JP3476916B2 - 潤滑油組成物 - Google Patents

潤滑油組成物

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Publication number
JP3476916B2
JP3476916B2 JP17631594A JP17631594A JP3476916B2 JP 3476916 B2 JP3476916 B2 JP 3476916B2 JP 17631594 A JP17631594 A JP 17631594A JP 17631594 A JP17631594 A JP 17631594A JP 3476916 B2 JP3476916 B2 JP 3476916B2
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JP
Japan
Prior art keywords
oil
lubricating oil
group
weight
ppm
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
JP17631594A
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English (en)
Other versions
JPH0841480A (ja
Inventor
庄蔵 松下
直美 鈴木
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.)
Tonen General Sekiyu KK
Original Assignee
Tonen General Sekiyu KK
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Filing date
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Application filed by Tonen General Sekiyu KK filed Critical Tonen General Sekiyu KK
Priority to JP17631594A priority Critical patent/JP3476916B2/ja
Priority to US08/750,263 priority patent/US5747430A/en
Priority to PCT/US1995/009564 priority patent/WO1996003480A1/en
Priority to CA002192491A priority patent/CA2192491A1/en
Publication of JPH0841480A publication Critical patent/JPH0841480A/ja
Application granted granted Critical
Publication of JP3476916B2 publication Critical patent/JP3476916B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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Description

【発明の詳細な説明】 【0001】 【産業上の利用分野】本発明は、抄紙機用潤滑油などの
軸受油、射出成型機用油圧油、フィルム延伸機用潤滑油
等に使用される潤滑油組成物であって、特に消泡性に優
れる潤滑油組成物に関する。 【0002】 【従来の技術】潤滑油に配合されている添加剤は、一般
に極性化合物が多く、それらは界面活性である為に、潤
滑油基油に添加されると、泡立ち易くなる。また、潤滑
油は使用中に酸化を受けて劣化すると、極性の大きい酸
化物が形成されたり、添加剤が分解すること等によって
さらに極性が大きくなり、界面活性となるため、泡立つ
傾向が出てくる。 【0003】潤滑油が泡立つと(1)潤滑油の圧縮性増
