JP3919444B2 - W / O emulsion type flame retardant hydraulic fluid - Google Patents
W / O emulsion type flame retardant hydraulic fluid Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、Ｗ／Ｏエマルション型難燃性油圧作動油に関するものであり、特には、特定のチアジアゾール化合物を含有する、金属材料、なかでも銅系材料に対する腐食防止性能と潤滑性能に優れたＷ／Ｏエマルション型難燃性油圧作動油に関する。
【０００２】
【従来の技術】
高熱源雰囲気にさらされる鉄鋼設備、ダイキャストマシーンなどの各種油圧装置に可燃性の鉱油系油圧作動油を用いると、突発的な油漏れにより火災の危険があるので、従来からこれらの設備には難燃性油圧作動油が用いられている。難燃性油圧作動油には、水−グリコール型、Ｗ／Ｏエマルション型、Ｏ／Ｗエマルション型などの含水系の難燃性油圧作動油と脂肪酸エステル型、リン酸エステル型などの合成油系のものがある。合成油系の難燃性油圧作動油は難燃性が充分でなかったり、毒性の問題があるため、実用性に欠けている。
Ｗ／Ｏエマルション型難燃性油圧作動油は、一般的に、基油約６０容量％に乳化剤を配合し、水約４０容量％を機械的に乳化したものであり、作動油としての特性を持たせるため、摩耗防止剤、防錆剤、酸化防止剤、抗菌剤、消泡剤等が適宜配合されている。この結果、Ｗ／Ｏエマルション型難燃性油圧作動油は、難燃性、潤滑性、廃水処理性に優れ、上記用途に多用されている。
【０００３】
Ｗ／Ｏエマルション型難燃性油圧作動油には、摩耗防止剤として、極圧性、摩耗防止性に優れたジチオリン酸亜鉛が広く用いられているが、ある種のジチオリン酸亜鉛は、銅部材又は銅含有部材等（以下、単に「銅部材」という）に対して腐食性が強く、また、水溶性抗菌剤も銅部材に対して好ましくない影響を及ぼすものが多いといわれている。銅部材は、反応性が比較的高い金属材料であるが、熱伝導性、加工性、経済性に優れており、油圧装置のオイルクーラーや油圧ポンプのピストンシューなどに広く採用されている。銅部材、ジチオリン酸亜鉛及び抗菌剤等は、油圧装置や油圧作動油を構成する材料として、特に経済性と効果を考慮すると非常に重要なものであるが、一方で、上述のように、銅部材の腐食をもたらし、腐食生成物は、油圧作動油を劣化してさらに腐食を促進するという問題もあった。
【０００４】
【発明が解決しようとする課題】
そこで、本発明は、摩耗防止剤や抗菌剤を含有する難燃性油圧作動油であっても、腐食防止作用と摩耗防止作用を持つ特定の化合物を配合して、潤滑性、エマルションの安定性といった難燃性油圧作動油の基本的な性能を失うことなく、特に銅部材に対して優れた腐食防止性能を有するＷ／Ｏエマルション型難燃性油圧作動油を提供することを課題とする。
【０００５】
【課題を解決するための手段】
本発明は、基油に界面活性剤を用いて水を分散させてなるＷ／Ｏエマルション型難燃性油圧作動油において、チアジアゾール骨格中の両炭素において炭素数５〜３０の炭化水素基を有する１〜４個の硫黄からなるスルフィド基又はポリスルフィド基により置換されたチアジアゾール誘導体を含有することからなるＷ／Ｏエマルション型難燃性油圧作動油であって、油圧作動油の銅部材に対する耐腐食効果を顕著に向上させたものである。
【０００６】
【発明の実施の態様】
本発明の油圧作動油に用いる基油には、鉱油、合成油及びそれらの混合油を用いることができる。前記鉱油は、原油を常圧蒸留及び／又は減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱蝋、水素化脱蝋、水素化精製、硫酸洗浄、白土処理等の潤滑油の精製に用いられる各種の精製処理を適宜組み合わせて得ることができる。
また、合成油としては、ポリ−α−オレフィン、低分子量エチレン・α―オレフィン共重合体，合成ナフテン、アルキルベンゼン等が挙げられる。
さらに、各種の鉱油基材を混合した混合油、あるいは合成油基材の混合油、及びそれら基材の任意な混合割合の混合油を使用することができる。安価に油圧作動油を提供する本発明の趣旨からは鉱油の占める割合が多い混合油又は鉱油単独で用いることが好ましい。
これらの基油の物性は、特に限定するものではないが、４０℃における動粘度が５〜１００mm2/sのものが好ましく、１０〜４０mm2/sのものがより好ましい。
【０００７】
本発明の油圧作動油に用いる水は、特に制限はないが、不純物や細菌の極めて少ない水を用いることが好ましい。
前記基油への水の配合割合は、０.１〜７０容量％が好ましく、難燃性、エマルション安定性及びエマルション粘度の観点からは、水分割合２０〜５５容量％がより好ましい。エマルジョンは、基油と水を界面活性剤とともに公知の方法で混合することにより得ることができるが、基油と水それぞれに好適な添加剤を配合した油側母液、水側母液を予め調製した後、両母液を強力に攪拌混合して得ることが好ましい。
【０００８】
前記界面活性剤（乳化剤）としては、非イオン系界面活性剤やイオン系界面活性剤などＷ／Ｏエマルションに用いられている周知のものを適宜用いることができる。具体的には、非イオン系界面活性剤として、アルキル化フェニルエーテル、脂肪酸エステルなどが挙げられ、また、アニオン系界面活性剤としては、Ｃａスルホネート、Ｂａスルホネート、Ｎａスルホネートなどがその一例として挙げられる。これらのうち、少なくとも１種以上の界面活性剤を、基油に対して０．５〜２０重量％、好ましくは１〜１０重量％添加する。
