JP4666694B2 - 作動液 - Google Patents

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Publication number
JP4666694B2
JP4666694B2 JP52231797A JP52231797A JP4666694B2 JP 4666694 B2 JP4666694 B2 JP 4666694B2 JP 52231797 A JP52231797 A JP 52231797A JP 52231797 A JP52231797 A JP 52231797A JP 4666694 B2 JP4666694 B2 JP 4666694B2
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Prior art keywords
ester
fatty acids
composition
hydraulic
acid
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JP2000507277A5 (ja
JP2000507277A (ja
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ブネマン，トーマン，エフ
カルドール，アリー，デイック
モーイ，アブラハム，シイ デ
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ユニケマ ケミー ベスローテム ベンノットシャップ
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Description

本発明は作動液に関する。更に詳しく言えば本発明は低温特性が向上したエステル基剤の作動液に関する。
油圧系統（hydraulic systems）は広範囲の機械装置例えば自動車、トラック、クレーン、列車、他の輸送装置、農業用装置、船舶及び海洋装置（全ての可動システム）及び工場や鉄道における如き不動システムに用いられる。かゝる油圧系統は作動液即ち圧媒液を含有し、作動液は石油化学流体（伝統的）又はエステル／油化学薬剤（oleochemical）基剤（環境上からは更に満足できる）に基づくことができる。
多数の応用において、これらの油圧系統は環境上の又は油圧系統それ自体の何れかの低温を受ける。これは特に油圧系統を北極圏近くの又は北極圏内の国土で用いた場合に該当する。作動液の多数の特性が作動液の温度変化に応じて変化することは既知の事実である。低温は作動液の多数の特性に一般に悪影響を及ぼすことも既知であり、例えば余りにも高い流動点及び（動的）粘度及び不十分な低温安定性等に不利となる。
石油化学流体を基剤とする作動液（hydraulic fluid）については、低温特性の若干を改良するために例えば流動点降下剤の如き添加剤の使用によって多数の解決策が提案されてきた。然しながら、今日まで、かゝる添加剤は、エステル／油化学薬剤を基剤とする作動液には使用できないことが知られている。何故ならば、該添加剤はエステル／油化学薬剤と非混和性であるか又は該添加剤は不十分な効果を奏するからである（所望の効果は低温での良好な諸特性である）。従って、慣用のエステル／油薬剤基剤の作動液と比較した時に、向上した低温特性を有するエステル／油薬剤基剤の作動液に対する必要性があった。「エステル／油薬剤基剤の作動液」とはこゝでは、少なくとも主要部分（即ち50重量％より多い）がポリオールとカルボン酸とのエステルから構成される、油圧系統で用いるための作動（基剤）液として応用するのに適当な流体であると理解すべきである。エステル／含油薬剤基剤の作動液が向上した低温特性に加えて、「常用の」温度で尚満足な特性を有することは本発明の別の目的である。「常用」温度に関連する重要な特性は40℃及び100℃における動粘度である。向上した低温諸特性とは、作動液の諸特性が少なくとも１つの観点から見て向上されており、好ましくは低温安定性であることを意味する。
低温安定性とは作動液が低温でかなりの長期間（多数の日数）保持した後でも尚適当な特性を有することを意味する。低温安定性を定量する仕方はASTM D2531による試験方法により行なう。要するに、この方法は−30℃で168時間保持した後に作動液の（動）粘度を測定することよりなる。こうして測定した粘度は特定の限界値以下であるべきである。
今般見出された所によれば、ポリオールと脂肪酸混合物とのエステルを含有してなる、作動油（hydraulic）組成物であって、該ポリオールはトリメチロールプロパン、ペンタエリスリトール、ネオペンチルグリコール、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）、ジ−（ペンタエリスリトール）及びトリ−（ペンタエリスリトール）よりなる群から選ばれ、該脂肪酸は一部（I）が直鎖又は分枝鎖C8及び／又はC10脂肪酸よりなり、別の部分（II）がオレイン酸よりなり、エステル化した脂肪酸（I）：（II）の比率が重量比で2：1〜1：20の範囲にあり、該組成物がASTM（D2531）により試験した時には7000mm2／秒又はそれ以下の粘度を有する作動油組成物によって、前記の目的に適合させ得る。かゝるエステルは混合エステルと記載されることが多く、（平均して）各々のエステル分子が少なくとも２種の相異なるカルボン酸部分を含有することを意味する。前記の短鎖脂肪酸並びに長鎖脂肪酸は直鎖又は分枝鎖の脂肪酸（又はこれらの混合物）であり得る。