大のため、油圧作動が不良となる、(2)油圧ポンプの
効率が低下する、(3)摩擦部への給油が不十分とな
り、摩耗、焼き付き等の原因となる、(4)潤滑油と空
気の接触面積の増加により酸化が促進されるなどの弊害
を招くといった問題を生じるので、消泡性は、潤滑油に
とって非常に重要な性能の1つである。 【0004】そのため、潤滑油用消泡剤としては、一般
にジメチルシリコーン(ジメチルシロキサン)が最も良
く使用されており、これらのジメチルシリコーンは潤滑
油の基油組成や、潤滑油使用温度に応じて、40℃での
粘度が100mm2 /s〜100,000mm2 /sの
ものを単独又は混合して使用されている。 【0005】潤滑油の消泡性の評価は、JIS K25
18で規定される試験法で実施されるのが一般的であ
り、潤滑油に油温のちがい〔低温(24℃)及び高温
(93.5℃)での測定〕及び温度履歴を与えて泡立ち
度、泡安定度を見るもので、油温は最高93.5℃であ
る。この消泡性評価試験では、泡立ち度及び泡安定度は
50ml以下及び0mlが望ましく、この規格に対して
は、ジメチルシロキサン消泡剤を潤滑油に約100pp
m添加することで満足出来る結果が得られる。 【0006】 【発明が解決しようとする課題】しかしながら、潤滑油
の使用条件は、装置の小型化、高出力化の方向のため、
油温は高くなる傾向にあり、100℃を越えて使用され
るケースも多くなってきており、例えば、抄紙機用潤滑
油などの軸受油や射出成型機用油圧油では100℃を越
える摩擦箇所があり、高温による酸化安定性、消泡性が
重要な性能となっている。 【0007】潤滑油の消泡性の評価方法で100℃以上
の油温で実施するものとして、ILSAC(国際潤滑油
標準化委員会)に規定される油温150℃での油の消泡
性評価法がある。これはエンジン油の消泡性の評価を目
的に作成された試験であるが、抄紙機油などの極めて高
温で使用される工業用潤滑油の消泡性を評価することが
できる。 【0008】潤滑油は高粘度になる程、泡沫膜厚が大き
くなり、消泡性が悪くなる。特にVG68(68mm2
/s、at40℃)以上の粘度の潤滑油では、ジメチル
シリコーンを1〜100ppm添加しても150℃のI
RSAC試験法では、泡立ち度/泡安定度ともいずれも
100ml以上で、ジメチルシリコーンでは改善出来な
い。また、ジメチルシリコーンを100ppm以上添加
しても、ジメチルシリコーンの油中への均一分散に限界
があり、沈降し、消泡性も改善されない。本発明は、高
温条件下でも、消泡性に優れる潤滑油組成物の提供を課
題とする。 【0009】 【課題を解決するための手段】本発明の潤滑油組成物
は、40℃での粘度が10mm/s〜700mm
sの基油に、基油に対して、40℃での粘度が1,00
0mm/s〜100,000mm/sのオルガノポ
リシロキサンを1ppm〜500ppm、及び下記一般
式(1)で示されるエチレングリコール−プロピレング
リコール重合物を1ppm〜5,000ppmの割合で
配合したことを特徴とする。一般式(1): O(C O) (C O) (C
O) (式中、R 、R は水素原子または炭素数1〜4のア
ルキル基を表わし、a、cは1〜30の整数、bは1〜
60の整数を表わす。) 【0010】基油としては、鉱油系、ポリ−α−オレフ
ィン類、アルキルベンゼン等の合成炭化水素系、エステ
ル系、ポリアルキレングリコール、アルキルジフェニル
エーテル、アルキルジフェニル等またはこれらの混合油
が挙げられる。 【0011】鉱油としては、溶剤精製または水添精製に
よる60ニュートラル油、100ニュートラル油等及び
これらの基油からワックス分を除くことにより低温流動
性を改善した低流動点基油等があり、これらを単独また
は適当な割合で混合して用いることができる。 【0012】ポリ−α−オレフィン類としては、炭素数
2〜14、好ましくは4〜12の範囲の分枝を有する、
或いは有しないオレフィン炭化水素から選択された任意
の1種の単独重合体又は2種以上の共重合により得られ
るものであり、平均分子量100〜約2000、好まし
