阅读说明：本技术 润滑油用添加剂、润滑油用添加剂组合物及含有该添加剂或添加剂组合物的润滑油组合物 (Additive for lubricating oil, additive composition for lubricating oil, and lubricating oil composition containing additive or additive composition ) 是由 小田和裕 清水湧太郎 川本英贵 于 2020-03-10 设计创作，主要内容包括：本发明提供一种润滑油用添加剂,其由式(1)所表示的单酯羧酸盐(A)形成。式(1)中,R～(1)表示羰基的碳原子彼此键合而成的单键、或碳原子数为1～4的二价烃基,R～(2)表示碳原子数为1～22的烃基。AO表示选自碳原子数为2～4的氧化烯基中的一种的单独氧化烯基或两种以上的混合氧化烯基,n为AO所表示的氧化烯基的平均加成摩尔数,其表示0～5。M表示有机铵。(The invention provides an additive for lubricating oil, which is formed by monoester carboxylate (A) represented by formula (1). In the formula (1), R 1 A single bond formed by bonding carbon atoms of carbonyl groups or a divalent hydrocarbon group with 1-4 carbon atoms, R 2 Represents a hydrocarbon group having 1 to 22 carbon atoms. AO represents one oxyalkylene group alone or a mixed oxyalkylene group of two or more oxyalkylene groups selected from oxyalkylene groups having 2 to 4 carbon atoms, and n represents 0 to 5 in terms of the average molar number of addition of the oxyalkylene groups represented by AO. M represents an organic ammonium.)

1. An additive for lubricating oils, which is formed from a monoester carboxylate (A) represented by formula (1),

[ chemical formula 1]

Formula (1)

In the formula (1), R¹A single bond formed by bonding carbon atoms of carbonyl groups or a divalent hydrocarbon group with 1-4 carbon atoms, R²Represents a hydrocarbon group having 1 to 22 carbon atoms; AO represents one oxyalkylene group selected from oxyalkylene groups having 2 to 4 carbon atoms or a mixed oxyalkylene group of two or more, and n is an average molar number of addition of the oxyalkylene groups represented by AO and represents 0 to 5; m represents an organic ammonium.

2. An additive composition for lubricating oils, which comprises the additive for lubricating oils according to claim 1 and zinc dithiophosphate (B) represented by formula (2), wherein the mass ratio of monoester carboxylate (A) to zinc dithiophosphate (B) is (A): 99:1 to 1:99,

[ chemical formula 2]

Formula (2)

In the formula (2), R³～R⁶Each independently represents a hydrocarbon group having 1 to 24 carbon atoms.

3. A lubricating oil composition comprising 70 to 99.99% by mass of a base oil for lubricating oil and 0.01 to 30% by mass of the additive for lubricating oil according to claim 1.

4. A lubricating oil composition comprising 70 to 99.99% by mass of a base oil for lubricating oil and 0.01 to 30% by mass of the additive composition for lubricating oil according to claim 2.

Technical Field

The present invention relates to an additive for lubricating oil, an additive composition for lubricating oil, and a lubricating oil composition containing the additive for lubricating oil or the additive composition for lubricating oil. More specifically, the present invention relates to a multifunctional additive for ashless lubricating oils which can impart various functions such as wear resistance and metal corrosion resistance to a base oil for lubricating oils (hereinafter also simply referred to as "base oil") stably over time, does not contain a metal component such as zinc, phosphorus or sulfur, and does not generate ash when used; an additive composition for lubricating oils which can stably impart various functions such as load resistance and metal corrosion resistance to a base oil over time; and a lubricating oil composition containing the additive for lubricating oil or the additive composition for lubricating oil.

Background

Lubricating oils used in engine oils, hydraulic oils, metal working oils, and the like are composed of a base oil (base oil) and additives having various functions. Among the functions of lubricating oils, particular importance is placed on wear resistance and load resistance, and ZnDTP (zinc dithiophosphate) is generally used as a representative additive for imparting wear resistance and load resistance to lubricating oils.

