JP2017527665A - 潤滑組成物用液体無灰抗酸化剤添加剤 - Google Patents
潤滑組成物用液体無灰抗酸化剤添加剤 Download PDFInfo
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- JP2017527665A JP2017527665A JP2017510564A JP2017510564A JP2017527665A JP 2017527665 A JP2017527665 A JP 2017527665A JP 2017510564 A JP2017510564 A JP 2017510564A JP 2017510564 A JP2017510564 A JP 2017510564A JP 2017527665 A JP2017527665 A JP 2017527665A
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- JP
- Japan
- Prior art keywords
- component
- toltriazole
- naphthylamine
- phenyl
- alkylated
- 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.)
- Granted
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012964 benzotriazole Substances 0.000 claims abstract description 11
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- 230000003381 solubilizing effect Effects 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- C11B5/00—Preserving by using additives, e.g. anti-oxidants
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Abstract
Description
1.ホウ酸化および/または非ホウ酸化無灰分散剤
2.追加の抗酸化剤化合物
3.密封膨張組成物
4.有機および有機金属系摩擦調整剤
5.極圧/摩耗防止剤
6.粘度調整剤
7.流動点降下剤
8.金属系洗浄剤
9.リン酸塩
10.消泡剤
11.防錆剤
12.銅腐食抑制剤
非ホウ酸化無灰分散剤は、オイルフリーベースで10重量パーセントまでの量で、最終流体組成物中に組み入れることができる。以下に列挙する無灰分散剤の多くの種類が当技術分野で既知である。ホウ酸化無灰分散剤もまた含まれる。
所望の場合、その他の抗酸化剤も本発明の組成物中で使用できる。典型的な抗酸化剤は、ヒンダードフェノール抗酸化剤、第二級芳香族アミン抗酸化剤、硫化フェノール抗酸化剤、油溶性銅化合物、有機モリブデン化合物、リン含有抗酸化剤、有機の硫化物、二硫化物および多硫化物などを含む。
[式中、R1は、4〜12個の炭素原子(より好ましくは8または9個の炭素原子)を有するアルキル基(好ましくは分岐アルキル基)であり、R2は、水素原子または4〜12個の炭素原子(より好ましくは8または9個の炭素原子)を有するアルキル基(好ましくは分岐アルキル基)である]のアルキル化ジフェニルアミンである。最も好ましくは、R1およびR2は同一である。そのような好ましい化合物の1種が、Naugalube(登録商標)438Lとして市販されて入手可能であり、材料は主として4,4’−ジノニルジフェニルアミン(すなわち、ビス(4−ノニルフェニル)(アミン))で、その中のノニル基が分岐していると理解される。そのような好ましい別の化合物としては、VANLUBE(登録商標)961またはIRGANOX(登録商標)L57が市販されて入手可能であり、材料はブチル化およびオクチル化したアルキル化ジフェニルアミンの混合物と理解される。
柔軟に密封を保つように設計された組成物もまた、当技術分野で周知である。好ましい密封膨張組成物は、イソデシルスルホランである。密封膨張剤は、組成物中に約0.1〜3重量パーセントで組み入れられるのが好ましい。置換3−アルコキシスルホランは、参照として本明細書に組み入れる、米国特許第4,029,587号で開示されている。