【０００９】
本発明に用いるチアジアゾール誘導体は、例えば、１,３,４−チアジアゾール骨格のものは、下記一般式（１）で表される化合物で、当該骨格中の両炭素の置換基であるスルフィド基又はポリスルフィド基中のＲ1及びＲ2がそれぞれ独立して炭素数５〜３０の炭化水素基、ｍ及びｎがそれぞれ独立して１〜４の整数からなるものである。
【化１】
【００１０】
なお、上記化合物中のＲ1及びＲ2の炭化水素基は、直鎖及び／又は分枝、飽和及び／又は不飽和のいずれでも良く、特に、炭素数５〜１５のものが好ましい。
【００１１】
本発明で用いるチアジアゾール化合物は、腐食防止剤として基油に対して０.０１〜５重量％、さらには０.０５〜２重量％、特には０.１〜１重量％配合することが好ましい。該ポリサルファイド化合物を前記の範囲で配合することにより、銅部材に対する防食効果は格段に向上し、銅製オイルクーラーの腐食減量を大幅に低減することができる。特に、ジチオリン酸亜鉛と併用しても，その効果は損なわれることなく、十分発揮される。
【００１２】
本発明の作動油には、周知の極圧剤、摩耗防止剤、防錆剤、酸化防止剤、抗菌剤、及び消泡剤などの添加剤を適宜配合することができる。
極圧剤としてジアルキルジチオリン酸亜鉛、硫黄系化合物など、摩耗防止剤としてリン系化合物など、防錆剤として金属スルホネートなど、酸化防止剤としてフェノール系、アミン系化合物など、抗菌剤（防ばい剤）としてＮ系化合物など、及び消泡剤としてシリコーン系化合物、ＰＭＡポリマーなどが挙げられる。これらの添加剤は、仕上がりの作動油に対して適宜添加すればよい。
特に本発明の作動油は、極圧剤、摩耗防止剤として使用されるジアルキルジチオリン酸亜鉛と併用してもその機能を損なわれることなく、その効果を十分発揮する。
また、前記各種の添加剤は、数種が予め混合されたいわゆる添加剤パッケージの形で用いることもできる。
【００１３】
上記の各種添加剤を基油、又は水に配合し、それぞれ母液を調製する．油母液及び水母液を上記の割合で混合し、高速ホモジナイザーなどの撹拌機を用いて、機械的に乳化してＷ／Ｏエマルションを得ることができる。
【００１４】
【実施例】
以下、実施例に基づいて、本発明のＷ／Ｏエマルジョン型難燃性油圧作動油をより詳細に説明するが、本発明はそれらにより何ら制限されるものではない。
実施例及び比較例のＷ／Ｏエマルション型難燃性油圧作動油を調製するに当たり、次の基材を用いた。
ａ）基油：パラフィン系鉱油。動粘度（４０℃）が１５mm2/s、粘度指数が９０、流動点が−１５℃。
ｂ）水：精製水
ｃ）添加剤：乳化剤（界面活性剤）としてＣａスルホネートなどを、摩耗防止剤としてジアルキルジチオリン酸亜鉛を、抗菌剤として油溶性アミンを使用し，腐食防止剤兼摩耗防止剤として前述した１,３,４-チアジアゾール化合物の式（１）において、Ｒ1、Ｒ2の合計炭素数が２２の炭化水素基、ｎ、ｍのそれぞれが平均で３のポリスルフィド基を有するチアジアゾール化合物の混合物を配合した。
これらの基材を、表１に示す割合で混合し、高速ホモジナイザーで機械的に撹拌乳化して実施例１及び比較例１のＷ／Ｏエマルション型難燃性油圧作動油を調製した。
【００１５】
【表１】
【００１６】
上記のようにして調製した実施例１及び比較例１のＷ／Ｏエマルション型難燃性油圧作動油について、その銅腐食防止性能はオイルクーラーをシミュレートした銅循環腐食試験における銅減量にて、また潤滑性はＬＦＷ−１試験による摩耗痕及び摩擦係数、及びベーンポンプでの耐摩耗性にて評価した。これらの試験条件を次に示す。
（1）オイルクーラーの銅減量試験
・ＪＩＳ Ｈ３３００ 銅合金継ぎ目無し管 Ｃ１２００Ｔりん脱酸銅
・管内径 ６ｍｍ
・流量：２０Ｌ／ｍｉｎ
・油量：６０Ｌ
・油温：６０℃
・時間：５００ｈｒ
・銅管の腐食減量を測定
(2) ＬＦＷ−１試験
・ブロック／リング：Ｈ−６０／Ｓ−１０
・油温：室温
・荷重：１００ｌｂｓ
・回転数：３００ｒｐｍ
・時間：３０ｍｉｎ
・ブロック摩耗痕幅を測定
(3) ベーンポンプの耐摩耗性試験
・ベーンポンプ：油研工業製ＰＶ−２Ｒ
・試験圧力：連続１４ＭＰａ
・油温：５０℃
・油量：５０Ｌ
・試験時間：５００ｈｒ
・評価：試験終了後のベーン、カムリングの摩耗量を測定
上記評価試験の結果を表２に示す。
【００１７】
【表２】
表２から明らかなように、銅部材に対して優れた腐食防止性能を有するとともに、潤滑性も優れていることがわかる。
【００１９】
【発明の効果】
本発明はＷ／Ｏエマルション型難燃性油圧作動油に特定のチアジアゾール誘導体を配合したため、ジチオリン酸亜鉛などの摩耗防止剤や抗菌剤を含有するものであっても、潤滑性といった難燃性油圧作動油としての基本的な性能を強化しつつ、銅部材に対して優れた腐食防止性能を有するという格別の効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a W / O emulsion-type flame retardant hydraulic fluid, and in particular, W having excellent corrosion prevention performance and lubrication performance for a metal material, particularly a copper-based material, containing a specific thiadiazole compound. / O emulsion type flame retardant hydraulic fluid.
