JP5595999B2 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- JP5595999B2 JP5595999B2 JP2011225054A JP2011225054A JP5595999B2 JP 5595999 B2 JP5595999 B2 JP 5595999B2 JP 2011225054 A JP2011225054 A JP 2011225054A JP 2011225054 A JP2011225054 A JP 2011225054A JP 5595999 B2 JP5595999 B2 JP 5595999B2
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- Japan
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- carbon atoms
- acid
- phosphorothionate
- branched
- Prior art date
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- 125000000217 alkyl group Chemical group 0.000 claims description 130
- 150000001875 compounds Chemical class 0.000 claims description 81
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- 239000003795 chemical substances by application Substances 0.000 claims description 43
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- 239000002199 base oil Substances 0.000 claims description 31
- 125000002947 alkylene group Chemical group 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 18
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- 125000000962 organic group Chemical group 0.000 claims description 12
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- 150000001342 alkaline earth metals Chemical group 0.000 claims description 11
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 13
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 150000004671 saturated fatty acids Chemical class 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
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- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- WYFGCJADJYRNAK-UHFFFAOYSA-N tritetradecyl phosphate Chemical compound CCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCC)OCCCCCCCCCCCCCC WYFGCJADJYRNAK-UHFFFAOYSA-N 0.000 description 1
- XEQUZHYCHCGTJX-UHFFFAOYSA-N tritridecyl phosphate Chemical compound CCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC XEQUZHYCHCGTJX-UHFFFAOYSA-N 0.000 description 1
