WO2006025246A1 - Additive for lubricant - Google Patents

Abstract

Disclosed is an additive for lubricants having oxidation stability, thermal stability, NOx resistance and excellent functions for serving as an extreme-pressure additive or wear-resisting agent. Also disclosed is a lubricant composition containing such an additive. Specifically disclosed are an additive for lubricants which is composed of a phosphate derivative represented by the general formula (I) below and a lubricant composition containing such an additive. In the formula below, Y represents S (sulfur) or O (oxygen); R1 represents a monovalent organic group having 4-24 carbon atoms; R2 represents a divalent organic group having 1-6 carbon atoms; and n represents an integer of 1-3.

Description

 Specification

 Additive for lubricant

 Technical field

 [0001] The present invention relates to a lubricant additive, more specifically, excellent in oxidation stability, thermal stability and NOx degradation resistance, and an extreme pressure additive has an excellent function as an antiwear agent. New phosphoric acid ester derivative, reaction product of phosphoric acid ester derivative and zinc compound, or additive for lubricant comprising mixture of phosphoric acid ester derivative and organic zinc compound, and lubrication containing these additives It relates to an oil composition.

 Background art

 [0002] Lubricating oils are required to have an ability to prevent wear of metal surfaces due to sliding or rolling contact between parts when a mechanical device is operated and an ability to control wear. The Therefore, the role of the additive becomes extremely important in order to improve the wear resistance of the lubricating oil and extend the life of the equipment.

 On the other hand, the base oil alone cannot have many special properties required for the use of other lubricating oil compositions including internal combustion engine lubricating oil and drive system lubricating oil. Therefore, it is necessary to improve the performance of the lubricating oil composition by using a lubricating oil additive to impart each specific property. For this reason, there has been a search for lubricating oils having one or more properties suitable for use in these lubricating oil compositions.

 For example, Patent Document 1 describes a general formula as a lubricating oil.

 [0003] [Chemical 1]

ORXR '

0- P— ORXR '

 ORXR '

[Wherein R represents a saturated aliphatic hydrocarbon group having 2 to 3 carbon atoms, X represents O or S, respectively, and a plurality of R ′ are each an alkyl group having 1 to 18 carbon atoms, etc. is there. ] Although the phosphorus and sulfur-containing phosphate ester compounds represented by are disclosed, there is no description of specific uses.

 Patent Document 2 includes a general formula

[0005] [Chemical 2]

 CHu = CH 1 S— A 1 0— P ヽ,

 OR

[Wherein, A is an alkylene group having 2 to 6 carbon atoms, and R ′ is an alkyl group having 2 to 4 carbon atoms, respectively. ]

 The phosphoric acid ester derivative represented by the formula (1) is further disclosed and used as a flameproofing agent by copolymerizing with an acrylic ester.

 Patent Document 3 describes an aromatic amine and a general formula.

[0007] [Chemical 3]

[Wherein X is O or S (at least one is S), m is 0 or 1 (at least three m is 1), and a plurality of R are alkyl groups or aromatic groups. is there. ]

 An ester-based lubricating composition consisting of organic thiophosphoric acid or phosphorous acid represented by the formula S is disclosed and used as an antioxidant.

 Patent Document 4 includes a general formula

 Ya-S-Yb

 [Where Ya is

[0009] [Chemical 4] X

 II

 R— P— X — CH— Z R R,

[0010] wherein Z is a hydrocarbyl group, R is a hydrocarbyl group, a hydrocarbyloxy group, etc., and R 'is a hydrogen atom or a divalent hydrocarbyl group. X is S or O. Yb is a hydrocarbyl group or the like. ]

 The phosphorus- and sulfur-containing compounds represented by are described, and are used as oxidation stabilizers and antiwear agents.

 Patent Document 5 includes a general formula

[0011] [Chemical 5]

O

 ,

[RS- (R 0) _x ] _m — p II— (OH) _m ,

[In the formula, R is an alkyl group, a cycloalkyl group, etc., R ′ represents an alkyl group, X is 1 to 4, m is 1 or 2, and m + m ′ = 3. ]

 Is used as a corrosion inhibitor for ferrous metals.

