Lubricating oil composition

Abstract

To provide a lubricant composition comprising an oil agent-based friction modifier, having an improved friction reduction capability even with a low viscosity.SOLUTION: A lubricant composition contains (A): lubricant base oil including at least one mineral oil-type base oil or at least one synthetic base oil, or a combination thereof, and (B1): at least one first amide compound which is a monoamide of at least one fatty acid (a1) and at least one amine compound (a2), with the amine compound (a2) being an oligomer of at least one alkanolamine (a3) represented by general formula (1), and / or a salt thereof. (In the formula, n is 1 or 2; R1 represents a 1-4C linear alkylene group or a 3-10C branched alkylene group having a 2C main chain; and a plurality of R1 may be the same or mutually different when n is 2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition suitable for use in lubricating gears. [Background technology]

[0002] Lubricating oils are used in internal combustion engines, automatic transmissions, and bearings to ensure smooth operation. Generally, various additives are blended into lubricating oils to achieve the required performance characteristics.

[0003] Among lubricant additives, those that reduce frictional resistance (friction modifiers, sometimes referred to as "FM" below) are important components in reducing energy loss due to friction. Generally, FMs can be classified into two types: organic molybdenum-based FMs containing molybdenum, and oil-based FMs (also called ashless FMs) that reduce friction by improving oiliness.

[0004] Organic molybdenum-based friction modifiers (FMs) such as MoDTC (molybdenum dithiocarbamate) and MoDTP (molybdenum dithiophosphate) are widely known (see, for example, Patent Document 1). While these organic molybdenum-based FMs exhibit excellent friction reduction effects in the initial stages of use, there are limitations to maintaining this friction reduction effect over long periods. Furthermore, because organic molybdenum-based FMs contain ash, they make it difficult to reuse used lubricating oil. Therefore, there is a need to reduce the amount of organic molybdenum-based FMs added.

[0005] On the other hand, oily FMs have the potential to overcome the problems of organic molybdenum FMs, and therefore their importance is increasing (see, for example, Patent Documents 2-4). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2013-133453 [Patent Document 2] Japanese Patent Publication No. 2009-235252 [Patent Document 3] Japanese Patent Publication No. 2006-257383 [Patent Document 4] International Publication No. 2019 / 129793 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, conventional oil-based FMs still had room for improvement in terms of friction coefficient under conditions where the oil film thickness was reduced. One example of a means to improve the energy efficiency of machinery is to use low-viscosity lubricants with low-viscosity base oils. Low-viscosity lubricants can reduce stirring resistance and improve energy efficiency. However, using low-viscosity base oils makes it easier for the oil film thickness to decrease, so the transition from the fluid lubrication region to the mixed lubrication region begins at a lower load compared to conventional lubricants with higher-viscosity base oils, and the friction coefficient begins to increase. This problem is particularly serious in gear lubrication, where the load on the lubricated surface increases in proportion to the driving force being transmitted.

[0008] The present invention aims to provide a lubricating oil composition containing an oily friction modifier that has low viscosity while exhibiting improved friction reduction performance. [Means for solving the problem]

[0009] The present invention encompasses the following embodiments [1] to

[12] .

[0010] [1] (A) A lubricating oil base oil comprising one or more mineral oil-based base oils or one or more synthetic base oils or a combination thereof, (B1) A monoamide comprising one or more monounsaturated or unsaturated monounsaturated fatty acids (a1) having 6 to 30 carbon atoms in a straight or branched chain, and one or more amine compounds (a2), wherein there are no ester bonds, and the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1), one or more first amide compounds, and / or salts thereof, It contains, The kinematic viscosity at 100°C is 6.9 mm³. 2 A lubricating oil composition characterized by having a value of less than / s.

[0011] [ka] (In general formula (1), n ​​is 1 or 2; R 1 represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R 1 They may be the same or they may be different from one another.

[0012] [2] The lubricating oil composition according to [1], wherein the content of component (B1) is 0.005 to 10.0% by mass on a basis of the total lubricating oil composition, when converted to the content of the compound in a state that has not formed a salt.

[0013] [3] (B2) The lubricating oil composition according to [1] or [2], further comprising one or more second amide compounds having a structure in which the amino group and one or more hydroxyl groups of one or more alkanolamines (a3) ​​represented by the following general formula (1) are acylated with the monounsaturated fatty acid (a1).

[0014] [4] (B3) The lubricating oil composition according to any one of [1] to [3], further comprising one or more third amide compounds which are amides of the alkanolamine (a3) ​​and the monounsaturated fatty acid (a1) and do not have an ester bond.

[0015] [5] (B4) The lubricating oil composition according to any one of [1] to [4], further comprising one or more fourth amide compounds and / or salts thereof, wherein one or more amino groups and one or more hydroxyl groups of the amine compound (a2) are acylated with the monounsaturated fatty acid (a1).

[0016] [6] The lubricating oil composition according to any one of [1] to [5], wherein the monounsaturated fatty acid comprises one or more straight-chain fatty acids.

[0017] [7] The lubricating oil composition according to any one of [1] to [6], wherein the monounsaturated fatty acid comprises one or more branched-chain fatty acids.

[0018] [8] The lubricating oil composition according to [7], wherein the branched-chain fatty acid has a tertiary or quaternary carbon atom at the α, β, or γ position of the carbonyl carbon.

[0019] [9] A lubricating oil composition according to any one of [1] to [8], further comprising one or more additives selected from metal-based detergents, ashless dispersants, phosphorus-containing anti-wear agents, sulfur-containing extreme pressure agents, antioxidants, and viscosity index improvers.

[0020]

[10] The kinematic viscosity of the lubricating oil base oil (A) at 40°C is 40 mm² 2 A lubricating oil composition according to any of [1] to [9], wherein the s is less than or equal to / s.

[0021]

[11] Kinematic viscosity at 40°C is 2.0–50 mm 2 A lubricating oil composition according to any of [1] to

[10] , wherein the value is / s.

[0022]

[12] A lubricating oil composition according to any one of [1] to

[11] , used for lubricating gears. [Effects of the Invention]

[0023] The lubricating oil composition of the present invention is a lubricating oil composition containing an oily friction modifier, which can exhibit an improved friction reduction effect while having low viscosity.

