JPH10183152A - Extreme-pressure additive and industrial lubricating oil - Google Patents
Extreme-pressure additive and industrial lubricating oilInfo
- Publication number
- JPH10183152A JPH10183152A JP21989097A JP21989097A JPH10183152A JP H10183152 A JPH10183152 A JP H10183152A JP 21989097 A JP21989097 A JP 21989097A JP 21989097 A JP21989097 A JP 21989097A JP H10183152 A JPH10183152 A JP H10183152A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- oil
- sulfonate
- calcium hydroxide
- calcium
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は極圧添加剤に関し、
例えば工業用潤滑油、特に金属加工油、エンジン油、ギ
ヤ油、軸受油、圧縮機油、冷凍機油、摺動面油、さび止
め油およびグリース等に使用される。The present invention relates to extreme pressure additives,
For example, they are used as industrial lubricating oils, particularly metal working oils, engine oils, gear oils, bearing oils, compressor oils, refrigerator oils, sliding surface oils, rust preventive oils, greases, and the like.
【０００２】[0002]
【従来の技術】工業用潤滑油の中でも、金属加工におけ
る潤滑は、被削材と工具間の垂直応力が１０００kg／cm
2以上になり、しかも切削温度は４００℃以上になるた
め、使用される切削油は非常に厳しい潤滑環境下に置か
れる。このため、従来、切削油の性能を向上させるため
に、極圧添加剤が使用されている。この目的で使用され
る極圧添加剤としては、塩素化パラフィン、塩素化脂肪
酸エステル等の含塩素有機化合物、および硫化油脂、硫
化オレフィン、ジアルキルポリサルファイド等の硫黄含
有有機化合物が知られている。これらの中でも、塩素化
パラフィンは、潤滑油添加剤として特に極圧の用途に５
０年以上の間広く用いられている。2. Description of the Related Art Among industrial lubricating oils, lubrication in metal working involves a vertical stress between a work material and a tool of 1000 kg / cm.
Since it is 2 or more and the cutting temperature is 400 ° C. or more, the used cutting oil is placed under a very severe lubricating environment. For this reason, extreme pressure additives have conventionally been used to improve the performance of cutting oil. Known extreme pressure additives used for this purpose include chlorinated organic compounds such as chlorinated paraffins and chlorinated fatty acid esters, and sulfur-containing organic compounds such as sulfurized oils and fats, sulfurized olefins, and dialkyl polysulfides. Of these, chlorinated paraffins are particularly suitable for extreme pressure applications as lubricating oil additives.
Widely used for over 0 years.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、最近で
は、毒性および発癌性の可能性についての懸念が生じて
きている。ドイツとカナダにおける塩素化ワックスの禁
止およびこれらの国におけるこの物質のドラムに警告ラ
ベルを貼る必要性のために、代わりの潤滑油添加剤が探
し求められている。金属加工業における多くは塩素化オ
レフィンおよびポリエステルに切り換えられつつある
が、この幾つかの中にはこれらの塩素化生成物も発癌性
を持つかもしれないという懸念がある。米国公衆衛生協
会は化学業界に対して、塩素化有機化合物の使用をやめ
るか、あるいは作業者および環境への潜在的健康リスク
を低減できるように、製造プロセスを改変するよう求め
ている。それ故、非塩素化代替物が望ましいと考えられ
ている。さらに塩素化パラフィン等の塩素化生成物を含
有した切削油は、使用中の油温の上昇による熱分解によ
り塩化水素を発生し、工作機械、工具、被削材、さらに
は工場内の設備を腐食させる問題を生じさせている。一
方、硫黄含有有機化合物は軽度の機械加工の用途には十
分であるが、これらは塩素化パラフィンが賞用された過
酷な金属切削のような激しい機械加工には一般的に十分
ではなかった。Recently, however, concerns have arisen about the potential toxicity and carcinogenicity. Due to the ban on chlorinated waxes in Germany and Canada and the need to put warning labels on drums of this substance in these countries, alternative lubricant additives are being sought. While many in the metalworking industry are switching to chlorinated olefins and polyesters, there are concerns that some of these chlorinated products may also be carcinogenic. The US Public Health Association is calling on the chemical industry to stop using chlorinated organic compounds or modify manufacturing processes to reduce potential health risks to workers and the environment. Therefore, non-chlorinated alternatives are considered desirable. In addition, cutting oils containing chlorinated products such as chlorinated paraffins generate hydrogen chloride by thermal decomposition due to an increase in the oil temperature during use, and cause machine tools, tools, work materials, and equipment in factories to be damaged. Causing corrosion problems. On the other hand, while sulfur-containing organic compounds are sufficient for light machining applications, they have generally not been sufficient for intense machining such as harsh metal cutting where chlorinated paraffins have been awarded.
【０００４】また、潤滑性に有効な元素としては、以上
の塩素や硫黄の他にリンがあり、それゆえ自動車エンジ
ン油用添加剤として、摩耗防止や酸化防止を目的として
有機ジチオリン酸亜鉛（ＺnＤＴＰ）が用いられてい
る。しかし、近年において排気ガス浄化触媒の被毒を回
避するために潤滑油中のリン量の低減が要望されてお
り、リンの含有量規制が施行されている。規制値はます
ます厳しくなる傾向にあるが、潤滑油中のリン量はＺn
ＤＴＰの添加量と関係があり、添加量の低減は摩耗防止
性や酸化防止性の低下につながるため、摩耗防止効果が
期待できる非リン系添加剤の出現が強く望まれている。
このように大気汚染に間接的に悪影響を及ぼすリン系化
合物は、湖沼や内湾などへの富栄養化に直接影響し、自
然破壊の原因物質となっている。[0004] In addition to the above chlorine and sulfur, phosphorus is an effective element for lubricating properties. Therefore, as an additive for automobile engine oils, zinc organic dithiophosphate (ZnDTP) is used for the purpose of preventing wear and oxidation. ) Is used. However, in recent years, there has been a demand for a reduction in the amount of phosphorus in lubricating oil in order to avoid poisoning of the exhaust gas purification catalyst, and the content of phosphorus has been regulated. Regulatory values tend to be more stringent, but the amount of phosphorus in
This is related to the amount of DTP to be added, and a decrease in the amount of DTP leads to a decrease in anti-wear and anti-oxidation properties. Therefore, the emergence of a non-phosphorus-based additive that can be expected to have an anti-wear effect is strongly desired.
Such phosphorus compounds that indirectly adversely affect air pollution directly affect the eutrophication of lakes, marshes and bays, and are a cause of natural destruction.
【０００５】以上のように塩素、リン等を含有する有機
化合物は、潤滑性に有用な反面、人体、自然環境に対し
て有害性を有しており、様々な規制の対象物質となって
いるため、経済性をも悪化させる要因となっている。本
発明の目的は各種工業用潤滑油の潤滑作用を向上させる
ために有用な極圧添加剤及び工業用潤滑油を提供するこ
とにある。As described above, organic compounds containing chlorine, phosphorus and the like are useful for lubricity, but harmful to the human body and the natural environment, and are subject to various regulations. Therefore, it is also a factor that deteriorates economic efficiency. An object of the present invention is to provide an extreme pressure additive and an industrial lubricating oil useful for improving the lubricating action of various industrial lubricating oils.