However, ZnDTP is a compound containing zinc, phosphorus, and sulfur, and metal components such as zinc burn to generate ash. For example, when ZnDTP is contained in engine oil of a diesel vehicle, ash may be generated by driving the engine, and the ash may promote clogging of a dpf (diesel Particulate filter) mounted on the diesel vehicle. Further, if phosphorus or sulfur is contained, the influence on the three-way catalyst for purifying automobile exhaust gas may increase. Therefore, there is a demand for an ashless anti-wear agent which does not contain a metal component such as zinc, phosphorus, or sulfur and does not generate ash. As an ashless type anti-wear agent, for example, patent document 1 discloses a neutralized salt of a monoester carboxylic acid formed from a polybasic acid and an aliphatic alcohol and an aliphatic amine.

In recent years, with the demand for energy saving, it is desired to reduce the viscosity of lubricating oil in order to reduce the viscous resistance of the lubricating oil, but on the other hand, when the viscosity of the lubricating oil is reduced, the oil film on the friction surfaces becomes thin, and therefore wear due to contact between the friction surfaces may occur, and the equipment may deteriorate. Therefore, the anti-wear agent is required to exhibit good lubricity in various temperature and load regions, and further improvement of the above compound is desired.

In addition to wear resistance, various performances such as anti-emulsification properties and metal corrosion resistance are required for lubricating oils, and a plurality of additives are generally used in combination with an anti-wear agent.

However, depending on the type of the additive, there are additives that have poor compatibility in combination, and the functions of each may be impaired by the simultaneous use of the additives. Further, since it is desired to extend the life of the lubricating oil, there is a demand for a performance that can provide various functions with one additive and can stably exhibit the functions for a long period of time.

As the ashless type multifunctional additive, for example, patent document 2 discloses a neutralized product of a condensation reaction mixture obtained by reacting a polyhydric alcohol with a polycarboxylic acid for the purpose of improving metal corrosion resistance, but it is desired to develop an ashless type multifunctional additive having further improved stability with time.

On the other hand, when the amount of ZnDTP added is reduced, the load resistance may be lowered. Therefore, various studies have been made to reduce the amount of ZnDTP added and improve the load resistance. For example, patent document 3 discloses a lubricating oil agent containing a polysulfide extreme pressure agent and ZnDTP in combination, and patent document 4 discloses a lubricating oil composition containing a phosphonate ester and ZnDTP in combination.

With the recent increase in speed, pressure and size of industrial machines, mechanical elements such as hydraulic machines, compression machines and bearings are operated under more severe conditions. Therefore, lubricating oils used in these machines are required to exhibit excellent lubricating performance for a long period of time even under high-pressure, high-load, and high-temperature conditions. In addition to load resistance, various performances such as metal corrosion resistance are required for lubricating oils, and further improvement of additives for lubricating oils is desired.

Under such a background, for example, patent document 5 discloses an engine oil composition containing a glycerin fatty acid partial ester and ZnDTP in combination. However, this engine oil composition has insufficient load resistance, and development of an additive for lubricating oils having further improved stability over time has been desired.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 10-67995

Patent document 2: japanese laid-open patent publication No. 2015-168813

Patent document 3: japanese patent No. 4806198

Patent document 4: japanese laid-open patent publication No. 2005-2215

Patent document 5: japanese laid-open patent publication No. 2007-131792

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a multifunctional additive for ashless lubricating oils which can impart various functions such as wear resistance and metal corrosion resistance to base oils with stability over time, does not contain a metal component such as zinc, phosphorus or sulfur, and does not generate ash when used, and a lubricating oil composition containing the same.

Another object of the present invention is to provide an additive composition for lubricating oils which can reduce the amount of ZnDTP added and can stably impart various functions such as load resistance and metal corrosion resistance to a base oil over time, and a lubricating oil composition containing the additive composition.

Means for solving the problems

The inventors of the present invention have conducted extensive studies to achieve the above object and, as a result, have found that a lubricating oil having excellent various functions such as wear resistance and metal corrosion resistance can be obtained by incorporating a base oil containing a neutralized salt of a monoester carboxylic acid formed from a monohydric alcohol and a dibasic acid and an amine as an additive for lubricating oils.

Further, they have found that a lubricating oil excellent in various functions such as load resistance and metal corrosion resistance can be obtained by incorporating ZnDTP in a specific amount ratio to the above additive for lubricating oil in a base oil, and have completed the present invention. Based on the above findings, the present invention is [1] to [4] below.

[1] An additive for lubricating oils, which is formed from a monoester carboxylate (A) represented by formula (1).