くは200〜約1000の生成物から選択されるが、特
に水素化によって不飽和結合を除去したものが好まし
い。 【0013】アルキルベンゼンとしては、主としてアル
キルベンゼン型のものであり、ベンゼンやトルエンのよ
うな芳香族炭化水素をフリーデルクラフツ反応等でアル
キル化して、洗剤の原料を作る際に副生する、主として
ジアルキル化芳香族炭化水素を含む油である。アルキル
基としては直鎖及び/又は分枝のいずれのものもこれに
属する。 【0014】また、エステル系基油としては、ポリオー
ルエステル類、ジエステル類等を挙げることができ、単
独で使用してもよいが混合して使用してもよい。ポリオ
ールエステル、ジエステル等のエステルとしては、脂肪
族多価アルコールと直鎖状又は分枝状の脂肪酸とのポリ
オールエステル類、脂肪族多価アルコールと直鎖状又は
分枝状の脂肪酸との部分エステル類、ネオペンチルグリ
コールと、炭素数8〜20の直鎖状又は分枝状の脂肪酸
とのジエステル類、脂肪族多価アルコールと炭素数8〜
20の直鎖状又は分枝状の脂肪酸との部分エステル類と
直鎖状又は分枝状の脂肪族二塩基酸又は芳香族二塩基酸
とのコンプレックスエステル類、直鎖状又は分枝状の脂
肪族二塩基酸のジアルキルエステル類、芳香族二塩基酸
のジアルキルエステル類等が挙げられる。 【0015】上記の基油で好ましいのは、鉱油及び/又
は合成炭化水素である。また、基油としては40℃での
粘度が10mm2 /s〜700mm2 /sの範囲のもの
を使用できる。 【0016】次に、添加剤について説明する。消泡剤と
してのオルガノポリシロキサンとしては、平均単位式 【0017】 【化1】 【0018】(式中、Rは炭素数1〜18の、同じか又
は異なる、場合によりハロゲン化された炭化水素基を示
し、nは200〜1200の数である)で示されるもの
であり、40℃での粘度が100mm2 /s〜100,
000mm2 /s、好ましくは3,000mm2 /s〜
60,000mm2 /sのものが挙げられる。40℃で
の粘度が100mm2 /s未満であると高温での消泡性
が悪化するので好ましくなく、100,000mm2
sを越えると基油に微細粒子として分散しにくくなるた
め好ましくない。 【0019】式中、Rとしてはメチル基、エチル基、n
−プロピル基、i−プロピル基、n−ブチル基、i−ブ
チル基、t−ブチル基、n−ペンチル基、ネオペンチル
基、ヘキシル基、ヘプチル基、オクチル基、デシル基、
及びオクタデシル基のようなアルキル基、フェニル基、
ナフチル基のようなアリ−ル基、ベンジル基、1−フェ
ニルエチル基、2−フェニルエチル基のようなアラルキ
ル基、o−、m−、p−ジフェニル基のようなアルアリ
−ル基、o−、m−、p−クロルフェニル基、o−、m
−、p−ブロムフェニル基、3,3,3−トリフルオル
プロピル基、1,1,1,3,3,3−ヘキサフルオル
−2−プロピル基、ヘプタフルオルイソプロピル基及び
ヘプタフルオロ−n−プロピル基のようなハロゲン化炭
化水素基である。 【0020】オルガノポリシロキサンは、基油に対して
1ppm〜500ppm、好ましくは5ppm〜100
ppmの割合で添加される。 【0021】次に、エチレングリコール−プロピレング
リコール重合物について説明する。エチレングリコール
−プロピレングリコール重合物は、一般式(1) R1O (C2H4O)a (C3H6O)b (C2H4O)c R2 (式中、R1 、R2 は水素原子または炭素数1〜4のア
ルキル基を表わし、a、cは1〜30の整数、bは1〜
60の整数を表わす。)で示され、総分子中のエチレン
オキシド含有量は10重量%〜50重量%で、重量平均
分子量が900〜4,000、好ましくは1,500〜
3,000のものである。 【0022】また、エチレングリコール−プロピレング
リコール重合物の誘導体としては、例えばエチレングリ
コール−プロピレングリコールのアミン縮合物が挙げら
れ、一般式(2) 【0023】 【化2】 【0024】(式中、R1 〜R4 は水素原子または炭素
数1〜4のアルキル基を表わし、a、c、f、hは1〜