Best Mode for Carrying Out the Invention

[0024] The present invention will be described in detail below. In this specification, unless otherwise specified, the notation "A to B" for numerical values A and B shall be equivalent to "A or more and B or less". When a unit is attached only to numerical value B in such notation, the said unit shall also be applied to numerical value A. In this specification, the words "or" and "or alternatively" shall mean the logical sum unless otherwise specified. In this specification, the notation "E1 and / or E2" for elements E1 and E2 shall be equivalent to "E1, or E2, or a combination thereof", and for N elements E1, …, E i , …, E N (where N is an integer of 3 or more), the notation "E1, …, and / or E N " shall be equivalent to "E1, …, or E i , …, or E N , or a combination thereof" (where i is a variable taking values of all integers satisfying 1 < i < N). Also in this specification, "alkaline earth metal" shall include magnesium.

[0025] In this specification, unless otherwise specified, the contents of each element of calcium, magnesium, zinc, phosphorus, sulfur, boron, barium, and molybdenum in oil shall be measured by inductively coupled plasma optical emission spectrometry (intensity ratio method (internal standard method)) in accordance with JIS K0116. Also, the content of nitrogen element in oil shall be measured by chemiluminescence method in accordance with JIS K2609. Also in this specification, "weight average molecular weight" means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). The measurement conditions of GPC are as follows. [GPC Measurement Conditions] Apparatus: ACQUITY (registered trademark) APC UV RI system manufactured by Waters Corporation Columns: Two Waters Corporation ACQUITY® APC XT900A columns (gel particle size 2.5 μm, column size (inner diameter x length) 4.6 mm x 150 mm) and one Waters Corporation ACQUITY® APC XT200A column (gel particle size 2.5 μm, column size (inner diameter x length) 4.6 mm x 150 mm) are connected in series from upstream to downstream. Column temperature: 40℃ Sample solution: 1.0% by mass tetrahydrofuran solution of the sample. Eluent: Tetrahydrofuran Solution injection volume: 20.0μL Detection device: Differential refractive index detector Reference material: Standard polystyrene (Agilent EasiCal® PS-1, manufactured by Agilent Technologies) 8 points (molecular weight: 2,698,000, 597,500, 290,300, 133,500, 70,500, 30,230, 95,90, 2970) If the weight-average molecular weight measured under the above conditions is less than 10,000, the column and reference material will be changed to the following conditions and the measurement will be repeated. Columns: From upstream to downstream, one Waters Corporation ACQUITY® APC XT125A (gel particle size 2.5 μm, column size (inner diameter x length) 4.6 mm x 150 mm) and two Waters Corporation ACQUITY® APC XT45A (gel particle size 1.7 μm, column size (inner diameter x length) 4.6 mm x 150 mm) are connected in series. Reference material: Standard polystyrene (Agilent EasiCal® PS-1, manufactured by Agilent Technologies) 10 samples (molecular weight: 30230, 9590, 2970, 890, 786, 682, 578, 474, 370, 266)

[0026] <(A) Lubricant base oil> The lubricating oil composition of the present invention (hereinafter sometimes referred to as "lubricating oil composition" or "composition") comprises a base oil with a main amount of lubricating viscosity (lubricating oil base oil) and one or more additives other than the base oil. In the lubricating oil composition of the present invention, the lubricating oil base oil used is a lubricating oil base oil comprising one or more mineral oil-based base oils, one or more synthetic base oils, or a combination thereof.

[0027] As the lubricating oil base oil (hereinafter sometimes referred to as "component (A)"), one or more mineral oil-based base oils, one or more synthetic base oils, or a mixture thereof can be used. In one embodiment, as the lubricating oil base oil, a Group I base oil (hereinafter sometimes referred to as "API Group I base oil"), a Group II base oil (hereinafter sometimes referred to as "API Group II base oil"), a Group III base oil (hereinafter sometimes referred to as "API Group III base oil"), a Group IV base oil (hereinafter sometimes referred to as "API Group IV base oil"), or a Group V base oil (hereinafter sometimes referred to as "API Group V base oil") of the API base oil classification can be used. API Group I base oil is a mineral oil-based base oil having a sulfur content of more than 0.03% by mass and / or a saturation content of less than 90% by mass, and a viscosity index of 80 or more and less than 120. API Group II base oils are mineral oil-based base oils with a sulfur content of 0.03% by mass or less, a saturation content of 90% by mass or more, and a viscosity index of 80 or more and less than 120. API Group III base oils are mineral oil-based base oils with a sulfur content of 0.03% by mass or less, a saturation content of 90% by mass or more, and a viscosity index of 120 or more. API Group IV base oils are poly-α-olefin base oils. API Group V base oils are base oils other than those in Groups I to IV above, and a preferred example of such a base oil is an ester-based base oil.

[0028] In one embodiment, component (A) may preferably be one or more API group II base oils, one or more API group III base oils, one or more API group IV base oils, or one or more API group V base oils, or a combination thereof.

[0029] Examples of mineral oil-based base oils include paraffinic base oils, normal paraffinic base oils, isoparaffinic base oils, and mixtures thereof, which are obtained by refining a lubricating oil fraction obtained by atmospheric and / or vacuum distillation of crude oil using one or more refining processes selected from solvent delamination, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. API Group II and Group III base oils are usually produced through a hydrocracking process.

[0030] %C of mineral oil-based base oils P From the viewpoint of further improving the viscosity-temperature characteristics and fuel efficiency of the composition, the coefficient of gravity is preferably 60 or higher, more preferably 65 or higher, and from the viewpoint of improving the solubility of the additive, it is preferably 99 or lower, more preferably 95 or lower, and even more preferably 94 or lower, and in one embodiment it may be 60 to 99, or 60 to 95, or 65 to 95, or 65 to 94.

[0031] %C of mineral oil-based base oils A From the viewpoint of further improving the viscosity-temperature characteristics and fuel efficiency of the composition, the ratio is preferably 2 or less, more preferably 1 or less, even more preferably 0.8 or less, and particularly preferably 0.5 or less.

[0032] %C of mineral oil-based base oils N From the viewpoint of increasing the solubility of the additive, it is preferably 1 or more, more preferably 4 or more, and from the viewpoint of further improving the viscosity-temperature characteristics and fuel efficiency of the composition, it is preferably 40 or less, more preferably 35 or less, and in one embodiment it may be 1 to 40 or 4 to 35.

