. As shown in Table 1, Example Oil C exhibited excellent rust prevention performance, discoloration prevention performance, degreasing performance, bordering resistance performance, and press processing performance similar to Example Oil A.

実施例　４ＩＳＯ　　ＶＧ１５のナフテン系潤滑油基油７９２ｇに
１００〜５．０００大の粒径の炭酸力ルシウムを分散し
たカルシウムスルホネート［全塩基価３　７　０　ｍｇ
ＫＯＨ／ｇ　］を２　０　０　ｇ，ジノニルナフタレン
カルシウムスルホネート［全塩基価０，１膳ｇＫＯＨ／
ｇ　］　３　Ｇ　ｇを加え、６０℃で１時間加熱混合し
、淡黄色不透明の液体１，０２２ｇを得た。油中に分散
している炭酸カルシウムは２５℃、および−５℃で１０
日間放置しても沈でんを生じなかった。これを実施油Ｄ
とする。実施油Ｄは表１に示すように、実施油Ａと同様
すぐれた防錆性能、変色防止性能、脱脂性能、耐パウダ
リング性能、プレス加工性能を示した。Example 4 Calcium sulfonate in which lucium carbonate having a particle size of 100 to 5,000 is dispersed in 792 g of naphthenic lubricating base oil of ISO VG15 [total base number 370 mg]
KOH/g] was 200 g, dinonylnaphthalene calcium sulfonate [total base number 0, 1 serving g KOH/
g ] 3 G g was added and mixed under heating at 60° C. for 1 hour to obtain 1,022 g of a pale yellow opaque liquid. Calcium carbonate dispersed in oil has a temperature of 10% at 25°C and -5°C.
No precipitation occurred even after being left for several days. Do this with oil D
shall be. As shown in Table 1, Example Oil D exhibited excellent rust prevention performance, discoloration prevention performance, degreasing performance, powdering resistance performance, and press processing performance similar to Example Oil A.

［比較例］比較例　１現在、鉄鋼業界で亜鉛めっき鋼板に大量使用されている
防錆油を比較油１とする（粘度４０℃；１５ｃＳｔ．比
重；０．８８，引火点；１５０℃）。[Comparative Examples] Comparative Example 1 Comparative oil 1 is a rust preventive oil that is currently used in large quantities for galvanized steel sheets in the steel industry (viscosity: 40°C; 15 cSt. specific gravity: 0.88; flash point: 150°C).

比較試験結果を表１に示すが、耐パウダリング性能、プ
レス加工性能に劣る。The comparative test results are shown in Table 1, and the powdering resistance performance and press working performance are inferior.

比較例　２冷間圧延鋼板用の塩素系パラフィン、活性硫化油脂を配
合しているプレス油を比較油２とする［Ｓ；２．８ｖｔ
％，ＣＲ；　１　９．２ｗｔ％］。Comparative Example 2 Comparative oil 2 is a press oil containing chlorinated paraffin and active sulfurized oil for cold rolled steel sheets [S; 2.8vt
%, CR; 19.2wt%].

比較試験結果を表１に示す。プレス加工性は良いが、防
錆性能、変色防止性能、脱脂性能、耐バウダリング性能
に劣る。The comparative test results are shown in Table 1. Although it has good press workability, it has poor rust prevention performance, discoloration prevention performance, degreasing performance, and bordering resistance performance.

比較例　３９　０　０　ｇノ比較油１に硫化油脂［ｓ；１１．Ｏｗ
ｔ駕］を１００ｇ加え、６０”Ｃで１時間加熱混合した
ものを比較油３とした。比較試験結果を表１に示す。硫
化油脂を加えたことにより、プレス加工性能は比較油１
より改善したが、実施油やプレス加工油に比べ劣る。ま
た、変色防止性能、脱脂性能、プレス後のプレス品の防
錆性能が低下する。Comparative Example 3 9 0 0 gno Comparative Oil 1 was sulfurized fat [s; 11. Ow
Comparative oil 3 was prepared by adding 100g of sulfurized oil and mixing with heat at 60"C for 1 hour. The comparative test results are shown in Table 1. By adding sulfurized oil, the press working performance was better than that of comparative oil 1.
Although it has been improved, it is still inferior to the tested oil and press processing oil. In addition, the discoloration prevention performance, degreasing performance, and rust prevention performance of the pressed product after pressing are reduced.