20の整数、b、d、e、gは1〜30の整数、nは1
〜4の整数を表わす。)で示され、総分子中のエチレン
オキシド含有量は10重量%〜40重量%で、重量平均
分子量が500〜7000、好ましくは1,500〜
5,000のものを使用することができる。 【0025】その他、CAS登録番号No.68603
−58−7の化合物も同様に使用することができる。 【0026】エチレングリコール−プロピレングリコー
ル重合物、またはその誘導体は、単独でも混合して使用
してもよく、基油に対して1ppm〜5,000pp
m、好ましくは50ppm〜1,000ppmの割合で
添加される。 【0027】また、エチレングリコール−プロピレング
リコール重合物、またはその誘導体は、オルガノポリシ
ロキサンに対して1倍量〜1,000倍量、好ましくは
10倍量〜100倍量の割合で併用するとよく、また、
合計の配合量は、基油に対して1ppm〜5,000p
pm、好ましくは1ppm〜1,000ppm、更に好
ましくは10ppm〜500ppmである。 【0028】本発明の潤滑油組成物には、酸化防止剤、
流動点降下剤、摩耗防止剤、防錆剤、更には金属不活性
化剤等を添加してもよい。酸化防止剤としては、例えば
ジ(アルキルフェニル)アミン(アルキル基は炭素数4
〜20)、フェニル−α−ナフチルアミン、アルキルジ
フェニルアミン(アルキル基は炭素数4〜20)、N−
ニトロソジフェニルアミン、フェノチアジン、N,N’
−ジナフチル−p−フェニレンジアミン、アクリジン、
N−メチルフェノチアジン、N−エチルフェノチアジ
ン、ジピリジルアミン、ジフェニルアミン、フェノール
アミン、2,6−ジ−t−ブチル−α−ジメチルアミノ
パラクレゾール等のアミン系酸化防止剤、2.6−ジ−
t−ブチルパラクレゾ−ル、4.4’−メチレンビス
(2.6−ジ−t−ブチルフェノ−ル)、2.6−ジ−
t−ブチル−4−N,N−ジメチルアミノメチルフェノ
ール、2.6−ジ−t−ブチルフェノ−ル等のフェノ−
ル系酸化防止剤、また鉄オクトエ−ト、フェロセン、鉄
ナフトエ−ト等の有機鉄塩、セリウムナフトエ−ト、セ
リウムトルエ−ト等の有機セリウム塩、ジルコニウムオ
クトエ−ト等の有機ジルコニウム塩等の有機金属化合物
系酸化防止剤を使用するとよい。また上記の酸化防止剤
は単独で使用してもよいが、二種以上組み合わせて使用
することにより相乗効果を奏するようにして使用するこ
ともできる。酸化防止剤の使用割合は、基油に対して
0.001〜5重量%、好ましくは0.01〜2重量%
を使用するとよい。 【0029】流動点降下剤としては、ポリアルキルメタ
クリレート系、塩素化パラフィン系、エチレン−酢酸ビ
ニル系共重合体系、エチレン−アルキルアクリレート系
共重合体系、アルケニルこはく酸アミド系化合物等を使
用するとよく、基油に対して0.001重量%〜5重量
%、好ましくは0.01重量%〜1.0重量%の割合で
い配合するとよい。 【0030】摩耗防止剤には、チオ燐酸亜鉛が使用され
るが、燐酸エステル、チオ燐酸エステル、亜燐酸エステ
ル、チオカルバミン酸亜鉛、チオカルバミン酸エステ
ル、ポリスルフィド、ジスルフィド、硫化エステル、硫
化油脂などでもかまわない。摩耗防止剤の使用割合は、
基油に対して0.01重量%〜5重量%、好ましくは
0.1重量%〜3重量%使用するとよく、単独で使用し
てもよいが、二種以上組み合わせて使用することもでき
る。 【0031】防錆剤としては、エステル、カルボン酸、
アミン、アルコール、フェノール、カルボキシレート、
アミン塩、スルホン酸塩を使用するとよく、例えばコハ
ク酸、コハク酸エステル、オレイン酸牛脂アミド、バリ
ウムスルホネート、カルシウムスルホネート等が挙げら
れ、その使用割合は基油に対して0.01重量%〜10
重量%、好ましくは0.01重量%〜1.0重量%を使
用するとよい。 【0032】金属不活性化剤としては、例えばベンゾト
リアゾール、ベンゾトリアゾール誘導体、チアジアゾー
ル、チアジアゾール誘導体、トリアゾール、トリアゾー
ル誘導体、ジチオカルバメート等を、基油に対して0.