【０００６】[0006]
【課題を解決するための手段】本発明は油溶性芳香族炭
化水素スルホン酸亜鉛、水酸化カルシウムを含む溶剤中
で、使用する水酸化カルシウムの量に対して、１〜５重
量％の塩化カルシウムを併用して水酸化カルシウムを炭
酸化することによって得られる、油溶性芳香族炭化水素
スルホン酸亜鉛塩中に微粒子の炭酸カルシウムと微粒子
の水酸化カルシウムを分散させた過塩基性スルホン酸亜
鉛からなる極圧添加剤に係る。また本発明は油溶性芳香
族炭化水素スルホン酸亜鉛、水酸化カルシウムを含む溶
剤中で、水酸化カルシウムを炭酸化することによって得
られる、油溶性芳香族炭化水素スルホン酸亜鉛塩中に微
粒子の炭酸カルシウムと微粒子の水酸化カルシウムを分
散させてなる過塩基性スルホン酸亜鉛に、塩化カルシウ
ム水溶液を加え、還流温度まで加熱し、脱水することに
より得られる極圧添加剤に係る。さらに本発明は上記極
圧添加剤を含有する工業用潤滑油に係る。According to the present invention, there is provided a solvent containing oil-soluble zinc aromatic sulfonate and calcium hydroxide, wherein the amount of calcium chloride is 1 to 5% by weight based on the amount of calcium hydroxide used. It is composed of overbased zinc sulfonate in which fine calcium carbonate and fine calcium hydroxide are dispersed in an oil-soluble aromatic hydrocarbon sulfonate zinc salt obtained by carbonating calcium hydroxide in combination with Related to extreme pressure additives. In addition, the present invention provides a method of preparing fine particles of carbonized oil-soluble aromatic hydrocarbon sulfonate zinc salt, which is obtained by carbonating calcium hydroxide in a solvent containing oil-soluble zinc aromatic hydrocarbon sulfonate and calcium hydroxide. The present invention relates to an extreme pressure additive obtained by adding an aqueous calcium chloride solution to overbased zinc sulfonate in which calcium and fine particle calcium hydroxide are dispersed, heating the mixture to reflux temperature, and dehydrating. Further, the present invention relates to an industrial lubricating oil containing the above extreme pressure additive.
【０００７】本発明者らは、上記従来技術の問題を解決
するため、有機塩素化合物や有機リン化合物を使用しな
い極圧添加剤に関して、潤滑性、防食性、安定性等の性
能と組成物成分の関係について、鋭意研究を重ねた結
果、スルホン酸亜鉛塩を使用し、かつ使用する水酸化カ
ルシウムと共に塩化カルシウムを併用して水酸化カルシ
ウムを炭酸化して得られる過塩基性スルホン酸亜鉛を用
いるか、または過塩基性スルホン酸亜鉛に塩化カルシウ
ム水溶液を加え、還流温度まで加熱し、脱水することに
より得られる過塩基性スルホン酸亜鉛を用いることによ
り、従来の製品の持つ問題点を解消する更に一層優れた
性能が得られるとの知見を得て、本発明を完成した。[0007] In order to solve the above-mentioned problems of the prior art, the present inventors have developed an extreme pressure additive that does not use an organic chlorine compound or an organic phosphorus compound, and have properties such as lubricity, anticorrosion and stability and composition components. As a result of diligent research on the relationship, the use of zinc sulfonate and the use of overbased zinc sulfonate obtained by carbonating calcium hydroxide using calcium chloride together with calcium hydroxide used Further, by using an overbased zinc sulfonate obtained by adding an aqueous calcium chloride solution to an overbased zinc sulfonate, heating to a reflux temperature, and dehydrating, the problems with conventional products are further solved. The inventor found that excellent performance was obtained, and completed the present invention.
【０００８】[0008]
【発明の実施の形態】本発明で使用できる芳香族炭化水
素スルホン酸としては鉱物油に可溶のものであれば公知
のものを使用することができ、例えば油溶性石油スルホ
ン酸、アルキルナフタレンスルホン酸、ジアルキルナフ
タレンスルホン酸、アルキルベンゼンスルホン酸、ジア
ルキルベンゼンスルホン酸等が挙げられる。炭化水素系
溶剤は、混合物中に炭酸ガスを供給する際、混合物を流
動状に保持させるためのものであるから、混合物を流動
状態に保つに十分な量を使用する。芳香族炭化水素系溶
剤としては、例えばベンゼン、トルエン、キシレン等が
挙げられ、脂肪族炭化水素系溶剤としては、石油ナフ
サ、ヘキサン、ヘプタン等が挙げられる。メタノール
は、市販工業用メタノールで十分であり、メタノール以
外の炭素数２から５の低級アルコールの使用は、本発明
の組成物の取得のためには使用し得ない。なぜならば、
メタノール以外の低級アルコール中では炭酸カルシウム
が生成しないか、あるいは生成してもその結晶形はカル
サイト型であり、本発明の目的を達成し得ないためであ
る。水酸化カルシウムは、市販の安価な工業用消石灰で
十分である。使用量の好ましい範囲は、油溶性芳香族炭
化水素スルホン酸亜鉛に対して３０〜７０重量％である
ことが本発明の目的のためには好ましい。DETAILED DESCRIPTION OF THE INVENTION As the aromatic hydrocarbon sulfonic acid usable in the present invention, known aromatic hydrocarbon sulfonic acids can be used as long as they are soluble in mineral oil. For example, oil-soluble petroleum sulfonic acid, alkylnaphthalene sulfonic acid Acid, dialkylnaphthalenesulfonic acid, alkylbenzenesulfonic acid, dialkylbenzenesulfonic acid and the like. The hydrocarbon-based solvent is used to maintain the mixture in a fluid state when supplying carbon dioxide gas into the mixture, and therefore, an amount sufficient to keep the mixture in a fluid state is used. Examples of the aromatic hydrocarbon-based solvent include benzene, toluene, xylene and the like, and examples of the aliphatic hydrocarbon-based solvent include petroleum naphtha, hexane, heptane and the like. Commercially available methanol is sufficient for methanol, and the use of lower alcohols having 2 to 5 carbon atoms other than methanol cannot be used for obtaining the composition of the present invention. because,
This is because calcium carbonate is not produced in lower alcohols other than methanol, or even if it is produced, its crystal form is calcite, and the object of the present invention cannot be achieved. For calcium hydroxide, commercially available inexpensive industrial lime is sufficient. The preferred range of the amount used is preferably 30 to 70% by weight based on the oil-soluble zinc aromatic sulfonate for the purpose of the present invention.