[ chemical formula 1]

Formula (1)

In the formula (1), R¹A single bond formed by bonding carbon atoms of carbonyl groups or a divalent hydrocarbon group with 1-4 carbon atoms, R²Represents a hydrocarbon group having 1 to 22 carbon atoms. AO represents a group selected fromOne oxyalkylene group alone or a mixture of two or more oxyalkylene groups among oxyalkylene groups having 2 to 4 carbon atoms, and n is an average addition mole number of the oxyalkylene groups represented by AO and represents 0 to 5. M represents an organic ammonium.

[2] An additive composition for lubricating oils, comprising the additive for lubricating oils of the above [1] and zinc dithiophosphate (C) represented by formula (2), wherein the mass ratio of monoester carboxylate (a) to zinc dithiophosphate (B) is (a): 99:1 to 1: 99.

[ chemical formula 2]

Formula (2)

In the formula (2), R³～R⁶Each independently represents a hydrocarbon group having 1 to 24 carbon atoms.

[3] A lubricating oil composition comprising 70 to 99.99% by mass of a base oil for lubricating oil and 0.01 to 30% by mass of the additive for lubricating oil of the above [1 ].

[4] A lubricating oil composition comprising 70 to 99.99% by mass of a base oil for lubricating oil and 0.01 to 30% by mass of the additive composition for lubricating oil according to the above [2 ].

Effects of the invention

The additive for lubricating oils of the present invention can impart various functions such as wear resistance and metal corrosion resistance to the base oil for lubricating oils stably over time. Further, the additive for lubricating oils of the present invention is an ashless additive for lubricating oils which does not generate ash with use, and therefore does not cause clogging of filters such as DPF, and the additive for lubricating oils of the present invention does not contain phosphorus atoms or sulfur atoms, and therefore has a reduced effect on three-way catalysts. Therefore, even when the ZnDTP content of the lubricating oil composition containing the additive for lubricating oils and the base oil for lubricating oils of the present invention is zero, the lubricating oil composition is excellent in various functions such as wear resistance and metal corrosion resistance.

The additive composition for lubricating oils of the present invention can reduce the amount of ZnDTP added and can stably impart various functions such as load resistance and metal corrosion resistance to the base oil for lubricating oils over time. Therefore, a lubricating oil composition containing the additive composition for lubricating oils of the present invention and a base oil for lubricating oils is excellent in durability of each function such as load resistance and metal corrosion resistance, and can reduce the generation of ash.

Detailed Description

Hereinafter, embodiments of the additive for lubricating oil of the present invention (hereinafter, also simply referred to as "additive"), the additive composition for lubricating oil of the present invention (hereinafter, also simply referred to as "additive composition"), and the lubricating oil composition containing the additive or additive composition and the base oil for lubricating oil will be described in detail.

The numerical range defined by the symbols "to" includes numerical values at both ends (upper limit and lower limit) of "to" respectively. For example, "2 to 10" means 2 or more and 10 or less.

Further, where a concentration or amount is specifically stated, any higher concentration or amount can be correlated with any lower concentration or amount. For example, when there are descriptions of "2 to 10% by mass" and "preferably 4 to 8% by mass", the description further includes descriptions of "2 to 4% by mass", "2 to 8% by mass", "4 to 10% by mass", and "8 to 10% by mass".

[ additive for lubricating oil ]

The additive of the present invention is a compound represented by the following formula (1), which is a neutralized salt of a monoester carboxylic acid formed from a monohydric alcohol and a dibasic acid and an organic amine. In addition, the compound represented by the formula (1) may be hereinafter referred to simply as "monoester carboxylate (a)". The monoester carboxylate (a) may be used singly or in combination of two or more.

[ chemical formula 1]

Formula (1)

In the formula (1), R¹Represents a single bond formed by bonding carbon atoms of carbonyl groups or a divalent hydrocarbon group having 1 to 4 carbon atoms. The divalent hydrocarbon group having 1 to 4 carbon atoms isThe functional group composed of a carbon atom and a hydrogen atom is one selected from an alkylene group and an alkenylene group, and may be either linear or branched. When the number of carbon atoms of the hydrocarbon group is 5 or more, the chain length becomes long, and therefore, the wear resistance and the load resistance may not be sufficiently obtained.

R¹An alkylene group or an alkenylene group having 2 carbon atoms is preferable, and specifically, an ethylene group or an ethenylene group is exemplified, and an ethylene group is more preferable.