 Patent Document 6 includes a general formula

 RO- (CH CH O) P (R ') "OH

 twenty two

 [Wherein, R is an alkyl group or alkenyl, R ′ is OH, alkoxy or the like, and X is 2-4. ]

 An alkoxypolyethyleneoxyphosphate phosphite ester represented by the formula (1) is disclosed and used as an additive to improve water tolerance for oils.

 Patent Document 7 includes a general formula

[0013] [Chemical 6] , ^X — ^R \

R— (S) _M — (R 1 0) _M '— P (Y) _M ',

 \ X—R, /

[Wherein, R is alkyl or the like, R ′ is an alkylene group, and X represents O, NH or S.] m is 1 to 3, m ′ is 1 to 12, and m ″ is 0 or 1.]

 And is used as an antiwear agent, antioxidation agent and friction modifier for lubricating oil compositions such as automotive transmission fluids.

 Patent Document 8 discloses sulfur obtained by reacting at least one sulfur composition with a di- or tri-hydrocarbyl phosphite and / or an amine compound as a useful additive in fuel and lubricating and functional fluid compositions. The phosphorus and nitrogen-containing derivatives of the containing compounds are disclosed.

 [0015] Patent Document 9 and Patent Document 10 include (1) β-hydroxythioether reactant, (2) dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, (3) Reaction products of reaction mixtures containing nucleophilic reactants are disclosed and used as antiwear and antioxidant agents.

 Patent Document 11 includes a general formula

 (R-X '-R' -Y ') -P- (OH)

 m 3 ~ m

 [Wherein, X ′ represents S (sulfur) and Y ′ represents S (sulfur) or 0 (oxygen). R represents an organic group having 6 to 20 carbon atoms, and R ′ represents an organic group having 1 to 6 carbon atoms. m is an integer of 1 to 3. ]

 And general formula

[0016] [Chemical 7] I Y,) P

[0017] [where Χ ', Υ', R, R 'are the same as above. ρ is an integer from 0 to 2, q is an integer from 0 or 1, and 0 at the same time It will not be. ]

 And phosphorus-containing sulfur-containing phosphite compounds represented by

 Patent Document 12 includes a general formula

 A— (RO) (R'O) -P- (O)

 m

 [Where A is H or OH, m is 0 or 1, m is 0, A is OH, m is 1, A is H or OH, R and R 'are H or at least one, respectively. O represents hydrocarbons containing S or O]

 A composition obtained by heat-treating phosphoric acid and Z or phosphorous acid represented by formula (I) and an imide dispersant containing boron is disclosed.

 Patent Document 13 includes a general formula

[0018] [Chemical 8]

[In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, X is O or S, respectively, and Z is a metal atom. ]

 Are used as additives for maintaining the base number and for preventing wear.

 However, when these conventional additives are used in lubricating oils, the extreme pressure, wear resistance, and friction characteristics under severe conditions under high loads are still unsatisfactory.

 [0020] Patent Document 1: US Patent No. 2750342

 Patent Document 2: US Patent No. 2960523 Specification

 Patent Document 3: US Patent No. 3446738

 Patent Document 4: US Patent No. 4081387

 Patent Document 5: US Patent No. 4511480

Patent Document 6: US Patent No. 4579672 Patent Document 7: US Patent No. 4776969

 Patent Document 8: WO88Z03554 pamphlet

 Patent Document 9: Pamphlet of W089Z12666

 Patent Document 10: Japanese Patent Publication No. 3-500061

 Patent Document 11: JP-A-11 171892

 Patent Document 12: U.S. Pat.No. 6352962

 Patent Document 13: Japanese Patent Application Laid-Open No. 2002-294271

 Disclosure of the invention

 Problems to be solved by the invention

[0021] The present invention has been made under such circumstances, and provides a novel thio-containing organophosphorus compound, and an additive for lubricating oil containing the compound, and further includes an internal combustion engine, a drive train machine, etc. An object of the present invention is to provide a lubricating oil composition excellent in extreme pressure properties, wear resistance and friction characteristics even under severe operating conditions under high loads.

