JP2883134B2 - Grease composition with excellent rust prevention - Google Patents
Grease composition with excellent rust preventionInfo
- Publication number
- JP2883134B2 JP2883134B2 JP33869489A JP33869489A JP2883134B2 JP 2883134 B2 JP2883134 B2 JP 2883134B2 JP 33869489 A JP33869489 A JP 33869489A JP 33869489 A JP33869489 A JP 33869489A JP 2883134 B2 JP2883134 B2 JP 2883134B2
- Authority
- JP
- Japan
- Prior art keywords
- rust
- grease
- grease composition
- water
- oil
- 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
Links
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- Lubricants (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、錆止め性に優れた潤滑グリース組成物に関
するものである。より詳しくは、自動車部品のように走
行中における、路上の水、塩水或いは海水などの浸入に
より、また、製鉄産業では、冷却水の浸入により、錆が
問題となる転がり軸受部品などの潤滑部に使用されるグ
リース組成物に関するものである。Description: TECHNICAL FIELD The present invention relates to a lubricating grease composition having excellent rust prevention properties. More specifically, lubricating parts such as rolling bearing parts where rust becomes a problem due to ingress of water, salt water or seawater on the road during traveling like automobile parts, and in the steel industry, due to infiltration of cooling water. It relates to the grease composition used.
（従来の技術） 錆の発生が問題となる転がり軸受などは、適当なシー
ルやその他機構上の対策によって、直接、錆の起因とな
る物質の混入を防いでいる。例えば、自動車において
は、直接泥水等がかからない位置に配置したり、泥よけ
等を取付けたりの対策が行なわれている。しかし、転が
り軸受は機構上、完全な密封は不可能であるため、使用
する潤滑グリースにも、錆止め性能を求める事が通常で
ある。(Prior art) Rolling bearings and the like, in which rust is a problem, are prevented from being directly mixed with substances that cause rust by using appropriate seals and other mechanical measures. For example, in an automobile, measures are taken such as disposing it at a position where muddy water and the like are not directly applied, attaching a mudguard and the like. However, since a rolling bearing cannot be completely sealed due to its mechanism, it is usual that lubricating grease to be used is required to have rust prevention performance.
（発明が解決しようとする課題） このグリースに対する錆止め性の要求は近年、特に厳
しさを増している。例えば、自動車では海岸での走行
や、路面凍結防止の為に食塩を散布した海外での道路の
走行等、自動車の使用の多様化に伴い、グリースに対す
る錆止め性の要求が強くなってきている。また、製鉄産
業の連続鋳造設備でも使用するモールディングパウダー
の変遷に伴って、冷却水中にその成分の一部が溶解し、
発錆を促進させている事など、グリースに対する錆止め
性能向上の要求が強まってきているが、この要求に応え
るべき防錆性能を備えたグリースは無いのが現状であ
り、解決すべき課題とされてきた。(Problems to be Solved by the Invention) In recent years, requirements for rust prevention properties of grease have been particularly severe. For example, with the diversification of use of automobiles such as traveling on the coast and traveling on roads abroad where salt is sprayed to prevent freezing of the road surface, the demand for grease for rust prevention is increasing. In addition, along with the transition of molding powder used in continuous casting equipment in the steelmaking industry, some of its components dissolved in cooling water,
There is an increasing demand for improved grease rust prevention performance, such as the promotion of rust generation.However, there is no grease with rust prevention performance that meets this requirement, and this is a problem to be solved. Have been.
