JP5467843B2 - 難燃性油圧作動油組成物 - Google Patents
難燃性油圧作動油組成物 Download PDFInfo
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- JP5467843B2 JP5467843B2 JP2009258668A JP2009258668A JP5467843B2 JP 5467843 B2 JP5467843 B2 JP 5467843B2 JP 2009258668 A JP2009258668 A JP 2009258668A JP 2009258668 A JP2009258668 A JP 2009258668A JP 5467843 B2 JP5467843 B2 JP 5467843B2
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- oil
- hydraulic fluid
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Classifications
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10M2219/106—Thiadiazoles
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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Description
一方、最近は油圧システムの高圧化、メンテナンスフリー化が進み、このような環境下で使用される作動油には長寿命性と優れた耐摩耗性が要求されるようになってきた。ところが、動植物油などの天然系素材を原料とする天然系合成エステルは、脂肪酸が不飽和脂肪酸主体であるため、地球環境に優しくコスト的にも有利であるが、酸化安定性が飽和脂肪酸の合成エステルや合成系の炭化水素油などより大きく劣るのが欠点であった。
特に、酸化安定性が劣る不飽和脂肪酸を用いた合成エステルや動植物油脂を基油とした場合には、その傾向が著しい。この不飽和脂肪酸を原料とした合成エステルや動植物油に効果的に作用する添加剤は未だ見出されていないため、従来は、地球環境に悪影響があり、価格も高い飽和脂肪酸を用いた合成エステルを使用するか、あるいは油交換インターバルの短い不飽和脂肪酸を原料とした合成エステルあるいは動植物油脂を使用するか、いずれかの選択をせざるを得なかった。
上記の問題に加えて、最近問題となっているのが油圧システムの配管あるいはバルブなどに使用されている亜鉛メッキが、エステル系作動油中に存在あるいは使用過程で発生する酸により溶出することである。従来、この亜鉛溶出を抑制する技術はなく、その対策としては、亜鉛メッキを使用しないことが最良の対策とされてきた。
以上のように、従来の技術では、環境に優しく、比較的安価な天然原料を使用した合成エステルや動植物油脂を使用して、耐摩耗性に優れ、かつ配管中の亜鉛溶出を抑え、結果的に長寿命性に優れた難燃性作動油を開発することは、きわめて困難な状況にあった。
また、摩耗防止を目的として極圧添加剤が使用されるが、リン酸エステルのようなマイルドな極圧添加剤はエステル中では効果が小さい。一方、活性が強い極圧添加剤は、酸化安定性、スラッジ抑制性に悪影響を与え、亜鉛の溶出に対しても悪影響を与える場合が多い。
さらに、酸化安定性も亜鉛溶出の抑制には重要な課題であり、酸化安定性に劣るエステルを基油とした作動油の場合、使用中に酸価が増加し、亜鉛の溶出を促進させる。しかし、鉱油や合成系炭化水素油に使用されてきた従来のフェノール系酸化防止剤やアミン系酸化防止剤は、エステル油に対しては十分な酸化防止効果が得られない。
本発明は、このような実情に鑑みてなされたものであり、不飽和脂肪酸を主体とし、かつ特定値以下の酸価を有する合成エステルあるいは動植物油において、十分な酸化防止性能及び亜鉛溶出防止性に優れ、かつ良好な耐摩耗性を有し、最近の油圧システムの高圧化、メンテナンスフリー化に対応した長寿命の難燃性油圧作動油を提供することを目的とする。