比較例　４１３０　　ＶＧ１５のパラフィン系潤滑油基油７　８　
０　ｇ：　Ｉ：硫化油脂［Ｓ；　１　１．　　Ｏｖｔ％
コ　１００ｇを加え、６０℃で１時間加熱混合し、透明
の液体８８０ｇを得た。これを比較油４とする。比較試
験結果を表１に示す。プレス加工性は良いが、塩素、硫
黄を含むプレス油［比較油２コと同様、防錆性能、変色
防止性能、脱脂性能に劣り、また耐パウダリング性能が
劣る。Comparative example 4 130 VG15 paraffin lubricating base oil 7 8
0 g: I: Sulfurized fat [S; 1 1. Ovt%
100 g of the liquid was added, and the mixture was heated and mixed at 60° C. for 1 hour to obtain 880 g of a transparent liquid. This is designated as comparative oil 4. The comparative test results are shown in Table 1. Although press workability is good, press oil containing chlorine and sulfur [similar to the two comparison oils, has poor rust prevention performance, discoloration prevention performance, degreasing performance, and poor powdering resistance performance.

［発明の効果］本発明の組或物は上記のように構或されているので、従
来のようにプレス油性能を付与するために、亜鉛と反応
しやすい活性な極圧剤を配合することなく、亜鉛との反
応性の少ないアルカリ土類金属微粒子の滑剤としての作
用を応用したので、従来のように極圧剤と亜鉛めっき面
との反応によるバウタリング現象を生じることが無くな
ったため、治具やダイスの管理が容易になり、生産性を
著るしく向上させることができる。さらに、アルカリ土
類金属の微粒子を均一に潤滑油基油中に分散させるため
に用いる分子量８５０以上のアルカリ土類金属のスルホ
ン酸塩を組み合せることにより、すぐれた防錆性能、変
色防止性能、および脱脂性能も兼ね備えるので、本発明
の組成物を用いることにより亜鉛メッキ鋼板の防錆・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
ができるようになり、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
などに資するところが大である。[Effects of the Invention] Since the composition of the present invention is constructed as described above, an active extreme pressure agent that easily reacts with zinc must be blended in order to impart press oil performance as in the past. By using the lubricant action of fine alkaline earth metal particles that have little reactivity with zinc, there is no longer the buttering phenomenon caused by the reaction between the extreme pressure agent and the galvanized surface, which occurs in the past. This makes it easier to manage the machines and dies, and productivity can be significantly improved. Furthermore, by combining an alkaline earth metal sulfonate with a molecular weight of 850 or more, which is used to uniformly disperse alkaline earth metal fine particles in the lubricating base oil, it has excellent rust prevention performance, discoloration prevention performance, By using the composition of the present invention, a single lubricating oil composition can be used to prevent rust and discoloration of galvanized steel sheets, as well as degreasing properties, simplifying the process, It greatly contributes to streamlining, improving productivity, improving the quality of pressed parts, saving resources, and improving the work environment.

試験方法の説明１．粘度ＪＩＳ　　Ｋ　　２２８３［動粘度試験方法］による。Description of test method 1. viscosity According to JIS K 2283 [Kinematic viscosity test method].

２，湿潤試験２．１　　試験装置ＪＩＳ　　Ｋ　　２２４６さび止め油］に記載の装置に
よる。2. Wetness Test 2.1 Testing Apparatus According to the apparatus described in JIS K 2246 Rust Inhibiting Oil.