【０００９】さらに詳しくは、芳香族炭化水素スルホン
酸の亜鉛塩、鉱物油、炭化水素系溶剤、メタノール、塩
化カルシウムおよび水酸化カルシウムの混合物に対し
て、水酸化カルシウムのすべてを炭酸カルシウムに変換
するのに要する炭酸ガスの量の７０重量％から９０重量
％を使用して炭酸化し、次に副生する水分を加熱により
除去した後、加圧濾過により清澄な濾液を得る。濾液よ
り揮発成分を蒸発により除去することにより、炭酸カル
シウムと水酸化カルシウムの微粒子が透明に均一分散し
た組成物が得られる。ＣaＣＯ3，Ｃa(ＯＨ)2の粒子径は
０.００５〜０.１μmが好ましく、０.０１〜０.０５μm
が特に好ましい。More specifically, all of calcium hydroxide is converted to calcium carbonate with respect to a mixture of zinc salt of aromatic hydrocarbon sulfonic acid, mineral oil, hydrocarbon solvent, methanol, calcium chloride and calcium hydroxide. Carbonation is carried out using 70 to 90% by weight of the amount of carbon dioxide required for the above, and after removing water by-produced by heating, a clear filtrate is obtained by pressure filtration. By removing volatile components from the filtrate by evaporation, a composition in which fine particles of calcium carbonate and calcium hydroxide are transparently and uniformly dispersed is obtained. The particle diameters of CaCO 3 and Ca (OH) 2 are preferably 0.005 to 0.1 μm, and 0.01 to 0.05 μm.
Is particularly preferred.
【００１０】炭酸化時に併用する塩化カルシウムは使用
する水酸化カルシウムの量に対して、１〜５重量％用い
るのが本発明の目的のために好ましい。また炭酸化時に
は塩化カルシウムを使用せず、炭酸化終了後に、副生す
る水分を除去した反応混合物中に、塩化カルシウム水溶
液を添加して還流温度まで加熱し、脱水するという方法
でも使用することができる。この場合、後添加する塩化
カルシウムは水酸化カルシウムの量に対して、１〜５重
量％用いるのが好ましい。このような塩化カルシウムに
よる処理をすることにより、最終的に得られる組成物中
に微粒子状の炭酸カルシウムと水酸化カルシウムを最適
の構成比率で含有することができる。従来、芳香族炭化
水素スルホン酸の亜鉛塩中に、塩化カルシウムで処理し
た炭酸カルシウムと水酸化カルシウムの微粒子を、均一
に分散し清澄な組成物を得る方法の開示例はない。For the purpose of the present invention, it is preferable to use 1 to 5% by weight of calcium chloride to be used at the time of carbonation, based on the amount of calcium hydroxide used. In addition, calcium carbonate is not used at the time of carbonation, and after the completion of carbonation, a method of adding an aqueous solution of calcium chloride to a reaction mixture from which by-produced water has been removed, heating the mixture to a reflux temperature, and dehydrating the mixture can also be used. it can. In this case, the calcium chloride to be added later is preferably used in an amount of 1 to 5% by weight based on the amount of calcium hydroxide. By performing such treatment with calcium chloride, finely divided calcium carbonate and calcium hydroxide can be contained in the finally obtained composition in an optimum composition ratio. Conventionally, there is no disclosure of a method for uniformly dispersing fine particles of calcium carbonate and calcium hydroxide treated with calcium chloride in a zinc salt of an aromatic hydrocarbon sulfonic acid to obtain a clear composition.
【００１１】本発明による極圧添加剤の中に含まれる芳
香族炭化水素スルホン酸塩は亜鉛塩であり、亜鉛以外の
金属塩では本発明の目的を達成し得ない。また、芳香族
炭化水素スルホン酸亜鉛の含有率が、２０重量％未満で
も本発明の目的を達成し得ない。なぜなら芳香族炭化水
素スルホン酸亜鉛の含有率が低い場合には、十分な潤滑
性を示すに必要な量の炭酸カルシウム、水酸化カルシウ
ムを透明に安定分散し得ないためである。微粒子状で透
明に安定分散し得ない組成物は潤滑油に溶解させた場
合、沈澱を発生し潤滑油としての目的を果たすのに不都
合を生じる。芳香族炭化水素スルホン酸亜鉛の含有率
が、５０重量％を越える場合には、得られる組成物の粘
度が著しく増大し、取扱い上の不便が生じ好ましくな
い。さらに、本発明による潤滑添加剤組成物の中に存在
する微粒子状の炭酸カルシウムは本組成物中に１５〜４
０重量％、好ましくは２０〜３０重量％、水酸化カルシ
ウムは本組成物中に２〜１０重量％、好ましくは５〜８
重量％含まれているのが好適である。The aromatic hydrocarbon sulfonate contained in the extreme pressure additive according to the present invention is a zinc salt, and a metal salt other than zinc cannot achieve the object of the present invention. Further, even if the content of the zinc aromatic hydrocarbon sulfonate is less than 20% by weight, the object of the present invention cannot be achieved. This is because when the content of zinc zinc aromatic sulfonate is low, the amounts of calcium carbonate and calcium hydroxide necessary for exhibiting sufficient lubricity cannot be transparently and stably dispersed. When dissolved in a lubricating oil, a composition which is in a fine particle form and cannot be stably dispersed in a transparent manner causes precipitation and causes a problem in fulfilling the purpose as a lubricating oil. When the content of the zinc aromatic hydrocarbon sulfonate is more than 50% by weight, the viscosity of the obtained composition is remarkably increased, which is not preferable because the handling becomes inconvenient. Furthermore, the finely divided calcium carbonate present in the lubricating additive composition according to the present invention may be present in the composition in an amount of from 15 to 4%.
0% by weight, preferably 20-30% by weight, calcium hydroxide is 2-10% by weight, preferably 5-8% in the present composition.
Preferably, it is contained by weight.
【００１２】本発明による極圧添加剤を鉱物油に溶解さ
せた潤滑油を用いて、摩擦・摩耗試験を行い金属同志の
溶着が発生する前の摩擦面および非摩擦面の金属表面上
の元素組成を観察すると、摩擦面上ではカルシウム、酸
素、亜鉛および硫黄が非摩擦面上に比べ相対的に格段に
増加していることが認められた。このことより、本発明
による極圧添加剤の潤滑効果発現機構は、本発明の組成
物中にコロイド状に安定分散して含有している炭酸カル
シウムが摩擦面である鉄表面において、摩擦熱により分
解して酸化カルシウムに変化し、酸化カルシウムと酸化
鉄による固溶体を形成することにより、金属同志の焼き
付きを防止するものと推量できる。さらに同様に本組成
物中に共存する水酸化カルシウムは、本組成物のアルカ
リ度を向上させることにより炭酸カルシウムの上記の作
用を活性化するために、優れた極圧効果を示すものと考
えられる。すなわち水酸化カルシウムを殆ど含有しない
場合には、所期の効果が得られない。The lubricating oil in which the extreme pressure additive according to the present invention is dissolved in mineral oil is subjected to a friction / wear test to determine the elements on the frictional surface and the non-frictional surface of the metal surface before welding of metals occurs. Observation of the composition revealed that calcium, oxygen, zinc, and sulfur were significantly increased on the friction surface compared to the non-friction surface. From this, the mechanism of manifesting the lubricating effect of the extreme pressure additive according to the present invention is based on the fact that calcium carbonate, which is stably dispersed in the composition of the present invention in a colloidal state, is generated by frictional heat on the iron surface which is a friction surface. It can be guessed that it decomposes into calcium oxide and forms a solid solution of calcium oxide and iron oxide, thereby preventing seizure between metals. Further, similarly, calcium hydroxide coexisting in the present composition is considered to exhibit an excellent extreme pressure effect in order to activate the above-described action of calcium carbonate by improving the alkalinity of the present composition. . That is, when calcium hydroxide is scarcely contained, the desired effect cannot be obtained.