[0033] In this specification, %C P , %C N and %C A This refers to the percentage of paraffin carbons relative to the total number of carbons, the percentage of naphthenic carbons relative to the total number of carbons, and the percentage of aromatic carbons relative to the total number of carbons, respectively, determined by the method (ndM ring analysis) in accordance with ASTM D 3238-85. In other words, the %C mentioned aboveP , %C N and %C A The preferred range is based on the value obtained by the above method, and even for lubricating oil base oils that do not contain naphthenes, the %C obtained by the above method is also applicable. N This can represent a value greater than 0.

[0034] From the viewpoint of improving the viscosity-temperature characteristics of the composition, the saturation content in the mineral oil-based base oil is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, based on the total amount of base oil. In this specification, saturation content refers to the value measured in accordance with ASTM D 2007-93.

[0035] The aromatic content in the mineral oil-based base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, based on the total amount of base oil, and in one embodiment it may be 0.1% by mass or more. By keeping the aromatic content below the above upper limit, it is possible to improve the low-temperature viscosity characteristics and viscosity-temperature characteristics in the new oil state, further improve fuel efficiency, and reduce the amount of lubricant consumed by reducing evaporation loss of the lubricant. In addition, when additives are blended into the lubricant base oil, it becomes possible to effectively exert the effects of the additives. Furthermore, the lubricant base oil may not contain aromatics, but by keeping the aromatic content above the above lower limit, the solubility of the additives can be improved.

[0036] In this specification, the term "aromatic content" refers to values ​​measured in accordance with ASTM D 2007-93. Aromatic content typically includes alkylbenzenes, alkylnaphthalenes, anthracenes, phenanthrenes and their alkylates, as well as compounds in which four or more benzene rings are fused, pyridines, quinolines, phenols, naphthols, and other aromatic compounds containing heteroatoms.

[0037] Examples of API Group IV base oils include oligomers and co-oligomers of α-olefins having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, such as ethylene-propylene copolymers, polybutene, 1-octene oligomers, 1-decene oligomers, and their hydrogenation products, as well as their hydrogenation products.

[0038] Preferred examples of API Group V base oils include various ester-based base oils. Examples of ester-based base oils include monoester base oils (e.g., butyl stearate, octyl laurate, 2-ethylhexyl oleate, etc.); diester base oils (e.g., ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.); polycarboxylic acid ester base oils (e.g., trimellitic acid ester, etc.); and polyol ester base oils (e.g., trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, etc.). Other examples of API Group V base oils include aromatic synthetic base oils such as alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, dialkyldiphenyl ethers, and polyphenyl ethers.

[0039] The kinematic viscosity of lubricating oil base oil (whole base oil) at 40°C is 40 mm² from the viewpoint of energy saving and improving the low-temperature viscosity characteristics of the lubricating oil composition. 2 / s or less, or 30mm 2 / s or less, or 20mm 2 The coefficient of friction is less than or equal to / s, and is preferably 2.0 mm from the viewpoint of improving wear resistance and seizure resistance. 2 / s or more, or 5.0mm 2 / s or more, or 8.0mm 2 / s or more, and in one embodiment, 2.0~40mm 2 / s, or 5.0~30mm 2 / s, or 8.0~20mm 2It may be / s. In this specification, "kinematic viscosity at 40°C" means the kinematic viscosity at 40°C measured in accordance with JIS K 2283-2000 using an automatic viscometer (product name "CAV-2100", manufactured by Cannon Instruments).

[0040] The kinematic viscosity of the lubricating oil base oil (whole base oil) at 100°C is preferably 10.0 mm from the viewpoint of further improving energy efficiency and the low-temperature viscosity characteristics of the lubricating oil composition. 2 / s or less, or 7.0mm 2 / s or less, or 4.0mm 2 The value should be less than or equal to / s, and preferably 0.8 mm from the viewpoint of improving wear resistance and seizure resistance. 2 / s or more, or 1.2mm 2 / s or more, or 1.4mm 2 / s or more, or 1.6mm 2 It is 0.8 to 10.0 mm / s or more, and in one embodiment 2 / s, 1.2~10.0mm 2 / s, or 1.4~7.0mm 2 / s, or 1.6~4.0mm 2 It may be / s. In this specification, "kinematic viscosity at 100°C" means the kinematic viscosity at 100°C measured in accordance with JIS K 2283-2000 using an automatic viscometer (product name "CAV-2100", manufactured by Cannon Instruments).

[0041] The viscosity index of the lubricating oil base oil (whole base oil) is preferably 100 or higher, more preferably 105 or higher, even more preferably 110 or higher, particularly preferably 115 or higher, and most preferably 120 or higher, from the viewpoint of improving the viscosity-temperature characteristics of the composition, as well as further improving fuel efficiency and wear resistance. In this specification, the viscosity index refers to the viscosity index measured using an automatic viscometer (product name "CAV-2100", manufactured by Cannon Instruments) as the measuring device, in accordance with JIS K 2283-2000.

[0042] The pour point of the lubricating oil base oil (whole base oil) is preferably -10°C or lower, more preferably -12.5°C or lower, even more preferably -15°C or lower, particularly preferably -17.5°C or lower, and most preferably -20.0°C or lower, from the viewpoint of the low-temperature fluidity of the entire lubricating oil composition. In this specification, the pour point refers to the pour point measured in accordance with JIS K 2269-1987.

[0043] The sulfur content in the base oil depends on the sulfur content of its raw materials. For example, when using substantially sulfur-free raw materials such as synthetic wax components obtained by the Fischer-Tropsch reaction, a substantially sulfur-free base oil can be obtained. On the other hand, when using sulfur-containing raw materials such as slack wax obtained in the base oil refining process or microwax obtained in the refining process, the sulfur content in the resulting base oil is usually 100 ppm by mass or more. The sulfur content in lubricating oil base oil (total base oil) is usually 0.03% by mass or less, and preferably 0.01% by mass or less from the viewpoint of oxidation stability. In this specification, the sulfur content in the base oil refers to the amount of sulfur measured in accordance with JIS K 2541-2003.