 Means for solving the problem

[0022] As a result of intensive studies by the present inventors to achieve the above object, the specific phosphate ester derivative is excellent in thermal stability, oxidation stability, NOx resistance and base number maintenance. Thus, the present invention has been found to be useful as an extreme pressure agent, an antiwear agent and a friction property modifier, and the present invention has been completed.

 That is, the present invention provides the following additives for lubricants and the like.

1. General formula [I]

… ] [0023] [Chemical 9]

…]

[Wherein Y represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 3. ]

A lubricant additive comprising a phosphate ester derivative (A) represented by the formula: 2.—General formula [I]

[0025] [Chemical 10]

(R ¹ — S— R ² — Y) _n —

[In the formula, Y represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 3. ]

 A lubricant additive comprising a reaction product of a phosphate ester derivative (A) and a zinc compound (B) represented by the formula:

 3. General formula [I]

… ] [0027] [Chemical 11]

…]

[Wherein Y represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 3. ]

 A lubricant additive comprising a mixture of a phosphate ester derivative (A) represented by the formula (A) and an organic zinc compound (C).

 4. The additive for lubricant according to any one of 1 to 3 above, wherein Y is a phosphoric ester derivative in which Y is 0 (oxygen) in the general formula (I).

 5. The zinc compound (B) is at least one compound selected from the group forces of metal zinc, zinc oxide, organic zinc compound, zinc oxyacid salt, zinc, rogenyzinc and zinc complex.

2. Additive for lubricant according to 2.

6. Zinc compound (B) force The lubricant according to 2 above, which is at least one compound selected from the group consisting of zinc, zinc oxide, zinc hydroxide, zinc carbonate, dimethyl zinc, diphenyl zinc and zinc complexes. Additive. 7. Lubricating as described in 3 above, which is at least one compound selected from the group consisting of organic zinc compound (C) 1S zinc alkylcarboxylate, zinc alkylcarboxylate, zinc alkylphenol carboxylate and zinc alkarylcarboxylate Additive for pharmaceuticals.

 8. Organic Zinc Compound (C) Power Zinc Oleate, Zinc Isostearate, Zinc Stearate, Zinc Alkyl Phenolcarboxylate, Zinc Alkyl Salicylate For the lubricant according to 3 above, which is at least one compound selected. Additive.

 9. A lubricant additive composition comprising the lubricant additive according to any one of 1 to 8 above.

 10. Lubricating oil yarn composition comprising a lubricating base oil containing 0.001 to 0.5 mass% of the additive for lubricant according to any one of 1 to 8 above in terms of a phosphorus element conversion amount. .

 11. A lubricating oil thread for an internal combustion engine, wherein the lubricating base oil contains 0.001 to 0.5 mass% of the additive for lubricant according to any one of 1 to 8 above in terms of a phosphorus element conversion amount. And adult.

12. A method for producing an additive for lubricant, which is obtained by reacting the phosphate ester derivative (A) or the zinc compound (B) described in 2 or 4 above.

 The invention's effect

 [0029] The lubricating oil composition of the present invention is extremely excellent in base number maintenance in an NOx atmosphere, that is, long drain performance, and further has excellent wear prevention performance and high temperature cleaning performance.

 Therefore, lubricating oil for internal combustion engines with high NOx gas concentration and relatively high force, such as gasoline engines, diesel engines, and gas engines, natural gas, LPG (liquid petroleum gas), cracked gas It is effectively used as crankcase oil for internal combustion engines that use coal cracked gas as fuel. In addition, the lubricating oil composition of the present invention is a lubricating oil that requires base number maintenance, wear prevention performance, and high temperature cleanliness, such as lubricating oil for power transmission, gear oil, bearing oil, shock oil. It can also be used as absorber oil, industrial lubricating oil, etc.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0030] A first invention of the present application is an additive for a lubricant which also has a phosphate ester derivative (A) force represented by the above general formula [I]. In the general formula [I], R ¹ is preferably a hydrocarbon group having 4 to 24 carbon atoms, particularly an alkyl group having 8 to 16 carbon atoms. If the carbon number of R ¹ is smaller, oil solubility, extreme pressure characteristics, wear resistance, friction characteristics, and lubrication characteristics are inferior and corrosivity increases. Specifically, R ¹ is a butyl group, a pentyl group, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various types. Tetradecyl group, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, various eicodecyl groups, etc. alkyl groups; cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups Groups, various propyl cycloalkyl groups, various cycloalkyl groups such as dimethyl cycloalkyl groups; phenyl groups, various methyl phenyl groups, various ethyl phenyl groups, various propyl phenyl groups, various trimethyl phenyl groups, various butyl phenyl groups. Groups, aryl groups such as various naphthyl groups; benzyl groups, various phenyl groups And arylalkyl groups such as various methylbenzyl groups, various propyl groups, various butyl groups, and the like.

