JP2844804B2 - 潤滑油 - Google Patents

潤滑油

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Publication number
JP2844804B2
JP2844804B2 JP2045702A JP4570290A JP2844804B2 JP 2844804 B2 JP2844804 B2 JP 2844804B2 JP 2045702 A JP2045702 A JP 2045702A JP 4570290 A JP4570290 A JP 4570290A JP 2844804 B2 JP2844804 B2 JP 2844804B2
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JP
Japan
Prior art keywords
group
acid
oil
salt
salts
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 - Fee Related
Application number
JP2045702A
Other languages
English (en)
Other versions
JPH0347895A (ja
Inventor
新一 秋本
徹 安河内
和夫 古瀬
晋也 奥村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON YUSHI KK
Original Assignee
NIPPON YUSHI KK
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Filing date
Publication date
Application filed by NIPPON YUSHI KK filed Critical NIPPON YUSHI KK
Priority to JP2045702A priority Critical patent/JP2844804B2/ja
Priority to BR909001925A priority patent/BR9001925A/pt
Priority to DE9090107994T priority patent/DE69000787T2/de
Priority to EP90107994A priority patent/EP0399239B1/en
Priority to ES90107994T priority patent/ES2045624T3/es
Priority to KR1019900005866A priority patent/KR0150003B1/ko
Publication of JPH0347895A publication Critical patent/JPH0347895A/ja
Priority to US07/801,633 priority patent/US5250205A/en
Application granted granted Critical
Publication of JP2844804B2 publication Critical patent/JP2844804B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は潤滑油に関する。
〔従来の技術〕 ポリアルキレングリコール誘導体は潤滑油としていろ
いろな用途に使用されている。たとえば、水溶性のポリ
アルキレングリコール誘導体は作動油、切削油、研削
油、ギアー油等に、ポリオキシアルキレングリコール
(メタ)アクリレートの重合物は水系潤滑油(特開昭56
−47411号公報)に、ヒマシ油のポリオキシアルキレン
付加物をさらにエステル化した化合物は金属加工油(特
開昭57−207699号公報)に使用され、油溶性のポリアル
キレングリコール誘導体は鉱物油の粘度指数向上剤(特
公昭53−44196号公報)、冷凍機油(特開昭57−51795号
公報)等に使用されている。
〔発明が解決しようとする課題〕
ところが、ポリオキシアルキレングリコール(メタ)
アクリレートの重合物や、ヒマシ油の誘導体は長期にわ
たって水溶液として使用すると性能が変ってしまい、ま