[0044] The lubricating oil base oil may consist of a single base oil component or may contain multiple base oil components. In one preferred embodiment, the kinematic viscosity of the entire base oil (total base oil) at 40°C is 40 mm². 2 It may be less than / s.

[0045] In one embodiment, the lubricating oil base oil may contain 80-100% by mass, 90-100% by mass, 90-99% by mass, or 95-99% by mass of one or more API Group II base oils, one or more API Group III base oils, one or more API Group IV base oils, or one or more API Group V base oils, or a combination thereof, based on the total amount of base oil. The lubricating oil base oil may or may not contain API Group V base oil, but the content of one or more API Group V base oils in the lubricating oil base oil is preferably 0-50% by mass or 0-45% by mass based on the total amount of base oil from the viewpoint of increasing oxidation stability in one embodiment, and 1-50% by mass or 1-45% by mass from the viewpoint of increasing fatigue resistance. The lubricating oil base oil may or may not contain API group IV base oils, but in one embodiment, the content of one or more API group IV base oils in the lubricating oil base oil may be 0 to 70% by mass, or 0 to 65% by mass, or 1 to 70% by mass, or 1 to 65% by mass, based on the total amount of base oil.

[0046] The content of lubricating oil base oil (total base oil) in the lubricating oil composition is 60% by mass or more on a basis of the total amount of the lubricating oil composition, preferably 60 to 98.5% by mass, more preferably 70 to 98.5% by mass, and in one embodiment it may be 75 to 97% by mass.

[0047] <(B1) The first amide compound, and / or its salt> The lubricating oil composition of the present invention contains one or more first amide compounds and / or salts thereof (hereinafter referred to as "component (B1)" or "component (B1)"), which are monoamides of one or more monounsaturated or linear or branched monounsaturated fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2), which do not have ester bonds, and the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1).

[0048] [ka] (In general formula (1), n ​​is 1 or 2; R 1 represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R 1 They may be the same or they may be different from one another.

[0049] Fatty acid (a1) may be one type of fatty acid or a combination of two or more types of fatty acids. Fatty acid (a1) may be a saturated fatty acid or an unsaturated fatty acid. Furthermore, fatty acid (a1) may be a straight-chain fatty acid or a branched-chain fatty acid. In one preferred embodiment, fatty acid (a1) may be a branched-chain fatty acid. Examples of straight-chain saturated fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, and docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, etc. Examples of branched-chain saturated fatty acids include their branched-chain isomers. Examples of straight-chain unsaturated fatty acids include hexenoic acid, heptenic acid, octenoic acid, nonenic acid, 10-hydroxy-2-decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, heneicosenoic acid, docosenoic acid, tetracosenoic acid, hexacosenoic acid, octacosenoic acid, and triaconthenic acid. Examples of branched-chain unsaturated fatty acids include their branched-chain isomers. The arrangement of C=C double bonds in unsaturated fatty acids is not particularly limited. The number of C=C double bonds in an unsaturated fatty acid may be one (i.e., monoenoic acid), two (i.e., dienoic acid), three (i.e., trienoic acid), or four or more (i.e., tetraenoic acid). Furthermore, the C=C double bond in unsaturated fatty acids may be in the cis (Z) or trans (E) configuration, and cis (Z) and trans (E) C=C double bonds may coexist between different molecules or within the same molecule. For example, fatty acids derived from hydrogenated natural oils may contain, in addition to saturated fatty acids produced by hydrogenation, unsaturated fatty acids having cis C=C double bonds and unsaturated fatty acids having trans C=C double bonds, resulting from side reactions of the hydrogenation reaction.For example, specific examples of unsaturated fatty acids with 18 carbon atoms include oleic acid (cis-9-octadecenoic acid), paxenoic acid (11-octadecenoic acid), linoleic acid (cis,cis-9,12-octadecadienoic acid), linolenic acid (9,12,15-octadecantrienoic acid, 6,9,12-octadecantrienoic acid), and eleostearic acid (9,11,13-octadecantrienoic acid), among others, which are various related compounds with different numbers, arrangements, and / or geometric isomerisms of C=C double bonds. Similarly, for unsaturated fatty acids with other carbon atoms, various related compounds with different numbers, arrangements, and / or geometric isomerisms of C=C double bonds can be cited.

[0050] The number of carbon atoms in fatty acid (a1) is 6 or more, preferably 8 or more, or 10 or more, or 12 or more, from the viewpoint of enhancing the friction reduction effect in lubrication of gears, etc., and from the same viewpoint, it is 30 or less, preferably 24 or less, or 22 or less, or 20 or less, or 18 or less, and in one embodiment it may be 6 to 30, or 8 to 24, or 8 to 22, or 10 to 22, or 12 to 20, or 12 to 18. In one embodiment, fatty acid (a1) may be one or more straight-chain fatty acids. Preferred examples of straight-chain fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, vaccenic acid, elaidic acid, linoleic acid, linolenic acid, eleostearic acid, stearidonic acid, arachidic acid, gadoleic acid, eicosenoic acid, eicosapentaenoic acid, behenic acid, erucic acid, sardic acid, docosahexaenoic acid, lignoceric acid, nicinic acid, nervonic acid, cerotic acid, montanic acid, melissic acid, and mixtures thereof. As a mixture containing two or more fatty acids, fatty acids derived from natural oils or hydrogenated natural oils may be used. Examples of fatty acids derived from natural oils and fats include coconut oil fatty acids, palm kernel oil fatty acids, palm oil fatty acids, tuna oil fatty acids, tall oil fatty acids, corn oil fatty acids, rapeseed oil fatty acids, olive oil fatty acids, sesame oil fatty acids, soybean oil fatty acids, rice bran oil fatty acids, sunflower oil fatty acids, castor oil fatty acids, linseed oil fatty acids, fish oil fatty acids, beef tallow fatty acids, hydrogenated versions thereof, and mixtures thereof. These fatty acids derived from natural oils and fats are usually mixtures containing two or more fatty acids having 6 to 24 carbon atoms. In one embodiment, fatty acid (a1) may be one or more branched-chain fatty acids. In one embodiment, the branched-chain fatty acid preferably has a tertiary or quaternary carbon atom (i.e., branched) at the α, β, or γ position of the carbonyl carbon, and it is particularly preferable that it has a tertiary or quaternary carbon atom at the α position of the carbonyl carbon. A preferred example of such branched-chain fatty acids is the branched-chain fatty acid represented by the following general formula (2).