前記の組成物はASTM（D2531）により試験した時に5000mm2／秒又はそれ以下の粘度を有するのが好ましい。
良好な低温特性と高温特性とを組合せるには、混合したエステル中の短鎖脂肪酸：長鎖脂肪酸の重量比は２：１〜１：20であるのが好ましい。多数の場合に、比較的少量の短鎖脂肪酸が所望の効果を得るのに必要とされることが見出され、従って前記の重量比は１：１〜１：10であるのが尚更に好ましい。
本発明の組成物は乳化剤又は流動点降下剤の如き添加剤を含有しないのが好ましいけれども、酸化防止剤（例えばアミン型又はフェノール型の酸化防止剤）、粘度指数（VI）向上剤（例えばポリメタクリレート化合物）、摩耗防止化合物（例えばジチオホスフェート、スルホン酸カルシウム、スルホン酸バリウム）及び消泡化合物（例えば変性ジメチルポリシロキサン）の如き特定の添加剤を前記組成物に添加できる。
本発明の組成物はＴＭＰ（トリメチロールプロパン）、ＰＥ（ペンタエリスリトール）、ＮＰＧ（ネオペンチルグリコール）、ジ−ＴＭＰ、トリ−ＴＭＰ、ジ−ＰＥ、トリ−ＰＥよりなる群から選んだポリオールのエステルを含有してなるのが好ましい。最も好ましいポリオールはＴＭＰである。
ポリオールは、分枝鎖又は直鎖Ｃ8又はＣ10脂肪酸又はこれの混合物を有する短鎖脂肪酸を包含する混合物でエステル化するのが好ましい。長鎖部分については、これらの脂肪酸はオレイン酸又はイソステアリン酸を包含するのが好ましい。
本発明によるエステルは5.0mg ＫＯＨ／ｇ以下の酸価を有するのが好ましく、1.0mg ＫＯＨ／ｇ以下の酸価を有するのがより好ましい。
好ましくは、作動液として用いるべき組成物は少なくとも75重量％、より好ましくは少なくとも85重量％の前述の混合エステルを含有する。少なくとも95重量％のエステルを含有する作動液が最も好ましい。
若干の場合には本発明の組成物は油圧系統にそのまゝ用い得るけれども、かゝる組成物は例えばこれを別の流体又は添加剤と配合することにより作動液の製造に用いることもできる。
本発明の別の具体例は液圧装置に前記組成物を使用することである。かゝる液圧装置は可動システムの一部であり得る。
本発明は更に作動液の製造方法からなり、ポリオールを脂肪酸混合物でエステル化することからなり、その際脂肪酸の少なくとも一部は短鎖長（５〜12個の炭素原子）を有し、脂肪酸の別の部分は長鎖長（16〜22個の炭素原子）を有し、脂肪酸エステルは全組成物に基いて少なくとも75重量％の量で組成物中に存在するものとし、しかも場合によっては得られる混合エステルを別成分と混合することからなる、作動液の製造方法に関する。前記の短鎖脂肪酸並びに長鎖脂肪酸は直鎖又は分枝鎖脂肪酸（又はこれの混合物）であり得る。
本発明を次の実施例により更に例示するが、該実施例は本発明をこれに限定するものと解すべきでない。
実施例
実施例１
内部容量２リットルの四ッ首フラスコは攪拌機、温度計／温度調節装置、窒素ガスブロアー及び還流コンデンサーに接続したディーン・スターク水分離器を備えている。このフラスコに220.1ｇ（1.64モル）のトリメチロールプロパン、165ｇ（0.96モル）のオクタン酸／デカン酸混合物（約55：45の重量比）及び1115ｇ（3.97モル）のオレイン酸を装入した。該混合物をエステル化し、窒素流中でマントルヒーターにより加熱した。室温から開始して大体１時間熱を供給した後に、160℃の温度に到達させ、反応水を留去した。温度を徐々に250℃にまで昇温させ、90mlの水を収集した。この時点で水分離器を取去り、真空を反応混合物に印加した。反応は大体７時間の全反応期間で完了した。反応の最後の段階中に全部で75ｇの有機軽質フラクションを留出した。最後にエステル生成物を濾過して何れかの機械的不純物を除去した。
こうして得られたエステルのＧＬＣ分析が示す所によれば、エステルは13重量％のＣ8／Ｃ10混合物（比率は56.9：43.1）と87重量％のオレイン酸（オレイン酸フラクションの中には少量の別の長鎖脂肪酸がある）とを含有した。
得られたエステルの諸特性を表１に記載する。
実施例２
内部容量２リットルの四ッ首フラスコは攪拌機、温度計／温度調節装置、窒素ガスブロアー及び還流コンデンサーに接続したディーン・スターク水分離器を備えている。このフラスコに227.4ｇ（1.70モル）のトリメチロールプロパンと164ｇ（1.14モル）の２−エチルヘキサン酸と1109ｇ（3.95モル）のオレイン酸とを装入した。該混合物をエステル化し、窒素流中でマントルヒーターにより加熱した。大体１時間後に、160℃の温度に到達させ、反応水を留去した。温度を徐々に250℃まで昇温させ、90mlの水を収集した。この時点で水分離器を取去り、真空を反応混合物に印加した。反応は大体７時間の全反応期間で完了した。反応の最後の段階中に全部で75ｇの有機軽質フラクションを留出した。最後にエステル生成物を濾過して何れかの機械的不純物を除去した。
こうして得られたエステルのＧＬＣ分析が示す所によれば、エステルは13.4重量％の２−エチルヘキサン酸と86.6重量％のオレイン酸（オレイン酸フラクションの中には少量の別の長鎖脂肪酸がある）とを含有した。
こうして得られたエステルの諸特性を表１に記載する。
Figure 0004666694
ＴＭＰはトリメチロールプロパンである。Ｃ8／Ｃ10は８個又は10個の炭素原子を有する脂肪酸の混合物である。２−ＥＨは２−エチルヘキサン酸（分枝鎖Ｃ8）である。Ｃ18:1は（主として）オレイン酸である。
ぶつ形成とは作動液がゲル化し始めたり、結晶を形成し始めることを意味する。