In the general formula [I], R ² is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Specifically, methylene group, ethylene group, 1,2-propylene group; 1,3-propylene group, various butylene groups, various pentylene groups, divalent aliphatic groups such as various hexylene groups, cyclohexane, methyl Examples include alicyclic groups having two bonding sites on alicyclic hydrocarbons such as cyclopentane, and various phenylene groups. Y represents S (sulfur) or 0 (oxygen) and contains at least one or more S as the general formula [I]. n represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2.

Specific examples of the phosphoric acid ester derivative represented by the above general formula [I] include tri (hexylthioethoxy) phosphoric acid ester, tri (octylthioethoxy) phosphoric acid ester, tri (dodecylthioethoxy) phosphoric acid. Acid ester, tri (hexadecylthioethoxy) phosphate, di (hexylthioethoxy) phosphate, di (octylthioethoxy) phosphate, di (dodecylthioethoxy) phosphate, di (he Oxadecylthioethoxy) phosphate ester, mono (hexylthioethoxy) phosphate ester, mono (octylthioethoxy) phosphate Examples include acid esters, mono (dodecylthioethoxy) phosphate esters, and mono (hexadecylthioethoxy) phosphate esters.

 The method for producing the phosphate ester derivative represented by the above general formula [I] is not particularly limited. For example, the phosphate ester derivative is represented by the general formula [II]

R ¹ -S-R ² -YH---[II]

R²は前記同様である。 ] で表わされるヒドロカルビルチオアルキルアルコールまたは、一般式 [III] [Wherein Y represents s (sulfur) or o (oxygen).

R ² is the same as described above. Or a hydrocarbylthioalkyl alcohol represented by the general formula [III]

R ¹ -X-R YNa---[III]

R²は前記同様である。 ] [Where X, Y,

R ² is the same as described above. ]

The hydrocarbyl thioalkoxide represented by the formula and phosphorus oxychloride (POC1)

 Three

It can be obtained by reacting in the presence of a medium or a base.

 In these reactions, the hydrocarbyl thioalkyl alcohol or hydrocarbyl thioalkoxide and phosphorus oxychloride are usually used in a molar ratio of 1 mole of phosphorus oxychloride per mole of hydrocarbyl thioalkyl alcohol or hydrocarbyl thioalkoxide 0.1-5. The range is 0 monole, more preferably 1 to 3 monole, still more preferably 1.5 to 2.5 monole.

 The reaction temperature is usually selected in the range of 60 to 100 ° C, preferably 30 to 50 ° C. This reaction may be performed without a catalyst or in the presence of a base. As this base, for example, triethylamine, pyridine and the like can be used. In carrying out this reaction, a solvent such as xylene, toluene, tetrahydrofuran (THF), or jetyl ether can be used.

 Other production methods include the general formula [II]

R ¹ -S-R ² -YH---[II]

R²は前記同様である。 ] で表わされるアルキルチオアルキルアルコールと五酸化二リン（P o )とを反応させる [Wherein Y represents s (sulfur) or o (oxygen).

R ² is the same as described above. ] The alkylthioalkyl alcohol represented by this is reacted with diphosphorus pentoxide (P o).

 twenty five

Can be obtained.