- SUZOHRHSQCIJDK-UHFFFAOYSA-N triundecyl phosphate Chemical compound CCCCCCCCCCCOP(=O)(OCCCCCCCCCCC)OCCCCCCCCCCC SUZOHRHSQCIJDK-UHFFFAOYSA-N 0.000 description 1
- UKPASDNOVTUNJT-UHFFFAOYSA-N triundecyl phosphite Chemical compound CCCCCCCCCCCOP(OCCCCCCCCCCC)OCCCCCCCCCCC UKPASDNOVTUNJT-UHFFFAOYSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 description 1
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Description
R27−CO−NR28−(CH2)p−COOZ1 (11)
[式中、R27は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R28は炭素数1〜4のアルキル基、Z1は水素原子、炭素数1〜30のアルキル基又は炭素数1〜30のアルケニル基、pは1〜4の整数をそれぞれ示す。]
[R29−CO−NR30−(CH2)q−COO]rZ2 (12)
[式中、R29は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R30は炭素数1〜4のアルキル基、Z2はアルカリ金属又はアルカリ土類金属原子、sは1〜4の整数、rはZ2がアルカリ金属原子の場合は1、アルカリ土類金属原子の場合は2をそれぞれ示す。]
[R31−CO−NR32−(CH2)s−COO]t−Z3−(OH)u (13)
[式中、R31は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R32は炭素数1〜4のアルキル基、Z3は2価以上の多価アルコールの水酸基を除いた残基、sは1〜4の整数、tは1以上の整数、uは0以上の整数をそれぞれ示し、t+uはZ3の価数である。]
R33−CH2COOH (14)
[式中、R33は炭素数7〜29のアルキル基、炭素数7〜29のアルケニル基又は一般式(15)で表される基を示す。
R34−C6H4O− (15)
(式中、R34は炭素数1〜20のアルキル基又は水素原子を示す。)]
R27−CO−NR28−(CH2)p−COOZ1 (11)
[式中、R27は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R28は炭素数1〜4のアルキル基、Z1は水素原子、炭素数1〜30のアルキル基又は炭素数1〜30のアルケニル基、pは1〜4の整数をそれぞれ示す。]
[R29−CO−NR30−(CH2)q−COO]rZ2 (12)
[式中、R29は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R30は炭素数1〜4のアルキル基、Z2はアルカリ金属又はアルカリ土類金属原子、sは1〜4の整数、rはZ2がアルカリ金属原子の場合は1、アルカリ土類金属原子の場合は2をそれぞれ示す。]
[R31−CO−NR32−(CH2)s−COO]t−Z3−(OH)u (13)
[式中、R31は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R32は炭素数1〜4のアルキル基、Z3は2価以上の多価アルコールの水酸基を除いた残基、sは1〜4の整数、tは1以上の整数、uは0以上の整数をそれぞれ示し、t+uはZ3の価数である。]
R33−CH2COOH (14)
[式中、R33は炭素数7〜29のアルキル基、炭素数7〜29のアルケニル基又は一般式(15)で表される基を示す。
R34−C6H4O− (15)
(式中、R34は炭素数1〜20のアルキル基又は水素原子を示す。)]
[式中、R1及びR2は同一でも異なっていてもよく、それぞれ炭素数3〜20の直鎖状又は分枝状のアルキル基、炭素数6〜20のアリール基、炭素数6〜20のアルキルアリール基あるいは炭素数6〜20のアリールアルキル基を示し、xは2〜6、好ましくは2〜5の整数を示す。]
硫化エステルとしては、具体的には例えば、牛脂、豚脂、魚脂、菜種油、大豆油などの動植物油脂;不飽和脂肪酸(オレイン酸、リノール酸又は上記の動植物油脂から抽出された脂肪酸類などを含む)と各種アルコールとを反応させて得られる不飽和脂肪酸エステル;及びこれらの混合物などを任意の方法で硫化することにより得られるものが挙げられる。