（課題を解決するための手段） 本発明は、上記課題を解決すべく鋭意検討した結果達
成されたものであり、潤滑基油および増ちょう剤からな
るグリース組成物に、錆止め剤である油溶性有機インヒ
ビターとしての有機スルフォン酸塩、水溶性無機不働態
化剤、およびHLBが1.5〜９の非イオン界面活性剤を各々
0.1〜10重量％配合したことを特徴とする錆止め性に優
れたグリース組成物に関するものである。すなわち、本
発明は、従来より既知である錆止め剤をその溶解性に着
目し、油溶性、水溶性、界面活性剤に分類し、グリース
添加剤として併用することによって、従来では達し得な
かった錆止め性能を有するグリース組成物を得たもので
ある。(Means for Solving the Problems) The present invention has been achieved as a result of intensive studies to solve the above-mentioned problems, and the grease composition comprising a lubricating base oil and a thickener has an oil-soluble property as a rust inhibitor. Organic sulfonate as an organic inhibitor, a water-soluble inorganic passivator, and a nonionic surfactant having an HLB of 1.5 to 9 respectively
The present invention relates to a grease composition having excellent rust prevention properties, characterized in that the grease composition is blended at 0.1 to 10% by weight. That is, the present invention focuses on the solubility of a conventionally known rust inhibitor, and classifies it into oil-soluble, water-soluble, and a surfactant, and by using it as a grease additive, a rust inhibitor that could not be achieved in the past. A grease composition having performance was obtained.
油溶性の錆止め剤は、有機インヒビターとも呼ばれ、
単独あるいは、有機インヒビター同志の組み合わせ使用
の効果は多く報告されている。これらは、カルボン酸、
カルボン酸塩、スルフォン酸塩、アミンなどの極性基を
もつ化合物で、金属表面に極性基を向け配列、吸着する
ことによって防錆被膜を作るとされている。本発明で
は、油溶性を有機インヒビターとして有機スルフォン酸
塩を使用する。有機スルフォン酸塩は、一般にRSO3・Ｍ
で示されるもので、酸側のRSO3としては、例えば、石油
スルフォン酸、ジノニルナフタレンスルフォン酸が挙げ
られる。また、アルカリ側のＭとしては、Ba,Ca,Zn,Pb,
Na,Li等の金属および、NH4，H2N(CH2)2NH2などのアミン
が挙げられる。しかし、有機インヒビターのみの錆止め
能力は以下に述べる無機不働態化剤ほど強力ではなく、
特に塩水条件下では不満足であった。従って、有機イン
ヒビターのみの添加によるグリースの錆止め性の改良は
限界に達していた。Oil-soluble rust inhibitors are also called organic inhibitors,
Many effects have been reported, either alone or in combination with other organic inhibitors. These are carboxylic acids,
It is a compound having a polar group such as carboxylate, sulfonate, amine, etc., which is said to form a rust preventive film by arranging and adsorbing the polar group on the metal surface. In the present invention, an organic sulfonate is used as an oil-soluble organic inhibitor. Organic sulfonates are generally RSO 3 · M
In the formula, RSO 3 on the acid side includes, for example, petroleum sulfonic acid and dinonylnaphthalenesulfonic acid. Further, as M on the alkali side, Ba, Ca, Zn, Pb,
Examples include metals such as Na and Li, and amines such as NH 4 and H 2 N (CH 2 ) 2 NH 2 . However, the rust inhibiting ability of only organic inhibitors is not as strong as the inorganic passivators described below,
In particular, it was unsatisfactory under salt water conditions. Therefore, the improvement of the rust-preventing property of the grease by adding only the organic inhibitor has reached its limit.
また、本発明において水溶性錆止め剤としては、クロ
ム酸塩、亜硝酸塩、モリブデン酸塩、タングステン酸塩
のち少なくとも１種を使用する。これらは、無機不働態
化剤と言われており、Na塩がその代表として挙げられ、
これも単独での使用例、効果は既知のものである。ま
た、界面活性剤の併用により、油への分散を良くしたも
のも市販されているが、これらも使用可能である。不働
態化剤は、金属の腐食電位を貴の方向へ移動させ、不働
態化させる作用により効果を示すと言われている。この
錆止め性の効果は群を抜いており、グリースへの使用例
も少なくないが、これら物質が水溶性であり、水に溶解
しないことには拡散ができないという欠点を有する。即
ちグリースに使用した場合、作用するのはグリースと金
属面の界面に存在するもののみで、他は、有効に作用し
ておらず、錆止め性の限界もこの点にあった。In the present invention, as the water-soluble rust inhibitor, at least one of chromate, nitrite, molybdate and tungstate is used. These are said to be inorganic passivators, Na salts of which are mentioned as representatives,
This is also a single use example and the effect is known. In addition, there are also commercially available products in which the dispersion in oil is improved by using a surfactant in combination, but these can also be used. It is said that the passivating agent exhibits an effect by an action of moving the corrosion potential of the metal in a noble direction and passivating the metal. This rust-preventing effect is outstanding, and there are many examples of use in grease. However, these substances have the disadvantage that they are water-soluble and cannot be diffused unless dissolved in water. In other words, when used for grease, only those present at the interface between the grease and the metal surface act, the others are not effectively acting, and the rust-prevention limit is also at this point.