ここで、酸価とは、JIS K 2501「石油製品及び潤滑油−中和価試験方法」(電位差滴定法)に準拠して測定した値を意味する。
また本発明は、配管あるいはバルブに亜鉛メッキを使用している油圧システムに用いられることを特徴とする前記難燃性油圧作動油組成物である。
本発明の難燃性油圧作動油組成物に使用される基油としては、エステルを構成する脂肪酸中の不飽和脂肪酸比率が20モル%以上であり、かつエステルの酸価が1.0mgKOH/g以下の合成エステル及び油脂からなる群より選ばれる少なくとも1種の基油が用いられる。合成エステルとしては、脂肪酸エステル、ポリオールエステル、コンプレックスエステルを例示することができ、油脂としては、各種の植物油脂、動物油脂を例示することができる。また、40℃における動粘度が10〜200mm2/s、引火点が280℃以上のものが好ましく用いられる。
これらの中でもポリオールとしては、より加水分解安定性に優れることから、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ−(トリメチロールプロパン)、トリ−(トリメチロールプロパン)、ペンタエリスリトール、ジ−(ペンタエリスリトール)などのヒンダードアルコールが好ましい。
また、二塩基酸としては、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸などの炭素数5〜10の二塩基酸が使用できる。
これらの合成エステルの中でも、加水分解安定性に優れることから、ポリオールエステルが特に好ましい。
なお、エステルを構成する脂肪酸に占める不飽和脂肪酸の比率が20モル%未満であると、(C)成分を配合しても、油圧作動油の使用の初期段階では粘度上昇や酸価増加の抑制効果があるが、使用が進むと劣化生成物が急にスラッジ化し易く、油圧システム内でトラブルが発生することがある。
また、亜鉛溶出防止の効果をさらに高めるために、エステルの酸価は1.0mgKOH/g以下であることが必要である。エステルの酸価が1.0mgKOH/gを超えると、(B)成分である金属腐食防止剤としてのアルキルチアジアゾール、(D)成分である窒素系金属不活性化剤としてのトリアゾール化合物の効果が阻害されると共に、酸化劣化が促進され、ひいては酸化劣化により亜鉛溶出防止性が損なわれる。
アルキルチアジアゾールとしては、下記一般式(2)で表される1,3,4−チアジアゾール、下記一般式(3)で表される1,2,4−チアジアゾール、または下記一般式(4)で表される1,4,5−チアジアゾールが好ましく用いられる。また、これらの2種以上の混合物も好ましく用いられる。
一方、(C)成分の含有量は、組成物全量基準で、0.001質量%以上であることが好ましく、より好ましくは0.005質量%以上、さらに好ましくは0.01質量%以上である。(C)成分の含有量が0.001質量%に満たない場合は、エステルの酸化劣化を十分に抑制できず亜鉛溶出抑制性能が不足するので好ましくない。
R17O−CO−R16− (8)
R19O−CO−R18−CO− (9)
−C−CO−O−R20 (10)
(式(8)及び(9)中、R16は炭素数1〜12のアルキレン基、R18は炭素数1〜10のアルキレン基であり、R17及びR19は、それぞれ水素原子又は炭素数1〜10のアルキル基ある。式(10)中、R20は炭素数1〜10のアルキル基である。)
抗乳化剤としては、例えば、ポリオキシアルキレングリコール,ポリオキシアルキレンアルキルエーテル,ポリオキシアルキレンアルキルアミド,ポリオキシアルキレン脂肪酸エステル等が挙げられる。
スティックスリップ防止剤としては、具体的には、多価アルコールエステル(完全エステル、部分エステル)などが挙げられる。
油性剤としては、具体的には脂肪酸、エステル、アルコール等が挙げられる。通常、その含有量は、油圧作動油組成物全量基準で0.01〜0.5質量%であるのが望ましい。
JIS K 2265「原油及び石油製品−引火点試験方法(クリーブランド開放式)」に準拠して測定した。