リン酸エステルとしては、具体的には例えば、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリヘプチルホスフェート、トリオクチルホスフェート、トリノニルホスフェート、トリデシルホスフェート、トリウンデシルホスフェート、トリドデシルホスフェート、トリトリデシルホスフェート、トリテトラデシルホスフェート、トリペンタデシルホスフェート、トリヘキサデシルホスフェート、トリヘプタデシルホスフェート、トリオクタデシルホスフェート、トリオレイルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、及びキシレニルジフェニルホスフェートなどが挙げられる。
示す。]
一般式(6)中のR20で示される炭素数1〜18のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等のアルキル基(これらアルキル基は直鎖状でも分枝状でも良い)が挙げられる。
[式中、R27は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R28は炭素数1〜4のアルキル基、Z1は水素原子、炭素数1〜30のアルキル基又は炭素数1〜30のアルケニル基、pは1〜4の整数をそれぞれ示す。]
[R29−CO−NR30−(CH2)q−COO]rZ2 (12)
[式中、R29は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R30は炭素数1〜4のアルキル基、Z2はアルカリ金属又はアルカリ土類金属原子、sは1〜4の整数、rはZ2がアルカリ金属原子の場合は1、アルカリ土類金属原子の場合は2をそれぞれ示す。]
[R31−CO−NR32−(CH2)s−COO]t−Z3−(OH)u (13)
[式中、R31は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R32は炭素数1〜4のアルキル基、Z3は2価以上の多価アルコールの水酸基を除いた残基、sは1〜4の整数、tは1以上の整数、uは0以上の整数をそれぞれ示し、t+uはZ3の価数である。]
一般式(11)〜(13)中、R27、R29及びR31はそれぞれ炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基を表す。基油への溶解性などの点から、炭素数6以上のアルキル基又はアルケニル基であることが必要であり、炭素数7以上であることが好ましく、炭素数8以上であることがより好ましい。また、貯蔵安定性などの点から、炭素数30以下のアルキル基又はアルケニル基であることが必要であり、炭素数24以下であることが好ましく、炭素数20以下であることがより好ましい。このようなアルキル基及びアルケニル基としては、具体的には例えば、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等のアルキル基(これらアルキル基は直鎖状でも分枝状でも良い);ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基等のアルケニル基(これらアルケニル基は直鎖状でも分枝状でも良く、また二重結合の位置も任意である)等が挙げられる。
[式中、R33は炭素数7〜29のアルキル基、炭素数7〜29のアルケニル基又は一般式(15)で表される基を示す。
(式中、R34は炭素数1〜20のアルキル基又は水素原子を示す。)]
一般式(14)中、R33は炭素数7〜29のアルキル基、炭素数7〜29のアルケニル基または一般式(15)で表される基を示す。R33で示されるアルキル基の炭素数は、基油への溶解性などの点から、7以上であることが好ましく、9以上であることがより好ましい。また、貯蔵安定性などの点から、アルキル基の炭素数は、29以下であることが好ましく、22以下であることがより好ましく、19以下であることが更に好ましい。このようなアルキル基としては、具体的には例えば、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基等(これらアルキル基は直鎖状でも分枝状でも良い)が挙げられる。
(i)一価アルコールと一塩基酸とのエステル
(ii)多価アルコールと一塩基酸とのエステル
(iii)一価アルコールと多塩基酸とのエステル
(iv)多価アルコールと多塩基酸とのエステル
(v)一価アルコール、多価アルコールとの混合物と多塩基酸との混合エステル