本発明は、上記油溶性有機インヒビターと水溶性無機
不働態化剤を使用した上で、さらに親水性親油性バラン
ス（HLB）が1.5ないし、９の非イオン界面活性剤を併用
することに特徴を有する。この非イオン界面活性剤も、
有機インヒビターの一種として数えられることもある
が、単独での錆止め能力は上記２種より非常に小さい。
HLBが1.5ないし９の非イオン界面活性剤としては、グリ
セリン脂肪酸エステル、ポリグリセリン脂肪酸エステ
ル、ソルビタン脂肪酸エステル、ペンタエリスリトル脂
肪酸エステル、ポリオキシエチレン脂肪酸エステル等の
エステル化合物、ポリオキシエチレンアルキルフェニル
エーテル等のエーテル化合物が上げられる。The present invention is characterized in that the oil-soluble organic inhibitor and the water-soluble inorganic passivating agent are used, and a nonionic surfactant having a hydrophilic lipophilic balance (HLB) of 1.5 to 9 is further used. Have. This nonionic surfactant also
Although it may be counted as a kind of organic inhibitor, the rust inhibitor ability by itself is much smaller than the above two kinds.
Nonionic surfactants having an HLB of 1.5 to 9 include ester compounds such as glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester and polyoxyethylene fatty acid ester, and polyoxyethylene alkylphenyl ether. Of ether compounds.
また、油溶性有機インヒビター、水溶性無機不働態化
剤および非イオン界面活性剤の添加量を各々0.1ない
し、10重量％としたのは、0.1重量％未満では、錆止め
能力が不足しており、10重量％より多いと、基材グリー
スの耐熱性、せん断安定性などの物性に影響を与え、長
時間の使用に耐え得ないグリースとなる。また、本発明
は潤滑基油と増ちょう剤からなるグリース組成物を基材
とするが、潤滑基油、増ちょう剤の種類を問わず適用可
能である。例えば、潤滑基油としては、鉱油、ジエステ
ル、ポリオールエステルに代表されるエステル系合成
油、ポリαオレフィンに代表される合成炭化水素油、ア
ルキルジフェニルエーテルに代表されるエーテル系合成
油が上げられ、また増ちょう剤としては、Li石ケンに代
表される石けん系増ちょう剤、及び複合石けん系増ちょ
う剤、ジウレアに代表されるウレア系増ちょう剤、ベン
トナイトに代表される無機系増ちょう剤、ポリテトラフ
ルオロエチレン（PTFE）に代表される有機系増ちょう剤
などが挙げられる。Further, the addition amount of each of the oil-soluble organic inhibitor, the water-soluble inorganic passivating agent and the nonionic surfactant was set to 0.1 to 10% by weight. If the content is more than 10% by weight, physical properties such as heat resistance and shear stability of the base grease are affected, and the grease cannot be used for a long time. Further, the present invention is based on a grease composition comprising a lubricating base oil and a thickener, but is applicable regardless of the type of the lubricating base oil and the thickener. For example, as the lubricating base oil, mineral synthetic oils, diesters, ester synthetic oils represented by polyol esters, synthetic hydrocarbon oils represented by poly-α-olefins, ether synthetic oils represented by alkyl diphenyl ethers, and As the thickener, soap-based thickeners represented by Li soap, composite soap-based thickeners, urea-based thickeners represented by diurea, inorganic thickeners represented by bentonite, poly Organic thickeners represented by tetrafluoroethylene (PTFE) are exemplified.