【００１３】さらに、本発明では、塩化カルシウムによ
る処理を行っている。一般に、水酸化カルシウムは、塩
化物イオンの存在により、ＣaＣl2・３Ｃa(ＯＨ)2・１
３Ｈ2Ｏ等の複塩を形成して、水への溶解度が増加す
る。本組成物においても、塩化カルシウムによる処理に
よって、このような複塩が生成し、含有されているもの
と考えられる。この効果により、塩化カルシウム処理を
施さない一般の過塩基性スルホネートよりも極圧性によ
り優れたものになっていると推測される。また本組成物
中に含有される亜鉛と鉱物油等に含有される硫黄分との
摩擦面における反応膜の形成により、金属表面組成が改
質されるために高い潤滑性が得られるものと考えられ
る。Further, in the present invention, the treatment with calcium chloride is performed. In general, calcium hydroxide can be converted to CaCl 2 .3Ca (OH) 2 .1 by the presence of chloride ions.
A double salt such as 3H 2 O is formed to increase the solubility in water. In the present composition, it is considered that such a double salt is generated and contained by the treatment with calcium chloride. Due to this effect, it is presumed that it is more excellent in extreme pressure properties than a general overbased sulfonate not subjected to calcium chloride treatment. The formation of a reaction film on the friction surface between the zinc contained in the composition and the sulfur contained in mineral oil, etc., is believed to improve the metal surface composition, resulting in high lubricity. Can be
【００１４】本発明の組成物と類似の組成物として、高
度に塩基化された油溶性スルホン酸のカルシウム塩、す
なわち油溶性スルホン酸カルシウム中に炭酸カルシウム
と水酸化カルシウムを分散させた組成物があるが、本発
明による組成物は亜鉛塩であることを特徴としており、
類似の組成物は亜鉛塩ではないため十分な効果を示さな
い。As a composition similar to the composition of the present invention, a highly basic calcium salt of oil-soluble sulfonic acid, that is, a composition in which calcium carbonate and calcium hydroxide are dispersed in oil-soluble calcium sulfonate is used. However, the composition according to the invention is characterized in that it is a zinc salt,
Similar compositions are not zinc salts and thus do not show satisfactory results.
【００１５】本発明の組成物は、スルホン酸塩が亜鉛塩
でない他の組成物に比べ、亜鉛塩であるがゆえの特長を
合わせ有する。一般に、高度に塩基化された油溶性スル
ホン酸塩は、塩基化されていないスルホン酸塩または低
度に塩基化されたスルホン酸塩に比べさび止め性に劣る
とされているが、本発明の組成物は全塩基価［試料１g
中に存在する炭酸カルシウムのごとき全塩基成分を中和
するのに要する塩酸と当量の水酸化カリウムのmg数をい
い、単位はmgＫＯＨ／gで表され、以下ＴＢＮと略す］
が３００mgＫＯＨ／g以上の高度に塩基化された組成物
にもかかわらず湿潤試験で優れたさび止め性を有してい
る。また、非鉄金属の変色・腐食防止および潤滑油の熱
劣化防止に顕著な効果を発揮することを見出した。The composition of the present invention has the advantage of being a zinc salt as compared with other compositions in which the sulfonate is not a zinc salt. In general, highly basic oil-soluble sulfonates are said to be less rust-proof than unbased or less-basic sulfonates, although the invention is not limited to this. Composition is total base number [sample 1g
Means the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize all base components such as calcium carbonate present therein, and the unit is expressed in mg KOH / g, and hereinafter abbreviated as TBN.]
Have excellent rust resistance in a wet test despite a highly basic composition of 300 mg KOH / g or more. Further, they have found that they have a remarkable effect in preventing discoloration and corrosion of non-ferrous metals and preventing thermal deterioration of lubricating oil.
【００１６】本発明の極圧添加剤の使用量は、潤滑油の
用途によって異なるが、一般には潤滑油中に０.１〜８
０重量％、好ましくは１〜５０重量％の濃度で添加され
る。本発明の組成物は潤滑油中に単独で用いることもで
きるが、一般的には他の各種添加剤と共に用いられる。
そのような添加剤として代表的なものは、金属加工油で
あれば潤滑効果を高めるための油性剤、硫黄系添加剤、
リン系添加剤、塩素系添加剤、有機金属系添加剤、水系
で使用する場合のための界面活性剤等がある。またエン
ジン油であれば、粘度指数向上剤や清浄分散剤等があ
る。The amount of the extreme pressure additive used in the present invention varies depending on the use of the lubricating oil.
It is added at a concentration of 0% by weight, preferably 1 to 50% by weight. The compositions of the present invention can be used alone in lubricating oils, but are generally used with various other additives.
A typical example of such an additive is an oily agent for enhancing the lubricating effect if it is a metalworking oil, a sulfur-based additive,
There are phosphorus-based additives, chlorine-based additives, organometallic-based additives, surfactants for use in aqueous systems, and the like. In the case of engine oil, there are a viscosity index improver, a cleaning dispersant, and the like.
【００１７】油性剤としては、例えばパーム油、菜種油
などの植物油、牛脂、豚脂などの動物油、これら油脂か
ら得られる脂肪酸、またこれら脂肪酸に各種アルコール
などを反応させて得られるエステル類などが挙げられ
る。硫黄系添加剤としては、例えば硫化油脂、硫化脂肪
酸、ポリサルファイドなどが挙げられる。リン系添加剤
としては、例えばリン酸エステル、酸性リン酸エステル
などが挙げられる。塩素系添加剤としては、例えば塩素
化パラフイン、塩素化脂肪酸などが挙げられる。有機金
属系添加剤としては、例えばジアルキルジチオリン酸、
ジアルキルジチオカルバミン酸、ナフテン酸などの亜
鉛、モリブデン、鉛などとの金属塩などが挙げられる。Examples of the oil agent include vegetable oils such as palm oil and rapeseed oil, animal oils such as tallow and lard, fatty acids obtained from these oils and fats, and esters obtained by reacting these fatty acids with various alcohols. Can be Examples of the sulfur-based additive include sulfurized fats and oils, sulfurized fatty acids, and polysulfides. Examples of the phosphorus-based additive include a phosphoric acid ester and an acidic phosphoric acid ester. Examples of the chlorine-based additive include chlorinated paraffin, chlorinated fatty acid, and the like. As the organic metal-based additive, for example, dialkyldithiophosphoric acid,
Metal salts with zinc, molybdenum, lead and the like such as dialkyldithiocarbamic acid and naphthenic acid.