In the formula (1), R²Represents a saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms, and may be either linear or branched. As R²Examples thereof include straight-chain saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and docosyl; a branched saturated hydrocarbon group such as an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, an isooctyl group, a 2-ethylhexyl group, an isononyl group, a 3,5, 5-trimethylhexyl group, an isodecyl group, an isooctadecyl group, a 2-octyldecyl group, a 2-octyldodecyl group, and a 2-hexyldecyl group; and unsaturated hydrocarbon groups such as allyl, (meth) acrylic, palmitoyl, oleyl, and linoleyl groups. One of the compounds having these hydrocarbon groups may be used alone, or two or more of the compounds having these hydrocarbon groups may also be used in combination. When the number of carbon atoms is 23 or more, sufficient wear resistance and load resistance may not be obtained.

From the viewpoint of abrasion resistance or load resistance, R²Preferably a linear or branched saturated hydrocarbon group or a linear or branched unsaturated hydrocarbon group having 4 to 18 carbon atoms, more preferably a branched saturated hydrocarbon group or a branched unsaturated hydrocarbon group having 8 to 18 carbon atoms, and still more preferably a branched unsaturated hydrocarbon group having 16 to 18 carbon atoms. For example, 2-ethylhexyl group, isodecyl group, isooctadecyl group, oleyl group are preferable, and oleyl group is particularly preferable.

In the formula (1), AO represents an oxyalkylene group having 2 to 4 carbon atoms and may be either linear or branched. Examples of AO include oxyethylene group, oxypropylene group, oxybutylene group, and tetramethylene oxide. The oxyalkylene group having 2 to 3 carbon atoms is preferable, and the oxyethylene group having 2 carbon atoms is more preferable.

n represents the average molar number of addition of the oxyalkylene group, and n is 0 to 5. From the viewpoint of abrasion resistance, load resistance, and stability over time, n is preferably 1 or more. N is preferably 4 or less, and particularly preferably 3 or less. When n is 2 to 5, a plurality of oxyalkylene groups may be bonded (single oxyalkylene group) or a plurality of two or more oxyalkylene groups may be mixed and bonded (mixed oxyalkylene group).

In the formula (1), M represents organic ammonium. Examples of the organic ammonium include a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation in which a saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms is bonded to a nitrogen atom, and these ammonium cations may be linear, branched, or cyclic. In addition, the secondary ammonium cation, the tertiary ammonium cation, and the quaternary ammonium cation may have the same or different hydrocarbon groups. Examples of the organic ammonium include ethylammonium, diethylammonium, dioctylammonium, triethylammonium, trioctylammonium, dimethyldodecylammonium, and dimethyloctadecylammonium. From the viewpoint of metal corrosion resistance and stability over time, tertiary ammonium is preferable.

For the above R in formula (1)²The total number of carbon atoms contained in AO and M (organic ammonium) is preferably 0.5 to 2.0, more preferably 0.6 to 1.8, and particularly preferably 0.7 to 1.5 in terms of abrasion resistance and metal corrosion resistance.

[ (Total number of carbon atoms of Organoammonium)]/[(R²Carbon number of (3) + (carbon number of AO). times.n]The type (3)

Next, a method for producing the monoester carboxylate (a) represented by formula (1) will be described.

The method for producing the monoester carboxylate (a) represented by formula (1) is not particularly limited, and for example, the monoester carboxylate (a) represented by formula (1) can be produced through a first step of producing a monoester carboxylic acid and a second step of neutralizing the monoester carboxylic acid obtained in the first step with an amine compound.

The first step will be explained.

For example, there is a method of esterifying an alcohol having a hydrocarbon group having 4 to 22 carbon atoms or a polyether compound obtained by adding an alkylene oxide to the alcohol with a dibasic acid at 60 to 180 ℃. For the esterification reaction for producing the compound, an acid anhydride is preferably used as the dibasic acid from the viewpoint of reactivity. In addition, the reaction is preferably carried out using an alcohol in an equivalent molar ratio to the acid anhydride.

Next, the second step will be described.

The monoester carboxylate (a) can be produced, for example, by subjecting the monoester carboxylic acid produced by the above production method and an amine compound to a neutralization reaction at 20 to 60 ℃. From the viewpoint of abrasion resistance and load resistance, the monoester carboxylic acid/amine compound is preferably in a molar ratio of 60:40 to 40:60, more preferably in a molar ratio of 55:45 to 45:55, and still more preferably in a molar ratio of 52:48 to 48: 52.