た油溶性のポリアルキレングリコールは鉱油にはよく溶
けるが水には全く溶けず、鉱油等を水に乳化することも
できず、使用できる範囲が限定されるという問題があっ
た。
本発明は水溶液、油溶液、水−油乳化液のいずれの系
にも用いることのできる潤滑油を目的とする。
〔課題を解決するための手段〕
本発明は、一般式(1)で示されるアルケニルエーテ
ルと無水マレイン酸、マレイン酸、マレイン酸塩または
マレイン酸エステルとを単量体の必須成分とする共重合
体からなる潤滑油である。
(ただし、Zは2〜8個の水酸基をもつ化合物の残基、
AOは炭素数2〜18のオキシアルキレン基の1種または2
種以上で、2種以上のときはブロック状に付加していて
も、ランダム状に付加していてもよく、Rは炭素数2〜
5のアルケニル基、R1は炭素数1〜24の炭化水素基また
はアシル基、a≧0、b≧0、c≧0、lは正の整数、
mとnは0または正の整数、l+m+n=2〜8、n/
(l+m)≦1/2、al+bm+cn=1〜1000である。) 一般式(1)のZを残基とする2〜8個の水酸基をも
つ化合物としては、カテコール、レゾルシン、ヒドロキ
ノン、フロログルシン等の多価フエノール;エチレング
リコール、プロピレングリコール、ブチレングリコー
ル、ドデシレングリコール、オクタデシレングリコー
ル、ネオペンチルグリコール、スチレングリコール、グ
リセリン、ジグリセリン、ポリグリセリン、トリメチロ
ールエタン、トリメチロールプロパン、1,3,5−ペンタ
ントリオール、エリスリトール、ペンタエリスリトー
ル、ジベンタエリスリトール、ソルビトール、ソルビタ
ン、ソルバイド、ソルビトール−グリセリン縮合物、ア
ドニトール、アラビトール、キシリトール、マンニトー
ルなどの多価アルコール;キシロース、アラビノース、
リボース、ラムノース、グルコース、フルクトース、ガ
ラクトース、マンノース、ソルボース、セロビオース、
マルトース、イソマルトース、トレハロース、シユーク
ロース、ラフイノース、ゲンチアノース、メレジトース
などの糖類;さらにそれらの部分エーテル化物や部分エ
ステル化物等がある。
AOで示される炭素数2〜18のオキシアルキレン基とし
ては、オキシエチレン基、オキシプロピレン基、オキシ
ブチレン基、オキシテトラメチレン基、オキシスチレン
基、オキシドデシレン基、オキシテトラデシレン基、オ
キシヘキサデシレン基、オキシオクタデシレン基などが
あるが、とくに炭素数2〜4のオキシアルキレン基が好
ましい。
Rで示される炭素数2〜5のアルケニル基としては、
ビニル基、アリル基、メタリル基、3−ブテニル基、4
−ペンテニル基、3−メチル−3−ブテニル基等があ
る。
R1で示される炭素数1〜24の炭化水素基としてはメチ
ル基、エチル基、プロピル基、イソプロピル基、ブチル
基、イソブチル基、第三ブチル基、ペンチル基、イソペ
ンチル基、ヘキシル基、ヘプチル基、2−エチルヘキシ
ル基、オクチル基、ノニル基、デシル基、ウンデシル
基、ドデシル基、イソトリデシル基、テトラデシル基、
ヘキサデシル基、イソヘキサデシル基、オクタデシル
基、イソオクタデシル基、オレイル基、オクチルドデシ
ル基、ドコシル基、デシルテトラデシル基、ベンジル
基、クレジル基、ブチルフエニル基、ジブチルフエニル
基、オクチルフエニル基、ノニルフエニル基、ドデシル
フエニル基、ジオクチルフエニル基、ジノニルフエニル
基、ナフチル基、スチレン化フエニル基などがあり、ア
シル基としては、酢酸、プロピオン酸、酪酸、イソ酪
酸、カプリル酸、ペラルゴン酸、2−エチルヘキサン
酸、ノナン酸、カプリン酸、ウンデシレン酸、ラウリン
酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステ
アリン酸、アラキン酸、ベヘン酸、パルミトレイン酸、
オレイン酸、リノール酸、リノレン酸、エルカ酸、イソ
パルミチン酸、イソステアリン酸、安息香酸、ヒドロキ
シ安息香酸、桂皮酸、没食子酸等に由来するアシル基が
ある。
マレイン酸塩としては、リチウム塩、ナトリウム塩、
カリウム塩、マグネシウム塩、カルシウム塩等のアルカ
リ金属塩、アルカリ土類金属塩のほか、アンモニウム塩
や有機アミン塩がある。
有機アミン塩としては、メチルアミン塩、エチルアミ
ン塩、プロピルアミン塩、ブチルアミン塩、ペンチルア
ミン塩、ヘキシルアミン塩、オクチルアミン塩、2−エ