２．２　　試験片合金化溶融亜鉛めっき鋼板［６　０／６　０］６０Ｘ８
０Ｘ０．８ｍｍ２．３　　条件温　　　度　　　４　９±１℃ 相対湿度　　９５％以上２．４　　判定７２０時間後の錆発生度を測定する。2.2 Test piece Alloyed hot-dip galvanized steel plate [6 0/6 0] 60X8
0X0.8mm 2.3 Condition temperature 4 9±1℃ Relative humidity 95% or more 2.4 Judgment Measure the degree of rust occurrence after 720 hours.

Ａ；Ｏ％　　　　　Ｂ；１〜１０％Ｃ．１１　〜２５％　　Ｄ．２６　〜５０９６Ｅ；５０
％以上３，ＭＩＬステイン試験Ｍ　Ｉ　Ｌ　　Ｃ　　２　２　２　３　５　Ａ　［ｃｏ
ｒｒｏｓｌｏｎＰｒｅｖｅｎｔｉｖｅ　０１１，　Ｎｏ
ｎｓｔａ１ｎ．］に記載の方法に準拠する。A; O% B; 1-10% C. 11-25%D. 26 ~5096E;50
% or more 3, MIL stain test MILC 2 2 2 3 5 A [co
rroslonPreventive 011, No
nsta1n. ] Comply with the method described in .

３．１　　試験片片面電気亜鉛めっき鋼板［２　０／０］６０Ｘ８０ＸＯ
．８Ｂ３．２　　条件温度　　８２．５℃ 時間　　４８時間３．３　　判定試験後、試験片の重ね合せた面の錆、オイルステインの
発生を観察する。3.1 Test piece Single-sided electrogalvanized steel plate [2 0/0] 60X80XO
．． 8B 3.2 Conditions Temperature: 82.5°C Time: 48 hours 3.3 After the judgment test, observe the occurrence of rust and oil stain on the overlapping surfaces of the test pieces.

○　発生なし △　評価面の１０％以下の面積に発生 ×　評価面の１０％以上の面積に発生４，Ｖスタック試験４．１　　試験片合金化溶融亜鉛めっき鋼板［６０／６　０　コ　　　　　　６０Ｘ８０Ｘ０．８ｍｍ４．２
　　スタック試験片５枚の試験片に試料油をロール塗布法により１．５±０
．２ｇ／ｒｒｒ定量塗油し積み重ねる。この際、スベー
サーを用い、重ね面の片端に強制的なすき間をつくる。○ No occurrence △ Occurrence in an area of 10% or less of the evaluation surface × Occurrence in an area of 10% or more of the evaluation surface 4, V stack test 4.1 Test piece alloyed hot-dip galvanized steel plate [60/60 ko 60X80X0.8mm4 .2
Sample oil was applied to 5 stack test pieces by roll coating method to 1.5±0.
．． Apply 2g/rrr amount of oil and stack. At this time, a spacer is used to create a forced gap at one end of the stacked surfaces.

積み重ねた５枚の試験片の四隅をダブルクリップを用い
て固定する。これをスタック試験片とする。The four corners of the stacked five test pieces are fixed using double clips. This is used as a stack test piece.

４．３　　促進試験下記条件の恒湿恒温槽に３０日間投入する。4.3 Accelerated exam Place it in a constant temperature and humidity bath under the following conditions for 30 days.

温　　　度　　２　０℃×　６時間、５０℃×６時間のサイクル相対湿度　９８％以上４．４　　判定３、３と同じ方法で判定する。Temperature: 20°C x 6 hours, Cycle of 50℃ x 6 hours Relative humidity 98% or more 4.4 Judgment 3. Determine using the same method as 3.

５．脱脂性５．１　　試験片４．１と同じ試験片１０枚を４．２と同じ方法で塗油す
る。スベーサーは用いず積み重ねスタック試験片とする
。これを４，３の促進条件の恒湿恒温槽に１０日間格納
したものを使用する。5. Degreasing properties 5.1 Ten test pieces identical to those in test piece 4.1 were oiled in the same manner as in 4.2. A baser is not used and the test pieces are stacked. This was stored for 10 days in a constant humidity and temperature bath under conditions 4 and 3 for use.