摩擦調整剤もまた、当業者に周知である。摩擦調整剤の有用なリストは、米国特許第4,792,410号に含まれており、参照として本明細書に組み入れる。米国特許第5,110,488号は脂肪酸の金属塩、特に亜鉛塩を開示しており、参照として本明細書に組み入れる。有用な摩擦調整剤は、脂肪亜リン酸エステル、脂肪酸アミド、脂肪エポキシド、ホウ酸化脂肪エポキシド、脂肪アミン、グリセロールエステル、ホウ酸化グリセロールエステル、アルコキシル化脂肪アミン、ホウ酸化アルコキシル化脂肪アミン、脂肪酸の金属塩、硫化オレフィン、脂肪イミダゾリン、ジチオカルバミン酸モリブデン(例えば、米国特許第4,259,254号、参照として本明細書に組み入れる)、モリブデン酸エステル(例えば、米国特許第5,137,647号および米国特許第4,889,647号、ともに参照として本明細書に組み入れる)、イオウ供与体を伴うモリブデン酸アミン(例えば、米国特許第4,164,473号、参照として本明細書に組み入れる)、およびそれらの混合物を含む。
ジアルキルジチオホスフェートスクシネートは、耐摩耗性の保護をもたらすために添加できる。亜鉛塩は、ホスホロジチオ酸またはジチオカルバミン酸の亜鉛塩として好ましく添加される。中でも使用のために好ましい化合物は、ジイソオクチルジチオリン酸亜鉛およびジベンジルジチオリン酸亜鉛ならびにジチオカルバミン酸アミルである。亜鉛塩と同一の重量パーセントの範囲内で潤滑組成物に含まれて耐摩耗性/極圧性能も発揮するのは、亜リン酸水素ジブチル(DBPH)およびモノチオリン酸トリフェニル、ならびにジブチルアミン−二硫化炭素−と、アクリル酸のメチルエステルとの反応により形成されたチオカルバミン酸エステルである。チオカルバミン酸エステルは米国特許第4,758,362号に、リン含有金属塩は米国特許第4,466,894号に記載されている。両特許は参照として本明細書に組み入れる。アンチモンまたは鉛の塩もまた、極圧用に使用できる。好ましい塩は、ジアミルジチオカルバミン酸アンチモンなどのジチオカルバミン酸の塩である。使用できる市販の摩耗防止剤および極圧剤の例は、VANLUBE(登録商標)727、VANLUBE(登録商標)7611M、VANLUBE(登録商標)9123、VANLUBE(登録商標)871およびVANLUBE(登録商標)981を含み、すべてVanderbilt Chemicals,LLCにより製造された。トリアリールリン酸塩はまた、耐摩耗性添加剤として使用でき、トリフェニルリン酸塩、トリクレゾールリン酸塩およびトリ−ブチル化フェニルリン酸塩を含む。
粘度調整剤(VM)および分散剤粘度調整剤(DVM)は周知である。VMおよびDVMの例は、ポリメタクリレート、ポリアクリレート、ポリオレフィン、スチレン−マレイン酸エステルコポリマー、ならびにホモポリマー、コポリマーおよびグラフトコポリマーを含む同様のポリマー物質である。粘度調整剤の要約は、米国特許第5,157,088号、第5,256,752号および第5,395,539号に見出すことができ、これらは参照として本明細書に組み入れる。VMおよび/またはDVMは好ましくは、完全に配合された組成物に10重量%程度まで含まれる。
これらの成分は、潤滑油の低温品質の改善に特に有用である。好ましい流動点降下剤はアルキルナフタレンである。流動点降下剤は、米国特許第4,880,553号および第4,753,745号で開示されており、それらは参照として本明細書に組み入れる。PPDは一般に潤滑組成物に添加して、低温および低ずり速度で測定される粘度を低下させる。流動点降下剤は、0.1〜5重量パーセントの範囲内で好ましく使用される。
潤滑組成物はまた多くの場合に、洗浄剤を含むことが好まれる。本明細書で使用する洗浄剤は、好ましくは有機酸の金属塩である。洗浄剤の有機酸部分は、好ましくはスルホン酸塩、カルボン酸塩、石炭酸塩またはサリチル酸塩である。洗浄剤の金属部分は、好ましくはアルカリ金属またはアルカリ土類金属である。好ましい金属は、ナトリウム、カルシウム、カリウムおよびマグネシウムである。洗浄剤は過塩基化されることが好ましく、中性の金属塩を形成するのに必要であるよりも化学量論的に過剰な金属が存在することを意味する。
潤滑組成物はまた好ましくは、少なくとも1種の含リン酸、含リン酸塩、含リン酸エステルまたはそれらの誘導体を、イオウ含有類似物を含めて含むことができ、好ましくは0.002〜1.0重量パーセントの量である。含リン酸、塩、エステルまたはそれらの誘導体には、含リン酸エステルまたはその塩、亜リン酸エステル、リン含有アミド、リン含有カルボン酸またはエステル、リン含有エーテルおよびそれらの混合物から選択される化合物を含む。