チルヘキシルアミン塩、デシルアミン塩、ドデシルアミ
ン塩、イソトリデシルアミン塩、テトラデシルアミン
塩、ヘキサデシルアミン塩、イソヘキサデシルアミン
塩、オクタデシルアミン塩、イソオクタデシルアミン
塩、オクチルドデシルアミン塩、ドコシルアミン塩、デ
シルテトラデシルアミン塩、オレイルアミン塩、リノー
ルアミン塩、ジメチルアミン塩、トリメチルアミン塩、
アニリン塩等の脂肪族や芳香族のモノアミン塩、エチレ
ンジアミン塩、テトラメチレンジアミン塩、ドデシル−
プロピレンジアミン塩、テトラデシル−プロピレンジア
ミン塩、ヘキサデシル−プロピレンジアミン塩、オクタ
デシル−プロピレンジアミン塩、オレイル−プロピレン
ジアミン塩、ジエチレントリアミン塩、トリエチレンテ
トラミン塩、テトラエチレンペンタミン塩、ペンタエチ
レンヘキサミン塩等のポリアミン塩、モノエタノールア
ミン塩、ジエタノールアミン塩、トリエタノールアミン
塩、モノイソプロパノールアミン塩、ジイソプロパノー
ルアミン塩、トリイソプロパノールアミン塩、これらの
アルキレンオキシド付加物の塩、第一または第二アミン
のアルキレンオキシド付加物の塩等のアルカノールアミ
ン塩、リジン塩、アルギニン塩等のアミノ酸塩がある。
これらのうち、とくにアルカリ金属塩、アンモニウム塩
およびアルカノールアミン塩が好ましい。
マレイン酸エステルとしては、メタノール、エタノー
ル、アリルアルコール、メタリルアルコール、プロパノ
ール、イソプロパノール、ブタノール、イソブタノー
ル、第三ブタノール、ペンタノール、イソペンタノー
ル、ヘキサノール、ヘプタノール、2−エチルヘキサノ
ール、オクタノール、ノナノール、デカノール、ウンデ
カノール、ドデカノール、イソトリデカノール、テトラ
デカノール、ヘキサデカノール、イソセチルアルコー
ル、オクタデカノール、イソステアリルアルコール、オ
レイルアルコール、オクチルドデカノール、ドコサノー
ル、デシルテトラデカノール等のアルコールやこれらの
アルキレンオキシド付加物;フエノール、クレゾール、
ブチルフエノール、オクチルフエノール、ノニルフエノ
ール、ドデシルフエノール、カテコール、レゾルシン、
ヒドロキノン、フロログルシン等のフエノール類のアル
キレンオキシド付加物のマレイン酸エステルがある。さ
らにエチレングリコール、プロピレングリコール、ブチ
レングリコール、ドデシレングリコール、オクタデシレ
ングリコール、ネオペンチルグリコール、スチレングリ
コール、グリセリン、ジグリセリン、ポリグリセリン、
トリメチロールエタン、トリメチロールプロパン、1,3,
5−ペンタントリオール、エリスリトール、ペンタエリ
スリトール、ジペンタエリスリトール、ソルビトール、
ソルビタン、ソルバイド、ソルビトール−グリセリン縮
合物、アドニトール、アラビトール、キシリトール、マ
ンニトールなどの多価アルコール;キシロース、アラビ
ノース、リボース、ラムノーズ、グルコース、フルクト
ース、ガラクトース、マンノース、ソルボース、セロビ
オース、マルトース、イソマルトース、トレハロース、
シユークロース、ラフイノース、ゲンチアノース、メレ
ジトースなどの糖類;さらにそれらの部分エーテル化物
や部分エステル化物、あるいはそれらのアルキレンオキ
シド付加物;メチルアミン、エチルアミン、プロピルア
ミン、ブチルアミン、アミルアミン、ヘキシルアミン、
オクチルアミン2−エチルヘキシルアミン、デシルアミ
ン、ドデシルアミン、イソトリデシルアミン、テトラデ
シルアミン、ヘキサデシルアミン、イソヘキサデシルア
ミン、オクタデシルアミン、イソオクタデシルアミン、
オクチルドデシルアミン、ドオシルアミン、デシルテト
ラデシルアミン、オレイルアミン、リノールアミン、ジ
メチルアミン、トリメチルアミン、アニリン等の脂肪族
や芳香族のモノアミンのアルキレンオキシド付加物;エ
チレンジアミン、テトラメチレンジアミン、ドデシル−
プロピレンジアミン、テトラデシル−プロピレンジアミ
ン、ヘキサデシル−プロピレンジアミン、オクタデシル
−プロピレンジアミン、オレイル−プロピレンジアミ
ン、ジエチレントリアミン、トリエチレンテトラミン、
テトラエチレンペンタミン、ペンタエチレンヘキサミン
等のポリアミンのアルキレンオキシド付加物;モノエタ
ノールアミン、ジエタノールアミン、トリエタノールア
ミン、モノイソプロパノールアミン、ジイソプロパノー