【００１８】界面活性剤としては、例えばポリオキシエ
チレン系や多価アルコール系のようなノニオン系、脂肪
酸誘導体や硫酸エステル、スルホン酸系のようなアニオ
ン系などの界面活性剤が挙げられる。粘度指数向上剤と
しては、例えばポリメタクリレート、ポリイソブチレ
ン、オレフィン系共重合体、ポリアルキルスチレンなど
が挙げられる。清浄分散剤としては、例えば中性、塩基
性のスルホネート、中性、塩基性のフェネート等の金属
塩型清浄分散剤、コハク酸イミド型、ベンジルアミン
型、Ｎ−ビニルピロリジノンを含むメタクリレート共重
合物等の無灰型清浄分散剤などが挙げられる。これらの
添加剤は、本発明の性能を低下させない限り、一般に使
用されている量を用いることができる。エンジン油に使
用される清浄分散剤の中には酸中和作用に優れた金属系
清浄分散剤があり、本発明の組成物は、その用途にも使
用できる。Examples of the surfactant include nonionic surfactants such as polyoxyethylene and polyhydric alcohols, and anionic surfactants such as fatty acid derivatives, sulfates and sulfonic acids. Examples of the viscosity index improver include polymethacrylate, polyisobutylene, olefin-based copolymer, and polyalkylstyrene. Examples of the detergent and dispersant include metal salt detergents and dispersants such as neutral and basic sulfonates, neutral and basic phenates, and methacrylate copolymers containing succinimide, benzylamine and N-vinylpyrrolidinone. And the like. These additives can be used in an amount generally used as long as the performance of the present invention is not deteriorated. Among the detergent and dispersants used in engine oils, there are metal detergents and dispersants excellent in acid neutralizing action, and the composition of the present invention can be used for the purpose.
【００１９】[0019]
【実施例】以下、実施例により本発明を具体的に説明す
るが、その範囲を限定するものではない。EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited thereto.
【００２０】実施例１ 還流冷却器、温度計を備えた３リットル四つ口フラスコ
に、平均分子量５２０の石油スルホン酸ナトリウム塩７
００g、鉱油２５０g、トルエン５００gを入れて混合し
たのち２０重量％の塩化亜鉛の水溶液５００gを加え、
還流温度で加熱・攪拌を１時間行った。水層とトルエン
層を分離後、トルエン層に２０重量％の塩化亜鉛の水溶
液５００gを加え、還流温度で加熱・攪拌を行った。ト
ルエン層に溶解している全石油スルホン酸塩中に未反応
で残っている石油スルホン酸ナトリウム塩が２重量％未
満になるまで、上記の反応を繰り返した後、トルエン層
を遠心分離した。上澄みのトルエン溶液から揮発成分を
蒸発により留去し、石油スルホン酸亜鉛塩７３０gを得
た。次に還流冷却器、温度計、炭酸ガス導入管を備えた
５リットル四つ口フラスコに、上記で得られた石油スル
ホン酸亜鉛塩７３０g、トルエン１４７０g、鉱油１１０
g、メタノール１８５g、塩化カルシウム９gおよび消石
灰３００gを入れ、４０℃〜５０℃の水浴中に設置し
た。攪拌羽根によって混合後、炭酸ガス導入管により炭
酸ガスを９００ml／分の流量で８０分間バブリングし
た。次に反応混合物を１２０℃まで加熱し、系内の水分
を除去後常温まで冷却した。得られた反応混合物に濾過
助剤を添加して混合後、加圧濾過し、濾液と瀘滓層に分
離した。薄膜エバポレータにより濾液から揮発性物質を
除去し、炭酸カルシウムと水酸化カルシウムの微粒子を
含有する清澄な油溶性スルホン酸亜鉛１０００gを得
た。得られた組成物の油溶性スルホン酸亜鉛の含有量は
２８.４重量％で、炭酸カルシウム含有量は２０.９重量
％、水酸化カルシウム含有量は７.９重量％であった。Example 1 A 3 liter four-necked flask equipped with a reflux condenser and a thermometer was charged with sodium petroleum sulfonate 7 having an average molecular weight of 520.
After adding and mixing 00 g, 250 g of mineral oil and 500 g of toluene, 500 g of a 20% by weight aqueous solution of zinc chloride was added.
Heating and stirring were performed at the reflux temperature for 1 hour. After separating the aqueous layer and the toluene layer, 500 g of a 20% by weight aqueous solution of zinc chloride was added to the toluene layer, and the mixture was heated and stirred at the reflux temperature. The above reaction was repeated until the amount of sodium petroleum sulfonate remaining unreacted in all the petroleum sulfonates dissolved in the toluene layer was less than 2% by weight, and then the toluene layer was centrifuged. Volatile components were distilled off from the supernatant toluene solution by evaporation to obtain 730 g of zinc petroleum sulfonic acid salt. Next, 730 g of the zinc salt of petroleum sulfonic acid, 1470 g of toluene, and 110 mineral oil were added to a 5-liter four-necked flask equipped with a reflux condenser, a thermometer, and a carbon dioxide gas inlet tube.
g, methanol 185 g, calcium chloride 9 g and slaked lime 300 g were placed in a water bath at 40 ° C to 50 ° C. After mixing with the stirring blade, carbon dioxide gas was bubbled through the carbon dioxide gas introducing tube at a flow rate of 900 ml / min for 80 minutes. Next, the reaction mixture was heated to 120 ° C., and after removing water in the system, it was cooled to room temperature. A filter aid was added to the obtained reaction mixture, mixed, filtered under pressure, and separated into a filtrate and a cake layer. Volatile substances were removed from the filtrate by a thin film evaporator to obtain 1000 g of clear oil-soluble zinc sulfonate containing fine particles of calcium carbonate and calcium hydroxide. The resulting composition had an oil-soluble zinc sulfonate content of 28.4% by weight, a calcium carbonate content of 20.9% by weight, and a calcium hydroxide content of 7.9% by weight.
【００２１】実施例２ 石油スルホン酸ナトリウム塩の代わりに、平均分子量４
７０のジアルキルベンゼンスルホン酸ナトリウムからな
る合成スルホン酸ナトリウムを用いたほかは実施例１と
同様の操作を行い、ジアルキルベンゼンスルホン酸亜鉛
を２４.５重量％、炭酸カルシウムを２１.０重量％、水
酸化カルシウムを６.３重量％含有する清澄な組成物を
得た。Example 2 Instead of petroleum petroleum sulfonic acid sodium salt, an average molecular weight of 4
The same operation as in Example 1 was carried out except that a synthetic sodium sulfonate comprising sodium dialkylbenzene sulfonate of No. 70 was used, 24.5% by weight of zinc dialkylbenzenesulfonate, 21.0% by weight of calcium carbonate, water A clear composition containing 6.3% by weight of calcium oxide was obtained.