(vi)多価アルコールと一塩基酸、多塩基酸との混合物との混合エステル
(vii)一価アルコール、多価アルコールとの混合物と一塩基酸、多塩基酸との混合エ
ステル。
(ii−1)多価アルコールと不飽和脂肪酸とのモノエステル
(ii−2)多価アルコールと不飽和脂肪酸とのエステルであって、エステル化度が1である部分エステルとエステル化度が2以上である部分エステルとの双方を含むエステル
(ii−3)多価アルコールと脂肪酸との完全エステルであって、構成脂肪酸が炭素数1〜4の短鎖脂肪酸及び炭素数10〜24の長鎖脂肪酸の双方を含むエステル
(ii−4)多価アルコールと分岐飽和脂肪酸とのエステルであって、エステル化度が1である部分エステルとエステル化度が2以上である部分エステルとの双方を含むエステル。
3〜6価の脂肪族多価アルコールの具体例としては、グリセリン、トリメチロールプロパン、エリスリトール、ペンタエリスリトール、アラビトール、ソルビトール、マンニトールなどが挙げられる。上記一般式(16)〜(21)中のR35〜R59としては、メチル基、エチル基、n−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ウンデシル基、各種ドデシル基、各種トリデシル基、各種テトラデシル基、各種ペンタデシル基、各種ヘキサデシル基、各種ヘプタデシル基、各種オクタデシル基、フェニル基、ベンジル基などが挙げられる。また、上記エーテル化物は、R35〜R59の一部が水素原子である部分エーテル化物も包含する。
3〜6価の脂肪族多価アルコールの二分子縮合物,三分子縮合物の具体例としては、ジグリセリン、ジトリメチロールプロパン、ジペンタエリスリトール、ジソルビトール、トリグリセリン、トリトリメチロールプロパン、トリペンタエリスリトール、トリソルビトールなどが挙げられる。
モノビニルアミン、ジビニルアミン、トリビニルアミン、モノプロペニルアミン(全ての異性体を含む)、ジプロペニルアミン(全ての異性体を含む)、トリプロペニルアミン(全ての異性体を含む)、モノブテニルアミン(全ての異性体を含む)、ジブテニルアミン(全ての異性体を含む)、トリブテニルアミン(全ての異性体を含む)、モノペンテニルアミン(全ての異性体を含む)、ジペンテニルアミン(全ての異性体を含む)、トリペンテニルアミン(全ての異性体を含む)、モノヘキセニルアミン(全ての異性体を含む)、ジヘキセニルアミン(全ての異性体を含む)、モノヘプテニルアミン(全ての異性体を含む)、ジヘプテニルアミン(全ての異性体を含む)、モノオクテニルアミン(全ての異性体を含む)、ジオクテニルアミン(全ての異性体を含む)、モノノネニルアミン(全ての異性体を含む)、モノデセニルアミン(全ての異性体を含む)、モノウンデセニル(全ての異性体を含む)、モノドデセニルアミン(全ての異性体を含む)、モノトリデセニルアミン(全ての異性体を含む)、モノテトラデセニルアミン(全ての異性体を含む)、モノペンタデセニルアミン(全ての異性体を含む)、モノヘキサデセニルアミン(全ての異性体を含む)、モノヘプタデセニルアミン(全ての異性体を含む)、モノオクタデセニルアミン(全ての異性体を含む)、モノノナデセニルアミン(全ての異性体を含む)、モノイコセニルアミン(全ての異性体を含む)、モノヘンイコセニルアミン(全ての異性体を含む)、モノドコセニルアミン(全ての異性体を含む)、モノトリコセニルアミン(全ての異性体を含む)等のアルケニルアミン;
ジメチル(ビニル)アミン、ジメチル(プロペニル)アミン(全ての異性体を含む)、ジメチル(ブテニル)アミン(全ての異性体を含む)、ジメチル(ペンテニル)アミン(全ての異性体を含む)、ジメチル(ヘキセニル)アミン(全ての異性体を含む)、ジメチル(ヘプテニル)アミン(全ての異性体を含む)、ジメチル(オクテニル)アミン(全ての異性体を含む)、ジメチル(ノネニル)アミン(全ての異性体を含む)、ジメチル(デセニル)アミン(全ての異性体を含む)、ジメチル(ウンデセニル)アミン(全ての異性体を含む)、ジメチル(ドデセニル)アミン(全ての異性体を含む)、ジメチル(トリデセニル)アミン(全ての異性体を含む)、ジメチル(テトラデセニル)アミン(全ての異性体を含む)、ジメチル(ペンタデセニル)アミン(全ての異性体を含む)、ジメチル(ヘキサデセニル)アミン(全ての異性体を含む)、ジメチル(ヘプタデセニル)アミン(全ての異性体を含む)、ジメチル(オクタデセニル)アミン(全ての異性体を含む)、ジメチル(ノナデセニル)アミン(全ての異性体を含む)、ジメチル(イコセニル)アミン(全ての異性体を含む)、ジメチル(ヘンイコセニル)アミン(全ての異性体を含む)、ジメチル(トリコセニル)アミン(全ての異性体を含む)等のアルキル基及びアルケニル基を有するモノアミン;