[0002]
[Prior art]
If flammable mineral oil hydraulic fluid is used in various hydraulic equipment such as steel equipment and die-cast machines exposed to high heat source atmosphere, there is a risk of fire due to sudden oil leakage. Flame retardant hydraulic fluid is used. For flame retardant hydraulic fluids, water-based flame retardant hydraulic fluids such as water-glycol type, W / O emulsion type, O / W emulsion type and synthetic oil types such as fatty acid ester type and phosphate ester type There are things. Synthetic oil-based flame retardant hydraulic fluids lack practicability due to insufficient flame retardancy and toxicity issues.
W / O emulsion type flame retardant hydraulic fluid is generally obtained by blending emulsifier with about 60% by volume of base oil and mechanically emulsifying about 40% by volume of water. In order to have it, an antiwear agent, an antirust agent, an antioxidant, an antibacterial agent, an antifoaming agent and the like are appropriately blended. As a result, the W / O emulsion-type flame retardant hydraulic fluid is excellent in flame retardancy, lubricity, and wastewater treatment properties, and is frequently used in the above applications.
[0003]
In the W / O emulsion type flame retardant hydraulic fluid, zinc dithiophosphate having excellent extreme pressure and wear resistance is widely used as an antiwear agent, but certain types of zinc dithiophosphate are copper members or It is said that corrosiveness is strong with respect to copper-containing members and the like (hereinafter simply referred to as “copper members”), and that many water-soluble antibacterial agents have undesirable effects on copper members. Although the copper member is a metal material having a relatively high reactivity, it is excellent in thermal conductivity, workability and economy, and is widely used in oil coolers of hydraulic devices, piston shoes of hydraulic pumps, and the like. Copper members, zinc dithiophosphate, antibacterial agents, etc. are very important as materials constituting hydraulic devices and hydraulic fluids, especially considering economic efficiency and effects. There is also a problem that the corrosion of the member is caused, and the corrosion product deteriorates the hydraulic fluid and further accelerates the corrosion.