（作用） 本発明における有機インヒビター、無機不働態化剤、
界面活性剤の組み合わせは、各々錆止め能力以上の効果
を発揮する。いわゆる相乗効果と言われるものだが、こ
れは、各々の成分が持っている錆止め能力に加え、他の
成分が効果的に働ける作用をするためと考えられる。例
えば、本発明に使用した界面活性剤はHLBが1.5ないし９
の非イオン界面活性剤である。非イオン系である理由
は、電気的に中性を保て、かつ適当なHLBのものを選定
できるのが最も大きな理由である。HLBが1.5ないし９の
範囲のものは、用途としては、消泡剤、W/O型乳化剤、
潤滑剤等があり、油系溶媒に主に使用される。従って、
発錆の原因となる水をグリース基油中にエマルジョンと
してとり込む作用をし、有機インヒビターと、水に含ま
れる腐食物質の金属表面上の交換を妨げる。また、その
エマルジョン中に無機不働態化剤も溶解させることによ
り、エマルジョンがそのキャリヤとなってグリース中の
無機不働態化剤の拡散を補助する。(Action) The organic inhibitor, the inorganic passivating agent according to the present invention,
Combinations of surfactants each exhibit an effect that is greater than the rust inhibiting ability. This is a so-called synergistic effect, which is considered to be due to the effect that the other components work effectively in addition to the rust preventing ability of each component. For example, the surfactant used in the present invention has an HLB of 1.5 to 9
Is a nonionic surfactant. The main reason for the non-ionic system is that it can be kept electrically neutral and an appropriate HLB can be selected. Those having an HLB in the range of 1.5 to 9 are used as defoamers, W / O emulsifiers,
There are lubricants, etc., which are mainly used for oil-based solvents. Therefore,
It acts to incorporate the water that causes rust into the grease base oil as an emulsion, preventing the exchange of organic inhibitors and corrosive substances contained in the water on metal surfaces. Also, by dissolving the inorganic passivating agent in the emulsion, the emulsion serves as the carrier to assist the diffusion of the inorganic passivating agent in the grease.
また、本発明において有機インヒビターとして有機ス
ルフォン酸塩を選定したのは、それ自身の錆止め能力に
加え、水に対する溶解度が小さいことが挙げられる。カ
ルボン酸等は、若干でも水に溶解した場合、酸性を示
し、無機不働態化剤を分解させてしまう。従って、本発
明による有機インヒビター、無機不働態化剤、界面活性
剤の組み合わせによって、単独の使用で考えられるより
はるかに大きい錆止め性を有するグリースを提供するこ
とができる。The reason why the organic sulfonate is selected as the organic inhibitor in the present invention is that it has low solubility in water in addition to its own rust inhibiting ability. When slightly dissolved in water, carboxylic acid and the like show acidity and decompose the inorganic passivating agent. Thus, the combination of the organic inhibitors, inorganic passivators, and surfactants according to the present invention can provide greases with much greater rust inhibiting properties than would be conceivable with a single use.
（実施例） 本発明を次の実施例および比較例により説明する。(Examples) The present invention will be described with reference to the following examples and comparative examples.
実施例１〜6,比較例１〜７ 基グリース97.5g（実施例５のみは、97.0g）に表1,2
に示す錆止め添加剤を加え、３段ロールミルで混練し、
実施例１〜６および比較例１〜７のグリースを製造し
た。これ等のグリースにつき軸受防錆試験を行い、得た
結果を表１および２に示す。尚、実施例、比較例で使用
した基グリースは全て同一のものである。その内容を下
記する。Examples 1 to 6, Comparative Examples 1 to 7 97.5 g of base grease (97.0 g for Example 5 only)
Add the rust inhibitor shown in the above, knead with a three-stage roll mill,
Greases of Examples 1 to 6 and Comparative Examples 1 to 7 were produced. A bearing rust prevention test was performed on these greases, and the obtained results are shown in Tables 1 and 2. The base greases used in the examples and comparative examples are all the same. The contents are described below.