モノベンジルアミン、(1−フェニルチル)アミン、(2−フェニルエチル)アミン(別名:モノフェネチルアミン)、ジベンジルアミン、ビス(1−フェニエチル)アミン、ビス(2−フェニルエチレン)アミン(別名:ジフェネチルアミン)等の芳香族置換アルキルアミン;
モノシクロペンチルアミン、ジシクロペンチルアミン、トリシクロペンチルアミン、モノシクロヘキシルアミン、ジシクロヘキシルアミン、モノシクロヘプチルアミン、ジシクロヘプチルアミン等の炭素数5〜16のシクロアルキルアミン;
ジメチル(シクロペンチル)アミン、ジメチル(シクロヘキシル)アミン、ジメチル(シクロヘプチル)アミン等のアルキル基及びシクロアルキル基を有するモノアミン;
(メチルシクロペンチル)アミン(全ての置換異性体を含む)、ビス(メチルシクロペンチル)アミン(全ての置換異性体を含む)、(ジメチルシクロペンチル)アミン(全ての置換異性体を含む)、ビス(ジメチルシクロペンチル)アミン(全ての置換異性体を含む)、(エチルシクロペンチル)アミン(全ての置換異性体を含む)、ビス(エチルシクロペンチル)アミン(全ての置換異性体を含む)、(メチルエチルシクロペンチル)アミン(全ての置換異性体を含む)、ビス(メチルエチルシクロペンチル)アミン(全ての置換異性体を含む)、(ジエチルシクロペンチル)アミン(全ての置換異性体を含む)、(メチルシクロヘキシル)アミン(全ての置換異性体を含む)、ビス(メチルシクロヘキシル)アミン(全ての置換異性体を含む)、(ジメチルシクロヘキシル)アミン(全ての置換異性体を含む)、ビス(ジメチルシクロヘキシル)アミン(全ての置換異性体を含む)、(エチルシクロヘキシル)アミン(全ての置換異性体を含む)、ビス(エチルシクロヘキシル)アミン(全ての置換異性体を含む)、(メチルエチルシクロヘキシル)アミン(全ての置換異性体を含む)、(ジエチルシクロヘキシル)アミン(全ての置換異性体を含む)、(メチルシクロヘプチル)アミン(全ての置換異性体を含む)、ビス(メチルシクロヘプチル)アミン(全ての置換異性体を含む)、(ジメチルシクロヘプチル)アミン(全ての置換異性体を含む)、(エチルシクロヘプチルアミン(全ての置換異性体を含む)、(メチルエチルシクロヘプチル)アミン(全ての置換異性体を含む)、(ジエチルシクロヘプチル)アミン(全ての置換異性体を含む)等のアルキルシクロアルキルアミン;等
が挙げられる。また、前記モノアミンには牛脂アミン等の、油脂から誘導されるモノアミンも含まれる。
(F−1)フェニルグリシジルエーテル型エポキシ化合物
(F−2)アルキルグリシジルエーテル型エポキシ化合物
(F−3)グリシジルエステル型エポキシ化合物
(F−4)アリルオキシラン化合物
(F−5)アルキルオキシラン化合物
(F−6)脂環式エポキシ化合物
(F−7)エポキシ化脂肪酸モノエステル
(F−8)エポキシ化植物油。
上記式(26)中、R49は炭素数1〜18の炭化水素基を表すが、このような炭化水素基としては、炭素数1〜18のアルキル基、炭素数2〜18のアルケニル基、炭素数5〜7のシクロアルキル基、炭素数6〜18のアルキルシクロアルキル基、炭素数6〜10のアリール基、炭素数7〜18のアルキルアリール基、炭素数7〜18のアリールアルキル基等が挙げられる。この中でも、炭素数5〜15のアルキル基、炭素数2〜15のアルケニル基、フェニル基及び炭素数1〜4のアルキル基を有するアルキルフェニル基が好ましい。
、アルキル−1,2−エポキシスチレン等が例示できる。
(式中、R64及びR65は同一でも異なっていてもよく、それぞれ炭素数1〜6のアルキレン基を示す。)]
一般式(28)中のR50としては、具体的には、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基等が挙げられるが、酸化安定性に優れる点から、tert−ブチル基が好ましい。また、R51としては、水素原子または上述したような炭素数1〜4のアルキル基が挙げられるが、酸化安定性に優れる点から、メチル基またはtert−ブチル基が好ましい。
フェニル−α−ナフチルアミンを表す上記一般式(32)中、R66は水素原子または炭素数1〜16の直鎖状若しくは分枝状のアルキル基を示している。R66の炭素数が16を超える場合には分子中に占める官能基の割合が小さくなり、酸化防止能力が弱くなる恐れがある。R66のアルキル基としては、具体的には例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシ基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基等(これらのアルキル基は直鎖状でも分枝状でも良い)が挙げられる。