[ additive composition for lubricating oil ]

The additive composition of the present invention contains the monoester carboxylate (a) and the zinc dithiophosphate (B) described below.

< Zinc dithiophosphate (B) >

The zinc dithiophosphate (B) is a compound represented by the following formula (2), and may be used singly or in combination of two or more.

[ chemical formula 2]

Formula (2)

In the formula (2), R³～R⁶Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, R³～R⁶Optionally identical to or different from each other. The hydrocarbon group having 1 to 24 carbon atoms is a saturated or unsaturated hydrocarbon group composed of carbon atoms and hydrogen atoms, and may be either linear or branched. Examples of the hydrocarbon group having 1 to 24 carbon atoms include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

R³～R⁶The alkyl group is preferably a linear or branched alkyl group having 3 to 18 carbon atoms, more preferably a linear or branched alkyl group having 3 to 12 carbon atoms, and still more preferably a branched alkyl group having 3 to 12 carbon atoms.

Examples of the linear alkyl group having 3 to 12 carbon atoms include propyl, butyl, pentyl, hexyl, octyl, decyl, and the like, and butyl and pentyl are more preferable. Furthermore, R of zinc dithiophosphate (C)³～R⁶Two or more of the above-mentioned linear alkyl groups are preferable, and two groups of a linear butyl group and a linear pentyl group are particularly preferable.

Examples of the branched alkyl group having 3 to 12 carbon atoms include isopropyl group, isobutyl group, isopentyl group, neopentyl group, isohexyl group, 2-ethylhexyl group, 3,5, 5-trimethylhexyl group, and isodecyl group, with isohexyl group, 2-ethylhexyl group, and 3,5, 5-trimethylhexyl group being more preferable, and isohexyl group being still more preferable.

Typical examples of such ZnDTP include LUBRIZOL677A, LUBRIZOL 1371 commercially available from Lubrizol Corporation.

The mixing ratio of the monoester carboxylate (A) represented by the formula (1) to the zinc dithiophosphate (B) represented by the formula (2) is 99:1 to 1:99, preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and still more preferably 60:40 to 40:60 in terms of mass ratio. When the content of the monoester carboxylate (a) is too large, the load resistance may be lowered, and when the content of the monoester carboxylate (a) is too small, the stability of the load resistance with time may be lowered.

The additive composition of the present invention contains at least the monoester carboxylate (a) and the zinc dithiophosphate (B), and may further contain other additives such as an extreme pressure agent, an anti-wear agent, and an antioxidant, within a range not to inhibit the effects of the additive composition of the present invention.

[ lubricating oil composition ]

The lubricating oil composition of the present invention contains the additive of the present invention or the additive composition of the present invention and a base oil for lubricating oil. The lubricating oil composition containing the additive of the present invention and the base oil for lubricating oil is referred to as "lubricating oil composition (1)", and the lubricating oil composition containing the additive composition of the present invention and the base oil for lubricating oil is referred to as "lubricating oil composition (2)".

In the present invention, various lubricating base oils can be used as the lubricating base oil. Examples of the base oil include conventionally used base oils for lubricating oils such as mineral oils, highly purified mineral oils, animal and vegetable fats and oils, synthetic esters, polyalphaolefins, and GTL (natural gas synthetic) oils.

The respective contents of the base oil and the additive for lubricating oil in the lubricating oil composition (1) of the present invention are: 70 to 99.99 mass% of a lubricating base oil and 0.01 to 30 mass% of an additive. The content of the lubricating base oil is preferably 80 to 99.95% by mass, more preferably 90 to 99.9% by mass. The content of the additive is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass. When the content of the additive in the lubricating oil composition (1) of the present invention is too small, sufficient wear resistance may not be obtained. Further, when the content of the additive is too large, metal corrosion resistance according to the added amount may not be obtained.

The total content of the base oil and the additive for lubricating oil is 100% by mass.