・基グリースの内容 増ちょう剤：トリレンジイソシアネートとパラトルイジ
ンからなるジウレア化合物 基油:40℃の動粘度が97.0cStである、アルキルジフェニ
ルエーテル油 ちょう度:NLGINo,2グレード また、使用した添加剤は、スルフォネートは全て市販
のジノニルナフタレンスルフフォネートを使用し、亜硝
酸ソーダは、市販の100メッシュ通過のものを使用し
た。・ Contents of base grease Thickener: diurea compound consisting of tolylene diisocyanate and paratoluidine Base oil: kinematic viscosity at 40 ° C is 97.0 cSt, alkyl diphenyl ether oil Consistency: NLGINo, 2 grade , And sulfonates were all commercially available dinonylnaphthalenesulfonates, and sodium nitrite was commercially available through a 100 mesh.
亜硝酸ソーダ分散液とは、亜硝酸ソーダを油系に分散
させ易くするため、界面活性剤を含有しているもので、
亜硝酸ソーダの有効成分量としては、40重量％の市販品
であり、使用している界面活性剤は不明である。Sodium nitrite dispersion is a solution containing a surfactant to facilitate dispersing sodium nitrite in oil system.
The amount of the active ingredient of sodium nitrite is a commercial product of 40% by weight, and the surfactant used is unknown.
尚、軸受防錆試験方法は、ASTM D 1743−73に基づく
もので、条件を厳しくするためにグリース充填後に浸せ
きさせる水を蒸留水でなく、0.5重量％塩水、3.0重量％
塩水に変更した。評価は、軸受の外輪レース面の発錆状
況の観察によるもので、下記による。 Note that the bearing rust prevention test method is based on ASTM D 1743-73. In order to tighten the conditions, water to be immersed after filling with grease is not distilled water, but 0.5% by weight salt water, 3.0% by weight.
Changed to salt water. The evaluation is based on observation of the rusting condition of the outer race surface of the bearing, and is as follows.
＃１… 発錆なし ＃２… 小錆３点以内 ＃３… ＃２より発錆の大きい、あるいは多いもの 実施例にて示された通り、本発明のグリース組成物
は、３％塩水下の軸受防錆試験でも発錆が見られなかっ
た。# 1: No rusting # 2: Less than 3 small rusts # 3: Greater or more rusting than # 2 As shown in the examples, the grease composition of the present invention was obtained under 3% salt water. No rust was observed in the bearing rust test.
比較例にて示されたように、本発明による錆止め添加
剤の組み合わせの内、１種が抜けただけで、錆止め性は
極端に劣るようになる。また、油溶性の有機インヒビタ
ーも有機スルフォン酸塩以外では効果がない。さらに、
スルフォン酸塩、無機不働態化剤、界面活性剤を併用し
ても、その界面活性剤のHLBが、９を超えると防錆性が
劣るようになる。これは、O/Wエマルジョンの形成によ
り、グリース基油が錆止め剤を含んだ形で、水中に拡散
してしまうためと考えられる。As shown in the comparative examples, only one of the combinations of the rust inhibitor additives according to the present invention is omitted, and the rust inhibiting property becomes extremely poor. Also, oil-soluble organic inhibitors have no effect except for organic sulfonates. further,
Even when a sulfonate, an inorganic passivating agent, and a surfactant are used in combination, if the HLB of the surfactant exceeds 9, the rust-preventive properties become poor. This is probably because the formation of the O / W emulsion causes the grease base oil to diffuse into water in a form containing a rust inhibitor.