ルアミン、トリイソプロパノールアミン等のアルカノー
ルアミンやそれらのアルキレンオキシド付加物のマレイ
ン酸エステルがある。
本発明で用いる共重合体は一般式(1)の化合物と無
水マレイン酸、マレイン酸、マレイン酸塩またはマレイ
ン酸エステルとをラジカル触媒を用いて共重合させるこ
とによって得ることができるが、マレイン酸、その塩ま
たはそのエステルの共重合体は、無水マレイン酸共重合
体のエステル化、加水分解、それにつぐ中和反応等によ
って得る方が便利である。
一般式(1)で示される化合物と無水マレイン酸、マ
レイン酸、マレイン酸塩またはマレイン酸エステルとを
共重合させるときの比は、重合性の二重結合を基準にし
た当量比で3:7〜7:3、とくに約1:1が好ましい。
共重合の際、さらに他の単量体を加えて共重合させて
もよいが、他の単量体の量は全単量体中の30モル%以下
である。
他の単量体としては、アクリル酸、メタクリル酸、イ
タコン酸、クロトン酸、これらの一価または二価の金属
塩、アンモニウム塩、有機アミン塩、炭素数1〜24のア
ルコールとのエステル、多価アルコールとのエステル、
ポリオキシアルキレングリコールとのエステル、そのほ
かスチレン、メチルスチレンなどの芳香族ビニル化合
物、塩化ビニル、塩化ビニリデンなどのハロゲン化ビニ
ル化合物、イソブチレン、ジイソブチレンなどのオレフ
イン、酢酸ビニル、アクリロニトリル、アクリルアミド
などがある。
共重合体の重量平均分子量は1000〜200万、好ましく
は3000〜50万である。
Rの炭素数は重合性と関係があり、長すぎると重合性
が乏しくなるので、炭素数2〜5が適当である。
lで示されるRの数は1であると直線的な共重合体が
でき、2以上であると架橋した共重合体を形成する。
l,m,nの関係であるが、nは0〜2の範囲であれば良
いが、あまり多いと共重合反応中に酸とのエステルが生
成しやすい。エステルが生成すると、共重合体の分子量
が大きくなって高粘度になりすぎたり、水や油に溶解し
にくくなるので好ましくなく、少ない方が良い。従っ
て、l,m,nの関係はn/(l+m)≦1/2が好ましい。
また、a,bおよびcはa≧0、b≧0、c≧0で、al
+bm+cn=1〜1000であるが、好ましくは1〜300、と
くに好ましくは1〜100である。
一般式(1)のアルケニルエーテルにおけるAOの炭素
数、付加モル数、R1との組合せ、さらに無水マレイン
酸、マレイン酸、マレイン酸塩、マレイン酸エステルと
の組合せで本発明で用いる共重合体は親水性にも親油性
にもすることができる。
〔作用〕
本発明の潤滑油に使用する共重合体は水に溶けるが油
には溶けないもの、油に溶けるが水には溶けないもの、
油と水の両者に溶解し、両者を乳化するもの等、種々の
性質を示すものがあるので多くの用途に使用することが
できる。
本発明で用いる共重合体は単独で潤滑油として使用で
きるが、鉱物油、動植物油脂、水、エチレングリコー
ル、プロピレングリコール等と併用しても良い。この場
合、0.02重量%のような低濃度でも効果を示す。また冷
凍機油用に使用する場合は、フロンR−11(トリクロロ
モノフルオロメタン)、フロンR−12(ジクロロジフル
オロメタン)、フロンR−22(モノクロロジフルオロメ
タン)、フロンR−134a(1,1,1,2−テトラフルオロエ
タン)、フロンR−152a(1,1−ジフルオロエタン)等
の冷媒に溶解する必要があるので、冷媒に溶解する平均
分子量1000以下のポリオキシプロピレングリコール、そ
のモノ−またはジ−アルキルエーテル、ポリオキシプロ
ピレングリセリルエーテル、ポリオキシエチレンポリオ
キシプロピレングリコール(オキシエチレン基が50モル
%以下)、そのモノ−またはジ−アルキルエーテル、ポ
リオキシエチレンポリオキシプロピレングリセリルエー
テルなどのポリアルキレングリコール誘導体を併用する
ことが好ましい。なお、ポリアルキレングリコール誘導
体が、2種以上のアルキレンオキシドの付加物である場
合は、ブロック状付加物でもランダム状付加物でもよ
い。
〔発明の効果〕
本発明は一般式(1)のアルケニルエーテルと無水マ
レイン酸、マレイン酸、マレイン酸塩またはマレイン酸
エステルとを単量体の必須成分とする共重合体からなる
潤滑油であり、水溶液、乳化液、油溶液のいずれの系に
用いても優れた潤滑効果を示す。