実施例1〜3、参考例1、2及び比較例1〜8においては、それぞれ以下に示す基油及び添加剤を用いて表1〜3に示す組成を有する潤滑油組成物を調製した。
基油:
基油1:パラフィン系高度溶剤精製基油(40℃における動粘度:46.1mm2/s、粘度指数100)
基油2:パラフィン系水素化分解基油(40℃における動粘度:46.1mm2/s、粘度指数125)
(A)チオリン酸エステル:
A1:トリフェニルホスフォロチオネート
A2:トリ(ブチルフェニル)ホスフォロチオネート
(B)分散型粘度指数向上剤:
B1:炭素数1〜18のアルキルメタクリレート(90mol%)とモルホリノエチルメタクリレート(10mol%)との共重合体(数平均分子量:80,000)
B2:炭素数1〜18のアルキルメタクリレート(90mol%)とベンゾイルアミノメタクリレート(10mol%)との共重合体(数平均分子量:70,000)
(C)一般式(11)〜(13)で表される化合物:
C1:N−オレオイルサルコシン
(D)一般式(14)で表される化合物:
D1:ノニルフェノキシ酢酸
(G)フェノール系酸化防止剤:
G1:ジ−tert−ブチル−p−クレゾール
(H):アミン系酸化防止剤
H1:ジオクチルジフェニルアミン
その他の添加剤:
K1:ジオクチルジチオリン酸亜鉛
K2:トリクレジルホスフェート
K3:炭素数1〜18のアルキルメタクリレートの単独重合体(数平均分子量:150,000)
K4:ポリブテニルコハク酸無水物とテトラエチレンペンタミンとの反応により得られるモノタイプポリブテニルコハク酸イミド
K5:カルシウム ジノニルナフタレンスルホネート(50質量%溶液、キャリアオイル:パラフィン系溶剤精製鉱油、溶液の塩基価:170mgKOH/g)。
実施例1〜3、参考例1、2及び比較例1〜8の各潤滑油組成物について、JIS K 2540に規定する「潤滑油熱安定度方法」に準じ、容量50mlのビーカーに試料油50mlを採取し、鉄及び銅のコイル状触媒を加え、140℃の空気恒温槽で一定期間(10日、20日)熱安定性試験を行った。試験後の試料油をフィルターでろ過し、試料油中のスラッジ量を測定した。得られた結果を表1〜3に示す。
実施例1〜3、参考例1、2及び比較例1〜8の各潤滑油組成物について、SRV試験を行い、摩擦特性を評価した。より具体的には、図1に示すように、ディスク1とその上面上に配置されたボール2との点接触領域に試料油を塗布し、ボール2に鉛直下向き(図中の矢印A)に荷重を加えながらボール2をディスク1の上面に沿う方向(図中の矢印B)に相対的に往復動させた。このときの摩擦係数をディスク1保持器(図示せず)に取り付けたロードセル(図示せず)により測定した。ディスク1としては直径25mm、厚さ8mmのSPCC材製のものを用い、また、ボール2としては直径10mmのSPCC材製のものを用いた。また、ボール2に加える荷重は1,200N、ボール2の振幅は1mm、周波数は50Hz、温度は80℃とした。得られた結果を表1〜3に示す。
実施例1〜3,参考例1、2及び比較例1〜8の各潤滑油組成物について、JIS K 2520に規定する「石油製品−潤滑油−抗乳化性試験方法」に準じ、試験温度54℃で抗乳化性を評価した。得られた結果を表1〜3に示す。なお、表中の数値は、油層(ml)−水層(ml)−乳化層(ml)(経過時間(分))を意味する。
実施例1〜3、参考例1、2及び比較例1〜8の各潤滑油組成物について、ASTM D 2882に規定されたベーンポンプ試験を実施し、試験前後のベーン及びリングの重量を計測し、摩耗量を測定した。試験時間は100時間とした。得られた結果を表1〜3に示す。
実施例4〜6においては、上記の基油及び添加剤、並びに以下に示す油性剤を用いて、表4に示す組成を有する潤滑油組成物を調製した。
(E)油性剤:
E1:ソルビタンとオレイン酸とのエステル(ソルビタン モノオレエート25モル%、ソルビタン ジオレエート40モル%、ソルビタン トリオレエート30モル%、ソルビタン テトラオレエート5モル%)
E2:グリセリンと、酢酸及び炭素数16〜20の脂肪酸の混合脂肪酸とのトリエステル(脂肪酸組成:酢酸66モル%、炭素数16〜20の直鎖飽和脂肪酸30モル%、炭素数18の直鎖不飽和脂肪酸4モル%)