 In this reaction, the proportion of alkylthioalkyl alcohol and diphosphorus pentoxide used is

Usually, alkylthioalkyl alcohol 1 mol per mol of diphosphorus pentoxide in molar ratio 1 It is -12 mol, More preferably, it is 2-6 mol, More preferably, it is the range of 3-4 mol.

 The reaction temperature is usually selected in the range of about 0 to 140 ° C, preferably 30 to 110 ° C, more preferably 50 to 90 ° C. In carrying out this reaction, a solvent such as xylene, toluene, THF, jetyl ether, chloroform, etc. can be used.

[0033] A second invention of the present application is an additive for a lubricant comprising a reaction product of the phosphate ester derivative (A) and a zinc compound (B).

 Zinc compounds (B) are preferably metal zinc, zinc oxide, organic zinc compounds, zinc oxygenates, zinc halides, zinc complexes, etc. Specifically, zinc, zinc oxide, hydroxide亜 鉛 Zinc, zinc carbonate, dimethyl zinc, diphenyl zinc, zinc complexes, etc.

 The reaction of the phosphate ester derivative (A) and the zinc compound (B) can be obtained by reacting in the absence of a catalyst or in the presence of a catalyst. In this reaction, the proportion of the phosphoric acid ester derivative to the zinc compound is usually 0.1 to 5.0 mol of the phosphoric acid ester derivative per mol of the zinc compound. Preferably it is 1-3 mol, More preferably, it is the range of 1.5-2.5 mol.

 The reaction range is usually selected in the range of room temperature to 200 ° C, preferably 40 to 150 ° C. In carrying out this reaction, a solvent such as xylene, toluene, hexane or the like can be used.

[0034] The third invention of the present application is an additive for a lubricant comprising a mixture of a phosphate ester derivative (A) and an organozinc compound (C).

 As the organic zinc salt (C), alkyl or zinc zinc carboxylate, alkyl or zinc zinc carboxylate and the like are preferred. Specifically, zinc oleate, zinc isostearate, zinc stearate, alkylphenol Examples include zinc dicarboxylate and zinc alkylsalicylate.

 The lubricant additive in the present invention as described above can be used only in the phosphoric acid ester derivative (A), but the reaction product of the component (A) and the zinc compound (B), or the component (A) It is preferably used as a mixture with the organic zinc compound (C). These reactants and mixtures may be one kind or two or more kinds.

The effective blending amount of these additives is usually based on the strength base oil standard that varies depending on the application. The element content is preferably 0.001 to 1.0% by mass, more preferably 0.005 to 0.5% by mass.

 As the lubricating base oil, mineral oil or synthetic oil can be used. There are various types of mineral and synthetic oils, and they can be selected appropriately according to the application. Examples of mineral oils include paraffin-based mineral oils, naphthene-based mineral oils, intermediate-based mineral oils, etc., and specific examples include light-eutral oils, medium-eutral oils obtained by solvent refining or hydrorefining, Heavy-eutral oil, bright stock, etc.

 On the other hand, synthetic oils include, for example, poly-a-olefin, a-olefin copolymer, polybutene, alkylbenzene, polyol ester, dibasic acid ester, polyhydric alcohol ester, polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxy Examples include alkylene glycol ethers and cycloalkane compounds.

 These lubricating base oils can be used alone or in combination of two or more, and mineral oil and synthetic oil may be used in combination.

 In the additive composition for lubricants of the present invention, various additive components conventionally used in lubricant compositions, for example, cleaning dispersants, antioxidants, and the like, as long as the object of the present invention is not impaired. Agents, antifungal agents, antifoaming agents, viscosity index improvers, pour point depressants, demulsifiers, other extreme pressure agents, antiwear agents, and the like can be blended.

 Example

 Next, the power to explain the present invention by way of examples The present invention is not limited in any way by these examples.