001重量%〜10重量%、好ましくは0.01重量%
〜1.0重量%の添加割合で使用するとよい。 【0033】 【作用及び発明の効果】高粘度潤滑油(VG68以上)
で高温(150℃)での消泡性は、従来の100℃以下
の温度で有効な消泡性を示すジメチルシリコーン又はそ
の誘導体を使用しても効果がない。又、ジメチルシリコ
ーンを多量(100ppm以上)に添加すると潤滑油は
白濁し、シリコーン分散粒子は沈降する。 【0034】本発明者等は、高粘度潤滑油(VG68以
上)で高温での泡立ち度及び泡安定度が50ml以下に
なる消泡剤の検討を鋭意実施したところ、消泡剤として
ジメチルポリシロキサン消泡剤とエチレングリコール−
プロピレングリコール重合物とを併用することで消泡性
が大幅に改善される事を見出した。 【0035】エチレングリコール−プロピレングリコー
ル重合物を単独で配合しても消泡性を示すものではな
く、この効果は、ジメチルポリシロキサンと併用するこ
とにより、極めて高い消泡性を発現するものである。以
下、実施例により、本発明を説明する。 【0036】 【実施例】表1に示す実施例1〜実施例4、比較例1〜
比較例8の潤滑油組成物を調製した。表1における組成
は重量部で示す。表1での基油、添加剤について説明す
る。 基油:40℃での粘度220mm2 /s、n−d−M環
分析で%CP 70以上、%CN 30以下、%CA 1以
下、S分50ppm以下、N分50ppm以下のVG2
20の水素化精製鉱油 酸化防止剤:実施例1〜4、比較例1〜8における酸化
防止剤の内訳はヒンダードフェノール0.2重量%、ア
ルキル化PAN(フェニル−α−ナフチルアミン:アル
キル基はC4 〜C12の直鎖又は分岐状)0.2重量%、
アルキル化DPN(ジフェニルアミン:アルキル基はC
4 〜C12の直鎖又は分岐状)0.1重量%である。 【0037】流動点降下剤:ポリメチルメタクリレート 防錆剤:アルケニルこはく酸エステル 消泡剤A:40℃での粘度が350mm/sのジメチ
ルポリシロキサン 消泡剤B:40℃での粘度が12,500mm/sの
ジメチルポリシロキサン 消泡剤C:40℃での粘度が60,000mm/sの
ジメチルポリシロキサン PEG−PPG重合物A:上述した一般式(1)で表さ
れるエチレングリコール−プロピレングリコール重合物
で、旭電化(株)製、商品名プルロニックL61、重量
平均分子量2,000 PEG−PPG重合物B:上述した一般式(2)で表さ
れるエチレングリコール−プロピレングリコール重合物
の誘導体でローム&ハース社製、商品名トリトンCF3
2、重量平均分子量5,700 実施例、比較例での潤滑油組成物について、消泡試験
を、JIS K2518〔93.5℃(Seq2)〕及
び、下記に示すILSAC(150℃)により行った。
その結果を同時に表1に示す。結果はいずれも、泡立て
直後の泡の量(ml)/泡立て後5秒間放置後の泡の量
(ml)である。 【0038】ILSAC:消泡性試験法 1.浴槽の温度150±0.5℃に保持する。 【0039】2.試料容器に180ml目盛まで潤滑油
組成物を入れ、150℃浴槽中に容器の900ml目盛
まで浸す。 【0040】3.20分間浴槽に浸し、直ちに洗浄にし
たディフューザーストーン付、空気導入管を容器に差込
み、中央に直立させ、底面に接するように取付けて5分
間試料中に浸す。 【0041】4.空気導入管を空気供給装置につなぎ、
流量200±5ml/minでディフューザーストーン
から最初の泡が出たときから5分±3秒間乾燥空気を試
料中に吹き込む。 【0042】5.空気供給装置から供給を止め、すばや
く泡の量を読み取る。(泡立ち度) 6.そのまま5秒間放置し、再び泡の量を読み取る。
(泡安定度) 【0043】 【表1】 【0044】比較例1は、消泡剤、重合物共に添加しな
い場合で、消泡性が悪いことがわかる。これに消泡剤
A、B、Cを0.001%添加した場合、比較例2、
3、4のようにJIS法(93.5℃)では泡立ち度、
泡安定度とも0mlまで低下するが、測定温度が150
℃では泡立ち度、泡安定度は50ml以下にはならない
ことがわかる。 【0045】また、比較例1のサンプルにPEG−PP
G重合物A又はBを添加したケース、即ち比較例5、6
では、JIS法では泡立ち度、泡安定度とも比較例1よ
り若干良くなるものの、ILSAC法では全く改善され
ないことがわかる。 【0046】これに対して、実施例1〜4に見られるよ
うに、比較例1に消泡剤とPEG−PPG重合物を組み
合わせ添加すると、JIS法、ILSAC法共に消泡性
が顕著に改善されることがわかる。即ち、消泡剤単独
(比較例2〜4)及びPEG−PPG重合体単独(比較
例5、6)を添加する場合と比較すると、両添加剤の併