Claims (3)

  1. トリメチロールプロパンと脂肪酸混合物とのエステルを含有してなる、作動油組成物において、該脂肪酸は一部（I）が直鎖又は分枝鎖C8及び／又はC 10 脂肪酸よりなり、別の部分（II）がオレイン酸よりなり、エステル化した脂肪酸（I）：（II）の比率が重量比で2：1〜1：20の範囲にあり、該組成物がASTM（D2531）により試験した時には7000mm2／秒又はそれ以下の粘度を有する、作動油組成物。
  2. トリメチロールプロパンと脂肪酸混合物とのエステルを含有してなる、作動油組成物において、該脂肪酸は一部（I）が直鎖又は分枝鎖C8及び／又はC10脂肪酸よりなり、別の部分（II）がオレイン酸よりなり、エステル化した脂肪酸（I）：（II）の比率が重量比で2：1〜1：20の範囲にあり、該組成物がASTM（D2531）により試験した時には5000mm2／秒又はそれ以下の粘度を有する、作動油組成物。
  3. エステル化した酸の重量比（I）：（II）は1：1〜1：10である請求項１又は２記載の作動油組成物。
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KR100465466B1 (ko) 2005-02-28
NO984814L (no) 1998-12-15
MY118071A (en) 2004-08-30
DE898605T1 (de) 1999-07-22
KR970070169A (ko) 1997-11-07
WO1997039086A1 (en) 1997-10-23
AU2507297A (en) 1997-11-07
ES2144853T3 (es) 2000-06-16
US6693064B2 (en) 2004-02-17
NO325041B1 (no) 2008-01-21
DE69701800T3 (de) 2007-05-16
CA2250964A1 (en) 1997-10-23
DE69701800T2 (de) 2000-10-19
NO984814D0 (no) 1998-10-15
EP0898605B9 (en) 2007-11-07
EP0898605A1 (en) 1999-03-03
ATE192186T1 (de) 2000-05-15
EP0898605B2 (en) 2006-08-30
EP0898605B1 (en) 2000-04-26
CN1084786C (zh) 2002-05-15
US20020193259A1 (en) 2002-12-19
ES2144853T5 (es) 2007-04-01
CA2250964C (en) 2004-09-14
JP2000507277A (ja) 2000-06-13
CN1217016A (zh) 1999-05-19

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