E3:グリセリンと炭素数16〜20の分岐飽和脂肪酸とのエステル(グリセリンモノエステル25モル%、グリセリンジエステル75モル%、グリセリントリエステル0モル%)
次に、実施例4〜6の各潤滑油組成物について、上記と同様にして、熱安定度試験、SRV(微小往復動摩擦)試験及び耐摩耗性試験を実施した。得られた結果を表4に示す。
Claims (4)
- 鉱油、油脂及び合成油から選ばれる少なくとも1種の基油と、チオリン酸エステルと、分散型粘度指数向上剤と、下記一般式(11)〜(13)で表される化合物から選ばれる少なくとも1種及び/又は下記一般式(14)で表される化合物と、を含有し、
摩耗防止剤であるジチオリン酸亜鉛、無灰系分散剤であるコハク酸イミド及び金属清浄剤であるカルシウム スルホネートをそれらの効果が発揮されるのに必要な有効量を含有しない、
油圧作動油として用いられることを特徴とする潤滑油組成物。
R27−CO−NR28−(CH2)p−COOZ1 (11)
[式中、R27は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R28は炭素数1〜4のアルキル基、Z1は水素原子、炭素数1〜30のアルキル基又は炭素数1〜30のアルケニル基、pは1〜4の整数をそれぞれ示す。]
[R29−CO−NR30−(CH2)q−COO]rZ2 (12)
[式中、R29は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R30は炭素数1〜4のアルキル基、Z2はアルカリ金属又はアルカリ土類金属原子、sは1〜4の整数、rはZ2がアルカリ金属原子の場合は1、アルカリ土類金属原子の場合は2をそれぞれ示す。]
[R31−CO−NR32−(CH2)s−COO]t−Z3−(OH)u (13)
[式中、R31は炭素数6〜30のアルキル基又は炭素数6〜30のアルケニル基、R32は炭素数1〜4のアルキル基、Z3は2価以上の多価アルコールの水酸基を除いた残基、sは1〜4の整数、tは1以上の整数、uは0以上の整数をそれぞれ示し、t+uはZ3の価数である。]
R33−CH2COOH (14)
[式中、R33は炭素数7〜29のアルキル基、炭素数7〜29のアルケニル基又は一般式(15)で表される基を示す。
R34−C6H4O− (15)
(式中、R34は炭素数1〜20のアルキル基又は水素原子を示す。)] - 前記チオリン酸エステルが、トリブチルホスフォロチオネート、トリペンチルホスフォロチオネート、トリヘキシルホスフォロチオネート、トリヘプチルホスフォロチオネート、トリオクチルホスフォロチオネート、トリノニルホスフォロチオネート、トリデシルホスフォロチオネート、トリウンデシルホスフォロチオネート、トリドデシルホスフォロチオネート、トリトリデシルホスフォロチオネート、トリテトラデシルホスフォロチオネート、トリペンタデシルホスフォロチオネート、トリヘキサデシルホスフォロチオネート、トリヘプタデシルホスフォロチオネート、トリオクタデシルホスフォロチオネート、トリオレイルホスフォロチオネート、トリフェニルホスフォロチオネート、トリクレジルホスフォロチオネート、トリキシレニルホスフォロチオネート、クレジルジフェニルホスフォロチオネート、キシレニルジフェニルホスフォロチオネート、トリス(n−プロピルフェニル)ホスフォロチオネート、トリス(イソプロピルフェニル)ホスフォロチオネート、トリス(n−ブチルフェニル)ホスフォロチオネート、トリス(イソブチルフェニル)ホスフォロチオネート、トリス(s−ブチルフェニル)ホスフォロチオネート、及びトリス(t−ブチルフェニル)ホスフォロチオネートからなる群より選ばれる少なくとも一種類である、請求項1記載の潤滑油組成物。
- 前記分散型粘度指数向上剤が、下記一般式(6)、(7)又は(8)で表される化合物から選ばれる1種又は2種以上のモノマーと、下記一般式(9)又は(10)で表される化合物から選ばれる1種又は2種以上のモノマーとの共重合体である、請求項1又は2に記載の潤滑油組成物。
- 前記チオリン酸エステルを組成物全量基準で0.05〜1.5質量%、
分散型粘度指数向上剤を組成物全量基準で0.1〜2質量%、並びに、
前記一般式(11)〜(13)で表される化合物から選ばれる少なくとも1種を組成物全量基準で0.005〜1質量%、及び/又は、前記一般式(14)で表される化合物を組成物全量基準で0.005〜0.5質量%、
含有する、請求項1〜3のいずれか一項に記載の潤滑油組成物。
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