５．２　　試験方法アルカリクリーナー（ＦＣ　　４３２６Ｔ）により下記
条件でスプレー脱脂を行なう〇濃度　　　；　　１０ｇ
／Ｄ温度　　　；　５０℃ 時間　　　；　３０秒２　６０秒スプレー圧：　　ｌｋｇ／ｃｊ５．３　　判定脱脂後水洗を３０秒行ない、６０″に立てかけて３０秒
後の水ぬれ面積を目視により求める。5.2 Test method Spray degreasing using alkaline cleaner (FC 4326T) under the following conditions.〇Concentration: 10g
/D Temperature: 50°C Time: 30 seconds 2 60 seconds Spray pressure: lkg/cj 5.3 Judgment After degreasing, wash with water for 30 seconds, lean it against 60'', and visually determine the water-wet area after 30 seconds.

０　３０秒で９８％以上水ぬれする。0 98% or more of the water gets wet in 30 seconds.

△　６０秒で９８％以上水ぬれする。△ Wet more than 98% of water in 60 seconds.

Ｘ　　６０秒で９８％以上水ぬれしない。X: 98% or more does not get wet in 60 seconds.

６，パウダリング試験８．１　　試験装置オブチモール社（***）製ＳＲＶ　（振動式摩擦摩耗）
試験機６．２　　試験片試験片はステージにＪＩＳ　　Ｈ　　２１０７（純亜鉛
材）　２４φ×８關シリンダーにＳＵＪ−２　（ベアリング鋼）１５φ×２
２關６．３　　試験条件ステージとシリンダーの間に試料油の１滴を滴下し次の
条件で試験する。6. Powdering test 8.1 Test equipment Obtimol (West Germany) SRV (vibrating friction wear)
Testing machine 6.2 Test piece The test piece is JIS H 2107 (pure zinc material) on the stage, 24φ x 8 and SUJ-2 (bearing steel) 15φ x 2 on the cylinder.
2.6.3 Test conditions Drop one drop of sample oil between the stage and cylinder and test under the following conditions.

温　　度　　　８　０℃ 荷　　重　　　　６０Ｎ振　　幅　　　　１．０＋ｎ振動数　　ｓｏｃｐｓ時　　間　　　　６　０分８．４　　判定試験前後のステージの重量を測定し、重量差を摩耗ｆｆ
ｉ（Ｉｌｇ）とする。摩耗量により試料油の耐パウダリ
ング性を評価する。Temperature: 80℃ Load: 60N Amplitude: 1.0+n Frequency: socps Time: 60 minutes 8.4 Measure the weight of the stage before and after the judgment test, and calculate the difference in weight as wear ff
Let it be i(Ilg). Evaluate the powdering resistance of the sample oil based on the amount of wear.