[0004]
[Problems to be solved by the invention]
Therefore, the present invention blends a specific compound having anti-corrosion action and anti-wear action even if it is a flame-retardant hydraulic fluid containing anti-wear and anti-bacterial agents, and provides lubricity and emulsion stability. It is an object of the present invention to provide a W / O emulsion type flame retardant hydraulic fluid having excellent corrosion prevention performance particularly for a copper member without losing the basic performance of the flame retardant hydraulic fluid.
[0005]
[Means for Solving the Problems]
The present invention is a W / O emulsion type flame retardant hydraulic fluid obtained by dispersing water in a base oil using a surfactant, and has a hydrocarbon group having 5 to 30 carbon atoms in both carbons in the thiadiazole skeleton. A W / O emulsion-type flame retardant hydraulic fluid comprising a thiadiazole derivative substituted with 1 to 4 sulfur sulfide groups or polysulfide groups, and the corrosion resistance effect of the hydraulic fluid on copper members Is significantly improved.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Mineral oil, synthetic oil, and mixed oils thereof can be used as the base oil used in the hydraulic fluid of the present invention. The mineral oil is obtained by subjecting a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation, solvent desolvation, solvent extraction, hydrocracking, solvent dewaxing, hydrodewaxing, hydrorefining, sulfuric acid Various refining processes used for refining lubricating oil such as washing and clay treatment can be appropriately combined.
Synthetic oils include poly-α-olefins, low molecular weight ethylene / α-olefin copolymers, synthetic naphthenes, alkylbenzenes, and the like.
Furthermore, the mixed oil which mixed various mineral oil base materials, the mixed oil of a synthetic oil base material, and the mixed oil of arbitrary mixing ratios of these base materials can be used. From the gist of the present invention that provides hydraulic hydraulic oil at low cost, it is preferable to use a mixed oil or a mineral oil alone with a large proportion of mineral oil.
The physical properties of these base oils are not particularly limited, but those having a kinematic viscosity at 40 ° C. of 5 to 100 mm 2 / s are preferable, and those of 10 to 40 mm 2 / s are more preferable.
[0007]
The water used for the hydraulic fluid of the present invention is not particularly limited, but it is preferable to use water with very few impurities and bacteria.
The proportion of water in the base oil is preferably 0.1 to 70% by volume, and more preferably 20 to 55% by volume from the viewpoint of flame retardancy, emulsion stability and emulsion viscosity. The emulsion can be obtained by mixing the base oil and water together with the surfactant by a known method, but an oil-side mother liquor and a water-side mother liquor prepared by adding suitable additives to the base oil and water were prepared in advance. Thereafter, it is preferable to obtain both mother liquors by vigorously stirring and mixing them.
[0008]
As the surfactant (emulsifier), known ones used in W / O emulsions such as nonionic surfactants and ionic surfactants can be appropriately used. Specifically, examples of the nonionic surfactant include alkylated phenyl ether and fatty acid ester, and examples of the anionic surfactant include Ca sulfonate, Ba sulfonate, Na sulfonate, and the like. . Of these, at least one surfactant is added in an amount of 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the base oil.
[0009]
The thiadiazole derivative used in the present invention is, for example, a compound having a 1,3,4-thiadiazole skeleton, which is a compound represented by the following general formula (1), and is a sulfide group or polysulfide which is a substituent of both carbons in the skeleton. R 1 and R 2 in the group are each independently a hydrocarbon group having 5 to 30 carbon atoms, and m and n are each independently an integer of 1 to 4.
[Chemical 1]
[0010]
In addition, the hydrocarbon group of R < 1 > and R < 2 > in the said compound may be any of linear and / or branched, saturated and / or unsaturated, and those having 5 to 15 carbon atoms are particularly preferred.
[0011]
The thiadiazole compound used in the present invention is preferably blended in an amount of 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, and particularly preferably 0.1 to 1% by weight based on the base oil as a corrosion inhibitor. By mix | blending this polysulfide compound in the said range, the anticorrosion effect with respect to a copper member improves markedly, and the corrosion weight loss of copper oil coolers can be reduced significantly. In particular, even when used in combination with zinc dithiophosphate, the effect is sufficiently exerted without being impaired.