 Example 1

In a 500 ml flask, put 13.2 g (0.55 mol) of sodium hydride and 100 ml of xylene in a nitrogen stream, and stir a solution of 95.2 g (0.5 mol) of octylthioethanol in 100 ml of xylene. While dripping. The reaction was carried out for 5 hours while refluxing. On the other hand, 38.3 g (0.25 mol) of phosphorus oxychloride and 100 ml of THF were placed in a 1000 ml flask under ice-cooling under a nitrogen stream. The above reaction mixture was added dropwise over 2 hours, and then reacted at room temperature for 1 hour. To the reaction solution, 10 g (0.55 mol) of water was added dropwise and stirred at room temperature for 1 hour, and then 100 ml of water was added and stirred at room temperature for 1 hour. The organic layer and the aqueous layer were separated by standing, 100 ml of water was added to the organic layer again, and the mixture was stirred at room temperature. This was done twice. From the organic layer, xylene and THF were distilled, and unreacted octylthioethanol and by-product salt octylthioethyl were removed by distillation under reduced pressure. The yield of produced octylthioethyl phosphate is 75g.

[0037] Example 2

 Into a 300 milliliter flask, put 45 g of octylthioethyl phosphoric acid obtained in Example 1, 50 milliliters of toluene, lg of water, 70. The temperature was raised to C. 104. lg (0. 05 mol) of acid was added. The reaction was carried out at 70 ° C for 3 hours. Toluene and water were distilled off under reduced pressure, diluted with 15 g of 150N mineral oil, and the reaction product was filtered. The yield of the obtained reaction product was 60 g. Example 3

 In Example 1, it carried out like Example 1 except having used 123.3 g (0.5 mol) of dodecyl thioethanol instead of octyl thioethanol. The yield of the obtained reaction product (dodecylthioethyl phosphoric acid) was 92 g.

 Example 4

 In Example 2, Example 2 was used except that 55 g of the reaction product (dodecylthioethyl phosphoric acid) obtained in Example 3 was used instead of the reaction product obtained in Example 1. It was carried out in the same way. The yield of the obtained reaction product was 70 g.

[0038] Example 5

 In Example 1, it carried out like Example 1 except having used hexyl thioethanol 81.lg (0.5 mol) instead of octyl thioethanol. The yield of the obtained reaction product (hexylthioethyl phosphoric acid) was 6 lg.

 Example 6

 In Example 2, except that 33 g of the reaction product (hexylthioethyl phosphoric acid) obtained in Example 5 was used instead of the reaction product obtained in Example 1. This was carried out in the same way as 2. The yield of the obtained reaction product was 50 g.

Example 7 The same procedure as in Example 1 was performed except that 42.2 g (0.275 mol) of phosphorus oxychloride was used instead of 38.3 g (0.25 mol) of phosphorus oxychloride in Example 1. The yield of the obtained reaction product (octylthioethyl phosphoric acid) was 62 g.

Example 8

 In Example 2, Example 2 was used except that the reaction product (octylthioethyl phosphoric acid) obtained in Example 7 was used instead of the reaction product obtained in Example 1. It carried out like. The yield of the obtained reaction product was 60 g.

Example 9

 The same procedure as in Example 1 was performed except that 34.5 g (0.225 mol) of phosphorus oxychloride was used instead of 38.3 g (0.25 mol) of phosphorus oxychloride in Example 1. The yield of the reaction product obtained was 78 g.

Example 10

 In Example 2, except that the reaction product (octylthioethyl phosphoric acid) obtained in Example 9 was used instead of the reaction product obtained in Example 1, Example 2 was used. It carried out like. The yield of the reaction product obtained was 6 lg.

Example 11

 To a 1000 milliliter flask, 142.8 g (0. After completion of the addition, the mixture was reacted for 6 hours with stirring at 80 ° C., and then toluene was distilled under reduced pressure. The yield of the obtained reaction product was 178 g.

Example 12

 Into a 500 milliliter flask, add 112.8 g (0.4 mol) of selenic acid, 6.2 g (0.2 mol) of acid oxalic acid, 50 ml of toluene, and 2 g of water, and react at 70 ° C for 3 hours. It was. Toluene and water were distilled off under reduced pressure, diluted with 30 g of 150N mineral oil, and the reaction product was filtered. The yield of the reaction product obtained was 145 g.

Example 13

In Example 12, it carried out like Example 12 except having used stearic acid 113.6g (0.4 mol) instead of oleic acid. The yield of the reaction product obtained was 148 g Met.