[0051] [ka] (In general formula (2), k is an integer between 0 and 2, preferably 0 or 1, more preferably 0; R 2 and R 3 Each is independently a linear or branched alkyl group; R 4 (R) is a hydrogen atom or a linear or branched alkyl group, preferably a hydrogen atom; (R) 2 (Number of carbon atoms) ≥ (R 3 (Number of carbon atoms) ≥ (R 4 (The number of carbon atoms is) and (R 2 (Number of carbon atoms) + (R 3 (Number of carbon atoms) + (R 4 (The number of carbon atoms in a given molecule) + k + 2 is equal to the total number of carbon atoms in a branched-chain fatty acid. In one preferred embodiment, in general formula (2), k is 0, R 2 R is a linear or branched alkyl group having 3 to 19 carbon atoms. 3 R is a linear or branched alkyl group having 1 to 10 carbon atoms. 4is a hydrogen atom. Preferred examples of branched-chain fatty acids represented by general formula (4) include 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-decyltetradecanoic acid, 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanoic acid, etc. Such branched-chain fatty acids can be produced, if necessary, by the reaction of organometallic compounds such as Grignard reagents or alkyllithium compounds prepared from secondary or tertiary alkyl halides with carbon dioxide, or by synthesizing aldehydes and / or alcohols by the reaction of alkenes, carbon monoxide, and hydrogen in the presence of a hydroformylation catalyst, and then subjecting the resulting aldehydes and / or alcohols to further oxidation reactions. Secondary or tertiary alkyl halides can be produced, if necessary, by the addition reaction of the corresponding alkene with a hydrogen halide (e.g., hydrogen chloride, hydrogen bromide, or hydrogen iodide). Secondary or tertiary alkyl halides derived from alkenes are usually obtained as mixtures of isomers of secondary or tertiary alkyl halides with different halogen atom positions, and branched-chain fatty acids derived from such mixtures of secondary or tertiary alkyl halide isomers are usually R in general formula (2). 2 ~R 4 It is obtained as a mixture of isomers of branched-chain fatty acids with different combinations of carbon atoms. Another preferred example of a branched-chain fatty acid is a branched-chain fatty acid having methyl branching at the terminal. A preferred example of such a branched-chain fatty acid is a branched-chain fatty acid represented by the following general formula (3).

[0052] [ka] (In general formula (3), j+4 is equal to the total number of carbon atoms in branched-chain fatty acids.) Preferred examples of such branched-chain fatty acids include 16-methylheptadecanoic acid.

[0053] The amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more, having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1).

[0054] [ka] (In general formula (1), n ​​is 1 or 2; R 1 represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R 1 They may be the same or they may be different from one another. In general formula (1), R 1 R is a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms, with the main chain having 2 carbon atoms. 1 The number of carbon atoms is preferably 2 to 4, or 2 to 3, and in one embodiment it may be 2. In one embodiment, the branched alkylene group R 1 Each side chain is either a methyl group or an ethyl group, R 1 The number of carbon atoms may be 3 to 6, 3 to 5, or 3 to 4. In this specification, R 1 The number of carbon atoms in the main chain is R 1 R refers to the number of carbon atoms in the shortest carbon chain connecting the nitrogen atom and oxygen atom bonded together. 1 It is determined independently of the selection of the main chain used in naming. For example, R 1 When is a butane-1,2-diyl group, R 1 The main chain has 2 carbon atoms. 1 When R is a linear alkylene group, 1 The number of carbon atoms in the main chain is R 1 It is equal to the number of carbon atoms. 1 When R is a branched alkylene group, 1 Each side chain is preferably a methyl group or an ethyl group, and in one embodiment it may be a methyl group. For example, a linear alkylene group having 2 carbon atoms R 1Alkanolamines having the R group can be produced by the reaction of an unsubstituted oxirane with ammonia. For example, a linear alkylene group with 3 carbon atoms R 1 Alkanolamines having a linear alkylene group R4 can be produced by the reaction of an unsubstituted oxetane with ammonia. 1 Alkanolamines having this can be produced by the reaction of unsubstituted tetrahydrofuran with ammonia. For example, a branched alkylene group R having 2 carbon atoms in the main chain. 1 Alkanolamines having the following properties can be produced by the reaction of a substituted oxirane with ammonia, where each substituent of the substituted oxirane is a branched alkylene group R 1 These form the side chains of the alkylene group R. 1Preferred examples include linear alkylene groups such as ethane-1,2-diyl group and propane-1,3-diyl group; propane-1,2-diyl group; branched alkylene groups with 4 carbon atoms such as butane-1,2-diyl group, butane-2,3-diyl group and 1-methylpropane-1,2-diyl group; and carbon atoms such as pentane-1,2-diyl group, pentane-2,3-diyl group, 2-methylbutane-1,2-diyl group and 3-methylbutane-2,3-diyl group. Branched alkylene groups with 5 carbon atoms; branched alkylene groups with 6 carbon atoms such as hexane-1,2-diyl group, hexane-2,3-diyl group, hexane-3,4-diyl group, 2-methylpentane-2,3-diyl group, 3-methylpentane-2,3-diyl group, 2,3-dimethylbutane-2,3-diyl group; heptane-1,2-diyl group, heptane-2,3-diyl group, heptane-3,4-diyl group, 3-ethylpentane-2,3-diyl group, Branched alkylene groups with 7 carbon atoms, such as 3-methylpentane-3,4-diyl group; branched alkylene groups with 8 carbon atoms, such as octane-1,2-diyl group, octane-2,3-diyl group, octane-3,4-diyl group, octane-4,5-diyl group, 3-ethylhexane-3,4-diyl group, 3-ethyl-2-methylpentane-2,3-diyl group, 3,4-dimethylhexane-3,4-diyl group; nonane-1,2-diyl group, nonane- Examples include branched alkylene groups with 9 carbon atoms, such as 2,3-diyl group, nonane-3,4-diyl group, nonane-4,5-diyl group, and 2,3-diethylpentane-2,2-diyl group; and branched alkylene groups with 10 carbon atoms, such as decane-1,2-diyl group, decane-2,3-diyl group, decane-3,4-diyl group, decane-4,5-diyl group, decane-5,6-diyl group, and 3,4-diethylhexane-3,4-diyl group. 1 This may be a single alkylene group or a combination of two or more alkylene groups.