【００２２】実施例３ 平均分子量５２０の石油スルホン酸ナトリウム塩７００
g、トルエン５００gの混合物を、実施例１と同様に処理
し石油スルホン酸亜鉛塩７００gを得た。次に還流冷却
器、温度計、炭酸ガス導入管を備えた５Ｌ四つ口フラス
コに、上記で得られた石油スルホン酸亜鉛塩７００g、
トルエン１４００g、メタノール１７５g、塩化カルシウ
ム７gおよび消石灰２５０gを入れ、４０℃〜５０℃の水
浴中に設置した。攪拌、混合後、炭酸ガス導入管により
炭酸ガスを７５０ml／分の流量で８０分間バブリングし
た。その後は実施例１と同様の操作を行い、石油スルホ
ン酸亜鉛を４８.５重量％、炭酸カルシウムを１９.７重
量％、水酸化カルシウムを５.４重量％含有する清澄な
組成物８２８gを得た。Example 3 Sodium Petroleum Sulfonate 700 having an average molecular weight of 520
g, and a mixture of 500 g of toluene were treated in the same manner as in Example 1 to obtain 700 g of zinc petroleum sulfonic acid salt. Next, 700 g of the petroleum zinc sulfonate obtained above was placed in a 5 L four-necked flask equipped with a reflux condenser, a thermometer, and a carbon dioxide gas introducing tube.
Toluene (1400 g), methanol (175 g), calcium chloride (7 g) and slaked lime (250 g) were placed in a water bath at 40 ° C to 50 ° C. After stirring and mixing, carbon dioxide gas was bubbled through the carbon dioxide gas introducing tube at a flow rate of 750 ml / min for 80 minutes. Thereafter, the same operation as in Example 1 was performed to obtain 828 g of a clear composition containing 48.5% by weight of zinc petroleum sulfonate, 19.7% by weight of calcium carbonate, and 5.4% by weight of calcium hydroxide. Was.
【００２３】実施例４ 実施例１と同様に処理を行い、石油スルホン酸亜鉛塩
７３０gを得た。次に、塩化カルシウムを使用せずに行
った以外は実施例１と同様に炭酸ガスバブリングを行
い、続けて加熱して水分除去を行った。次に、塩化カル
シウム ９gを水 ９０gに溶解し、これを反応混合物に添
加し、還流温度で加熱・撹拌を１時間行った。その後、
反応混合物を１２０℃まで加熱し、系内の水分を除去
後、常温まで冷却した。得られた反応混合物に実施例１
と同様の濾過助剤を添加し、その後は実施例１と同様の
操作を行った。得られた組成物の石油スルホン酸亜鉛の
含有量は２８.３重量％で、炭酸カルシウム含有量は１
９.３重量％、水酸化カルシウム含有量は７.２重量％で
あった。Example 4 The same treatment as in Example 1 was carried out to obtain a zinc salt of petroleum sulfonic acid.
730 g were obtained. Next, carbon dioxide gas bubbling was carried out in the same manner as in Example 1 except that calcium chloride was not used, followed by heating to remove water. Next, 9 g of calcium chloride was dissolved in 90 g of water, added to the reaction mixture, and heated and stirred at the reflux temperature for 1 hour. afterwards,
The reaction mixture was heated to 120 ° C. to remove water in the system, and then cooled to room temperature. Example 1 was added to the obtained reaction mixture.
The same filter aid was added, and the same operation as in Example 1 was performed thereafter. The resulting composition had a zinc petroleum sulfonate content of 28.3% by weight and a calcium carbonate content of 1%.
The content was 9.3% by weight and the content of calcium hydroxide was 7.2% by weight.
【００２４】実施例５ 実施例１と同様に処理を行い、石油スルホン酸亜鉛塩
７３０gを得た。次に、塩化カルシウムを使用せずに行
った以外は実施例１と同様に炭酸ガスバブリングを行
い、続けて加熱して水分除去、加圧濾過を行った。次
に、塩化カルシウム９gを水 ９０gに溶解し、これと水
酸化カルシウム ６０gを反応混合物に添加し、還流温度
で加熱・撹拌を１時間行った。その後は実施例４と同様
の操作を行った。得られた組成物の石油スルホン酸亜鉛
の含有量は２８.５重量％で、炭酸カルシウム含有量は
２２.０重量％、水酸化カルシウム含有量は６.１重量％
であった。Example 5 The same treatment as in Example 1 was carried out to obtain a zinc salt of petroleum sulfonic acid.
730 g were obtained. Next, carbon dioxide bubbling was performed in the same manner as in Example 1 except that calcium chloride was not used, followed by heating to remove moisture and perform pressure filtration. Next, 9 g of calcium chloride was dissolved in 90 g of water, 60 g of calcium hydroxide and 60 g of this were added to the reaction mixture, and the mixture was heated and stirred at the reflux temperature for 1 hour. Thereafter, the same operation as in Example 4 was performed. The resulting composition has a zinc petroleum sulfonate content of 28.5% by weight, a calcium carbonate content of 22.0% by weight and a calcium hydroxide content of 6.1% by weight.
Met.
【００２５】比較例１ 還流冷却器、温度計、炭酸ガス導入管を備えた５リット
ル四つ口フラスコに、平均分子量約１０３０の市販の石
油スルホン酸カルシウム７００g、トルエン１４００g、
鉱油８８g、メタノール１７５g、塩化カルシウム８.５g
および消石灰２８５gを入れ、４０℃〜５０℃の水浴中
に設置した。攪拌しながら炭酸ガス導入管により炭酸ガ
スを８５５ml／分の流量で８０分間バブリングした。以
下、実施例１と同様の操作を行い、清澄な組成物９１０
gを得た。得られた組成物の油溶性スルホン酸カルシウ
ムの含有量は２８.５重量％で、炭酸カルシウム含有量
は２４.０重量％、水酸化カルシウム含有量は５.０重量
％であった。Comparative Example 1 700 g of commercially available calcium petroleum sulfonate having an average molecular weight of about 1030, 1400 g of toluene, were placed in a 5-liter four-necked flask equipped with a reflux condenser, a thermometer, and a carbon dioxide gas introducing tube.
Mineral oil 88g, methanol 175g, calcium chloride 8.5g
And 285 g of slaked lime were placed in a water bath at 40 ° C to 50 ° C. While stirring, carbon dioxide gas was bubbled through the carbon dioxide gas introducing tube at a flow rate of 855 ml / min for 80 minutes. Thereafter, the same operation as in Example 1 was performed, and a clear composition 910 was obtained.
g was obtained. The resulting composition had an oil-soluble calcium sulfonate content of 28.5% by weight, a calcium carbonate content of 24.0% by weight, and a calcium hydroxide content of 5.0% by weight.