[四球試験]
ASTM D 2783−88に規定する潤滑油の極圧性能測定用標準試験方法(四球法){Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids(Four- Ball Method}に準拠し、回転数1200min−1、荷重294N,油温75℃、試験時間1時間の条件で試験を実施し、3個の固定球の摩耗痕径(mm)の平均値を測定した。
[FZGギヤ試験]
ASTM D 5182にに準拠し、回転数1500min−1試験開始油温90℃で試験を開始し、各ステージで規定された重量でギヤに荷重をかけて15分間運転し、ギヤが焼き付く荷重のステージで油の耐焼き付き性の評価を行った。ギヤが焼き付いた荷重のステージを不合格と判定する。
[ベーンポンプ試験]
ASTM D 2882準拠し、100時間試験した後、試験前後のベーンとリングの重量を計測し、摩耗量(mg)を測定した。
[ドライTOST試験]
JIS K 2514に規定する「TOST法酸化安定度方法」に準拠し、規定の容器に試料油300mlを採取し、鉄および銅のコイル状触媒を加え、95℃の水浴槽で20日間、酸化安定性試験を行った。なお水は使用しない。試験中、少量づつ試料油を採取し、酸価増加(mgKOH/g)及びスラッジ量(mg/50mL)(一定量の試料油をフィルターでろ過し、残渣の重量から50mL当りに換算した)を測定した。
[亜鉛溶出試験]
JIS B 2301−1976に準拠し、規定されたねじ込み式可鍛鋳鉄製管継手1個を試料油200mLを採取したビーカー入れ、120℃で20日間浸漬試験を行う。試験後、試料油中の亜鉛溶出量(質量ppm)を測定して亜鉛の溶出性能を比較した。
(A)基油
A1:トリメチルロールプロパンとオレイン酸、オクチル酸及びデカン酸の混合脂肪酸のエステル(40℃の動粘度47.2mm2/s、粘度指数180、不飽和率70モル%、酸価0.5)
A2:トリメチルロールプロパンとオレイン酸、オクチル酸及びデカン酸の混合脂肪酸のエステル(40℃の動粘度45.2mm2/s、粘度指数185、不飽和率90モル%、酸価2.0)
A3:トリメチルロールプロパンと、オレイン酸、オクチル酸及びデカン酸の混合脂肪酸のエステル(40℃の動粘度34.2mm2/s、粘度指数130、不飽和率10モル%、酸価0.3)
A4:ペンタエシスリトールと、オレイン酸、オクチル酸及びデカン酸の混合脂肪酸のエステル(40℃の動粘度66.2mm2/s、粘度指数160、不飽和率70モル%、酸価1.0)
(B)金属腐食防止剤
B1:2,5−ビス(2エチルヘキシルジチオ)−1,3,4チアジアゾール
B2:2,5−ビス(n−ヘキシルジチオ)−1,3,4チアジアゾール
(C)酸化防止剤
C1:ビス(4−ジメチルアミノフェニル)メタン
C2:α−ナフチルアミン
C3:4,4’−メチレンビス(2,6−ジ−tert−ブチルフェノール)
(D)窒素系金属不活性化剤
D1:N,N−ビス(2−エチルヘキシル)−4−メチル−1H−ベンゾトリアゾール−1−メチルアミン
D2:ベンゾトリゾール
(E)摩耗防止剤
E1: 2−エチルヘキシルアシッドホスフェート
E2:トリクレジルホスフェート
(F)その他の添加剤
F3:ソルビタンモノオレイエート
また、酸価が2.0mgKOH/gの基油A2を用いた比較例1〜3は、エステルを構成する脂肪酸のうち不飽和脂肪酸の比率が90モル%と高いにもかかわらず、実施例2に比べて、亜鉛溶出量が多い。
Claims (3)
- (D)トリアゾール誘導体、ベンゾトリアゾール誘導体、およびトルトリアゾール誘導体からなる群から選ばれる少なくとも1種のトリアゾール化合物を組成物全量基準で0.001〜0.5質量%含有することを特徴とする請求項1に記載の難燃性油圧作動油組成物。
- 配管あるいはバルブに亜鉛メッキを使用している油圧システムに用いられることを特徴とする請求項1または2に記載の難燃性油圧作動油組成物。
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