The respective contents of the base oil for lubricating oil and the additive composition in the lubricating oil composition (2) of the present invention are: 70 to 99.99 mass% of a lubricating base oil and 0.01 to 30 mass% of an additive composition. The content of the lubricating base oil is preferably 80 to 99.95% by mass, more preferably 90 to 99.9% by mass. The content of the additive composition is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass. When the content of the additive composition in the lubricating oil composition (2) of the present invention is too small, the load resistance may not be sufficiently obtained. Further, when the content of the additive composition is too large, load resistance and metal corrosion resistance according to the added amount may not be obtained.

The total content of the base oil for lubricating oil and the additive composition is 100% by mass.

The lubricating oil compositions (1) and (2) of the present invention may contain additives such as a detergent dispersant, a viscosity index improver, a rust preventive agent, a corrosion preventive agent, a pour point depressant, and a metal deactivator, as required.

The order of blending, mixing and adding the additives is not particularly limited, and various methods can be employed. For example, in preparing the lubricating oil composition (2) of the present invention, the following method may be used: a method in which monoester carboxylate (A) and zinc dithiophosphate (B) are added to a base oil for lubricating oils, and various additives are added according to circumstances, followed by heating and mixing; a method of preparing a high-concentration solution of each additive in advance and mixing the solution with a base oil for lubricating oil, and the like.

Examples

The present invention will be described in further detail below with reference to examples and comparative examples.

An example of producing the monoester carboxylate (a) represented by formula (1) is shown in synthesis example 1 below. Further, a preparation example of the lubricating oil composition (1) containing the monoester carboxylate (a) is shown in the following blend example 1.

Synthesis example 1 Compound (A-1) of formula (1)

To a pressure-resistant vessel having a capacity of 5 liters made of stainless steel and equipped with a stirrer, a pressure gauge, a thermometer, a safety valve, an air-injection tube, an exhaust tube, a cooling coil and a steam jacket, 1,070g (4mol) of oleyl alcohol and 1.3g of potassium hydroxide were charged, and after nitrogen substitution, the temperature was raised to 120 ℃ with stirring. Under stirring, 180g (4mol) of ethylene oxide was added from a separately prepared pressure-resistant vessel while pressurizing with nitrogen gas through a gas injection tube under conditions of 120 ℃ and 0.05 to 0.50MPa (gauge pressure). After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. Then, the reaction product was taken out from the pressure vessel, neutralized to pH 6 to 7 with hydrochloric acid, subjected to a reduced pressure treatment at 100 ℃ for 1 hour to remove water contained therein, and finally subjected to filtration to remove salts, thereby obtaining 1,200g of a polyether compound. The obtained polyether compound had a hydroxyl value of 180 and a molecular weight of 312 determined from the hydroxyl group.

Then, 312g (1mol) of the polyether compound obtained above and 100g (1mol) of succinic anhydride were charged into a glass reaction vessel having a capacity of 1 liter and equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, and reacted at 100 ℃ for 2 hours. After confirming that 99% or more of the acid anhydride was half-esterified by acid value measurement, the reaction mixture was cooled to room temperature. Then, 213g (1mol) of dimethyldodecylamine was added, stirred and neutralized at 60 ℃ or lower for 0.5 hour. Thus, Compound (A-1) was obtained.

The oleyl alcohol, ethylene oxide, succinic anhydride, and dimethyldodecylamine in synthesis example 1 were changed to other compounds as appropriate, and the compounds (a-2) to (a-7) of formula (1) shown in table 1 were synthesized by performing the operation based on synthesis example 1. Lubricating oil compositions (1-1) to (1-7) were prepared as described in blend example 1 using the above-mentioned compounds (A-2) to (A-7) as additives for lubricating oils.

The relationships between the compounds (A-1) to (A-7) and the symbols in the formula (1) and the values of the formula (3) are shown in Table 1.

[ Table 1]

Compound (I)

R1

R2

AO

n

M

Value of formula (3)

A-1

Ethylene radical

Oleyl radical

Oxyethylene radical

1

Dimethyl dodecyl ammonium

0.70

A-2

Ethylene radical

Isooctadecyl

Oxyethylene radical

1

Dimethyl octadecyl ammonium

1.00

A-3

Ethylene radical

2-ethylhexyl group

Oxyethylene radical

1

Dimethyl dodecyl ammonium

1.40

A-4

Ethylene radical

2-ethylhexyl group

Oxypropylene radical

1

Dimethyl dodecyl ammonium

1.70

A-5

Ethylene radical

Butyl radical

Oxyethylene radical

2

Dioctyl amine salt

2.00

A-6

Ethylene radical

Isooctadecyl

Oxyethylene radical

1

Hydrogen atom

0

A-7

Ethylene radical

Oleyl radical

Oxyethylene radical

7

Dimethyl dodecyl ammonium

0.44

Blend example 1 preparation of lubricating oil composition (1)