また、本発明の潤滑油は、作動油、ギアー油、切削
油、研削油、プレス油、圧延油、引抜油、摺動面油な
ど、潤滑性を要求される種々の用途に利用することがで
きる。
〔実施例〕
以下に実施例を記載する。
表1に以下の実施例に使用した共重合体を構成する単
量体組成と共重合体の重量平均分子量を示す。
実施例 1. 水系の潤滑油の基剤として表1のNo.1〜5に示した共
重合体を用い、下記の配合処方の潤滑油について性能を
評価した。比較として、共重合体の代りに既存のポリオ
キシアルキレングリコールを基剤として用いた潤滑油に
ついても性能試験を実施した。
配合処方 基剤 18.00重量% プロピレングリコール 37.00 〃 イオン交換水 40.00 〃 オレイン酸 3.45 〃 モルホリン 0.60 〃 ベンゾトリアゾール 0.10 〃 水酸化カリウム 0.85 〃 ジメチルシロキサン(粘度 上記合計量に対して350c
st) 100ppm 性能試験の結果を表2に示すが、本発明の共重合体を
基剤とする潤滑油が優れた潤滑剤であることがわかる。
実施例 2. 表1のNo.3、No.4、No.6、No.7、No.8およびNo.9の共
重合体を用いて、以下に示す配合処方で切削油を調製
し、下記の条件で切削加工試験(JIS B−4012)を行な
った。その結果を表3に示す。
配合処方 マシーン油 80.0重量% 共重合体 20.0 〃 切削加工試験の条件 切削される材料 快削ステンレス鋼(SAE51−416F) 40φ×300(mm) 切削工具 SKH−4B(JIS G−4403) 切削速度 70m/min 加工速度 8μ/min 切削油流量 1/min 比較のため共重合体の代りに、ポリエチレングリコー
ル(7モル)モノオレエートを使用して試験した。評価
は、1本のバイトで切削された材料の数で評価した。結
果を表4に示すが、本発明の共重合体を用いた切削油は
効果が大きいことがわかる。
実施例 3. 実施例2に使用した配合処方の切削油2重量%とイオ
ン交換水98重量%からなる乳化液を調製し、実施例2と
同じ条件で切削試験を行なった。その結果を表4に示す
が、乳化系切削油においても本発明の潤滑油が優れてい
ることがわかる。
実施例 3. 表5に示す組成物について、フロンR−12およびR−
134aへの溶解性試験とチムケン式油性試験を行った。そ
の結果を表6に示す。
なお、溶解性試験は表5の組成物とフロンとを耐圧ガ
ラス溶器にとり、−5〜60℃の範囲で白濁が生ずるかど
うかを目視により観察し、白濁を生じる場合を溶解しな
いと判断した。
表6より本発明の潤滑油が冷媒であるフロンの溶解性
にすぐれ、潤滑性能にも優れていることがわかる。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C10N 40:08 40:22 40:24

Claims (1)

    (57)【特許請求の範囲】
  1. 【請求項1】一般式(1)で示されるアルケニルエーテ
    ルと無水マレイン酸、マレイン酸、マレイン酸塩または
    マレイン酸エステルとを単量体の必須成分とする共重合
    体からなる潤滑油。 (ただし、Zは2〜8個の水酸基をもつ化合物の残基、
    AOは炭素数2〜18のオキシアルキレン基の1種または2
    種以上で、2種以上のときはブロック状に付加していて
    も、ランダム状に付加していてもよく、Rは炭素数2〜
    5のアルケニル基、R1は炭素数1〜24の炭化水素基また
    はアシル基、a≧0、b≧0、c≧0、lは正の整数、
    mとnは0または正の整数、l+m+n=2〜8、n/
    (l+m)≦1/2、al+bm+cn=1〜1000である。)
JP2045702A 1989-04-26 1990-02-28 潤滑油 Expired - Fee Related JP2844804B2 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2045702A JP2844804B2 (ja) 1989-04-26 1990-02-28 潤滑油
BR909001925A BR9001925A (pt) 1989-04-26 1990-04-25 Oleo lubrificante e composicao de oleo lubrificante