[0055] In one preferred embodiment, alkylene group R 1 This can be an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,2-diyl group, a butane-1,4-diyl group, or a butane-2,3-diyl group, or a combination thereof.

[0056] The alkanolamine represented by general formula (1) is a monoalkanolamine when n=1, and a dialkanolamine when n=2. 1 When the R is an asymmetric branched alkylene group, that is, when the side chains attached to the two free valencies are different alkylene groups (e.g., propane-1,2-diyl group, butane-2,3-diyl group, pentane-2,3-diyl group, etc.), either of the two free valencies may be attached to the nitrogen atom. For example, in the reaction between propylene oxide and ammonia, a reaction pathway that gives a propanolamine structure in which the 1-position of the propylene-1,2-diyl group is attached to the nitrogen atom (i.e., a 2-hydroxypropyl group is attached to the nitrogen atom) competes with a reaction pathway that gives a propanolamine structure in which the 2-position of the propylene-1,2-diyl group is attached to the nitrogen atom (i.e., a 1-hydroxypropan-2-yl group is attached to the nitrogen atom), and a mixture of the products of both can be obtained. In the dialkanolamine of general formula (1) where n=2, the two R 1 They may be the same or different from each other. Two R 1 If they are the same asymmetric branched alkylene group, then the two R 1 The orientations of the Rs may be the same or they may be different. For example, two Rs 1 In dipropanolamine, where is a propane-1,2-diyl group, two HO-R 1 Both - groups may be 2-hydroxypropyl groups, both may be 1-hydroxypropan-2-yl groups, or one may be a 2-hydroxypropyl group and the other a 1-hydroxypropan-2-yl group. When dipropanolamine is produced by the reaction of propylene oxide with ammonia, these compounds may be produced simultaneously to give a mixture. The one or more alkanolamines (a3) ​​represented by general formula (1) may be one or more monoalkanolamines, one or more dialkanolamines, or a combination of one or more monoalkanolamines and one or more dialkanolamines, but it is particularly preferred that there be one or more dialkanolamines.

[0057] The amine compound (a2) forming a monoamide with the monounsaturated fatty acid (a1) in component (i) is an alkanolamine oligomer having a structure formed by the dehydration condensation of one or more alkanolamines (a3) ​​represented by general formula (1), and having a degree of polymerization of 2 or more. For example, general formula (4) below represents a reaction in which two molecules of dialkanolamine (a3d) undergo a dehydration condensation to produce an alkanolamine dimer (a2-dd) with a degree of polymerization of 2. Also, for example, general formula (5) below represents a reaction in which two molecules of monoalkanolamine (a3m) undergo a dehydration condensation to produce an alkanolamine dimer (a2-mm) with a degree of polymerization of 2. Also, for example, general formula (6) below represents a reaction in which one molecule of dialkanolamine (a3d) and one molecule of monoalkanolamine (a3m) undergo a dehydration condensation to produce an alkanolamine dimer (a2-2dm or a2-2md) with a degree of polymerization of 2. As shown in general formula (6), the dehydration condensation reaction between a dialkanolamine and a monoalkanolamine may produce products containing structural isomers. Which structural isomer is formed depends on which molecule's hydroxyl group is eliminated.

[0058] [ka] As shown in general formulas (4) to (6), in the dehydration condensation of alkanolamine (a3), a hydroxyl group is removed from one molecule, and a new CN bond is formed between the carbon atom to which the removed hydroxyl group was bonded (the α-carbon of the hydroxyl group) and the primary or secondary amine nitrogen atom of the other molecule. For example, general formula (7) below represents the reaction in which three molecules of dialkanolamine undergo dehydration condensation to produce an alkanolamine trimer (a2-ddd1 or a2-ddd2) with a degree of polymerization of 3.

[0059] [ka] In general formula (7), the formation of the dimer (a2-dd) is shown in general formula (4). As shown in general formula (7), the dialkanolamine trimer may contain structural isomers (a2-ddd1 and a2-ddd2) corresponding to the hydroxyl group removed from the dialkanolamine dimer (2a-dd). Similarly, alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers. For example, general formula (8) below represents a reaction in which three monoalkanolamine molecules undergo dehydration condensation to produce an alkanolamine trimer with a degree of polymerization of 3 (a2-mmm1 or a2-mmm2).

[0060] [ka] In general formula (8), refer to general formula (5) for the formation of the dimer (a2-mm). As shown in general formula (8), the monoalkanolamine trimer may contain structural isomers (a2-mmm1 and a2-mmm2) corresponding to the hydroxyl group removed from the monoalkanolamine dimer (2a-mm). Similarly, alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers. For example, general formulas (9a) to (9c) below represent a reaction in which a mixed alkanolamine trimer with a degree of polymerization of 3 (a2-ddm1, a2-ddm2, a2-dmd, or a2-mdd) is formed by the dehydration condensation of two molecules of dialkanolamine and one molecule of monoalkanolamine.

[0061] [ka] In general formulas (9a) to (9c), refer to general formulas (4) and (6) regarding the formation of dimers (a2-dd, a2-dm, a2-md). As shown in general formulas (9a) to (9c), corresponding to the hydroxy group to be eliminated, the mixed alkanolamine trimer may include structural isomers (a2-ddm1, a2-ddm2, a2-dmd, and a2-mdd). Similarly, the mixed alkanolamine oligomers with a polymerization degree of 4 or more may also include a plurality of structural isomers. Further, for example, the following general formulas (10a) to (10c) represent the reaction in which a mixed alkanolamine trimer (a2-mmd, a2-dmm1, or a2-dmm2) with a polymerization degree of 3 is formed by the dehydration condensation of one molecule of dialkanolamine and two molecules of monoalkanolamine.

[0062]

Chemical formula

[0063]

Chemical formula

[0064]

Chemical formula

[0065] [ka] (In general formula (13), m corresponds to the degree of polymerization of the alkanolamine oligomer m+2, so m≧2.)