To a base oil for lubricating oil (polyalphaolefin, kinematic viscosity (40 ℃ C.): about 50mm²0.5 mass% of each of the above-mentioned compounds (A-1) to (A-7) was blended per second) to obtain lubricating oil compositions (1-1) to (1-7) of examples (1-1) to (1-5) and comparative examples (1-1) to (1-2). The obtained lubricating oil composition (test oil) was subjected to the following evaluation test. The evaluation results of examples (1-1) to (1-5) are shown in Table 2 below, and the evaluation results of comparative examples (1-1) to (1-2) are shown in Table 3 below.

Abrasion resistance test

The abrasion resistance was evaluated by using an SRV tester (model 4 of Schwingung Reihungund Verschleiss tester, manufactured by Ohio Co., Ltd.). The SRV test was carried out using a ball/disk (ball/disc), and test pieces were each manufactured using SUJ-2. The test conditions were a test temperature of 150 ℃, a load of 100N, an amplitude of 1mm, and a frequency of 50Hz, and the wear scar diameter after the lapse of 25 minutes from the test time was measured.

The evaluation settings were as follows: good: less than 350 μm, pass: 350 μm or more and less than 400 μm, fail: more than 400 μm.

Further, the wear resistance of the lubricating oil compositions (1-1) to (1-7) after being left to stand in a thermostatic bath at 80 ℃ for 3 days was evaluated under the same conditions as described above by adding 100ml of the test oil to a 100ml glass bottle and sealing the bottle in an air atmosphere.

Metal corrosion resistance test

As the metal corrosion resistance, copper corrosion resistance was evaluated. A copper wire cut to a length of 4cm was polished with P150 abrasive cloth. 2ml of test oil was added to a 5ml screw bottle, and the copper wire was immersed in the test oil and heated at 100 ℃ for 3 hours. The surface states before and after the test were compared, and the presence or absence of corrosion was evaluated.

The evaluation settings were as follows: good: no corrosion and failure: there is corrosion.

Furthermore, 100mL of a test oil was put into a glass bottle having a volume of 100mL, a copper wire was immersed in the test oil, the sealed structure was sealed in an air atmosphere, and the metal corrosion resistance of the lubricating oil compositions (1-1) to (1-7) after standing in a constant temperature bath at 80 ℃ for 3 days was evaluated under the same conditions as described above.

[ Table 2]

[ Table 3]

From the results shown in Table 2, it is understood that the compounds (A-1) to (A-5) relating to the additive of the present invention can stably impart excellent wear resistance and metal corrosion resistance to the base oil for lubricating oils over time. Further, since the compounds (A-1) to (A-5) do not contain a metal component such as zinc, the lubricating oil compositions (1-1) to (1-5) of examples (1-1) to (1-5) containing the compounds (A-1) to (A-5) do not generate ash with use, and are less likely to cause clogging of a filter such as a DPF. Further, since the compounds (A-1) to (A-5) do not contain a phosphorus atom or a sulfur atom, the effects of the lubricating oil compositions (1-1) to (1-5) of examples (1-1) to (1-5) on the three-way catalyst can be reduced.

On the other hand, as shown in Table 3, the compound (A-6) in which M in the formula (1) is outside the range specified in the present invention has good wear resistance, but has poor wear resistance and metal corrosion resistance with time.

Further, the compound (a-7) in which n in the formula (1) is out of the range specified in the present invention is excellent in wear resistance and metal corrosion resistance with time, but is poor in wear resistance immediately after production.

Next, preparation examples of additive compositions containing the compounds (A-1), (A-5), (A-6) and (A-7) of the formula (1) shown in Table 1 and the following zinc dithiophosphate (B) are shown in the following blend example 2. Further, a preparation example of a lubricating oil composition (2) containing the additive composition prepared in blend example 2 is shown in blend example 3 below.

[ zinc dithiophosphate: compounds (B-1) and (B-2) of formula (2)

As zinc dithiophosphate, LUBRIZOL677A (alkyl group: branched hexyl) and LUBRIZOL 1395 (alkyl group: linear butyl group and linear pentyl group) from Lubrizol Corporation were used. Compound (B-1) is LUBRIZOL677A, and compound (B-2) is LUBRIZOL 1395.