用効果が著しい事がわかる。 【0047】また、消泡剤は消泡剤Aのように低粘度の
ものでは、PEG−PPG重合体と併用しても、比較例
7、8のように効果が無いことがわかる。消泡剤B及び
Cのような高粘度のものがPEG−PPG重合体A及び
Bと併用効果を発現することがわかる。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C10N 20:02 C10N 30:08 30:08 30:18 30:18 40:02 40:02 40:08 40:08 (56)参考文献 特開 昭49−47498(JP,A) 特開 昭57−159892(JP,A) 特開 昭59−105091(JP,A) 特開 平6−57276(JP,A) 特開 平1−161091(JP,A) 米国特許3235501(US,A) (58)調査した分野(Int.Cl.7,DB名) C10M 157/10 C10M 145/26 - 145/38 C10M 149/12 - 149/14 C10M 155/02 C10N 20:02 C10N 30:08 C10N 30:18 C10N 40:02 C10N 40:08

Claims (1)

  1. (57)【特許請求の範囲】 【請求項1】 40℃での粘度が10mm/s〜70
    0mm/sの基油に、基油に対して、40℃での粘度
    が1,000mm/s〜100,000mm/sの
    オルガノポリシロキサンを1ppm〜500ppm、及
    下記一般式(1)で示されるエチレングリコール−プ
    ロピレングリコール重合物を1ppm〜5,000pp
    mの割合で配合したことを特徴とする潤滑油組成物。一般式(1): O(C O) (C O) (C
    O) (式中、R 、R は水素原子または炭素数1〜4のア
    ルキル基を表わし、a、cは1〜30の整数、bは1〜
    60の整数を表わす。)
JP17631594A 1994-07-28 1994-07-28 潤滑油組成物 Expired - Fee Related JP3476916B2 (ja)

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US08/750,263 US5747430A (en) 1994-07-28 1995-07-08 Lubricant composition
PCT/US1995/009564 WO1996003480A1 (en) 1994-07-28 1995-07-28 Lubricant composition
CA002192491A CA2192491A1 (en) 1994-07-28 1995-07-28 Lubricant composition

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JP2002097485A (ja) * 2000-09-22 2002-04-02 Nippon Mitsubishi Oil Corp 抄紙機用潤滑油組成物
US7662271B2 (en) * 2005-12-21 2010-02-16 Chevron U.S.A. Inc. Lubricating oil with high oxidation stability
US7547666B2 (en) * 2005-12-21 2009-06-16 Chevron U.S.A. Inc. Ashless lubricating oil with high oxidation stability
JP5577954B2 (ja) * 2010-08-26 2014-08-27 トヨタ自動車株式会社 潤滑油組成物
JP6924693B2 (ja) * 2017-12-26 2021-08-25 Eneos株式会社 潤滑油組成物
WO2023189764A1 (ja) * 2022-03-30 2023-10-05 出光興産株式会社 潤滑油組成物並びに引火点向上剤及び引火点向上方法

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US3235501A (en) * 1962-06-11 1966-02-15 Socony Mobil Oil Co Inc Foam-inhibited oil compositions
US4125470A (en) * 1976-04-02 1978-11-14 Dow Corning Corporation Band-ply lubricant concentrates
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