 Example 14

 Execution ί Row 12 Executed in the same manner as in Example 12 except that 124.0 g (0.4 mol) of [kododecinoresalicinorelic acid] was used instead of oleic acid. . The yield of the obtained reaction product was 156 g.

[0040] Examples 15-23 and Comparative Examples 1, 2

 According to the formulation in Table 1, the phosphate ester derivative obtained above or a commercially available anti-wear agent or dibutyl ester phosphate and various additives were added to the base oil of 100N mineral oil or 500N mineral oil. Lubricating oil compositions (Examples 15 to 23) and comparative lubricating oil compositions (Comparative Examples 1 and 2) were prepared, respectively.

[0041] [Table 1]

Table 1

Lubricating oil composition (parts by mass)

 100N mineral oil 62.70 62.60 62.70 62.70 62.70 62.07 62.10 61.52 62.07 63.30 62.72

500N mineral oil * ² 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Example 1 compound--One--1.20 1.20 1.20---Example 2 compound 1.60------One---Example 4 Compound-1 J0 One-------Example 6 Compound-One 1.60--------Example 8 Compound---1.60---One---Example 10 Compound----1.60------Compound of Example 1 1---One----1.20--Compound of Example 12-----1.03--1.03--Example 1 of 3 Compound------1.00---1.00 Compound of Example 14-One-----1.58---Antiwear agent * ³ ---------1.00-Dibutyl esterolate phosphate ----------0.58 Viscosity index improver 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Pour point depressant 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Metal detergent * ⁴ 3.20 3.20 3.20 3.20 3.20 3.20 3.20 3.20 3.20 3.20 3.20 Ashless dispersant A * ⁵ 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.5 0 3.50 3.50 3.50 Ashless dispersant B * ⁶ 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Antioxidant ' ⁷ 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Other additives * ⁸ 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Phosphorus concentration in the composition 0.084 0.082 0.082 0.084 0.084 0.082 0.082 0.082 0.082 0.082 0.085

(mass%)

[0042] (Note)

* 1 Hydrorefined mineral oil, 100 ° C kinematic viscosity 4.5mm ² / s, sulfur content 0.0% by mass or less

* 2 Hydrorefined mineral oil, 100 ° C kinematic viscosity 10.9mm ² / s, sulfur content 0.01% or less

 * 3 Zinc secondary dialkyldithiophosphate, phosphorus content 8.2 mass%, zinc content 9.0 mass

%, Sulfur content 17.1% by mass

* 4 Ca salicylate, Ca: 7. 94 mass ^_0/0

 * 5 Polybutyrsuccinimide, nitrogen content 1.56% by mass

 * 6 Boron-modified polybutenyl succinimide, nitrogen content 1.76% by mass, boron content 2.0% by mass

 * 7 Mixture of dialkyldiphenylamine and hindered phenolic antioxidant * 8 Metal deactivator, antifoaming agent, demulsifier, etc.

[0043] Each composition obtained above was subjected to a NOx resistance test, a valve wear test, and a Falex load resistance test by the following methods.

 (1) NOx resistance test

 In the presence of iron and copper catalyst (oxidation test sample IS K-2514), nitrogen monoxide (NO) gas was blown into 6 ml of Zhr and air at a rate of 6 liter Zhr in 250 ml of sample oil. It is. The base number (hydrochloric acid method) was measured when the sample oil was forced to deteriorate while maintaining the temperature of the sample oil at 140 ° C. The smaller the base number decrease, the higher the base number maintainability even in a nitrogen oxide gas atmosphere used in an internal combustion engine.

 (2) Valve system wear test

 JASO M 328-95 valve train wear test was conducted, and the rocker arm pad scuff area, rocker arm wear, and cam wear after 100 hours test were measured. A value of 10 or less for each indicates a lubricating oil composition with excellent wear resistance.