The relationship between the symbols in the formula (2) and the compounds is shown in Table 4.

[ Table 4]

Compound (I)	R3～R6
		B-1	Isohexyl radical
B-2	Straight-chain butyl and straight-chain pentyl

Blend example 2 preparation of additive composition

Each additive described in Table 5 was blended with a 300 mL-1L four-necked flask, into which a thermometer and a nitrogen gas inlet tube were inserted, at 25 ℃ for 1 hour under stirring to obtain additive compositions 1-8.

[ Table 5]

Blend example 3 preparation of lubricating oil composition (2)

To a base oil for lubricating oil (polyalphaolefin, kinematic viscosity (40 ℃ C.): about 50mm²0.5 mass% of each of additive compositions 1 to 8 shown in Table 5 was blended per second) to obtain lubricating oil compositions of examples (2-1) to (2-5) and comparative examples (2-1) to (2-3). The following evaluation test was performed on the obtained lubricating oil composition (2) (test oil). The evaluation results are shown in tables 6 and 7.

Load resistance test

The sintering load was evaluated using a shell (shell) four-ball tester. The test piece was manufactured using SUJ-2. The test was carried out under the conditions of a test temperature of 25 ℃, a rotation speed of 1,800rpm, and a test time of 10 seconds, and loads were applied in the order of 50kg, 63kg, 80kg, 100kg, 126kg, 160kg, and 200 kg. The load at which a sudden increase in friction torque, abnormal noise, or the like occurs during the test and a sintered streak is generated on the wear surface is taken as the sintering load.

The evaluation settings were as follows: good: above 160kg, qualified: 126kg or more and less than 160kg, failure: less than 126 kg.

Further, 100ml of a test oil was put into a 100ml glass bottle, the bottle was sealed under an air atmosphere, and the load resistance of the lubricating oil composition (2) (test oil) after standing in a thermostatic bath at 80 ℃ for 3 days was evaluated under the same conditions as described above.

Metal corrosion resistance test

As the metal corrosion resistance, copper corrosion resistance was evaluated. A copper wire cut to a length of 4cm was polished with P150 abrasive cloth. 2ml of test oil was added to a 5ml screw bottle, and the copper wire was immersed in the test oil and heated at 100 ℃ for 3 hours. The surface states before and after the test were compared, and the presence or absence of corrosion was evaluated.

The evaluation settings were as follows: good: no corrosion and failure: there is corrosion.

Further, 100mL of a test oil was put into a glass bottle having a volume of 100mL, a copper wire was immersed in the test oil, the sealed glass bottle was sealed in an air atmosphere, and the metal corrosion resistance of the lubricating oil composition (2) (test oil) after standing in a constant temperature bath at 80 ℃ for 3 days was evaluated under the same conditions as described above.

[ Table 6]

[ Table 7]

From the results shown in Table 6, it is understood that the lubricating oil compositions (2) of examples (2-1) to (2-5) using the additive compositions 1 to 5 of the present invention stably obtained excellent load resistance and metal corrosion resistance over time. That is, the additive compositions 1 to 5 can impart load resistance and metal corrosion resistance to the base oil and are excellent in the durability of these properties. In addition, the additive compositions 1 to 5 can reduce the amount of zinc dithiophosphate (B) blended with the base oil (PAO) for lubricating oils, and therefore can reduce the generation of ash.

On the other hand, in comparative example (2-1) using additive composition 6 containing compound (a-6) in formula (1) in which M is outside the range specified in the present invention, the load resistance and metal corrosion resistance of the lubricating oil composition (test oil) immediately after the preparation were good, but the stability (durability) with time was poor.

In addition, in comparative examples (2-2) using additive composition 7 containing compound (a-7) in formula (1) in which n is outside the range specified in the present invention, and comparative examples (2-3) using additive composition 8 consisting of only zinc dithiophosphate (B), the metal corrosion resistance and the durability thereof were both good, but the load resistance immediately after the production was poor.

[ related applications ]

The present application has priority over japanese patent applications filed on 3/14/2019 (japanese patent application 2019-047823) and filed on 20/2/2020 (japanese patent application 2020-027132), the entire contents of which are incorporated herein by reference.