（発明の効果） 以上の例から明らかなように、本発明によるグリース
組成物は、厳しい条件下におても優れた錆止め性能を有
していることが示され、錆が問題となる潤滑部に適用で
きるグリースと成り得た。(Effects of the Invention) As is clear from the above examples, the grease composition according to the present invention has been shown to have excellent rust prevention performance even under severe conditions, and the lubricating part where rust is a problem. It can be applied to grease.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ１０Ｎ 10:02 10:04 30:12 30:14 50:10 (58)調査した分野(Int.Cl.6，ＤＢ名) C10M 161/00,135/10,125/20 C10M 129/74,145/38 C10N 30:12,30:14,50:10 Continuation of the front page (51) Int.Cl. 6 identification symbol FI // C10N 10:02 10:04 30:12 30:14 50:10 (58) Investigated field (Int.Cl. 6 , DB name) C10M 161 / 00,135 / 10,125 / 20 C10M 129 / 74,145 / 38 C10N 30: 12,30: 14,50: 10
Claims (1)
なる錆止め性に優れたグリース組成物であって、錆止め
添加剤である油溶性有機インヒビターとしての有機スル
フォン酸塩、水溶性無機不働態化剤、およびHLBが1.5〜
９の非イオン界面活性剤を各々0.1〜10重量％配合した
ことを特徴とする、前記錆止め性に優れたグリース組成
物。1. A grease composition comprising a lubricating base oil, a thickener, and an additive, which is excellent in rust-preventing properties. The rust-preventive additive is an organic sulfonate as an oil-soluble organic inhibitor, Activator and HLB 1.5 ~
9. The grease composition having excellent rust-preventive properties, wherein each of the non-ionic surfactants is mixed with 0.1 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33869489A JP2883134B2 (en) | 1989-12-28 | 1989-12-28 | Grease composition with excellent rust prevention |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33869489A JP2883134B2 (en) | 1989-12-28 | 1989-12-28 | Grease composition with excellent rust prevention |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200898A JPH03200898A (en) | 1991-09-02 |
| JP2883134B2 true JP2883134B2 (en) | 1999-04-19 |
Family
ID=18320581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33869489A Expired - Lifetime JP2883134B2 (en) | 1989-12-28 | 1989-12-28 | Grease composition with excellent rust prevention |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2883134B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112010005707T5 (en) | 2010-06-28 | 2013-05-02 | Kyodo Yushi Co., Ltd. | Lubricant composition and mechanical component |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3519417B2 (en) * | 1991-10-04 | 2004-04-12 | 協同油脂株式会社 | Grease composition for bearings with excellent low starting torque for high temperature, high speed and high load application |
| IT1263745B (en) * | 1992-01-22 | 1996-08-27 | Ntn Toyo Bearing Co Ltd | CONTACT ROLLING BEARING CLOSED WITH GREASE |
| JP2544560B2 (en) * | 1992-01-22 | 1996-10-16 | エヌティエヌ株式会社 | Grease composition for bearing encapsulation |
| JP2557597B2 (en) * | 1992-01-22 | 1996-11-27 | エヌティエヌ株式会社 | Rolling bearing with grease for alternator |
| JP3500734B2 (en) * | 1993-11-11 | 2004-02-23 | 日本精工株式会社 | Ball bearings coated with anti-rust lubricant |
| JP2005290278A (en) | 2004-04-02 | 2005-10-20 | Ntn Corp | Rustproof grease composition, grease-filled bearing and rust preventive |
| JP5005931B2 (en) * | 2006-03-03 | 2012-08-22 | Ｎｔｎ株式会社 | Rolling bearings for automotive electrical equipment and accessories |
| JP4877343B2 (en) * | 2009-03-05 | 2012-02-15 | 日本精工株式会社 | Rolling bearing |
-
1989
- 1989-12-28 JP JP33869489A patent/JP2883134B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112010005707T5 (en) | 2010-06-28 | 2013-05-02 | Kyodo Yushi Co., Ltd. | Lubricant composition and mechanical component |
| US9909080B2 (en) | 2010-06-28 | 2018-03-06 | Kyodo Yushi Co., Ltd. | Grease composition and mechanical part |
| DE112010005707B4 (en) | 2010-06-28 | 2022-04-07 | Kyodo Yushi Co., Ltd. | Lubricant composition and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03200898A (en) | 1991-09-02 |
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