７．低速深絞り最大加工カ試験７．１　　試験機ＲＨ−　　３７．２　　試験条件ａ．ボンチｂ，ダイスｃ．Ｌわ押え力ｄ．ボンチスビ− ７．３　　試験片ａ．供試材０型（島津製作所）ド３６．０φ−３，５Ｒ３８．０φ−２．５Ｒ２８０　　Ｋｇｆ’ ０．５ｍｍ／ｓｅｃ合金化溶融亜鉛めっき（６　０／６　０）鋼板ｂ．　寸　　法　　０．　　８Ｘ７０　　φ市Ｃ．塗油
量　１．５±０．２ｇ／ボ判定深絞り加工時の最大加工力（Ｋｇｆ）８．低速深絞り破断限界試験８．１　　試験機ＲＨ−３０型（島津製作所）試験条件ａ．ポンチ　　　　　３Ｂ．０φ−３．５Ｒｂ．ダイｘ
　　　　　　３８．０φ−２．５Ｒｃ．Ｌわ押え力　　
　１３０　−１，３００７．４８．２ｄ．ポンチスピード　０．５ｍｍ／ｓｅｃ８．３　　試
験片ａ．供試材　片面電気亜鉛めっき（２　０／０）鋼板ｂ．　寸　　法　　０．８Ｘ７０　　φ市Ｃ．塗油量　
１．５±０．　　２ｇ／ｒｒｒ７．４　　判定ポンチスピード０．５關／ｓｅｃで絞り、破断に至るま
でのしわ押え力（Ｋｇｆ’）９．高速深絞り破断限界試験９．１　　試験機高速深絞り試験機（東京試験機）９．２　　試験条件ａ，ポンチ　　　　　４０．０φ−８．ＯＲ　　ａｓｂ
．ダイス　　　　　４２．０φ−８．０Ｒ　　關ｃ．Ｌ
わ押え力　　　１．０００　〜１０，０００Ｋｇｆｄ．
ポンチスピード　１，８００ｍｍ／ｓｅｃ９．３　　試
験片ａ、供試材　溶融亜鉛めっき（６　０／６　０）Ｍ板１ｂ．　寸　　法　　０，　　８Ｘ８４　　φ關Ｃ．塗油
量　１．５±０．２ｇ／耐９．４　　判定ポンチスピードｌ　，　８００＋ａｍ　／ｓｅｅで絞り
、破断に至るまでのしわ押え力（Ｋｇｆ）０，プレス加工後の防錆試験ＩＯ．１　　試験装置ＪＩＳ　　Ｋ　　２２４６に記載の格納貯蔵箱１０．２　　試験片７．３の低速深絞り最大加工力試験後の成形品ｌＯ，３　　試験試験片を格納貯蔵箱に凸部を上に向けて１０日間格納す
る。7. Low speed deep drawing maximum machining force test 7.1 Testing machine RH-3 7.2 Test conditions a. Bonchi b, dice c. L presser force d. Bontisbee 7.3 Test piece a. Test material Type 0 (Shimadzu Corporation) 36.0φ-3,5R 38.0φ-2.5R 280 Kgf' 0.5mm/sec Alloyed hot-dip galvanized (60/60) steel plate b. Dimensions 0. 8X70 φ city C. Oil application amount 1.5±0.2g/bo judgment Maximum working force during deep drawing (Kgf) 8. Low speed deep drawing rupture limit test 8.1 Testing machine RH-30 type (Shimadzu Corporation) Test conditions a. Punch 3B. 0φ-3.5Rb. die x
38.0φ-2.5Rc. L presser force
130 -1,3007.4 8.2 d. Punch speed 0.5mm/sec8.3 Test piece a. Test material Single-sided electrogalvanized (20/0) steel plate b. Dimensions 0.8X70 φ City C. Oil amount
1.5±0. 2g/rrr7.4 Judgment Wrinkle pressing force (Kgf') until breaking when squeezed at punch speed of 0.5/sec 9. High-speed deep drawing rupture limit test 9.1 Testing machine High-speed deep drawing tester (Tokyo Test Machine) 9.2 Test conditions a, punch 40.0φ-8. OR asb
．． Dice 42.0φ-8.0R C. L
Holding force 1.000 ~ 10,000Kgfd.
Punch speed 1,800mm/sec9.3 Test piece a, sample material Hot-dip galvanized (60/60) M plate 1 b. Dimensions 0, 8 x 84 φ C. Amount of oil applied: 1.5±0.2g/Resistance: 9.4 Judgment: Punch speed 1, Squeezing at 800+am/see, wrinkle pressing force until breakage (Kgf): 0, Rust prevention test after pressing IO. 1 Storage box described in test equipment JIS K 2246 10.2 Molded product after low speed deep drawing maximum working force test of test piece 7.3 3 Place the test specimen in the storage box with the convex portion facing upward. Store for 10 days.