(i)式の化合物
(ii)BASF Corp.からIRGALUBE(登録商標)63として市販されているものなどのカルボン酸のジチオリン酸エステル、
(iii)BASF Corp.からIRGALUBE(登録商標)TPPTとして市販されているものなどのトリフェニルホスホロチオネート、および
を含む。
消泡剤は、当技術分野でシリコーンまたはフルオロシリコーン組成物として周知されている。そのような消泡剤は、Dow Corning CorporationおよびUnion Carbide Corporationから入手できる。好ましいフルオロシリコーン消泡剤製品はDow FS−1265である。好ましいシリコーン消泡剤製品は、Dow Corning DC−200およびUnion Carbide UC−L45である。また、ミシガン州Farmington HillsのOSI Specialities,Inc.から入手できるシロキサンポリエーテルコポリマー消泡剤も含めてよい。そのような材料の1種は、SILWET−L−7220として販売されている。消泡剤製品は、本発明の組成物中に、オイルフリーベースで5から80百万分率の程度で、存在する有効成分と共に含まれることが好ましい。
防錆剤の実施形態では、アルキルナフタレンスルホン酸の金属塩を含む。
任意で添加できる銅腐食抑制剤の実施形態では、チアゾール、トリアゾールおよびチアジアゾールを含む。そのような化合物の例示的実施形態では、ベンゾトリアゾール、トリルトリアゾール、オクチルトリアゾール、デシルトリアゾール、ドデシルトリアゾール、2−メルカプトベンゾチアゾール、2,5−ジメルカプト−1,3,4−チアジアゾール、2−メルカプト−5−ヒドロカルビルチオ−1,3,4−チアジアゾール、2−メルカプト−5−ヒドロカルビルジチオ−1,3,4−チアジアゾール、2,5−ビス(ヒドロカルビルチオ)−1,3,4−チアジアゾールおよび2,5−ビス(ヒドロカルビルジチオ)−1,3,4−チアジアゾールを含む。
回転圧力容器式酸化安定度試験(RPVOT、ASTM D 2272)は、組成が既知の未使用および使用済みタービン油用の品質管理手法として使用され、ならびに実験用油の酸化安定度を推定するための研究手法としても使用される、タービン油の酸化試験である。その試験は、温度と酸素圧力を上昇させて、銅コイル酸化触媒と水の存在下で、タービン油の酸化安定度を評価する。回転するガラス圧力容器によって、最大限の油−酸素の接触をもたらす。結果は、酸素圧力が25psiに低下するまでの時間として報告される。試験油、銅コイルおよび水をガラスの酸化圧力容器に装填する。容器を密封し、酸素で90psiまで加圧する。加圧した容器を150℃に維持した高温浴に装填し、試験期間中連続して回転させる。酸素の消費で試験を監視する。試験の開始から容器の圧力が25psiに低下する時点までの時間を、酸化寿命または酸化誘導時間として定義する。
加圧示差走査熱量計(PDSC)は、幅広い種類のエンジンおよび工業用潤滑油の評価用に一般に使用される技法である。その優れた再現性と共に試験の単純さ、および試験条件の容易な変更能力により、この手法は品質管理と潤滑剤研究の有益な手法となっている。試験は潤滑剤の薄膜の酸化安定度を、高温、高酸素圧の下で評価する。結果は通常、油の薄膜の酸化に起因する発熱放出の誘導時間として報告される。油の薄膜を試料保持器に置き、次いでDSCの圧力セルに装填する。指定のガスでセルを加圧し、DSCのコンピューター制御システムにより精密に制御される指定の加熱シーケンスに供する。一般に最も使用される加熱シーケンスは等温法である。実験は発熱放出が観察されるまで行う。実験の開始から発熱放出までの時間は、油の酸化の開始期を表し、酸化誘導時間として報告される。標準化試験手順ASTM D 6186、加圧示差走査熱量計(PDSC)による潤滑油の酸化誘導時間のための標準試験方法を、以下の例の試験手順として利用した。
Claims (14)
- 潤滑油用液体抗酸化剤組成物であって、成分
(1)固体のアルキル化−フェニル−α−ナフチルアミン、
(2)トリアゾール、トルトリアゾールまたはベンゾトリアゾールのアルキル化ジフェニルアミン誘導体、
(3)メチレンビス(ジ−n−ブチルジチオカルバメート)
を含み、
各成分は以下の重量比(1):(2):(3)約1〜13:1〜13:1〜13で存在する、組成物。 - 各成分が以下の重量比(1):(2):(3)約1〜8:1〜8:1〜8で存在する、請求項1に記載の組成物。