 (3) Falex load capacity test

Pin material; AISI-3153, Block material; AISI-1137, Oil amount: 300ml, Rotation speed: 290rpm, Oil temperature: 100 ° C, Load 1112N After running-in for 5 minutes, oil The load is continuously increased at a temperature of 100 ° C, and seized according to ASTM D3233. The weight was measured. The higher the seizure load, the more excellent the load bearing capacity.

 [Table 2]

 Table 2-

[0045] [Table 3]

[0046] [Table 4] Table 4

[0047] From the NOx resistance test results shown in Table 2 above, the lubricating oil compositions (Examples 15 to 23) of the present invention show excellent base number maintenance in a nitrogen oxide gas atmosphere. On the other hand, it can be seen that in Comparative Example 1 in which the antiwear agent in the present invention was replaced with zinc dithiophosphate and tested in the same manner, the base number maintaining property was remarkably inferior.

 Also, from the results of the valve system wear test shown in Table 3, the wear resistance performance of the lubricating oil composition of the present invention (Examples 15 and 20) is excellent. It is obvious that is extremely inferior.

Comparative Example ² shows excellent base number durability even in a nitrogen atmosphere (Table 2), and also has excellent wear resistance performance (Table 3), but the load bearing performance is the lubricating oil composition of the present invention. It is markedly inferior to the product (Examples 15 and 20)! /,! /, (Table 4).

Industrial applicability The lubricating oil composition of the present invention can be used as, for example, an internal combustion engine lubricating oil, a power transmission lubricating oil, a gear oil, a bearing oil, a shock absorber oil, an industrial lubricating oil, and the like.

Claims

Claim [1] General formula [I] [Chemical 1]

3_n ■ ■, [I] [Wherein Y represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. n is an integer of 1 to 3. ]  A lubricant additive comprising a phosphate ester derivative (A) represented by the formula: [2] General formula [I] [Chemical 2]

… [I] [Wherein Υ represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. η is an integer of 1 to 3. ]  A lubricant additive comprising a reaction product of a phosphate ester derivative (誘導 体) and a zinc compound (Β) represented by the formula: [3] General formula [I] [Chemical 3]

3_η ■ ■, [I] [Wherein Υ represents S (sulfur) or 0 (oxygen). R ¹ represents a monovalent organic group having 24 carbon atoms and R ² represents a divalent organic group having 1 to 6 carbon atoms. η is an integer of 1 to 3. ] A lubricant additive comprising a mixture of a phosphate ester derivative (Α) represented by the formula (I) and an organic zinc compound (C). [4] The lubricant additive according to any one of claims 1 to 3, wherein in the general formula (I), Y is 0 (oxygen).  [5] The zinc compound (B) is at least one compound selected from the group consisting of metal zinc, zinc oxide, organic zinc compound, zinc oxyacid salt, zinc halide and zinc complex. 2. Additive for lubricant according to 2. [6] The zinc compound (B) force is at least one compound selected from the group consisting of zinc, zinc oxide, zinc hydroxide, zinc carbonate, dimethyl zinc, diphenyl zinc and zinc complexes. Additive for pharmaceuticals.  [7] The organozinc compound (C) power is at least one compound selected from the group consisting of zinc alkylcarboxylate, zinc alkylcarboxylate, zinc alkylcarboxylate and zinc alkylcarboxylate. The additive for lubricants as described.  [8] The organic zinc compound (C) is at least one compound selected from the group consisting of zinc oleate, zinc isostearate, zinc stearate, zinc alkylphenol carboxylate and zinc alkylsalicylate. Lubricant additive.  [9] A lubricant additive composition comprising the lubricant additive according to any one of claims 1 to 8, wherein the lubricant additive is blended.  [10] A lubricating oil yarn comprising the lubricating base oil containing 0.001 to 0.5 mass% of the additive for lubricant according to any one of claims 1 to 8 in terms of phosphorus element And adult.  [11] A lubricating oil for internal combustion engines, wherein the lubricating base oil contains 0.001 to 0.5 mass% of the additive for lubricant according to any one of claims 1 to 8 in terms of phosphorus element Yarn and adult product.  [12] A method for producing an additive for lubricant, which is obtained by reacting the phosphate ester derivative (A) according to claim 2 or 4 with a zinc compound (B).