[0066] The degree of polymerization of the amine compound (a2), i.e., the alkanolamine oligomer, is 2 or higher, preferably 2 to 15, or 2 to 10, and in one embodiment it may be 2 to 4 or 2 to 3. The alkanolamine oligomer (a2) may have a single degree of polymerization, or it may be a combination of oligomers having multiple different degrees of polymerization. In one embodiment, the alkanolamine oligomer (a2) may be a combination of multiple consecutive oligomers having multiple different degrees of polymerization. In this specification, an oligomer is described as "a combination of multiple consecutive oligomers having multiple different degrees of polymerization" if the minimum and maximum degrees of polymerization of the oligomer are d, respectively. min and d MAX In that case, the oligomer is d min more than d MAX This means that it contains oligomers of all the following degrees of polymerization.

[0067] The first amide compound is a monoamide of one or more monounsaturated fatty acids (a1) and one or more amine compounds (a2), and does not have an ester bond. Component (B1) is the first amide compound and / or a salt thereof. Since the first amide compound has one or more unacylated amine nitrogen atoms, it can form a salt with an acid. The salt of the first amide compound may be a salt of the first amide compound with an organic acid (organic acid salt), a salt of the first amide compound with an inorganic acid (inorganic acid salt), or a combination of one or more organic acid salts and one or more inorganic acid salts. The organic acid salt may be one organic acid salt or a combination of two or more organic acid salts. The inorganic acid salt may be one inorganic acid salt or a combination of two or more inorganic acid salts. Furthermore, as will be described later, the organic acid constituting the organic acid salt may be one of the monounsaturated fatty acids (a1).

[0068] Examples of inorganic acids that constitute the first amide compound and inorganic salt include hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide; oxyhalogens such as hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, perbromous acid, hypoiodic acid, iodic acid, iodic acid, and periodic acid; nitric acid, nitrite, sulfuric acid, sulfurous acid, phosphoric acid (meaning an oxoacid of phosphorus in which the formal oxidation state of the phosphorus atom is +V, and may be orthophosphoric acid or condensed phosphoric acid such as pyrophosphoric acid or polyphosphoric acid), phosphorous acid, boric acid (meaning an oxoacid of boron in which the formal oxidation state of the boron atom is +III, and may be orthoboric acid or condensed boric acid such as tetraboric acid or metaboric acid), carbonic acid, and other inorganic oxoacids; and inorganic Brønsted acids such as hydrogen cyanide.

[0069] Examples of organic acids that constitute the first amide compound and organic salt include organic Brønsted acids such as carboxylic acids, organic sulfonic acids, organic phosphonic acids and their monoesters, organic boronic acids and their monoesters, sulfuric acid monoesters, phosphate monoesters, phosphate diesters, phosphite monoesters, phosphite diesters, boric acid monoesters, boric acid diesters, substituted or unsubstituted phenols, and so on.

[0070] Examples of carboxylic acids that constitute the first amide compound and salt include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monounsaturated fatty acids with 1 to 5 carbon atoms, monounsaturated fatty acids with 6 to 30 carbon atoms, diunsaturated aliphatic carboxylic acids with 2 to 10 carbon atoms and their monoesters, aliphatic hydroxy acids, and the like. Examples of monounsaturated fatty acids with 1 to 5 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, etc., and their carbon number is preferably 2 to 5. Examples of monounsaturated fatty acids with 6 to 30 carbon atoms include the various monounsaturated fatty acids described above in relation to monounsaturated fatty acids (a1). Examples of divalent aliphatic dicarboxylic acids having 2 to 10 carbon atoms include oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Examples of their monoesters include monoesters of the divalent aliphatic dicarboxylic acid with alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, etc., for example, alkyl alcohols having 1 to 12, 1 to 10, or 1 to 8 carbon atoms. Examples of aliphatic hydroxy acids include glycolic acid, lactic acid, tartaric acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricineradicic acid, quinic acid, shikimic acid, and other aliphatic hydroxy acids with 2 to 18 carbon atoms. Other examples of aliphatic carboxylic acids include halogenated (e.g., fluorinated) aliphatic carboxylic acids such as trifluoroacetic acid, 3,3,3-trifluoropropionic acid, and 4,4,4-trifluorobutyric acid. Examples of aromatic carboxylic acids include aromatic monocarboxylic acids, aromatic dicarboxylic acids and their monoesters, aromatic hydroxy acids, aromatic polycarboxylic acids, and the like. Examples of aromatic monocarboxylic acids include compounds with 7 to 10 carbon atoms, such as benzoic acid, o-, m-, or p-toluic acid, phenylacetic acid, and cinnamic acid. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and the like. Examples of their monoesters include monoesters of the aromatic dicarboxylic acid with the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids. Examples of aromatic hydroxy acids include salicylic acid, (m- or p-)hydroxybenzoic acid, (o-, m-, or p-)hydroxymethylbenzoic acid, vanillic acid, syringic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dihydroxybenzoic acid, orceric acid, gallic acid, mandelic acid, hydroxydiphenylacetic acid (benzyl acid), atrolactinic acid, floretic acid, (o-, m-, or p-)hydroxycinnamic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dihydroxycinnamic acid, ferulic acid, synapic acid, and other compounds with 7 to 14 carbon atoms. Examples of aromatic polycarboxylic acids include trimellitic acid and mellitic acid, which are compounds having a structure in which 3 to 6 hydrogen atoms of benzene are replaced by carboxyl groups.

[0071] Examples of organic sulfonic acids include compounds represented by the following general formula (14).

[0072] [ka] (In general formula (14), R 10 (This represents an organic group with one or more carbon atoms, for example, one to 18 carbon atoms.) R 10Examples include linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and oleyl groups; aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenyl, tolyl, xylyl, mesityl, cumyl, and naphthyl groups; halogenated hydrocarbon groups such as trifluoromethyl, 2,2,2-trifluoroethyl, fluorophenyl, chlorophenyl, dichlorophenyl, and trichlorophenyl groups; and camphor-10-yl groups. Preferred examples of organic sulfonic acids include compounds having 1 to 10 carbon atoms, such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 10-camphorsulfonic acid.

[0073] Examples of organic phosphonic acids include compounds represented by the following general formula (15).