- 各成分が以下の重量比(1):(2):(3)約1〜2:0.125〜1:1〜2で存在する、請求項1に記載の組成物。
- 成分(1)がオクチル化フェニル−α−ナフチルアミンであり、成分(2)がトルトリアゾールのオクチル化ジフェニルアミン誘導体である、請求項1に記載の組成物。
- 少なくとも90重量%の潤滑剤基剤と、前記潤滑組成物の重量%として表記して、成分
(1)固体のアルキル化−フェニル−α−ナフチルアミン0.01〜1.0%、
(2)トリアゾール、トルトリアゾールまたはベンゾトリアゾールのアルキル化ジフェニルアミン誘導体0.01〜0.50%、および
(3)メチレンビス(ジ−n−ブチルジチオカルバメート)0.01〜1.0%
を含む液体抗酸化剤組成物と、を含む潤滑組成物。 - (1)固体のアルキル化−フェニル−α−ナフチルアミン0.10〜0.50%、
(2)トリアゾール、トルトリアゾールまたはベンゾトリアゾールのアルキル化ジフェニルアミン誘導体0.01〜0.30%、および
(3)メチレンビス(ジ−n−ブチルジチオカルバメート)0.10〜0.50%
を含む、請求項5に記載の潤滑組成物。 - (1)固体のアルキル化−フェニル−α−ナフチルアミン0.15〜0.30%、
(2)トリアゾール、トルトリアゾールまたはベンゾトリアゾールのアルキル化ジフェニルアミン誘導体0.01〜0.15%、および
(3)メチレンビス(ジ−n−ブチルジチオカルバメート)0.15〜0.30%
を含む、請求項6に記載の潤滑組成物。 - 成分(1)がオクチル化フェニル−α−ナフチルアミンであり、成分(2)がトルトリアゾールのオクチル化ジフェニルアミン誘導体である、請求項5に記載の潤滑組成物。
- 成分(1)がオクチル化フェニル−α−ナフチルアミンであり、成分(2)がトルトリアゾールのオクチル化ジフェニルアミン誘導体である、請求項6に記載の潤滑組成物。
- 成分(1)がオクチル化フェニル−α−ナフチルアミンであり、成分(2)がトルトリアゾールのオクチル化ジフェニルアミン誘導体である、請求項7に記載の潤滑組成物。
- 前記潤滑剤基剤がグリース、タービン油、コンプレッサー油、工業用潤滑油およびエンジン潤滑油の1種から選択される、請求項5に記載の潤滑組成物。
- 前記潤滑剤基剤がグリースまたはタービン油である、請求項11に記載の潤滑組成物。
- 分散剤、洗浄剤、摩擦調整剤、腐食抑制剤、防錆剤、耐摩耗添加剤、流動点降下剤、粘度指数調節剤、追加の抗酸化剤および極圧添加剤から選択される1種または複数の添加剤をさらに含む、請求項5に記載の潤滑組成物。
- 前記追加の抗酸化剤がアルキル化ジフェニルアミン抗酸化剤およびヒンダードフェノール抗酸化剤から選択される、請求項13に記載の潤滑組成物。
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CA2955240C (en) | 2019-02-19 |
CA2955240A1 (en) | 2016-03-10 |
ES2864718T3 (es) | 2021-10-14 |
AU2015312304B2 (en) | 2018-04-19 |
WO2016036493A1 (en) | 2016-03-10 |
MX2017002684A (es) | 2017-05-23 |
CN106604980B (zh) | 2020-04-17 |
KR20170033337A (ko) | 2017-03-24 |
ZA201700462B (en) | 2018-04-25 |
EP3189125A4 (en) | 2018-01-24 |
US20160068781A1 (en) | 2016-03-10 |
AU2015312304A1 (en) | 2017-02-02 |
KR101925224B1 (ko) | 2018-12-04 |
SG11201700335WA (en) | 2017-03-30 |
EP3189125B1 (en) | 2021-03-03 |
RU2660335C1 (ru) | 2018-07-10 |
CN106604980A (zh) | 2017-04-26 |
BR112017004423A2 (pt) | 2017-12-05 |
JP6336677B2 (ja) | 2018-06-06 |
EP3189125A1 (en) | 2017-07-12 |
BR112017004423B1 (pt) | 2021-02-23 |
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