[0012]
In the hydraulic oil of the present invention, known extreme pressure agents, antiwear agents, rust inhibitors, antioxidants, antibacterial agents, antifoaming agents, and other additives can be appropriately blended.
Zinc dialkyldithiophosphate and sulfur compounds as extreme pressure agents, phosphorus compounds as antiwear agents, metal sulfonates as rust preventive agents, phenolic and amine compounds as antioxidants, antibacterial agents (antifungal agents) N-based compounds and the like, and antifoaming agents include silicone compounds and PMA polymers. These additives may be appropriately added to the finished hydraulic oil.
In particular, the hydraulic oil of the present invention sufficiently exhibits its effect without impairing its function even when used in combination with a zinc dialkyldithiophosphate used as an extreme pressure agent and an antiwear agent.
The various additives can also be used in the form of a so-called additive package in which several kinds are mixed in advance.
[0013]
The above-mentioned various additives are mixed with base oil or water to prepare mother liquors. The oil mother liquor and the aqueous mother liquor can be mixed at the above ratio and mechanically emulsified using a stirrer such as a high-speed homogenizer to obtain a W / O emulsion.
[0014]
【Example】
Hereinafter, the W / O emulsion type flame-retardant hydraulic fluid of the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
In preparing the W / O emulsion type flame-retardant hydraulic fluids of Examples and Comparative Examples, the following base materials were used.
a) Base oil: Paraffinic mineral oil. The kinematic viscosity (40 ° C.) is 15 mm 2 / s, the viscosity index is 90, and the pour point is −15 ° C.
b) Water: Purified water c) Additive: Ca sulfonate as an emulsifier (surfactant), zinc dialkyldithiophosphate as an antiwear agent, oil-soluble amine as an antibacterial agent, corrosion inhibitor / antiwear agent In the formula (1) of the 1,3,4-thiadiazole compound described above, a thiadiazole compound having R 1 and R 2 having a total carbon number of 22 and n and m each having an average of 3 polysulfide groups A mixture of
These base materials were mixed at a ratio shown in Table 1, and mechanically stirred and emulsified with a high-speed homogenizer to prepare W / O emulsion-type flame-retardant hydraulic fluids of Example 1 and Comparative Example 1.
[0015]
[Table 1]
[0016]
About the W / O emulsion type flame-retardant hydraulic fluid of Example 1 and Comparative Example 1 prepared as described above, the copper corrosion prevention performance is copper weight loss in a copper cyclic corrosion test simulating an oil cooler. The lubricity was evaluated based on the wear trace and friction coefficient by the LFW-1 test, and the wear resistance of the vane pump. These test conditions are as follows.
(1) Copper cooler test of oil cooler ・ JIS H3300 copper alloy seamless pipe C1200T phosphorous deoxidized copper ・ Pipe inner diameter 6mm
・ Flow rate: 20L / min
・ Oil quantity: 60L
・ Oil temperature: 60 ℃
・ Time: 500hr
・ Measures corrosion loss of copper pipes
(2) LFW-1 test block / ring: H-60 / S-10
-Oil temperature: room temperature-Load: 100 lbs
・ Rotation speed: 300rpm
・ Time: 30min
・ Measures block wear scar width
(3) Wear resistance test of vane pump ・ Vane pump: PV-2R made by Yuken Kogyo
・ Test pressure: 14MPa continuous
・ Oil temperature: 50 ℃
・ Oil quantity: 50L
・ Test time: 500 hr
Evaluation: Measure the amount of vane and cam ring wear after the test. The results of the evaluation test are shown in Table 2.
[0017]
[Table 2]
As is clear from Table 2, it can be seen that the copper member has excellent corrosion prevention performance and is excellent in lubricity.
[0019]
【The invention's effect】
In the present invention, since a specific thiadiazole derivative is blended with a W / O emulsion type flame retardant hydraulic fluid, a flame retardant hydraulic fluid such as lubricity even if it contains an antiwear agent or antibacterial agent such as zinc dithiophosphate. While strengthening the basic performance as hydraulic oil, the copper member has an excellent effect of having excellent corrosion prevention performance.
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| JP2000367284A JP3919444B2 (en) | 2000-12-01 | 2000-12-01 | W / O emulsion type flame retardant hydraulic fluid |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000367284A JP3919444B2 (en) | 2000-12-01 | 2000-12-01 | W / O emulsion type flame retardant hydraulic fluid |
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| JP2002167590A JP2002167590A (en) | 2002-06-11 |
| JP3919444B2 true JP3919444B2 (en) | 2007-05-23 |
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