EP90107994A EP0399239B1 (en) 1989-04-26 1990-04-26 The use of a copolymer of polyalkylene alkenyl ether and maleic anhydride, maleic acid, or a salt or ester of maleic acid as a lubricating agent.
ES90107994T ES2045624T3 (es) 1989-04-26 1990-04-26 El uso de un copolimero de monomeros.
DE9090107994T DE69000787T2 (de) 1989-04-26 1990-04-26 Verwendung eines copolymers aus polyoxyalkylen-alkenyl-ether und maleinsaeureanhydrid, maleinsaeure, einem maleinsaeuresalz oder maleinsaeureester als schmiermittel.
KR1019900005866A KR0150003B1 (ko) 1989-04-26 1990-04-26 윤활유
US07/801,633 US5250205A (en) 1989-04-26 1991-12-04 Lubricating oil

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP1-104646 1989-04-26
JP10464689 1989-04-26
JP2045702A JP2844804B2 (ja) 1989-04-26 1990-02-28 潤滑油

Publications (2)

Publication Number Publication Date
JPH0347895A JPH0347895A (ja) 1991-02-28
JP2844804B2 true JP2844804B2 (ja) 1999-01-13

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Country Link
EP (1) EP0399239B1 (ja)
JP (1) JP2844804B2 (ja)
KR (1) KR0150003B1 (ja)
BR (1) BR9001925A (ja)
DE (1) DE69000787T2 (ja)
ES (1) ES2045624T3 (ja)

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* Cited by examiner, † Cited by third party
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DE69229859T2 (de) * 1991-12-26 2000-04-20 Tonen Corp Schmieröl für kühlschrank
AU2004237804B2 (en) * 1999-08-16 2006-08-24 Ecolab Inc. Conveyor lubricant, passivation of a thermoplastic container to stress cracking and thermoplastic stress crack inhibitor
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EP0399239A1 (en) 1990-11-28
JPH0347895A (ja) 1991-02-28
EP0399239B1 (en) 1993-01-20
DE69000787T2 (de) 1993-07-01
ES2045624T3 (es) 1994-01-16
KR900016439A (ko) 1990-11-13
DE69000787D1 (de) 1993-03-04
KR0150003B1 (ko) 1998-10-01
BR9001925A (pt) 1991-07-30

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