ＩＯ，４　　判定試験後、試験片の円筒側面について錆、オイルステイン
の発生を観察する。IO, 4 After the judgment test, observe the occurrence of rust and oil stain on the cylindrical side surface of the test piece.

Ｏ　発生なし Δ　評価面の１０％以内の面積に発生評価面の０％以上の面積に発生O No occurrence Δ Occurs within 10% of the evaluation surface evaluation aspect Occurs in 0% or more area

Claims

【特許請求の範囲】１、潤滑油基油に１００〜１０，０００Åの粒径のアル
カリ土類金属の炭酸塩の群から選ばれた少なくとも１種
と、アルカリ土類金属の油溶性スルホン酸塩の群から選
ばれた少なくとも１種とを配合し、全塩基価を５〜１０
０ｍｇＫＯＨ／ｇになるように調合してなることを特徴
とする亜鉛めっき鋼板用のプレス加工油兼用防錆油組成
物。２、潤滑油基油の４０℃の粘度が５〜５００ｃＳｔであ
る請求項１記載のプレス加工油兼用防錆油組成物。３、アルカリ土類金属の炭酸塩が炭酸カルシウムである
請求項１記載の組成物。４、アルカリ土類金属の油溶性スルホン酸塩がカルシウ
ムスルホネートである請求項１記載のプレス加工油兼用
防錆油組成物。５、アルカリ土類金属の炭酸塩とアルカリ土類金属の油
溶性スルホン酸塩が複合された超塩基性スルホン酸塩で
ある請求項１記載のプレス加工油兼用防錆油組成物。６、粒径１００〜１０，０００Åの炭酸カルシウムをカ
ルシウムスルホネートに分散してなる全塩基価１００ｍ
ｇＫＯＨ／ｇ以上の超塩基性カルシウムスルホネートを
潤滑油基油に加え、全塩基価を５〜１００ｍｇＫＯＨ／
ｇになるように調合してなる請求項１記載のプレス加工
油兼用防錆油組成物。７、請求項１記載の組成物に、酸化防止剤、油性剤、極
圧剤、防錆剤、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系表面処理鋼板
のプレス加工油兼用防錆油組成物。[Scope of Claims] 1. At least one selected from the group of carbonates of alkaline earth metals having a particle size of 100 to 10,000 Å and an oil-soluble sulfonate of alkaline earth metals in a lubricating base oil. and at least one selected from the group of
A rust-preventing oil composition that can also be used as a press working oil for galvanized steel sheets, characterized in that it is formulated to have a concentration of 0 mg KOH/g. 2. The rust-preventing oil composition that can also be used as a press working oil according to claim 1, wherein the lubricating base oil has a viscosity of 5 to 500 cSt at 40°C. 3. The composition according to claim 1, wherein the alkaline earth metal carbonate is calcium carbonate. 4. The rust-preventing oil composition that can also be used as a pressing oil according to claim 1, wherein the oil-soluble sulfonate of an alkaline earth metal is calcium sulfonate. 5. The anticorrosive oil composition for press working oil as claimed in claim 1, which is a superbasic sulfonate which is a composite of an alkaline earth metal carbonate and an alkaline earth metal oil-soluble sulfonate. 6. Total base number 100m made by dispersing calcium carbonate with a particle size of 100 to 10,000 Å in calcium sulfonate.
Add gKOH/g or more of ultrabasic calcium sulfonate to the lubricant base oil to bring the total base number to 5 to 100 mgKOH/g.
2. The anticorrosive oil composition for press processing oil according to claim 1, which is formulated to have a composition of g. 7. A galvanized surface treatment in which the composition according to claim 1 is blended with at least one lubricating oil additive such as an antioxidant, an oil agent, an extreme pressure agent, a rust preventive agent, a water displacement agent, etc. A rust preventive oil composition that can also be used as a pressing oil for steel sheets.