【００２６】比較例２ 塩化カルシウムを使用せずに行った以外は、実施例１と
同様に処理し、石油スルホン酸亜鉛を２７.４重量％、
炭酸カルシウムを２４.１重量％、水酸化カルシウムを
３.５重量％含有する清澄な組成物を得た。Comparative Example 2 The same treatment as in Example 1 was carried out except that calcium chloride was not used, and zinc petroleum sulfonate was used in an amount of 27.4% by weight.
A clear composition containing 24.1% by weight of calcium carbonate and 3.5% by weight of calcium hydroxide was obtained.
【００２７】表１に、実施例１〜５、比較例１〜２で得
られた組成物の成分と市販潤滑剤の成分を示した。表２
〜表５に、実施例、比較例で示した組成物および市販潤
滑剤の性能面での比較を示した。各表の中で市販品１と
２は、油溶性スルホン酸カルシウム組成物、市販品３は
直鎖・分岐アルキルＺnＤＴＰ、市販品４は直鎖アルキ
ルＺnＤＴＰを示す。また市販品５は塩素化パラフィン
（塩素分５０％）を用いた。Table 1 shows the components of the compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and the components of the commercially available lubricant. Table 2
Table 5 shows a comparison of the compositions shown in Examples and Comparative Examples and commercial lubricants in terms of performance. In each table, commercially available products 1 and 2 represent oil-soluble calcium sulfonate compositions, commercially available product 3 represents linear / branched alkyl ZnDTP, and commercial product 4 represents linear alkyl ZnDTP. Commercially available product 5 used chlorinated paraffin (chlorine content 50%).
【００２８】[0028]
【表１】 ＊１）透過型電子顕微鏡で測定した。[Table 1] * 1) Measured with a transmission electron microscope.
【００２９】[0029]
【表２】 ＊１）各組成物をマシン油（４０℃動粘度４６mm2／s）
に５重量％添加した油を供試油として、耐圧性を曽田式
四球試験機によるステップ法で焼付が生じるまでの最大
油圧荷重として測定した。 ［試験条件：回転数＝２００rpm、ステップ荷重＝０.５
kgf／cm2、試験温度＝室温］[Table 2] * 1) Each composition was machine oil (Kinematic viscosity at 40 ° C: 46 mm 2 / s)
5% by weight was used as a test oil, and the pressure resistance was measured as the maximum hydraulic load until seizure occurred by a step method using a Soda four-ball testing machine. [Test conditions: rotation speed = 200 rpm, step load = 0.5
kgf / cm 2 , test temperature = room temperature]
【００３０】[0030]
【表３】 [Table 3]
【００３１】＊１）各組成物をマシン油（４０℃動粘度
１０mm2／s）に３重量％添加した油を供試油として、さ
び止め油の湿潤試験（ＪＩＳ Ｋ ２２４６）に準拠し
てさび止め性をみた。Ａ級日数とは、試験鋼板の所定域
にさびが発生するまでの日数を表す。 ＊２）各組成物をマシン油（４０℃動粘度１０mm2／s）
に５重量％添加した油中に、鋳鉄板（ＦＣ２０）を半浸
漬し、１２０℃、３６０時間静置した後の鋳鉄板表面の
変色または腐食度合を観察した。（○；変化なし、△；
わずかにくすみあり、×；中程度の変色、××；著しい
変色・腐食）* 1) An oil obtained by adding 3% by weight of each composition to a machine oil (kinematic viscosity at 40 ° C., 10 mm 2 / s) as a test oil was used as a test oil in accordance with a wetting test of rust preventive oil (JIS K 2246). We saw rust prevention. The class A days refers to the number of days until rust occurs in a predetermined area of the test steel sheet. * 2) Each composition was machine oil (40 ° C kinematic viscosity 10 mm 2 / s)
The cast iron plate (FC20) was half-immersed in oil added with 5% by weight, and the surface of the cast iron plate was discolored or corroded after standing at 120 ° C. for 360 hours. (○; no change, △;
Slightly dull, x: moderate discoloration, xx; remarkable discoloration / corrosion)
【００３２】[0032]
【表４】 [Table 4]
【００３３】＊１）各組成物をマシン油（４０℃動粘度
１０mm2／s）に５重量％添加した油中に、アルミニウム
板（ＡＤＣ１２）および銅板を別々に全浸漬し、１２０
℃、３６０時間静置した後の金属板表面の変色または腐
食度合を観察した。銅板の変色度合は、石油製品銅板腐
食試験方法（ＪＩＳ Ｋ ２５１３）の銅板腐食基準に
準拠した変色番号（細分記号）で表した。* 1) An aluminum plate (ADC12) and a copper plate were completely immersed separately in oil obtained by adding 5% by weight of each composition to a machine oil (kinematic viscosity at 40 ° C., 10 mm 2 / s), and then 120
After standing at 360 ° C. for 360 hours, the surface of the metal plate was observed for discoloration or corrosion. The degree of discoloration of the copper plate was represented by a discoloration number (subdivision symbol) based on the copper plate corrosion standard of the petroleum product copper plate corrosion test method (JIS K 2513).
【００３４】[0034]
【表５】 ＊１）各組成物を工業用流動パラフィンに２０重量％添
加した油を、潤滑油熱安定性試験（ＪＩＳ Ｋ ２５４
０）に準拠して、１２０℃で４８０時間試験した。[Table 5] * 1) Lubricating oil thermal stability test (JIS K 254) was conducted by adding 20% by weight of each composition to industrial liquid paraffin.
Tested at 120 ° C. for 480 hours according to 0).
【００３５】[0035]
【発明の効果】表２より実施例１〜５の組成物は、比較
例１および市販品１の組成物と、炭酸カルシウム、水酸
化カルシウム等の含有量が、おおよそ類似しているにも
かかわらず、耐圧性で顕著な優位性があることが確かめ
られた。また表３に示したさび止め性においても、本発
明の組成物は高度に塩基化された組成物にもかかわら
ず、他の組成物に比べて格段に優れた性能を持つことが
明らかである。これらの結果は、本発明の組成物が芳香
族炭化水素スルホン酸の亜鉛塩からなることに起因して
いることを示している。According to Table 2, the compositions of Examples 1 to 5 are similar to the compositions of Comparative Example 1 and the commercially available product 1 although the contents of calcium carbonate, calcium hydroxide and the like are almost similar. It was confirmed that there was a remarkable advantage in pressure resistance. Also, in the rust preventive properties shown in Table 3, it is apparent that the composition of the present invention has remarkably superior performance as compared with other compositions despite the highly basic composition. . These results indicate that the composition of the present invention is derived from the zinc salt of aromatic hydrocarbon sulfonic acid.
【００３６】本発明の組成物は、表４に示したように、
アルミニウム、銅等の非鉄金属に対しても悪影響を及ぼ
さないことが確認できた。また、表５に示したように高
温雰囲気において、市販潤滑剤の一部がゲル化や多量の
析出物を発生するのに対し、本発明の組成物は十分な安
定性を有している。これらのことは、本発明の組成物
が、アルミニウムや銅などの非鉄金属と接触または接触
する可能性のある潤滑油にも、さらには高温条件で長時
間使用される潤滑油にも支障なく使用できることを示し
ている。The composition of the present invention, as shown in Table 4,
It has been confirmed that there is no adverse effect on non-ferrous metals such as aluminum and copper. Further, as shown in Table 5, in a high-temperature atmosphere, a part of the commercially available lubricant generates gelation and a large amount of precipitate, whereas the composition of the present invention has sufficient stability. These facts indicate that the composition of the present invention can be used without trouble in lubricating oils that may or may come into contact with non-ferrous metals such as aluminum and copper, and also in lubricating oils that are used for a long time under high temperature conditions. Indicates that you can do it.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 赤田 民生 兵庫県西宮市芦原町10−33 株式会社松村 石油研究所内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Tamio Akada 10-33 Ashiharacho, Nishinomiya City, Hyogo Prefecture Matsumura Oil Research Laboratory Co., Ltd.
Claims (7)
水酸化カルシウムを含む溶剤中で、使用する水酸化カル
シウムの量に対して、１〜５重量％の塩化カルシウムを
併用して水酸化カルシウムを炭酸化することによって得
られる、油溶性芳香族炭化水素スルホン酸亜鉛塩中に微
粒子の炭酸カルシウムと微粒子の水酸化カルシウムを分
散させた過塩基性スルホン酸亜鉛からなる極圧添加剤。1. An oil-soluble zinc zinc aromatic sulfonate,
An oil-soluble aromatic hydrocarbon obtained by carbonating calcium hydroxide in combination with 1 to 5% by weight of calcium chloride in a solvent containing calcium hydroxide based on the amount of calcium hydroxide used. An extreme pressure additive comprising an overbased zinc sulfonate in which fine particles of calcium carbonate and fine particles of calcium hydroxide are dispersed in a zinc sulfonate salt.
水酸化カルシウムを含む溶剤中で、水酸化カルシウムを
炭酸化することによって得られる、油溶性芳香族炭化水
素スルホン酸亜鉛塩中に微粒子の炭酸カルシウムと微粒
子の水酸化カルシウムを分散させてなる過塩基性スルホ
ン酸亜鉛に、塩化カルシウム水溶液を加え、還流温度ま
で加熱し、脱水することにより得られる極圧添加剤。2. An oil-soluble zinc aromatic sulfonate,
An overbased obtained by dispersing fine-particle calcium carbonate and fine-particle calcium hydroxide in an oil-soluble aromatic hydrocarbon sulfonate zinc salt obtained by carbonating calcium hydroxide in a solvent containing calcium hydroxide. Extreme pressure additive obtained by adding calcium chloride aqueous solution to water-soluble zinc sulfonate, heating to reflux temperature and dehydrating.
油芳香族成分スルホン酸および合成系アルキルアリール
スルホン酸よりなる群より選ばれた油溶性のスルホン酸
である請求項１〜２記載の極圧添加剤。3. The electrode according to claim 1, wherein the aromatic hydrocarbon sulfonic acid is an oil-soluble sulfonic acid selected from the group consisting of an aromatic component sulfonic acid of petroleum-based lubricating oil and a synthetic alkylaryl sulfonic acid. Pressure additive.
が、２０〜５０重量％である請求項１〜２記載の極圧添
加剤。4. The extreme pressure additive according to claim 1, wherein the content of the zinc aromatic hydrocarbon sulfonate is 20 to 50% by weight.
を１５〜４０重量％含有する請求項１〜２記載の極圧添
加剤。5. The extreme pressure additive according to claim 1, which contains 15 to 40% by weight of calcium carbonate having a particle size of 0.05 μm or less.
ムを２〜１０重量％分散させた請求項１〜２記載の極圧
添加剤。6. The extreme pressure additive according to claim 1, wherein 2 to 10% by weight of calcium hydroxide having a particle size of 0.05 μm or less is dispersed.
る工業用潤滑油。7. An industrial lubricating oil containing the extreme pressure additive according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21989097A JP2931570B2 (en) | 1996-10-30 | 1997-07-30 | Extreme pressure additives and industrial lubricants |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30561496 | 1996-10-30 | ||
| JP8-305614 | 1996-10-30 | ||
| JP21989097A JP2931570B2 (en) | 1996-10-30 | 1997-07-30 | Extreme pressure additives and industrial lubricants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10183152A true JPH10183152A (en) | 1998-07-14 |
| JP2931570B2 JP2931570B2 (en) | 1999-08-09 |
Family
ID=26523391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21989097A Expired - Fee Related JP2931570B2 (en) | 1996-10-30 | 1997-07-30 | Extreme pressure additives and industrial lubricants |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931570B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256695A (en) * | 1999-03-05 | 2000-09-19 | Kyodo Yushi Co Ltd | Water soluble lubricant for metal working |
| JP2005330948A (en) * | 2004-05-21 | 2005-12-02 | Mitsuo Kobayashi | Method and device for tuning engine |
| JP2006182809A (en) * | 2004-12-24 | 2006-07-13 | Sumitomo Metal Ind Ltd | Lubricating agent composition for cold plastic working and cold plastic working method using the same |
| JP2006328148A (en) * | 2005-05-24 | 2006-12-07 | Toyota Motor Corp | Grease additive |
| JP2007332383A (en) * | 2007-08-06 | 2007-12-27 | Nippon Oil Corp | Grease composition |
| JP2009293038A (en) * | 2000-06-02 | 2009-12-17 | Chemtura Corp | Clarification method for oil dispersion comprising overbased detergent containing calcite |
-
1997
- 1997-07-30 JP JP21989097A patent/JP2931570B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256695A (en) * | 1999-03-05 | 2000-09-19 | Kyodo Yushi Co Ltd | Water soluble lubricant for metal working |
| JP4531882B2 (en) * | 1999-03-05 | 2010-08-25 | 協同油脂株式会社 | Water-soluble metalworking fluid |
| JP2009293038A (en) * | 2000-06-02 | 2009-12-17 | Chemtura Corp | Clarification method for oil dispersion comprising overbased detergent containing calcite |
| JP2005330948A (en) * | 2004-05-21 | 2005-12-02 | Mitsuo Kobayashi | Method and device for tuning engine |
| JP2006182809A (en) * | 2004-12-24 | 2006-07-13 | Sumitomo Metal Ind Ltd | Lubricating agent composition for cold plastic working and cold plastic working method using the same |
| JP4611014B2 (en) * | 2004-12-24 | 2011-01-12 | 住友金属工業株式会社 | Lubricant composition for cold plastic working and cold plastic working method using the same |
| JP2006328148A (en) * | 2005-05-24 | 2006-12-07 | Toyota Motor Corp | Grease additive |
| JP2007332383A (en) * | 2007-08-06 | 2007-12-27 | Nippon Oil Corp | Grease composition |
| JP4659002B2 (en) * | 2007-08-06 | 2011-03-30 | Ｊｘ日鉱日石エネルギー株式会社 | Grease composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2931570B2 (en) | 1999-08-09 |
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