[0074] [ka] (In general formula (15), R 11 (This represents an organic group with one or more carbon atoms, for example, one to 18 carbon atoms.) R 11 For example, R 10 In relation to this, examples include linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, and so on, as described above. Examples of monoesters of organic phosphonic acids include monoesters of the organic phosphonic acid with the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids.

[0075] Examples of organic boronic acids include compounds represented by the following general formula (16).

[0076] [ka] (In general formula (16), R 12 (This represents an organic group with one or more carbon atoms, for example, one to 18 carbon atoms.) R 12 For example, R 10 In relation to this, examples include linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, etc. 12 Other examples include cycloalkyl groups with 5-6 carbon atoms, such as cyclopentyl and cyclohexyl groups; arylalkyl groups such as phenylethyl; halogenated aromatic hydrocarbon groups (e.g., with 6-7 carbon atoms), such as fluorophenyl, difluorophenyl, trifluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, iodophenyl, fluorotolyl, and chlorotolyl groups; hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, and trimethoxyphenyl groups. Examples include hydroxy, alkoxy, cyano, formyl, or nitro-substituted or acylated aromatic hydrocarbon groups (e.g., having 6 to 10 carbon atoms), such as phenyl groups, methoxytolyl groups, ethoxyphenyl groups, propoxyphenyl groups, isopropoxyphenyl groups, butoxyphenyl groups, nitrophenyl groups, cyanophenyl groups, formylphenyl groups, and acetylphenyl groups; and heterocyclic groups such as furan-2-yl groups, thiophene-3-yl groups, thiophene-2-yl groups, benzofuran-2-yl groups, and benzo[b]thiophene-2-yl groups. Examples of monoesters of organic boronic acids include monoesters of the organic phosphonic acid with the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids.

[0077] Examples of sulfuric acid monoesters, phosphate monoesters, phosphorous acid monoesters, and boric acid monoesters include monoesters of sulfuric acid, orthophosphoric acid, phosphorous acid, or orthoboric acid with the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids, respectively. Examples of phosphate diesters and borate diesters include monoesters of orthophosphoric acid or orthoboric acid with the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids, respectively.

[0078] A preferred example of a substituted phenol is a substituted phenol having a lower pKa than an unsubstituted phenol. Such substituted phenols usually have one or more substituents that act as electron-withdrawing groups on the aromatic ring. Examples of such electron-withdrawing groups include acyl groups such as acetyl groups, formyl groups, carboxyl groups, alkoxycarbonyl groups, nitro groups, cyano groups, halogeno groups (e.g., fluoro groups, chloro groups, bromo groups, and iodo groups). Examples of alcohols corresponding to the alkoxy group of an alkoxycarbonyl group include the various alcohols described above in relation to monoesters of divalent aliphatic dicarboxylic acids. Examples of such substituted phenols include acetylphenol, formylphenol, carboxyphenol, methoxycarbonylphenol, ethoxycarbonylphenol, nitrophenol, cyanophenol, fluorophenol, chlorophenol, bromophenol, and iodophenol. The number of carbon atoms in the substituted phenol is preferably 6 to 13, or 6 to 11, or 6 to 9.

[0079] The content of component (B1) in the lubricating oil composition is preferably 0.001% by mass or more, or 0.010% by mass or more, or 0.050% by mass or more, on a basis of the total lubricating oil composition, in terms of the compound in a state that has not formed a salt, from the viewpoint of further enhancing friction reduction performance, particularly in mixed lubrication regions such as gear lubrication conditions. From the same viewpoint, it is preferably 10.0% by mass or less, or 5.0% by mass or less, or 1.00% by mass or less, and in one embodiment it may be 0.001 to 10.0% by mass, or 0.010 to 5.0% by mass, or 0.050 to 1.00% by mass. The first amide compound has at least one amino group capable of forming a salt. In this specification, the content of component (B1) "on a basis of the compound in a state that has not formed a salt" means the content as is if the first amide compound has not formed any salt, and if all or part of the first amide compound has formed a salt with the acid, it means the content converted to the mass in a state that has not been neutralized by the acid.

[0080] <(B2) Second amide compound> In one embodiment, the lubricating oil composition of the present invention may further contain one or more second amide compounds (hereinafter referred to as "component (B2)" or "component (B2)") having a structure in which the amino group and one or more hydroxyl groups of one or more alkanolamines (a3) ​​represented by general formula (1) are acylated with the monounsaturated fatty acid (a1). Component (B2) has a structure represented by the following general formulas (17a), (17b), or (17c). General formulas (17a) and (17b) show structures corresponding to dialkanolamines, and general formula (17c) shows a structure corresponding to monoalkanolamines. In one preferred embodiment, component (B2) has a structure in which the amino group and one or more hydroxyl groups of one or more dialkanolamines represented by general formula (1) are acylated with the monounsaturated fatty acid (a1), and its structure is represented by general formula (17a) or (17b).

[0081] [ka] (In general formulas (17a) to (17c), R 1 The above definition is as follows; in general formulas (17a) and (17b), two R in the same molecule 1 R may be the same or different from each other, and represents the two alkylene groups of the corresponding dialkanolamine; in general formula (17c), R 1 R represents the alkylene group of the corresponding monoalkanolamine; 13 R is an aliphatic hydrocarbon group obtained by removing a carboxyl group from the above monounsaturated fatty acid (a1); if the above monounsaturated fatty acid (a1) is one type of fatty acid, then multiple R in the same molecule 13 If the above monounsaturated fatty acid (a1) is a combination of two or more different fatty acids, then multiple R groups in the same molecule 13 This corresponds to the same aliphatic hydrocarbon group or a combination of two or more different aliphatic hydrocarbon groups, in relation to the combination of two or more different fatty acids.

[0082] The lubricating oil composition may or may not contain component (B2). In one embodiment, the content of component (B2) in the lubricating oil composition is preferably 0.001% by mass or more, or 0.010% by mass or more, or 0.050% by mass or more, based on the total amount of the composition, from the viewpoint of improving storage stability and improving friction reduction performance, particularly improving friction reduction performance in mixed lubrication regions such as gear lubrication conditions. Furthermore, from the viewpoint of further improving friction reduction performance, particularly further improving friction reduction performance in mixed lubrication regions such as gear lubrication conditions, it is preferably 5.0% by mass or less, or 3.0% by mass or less, or 1.00% by mass or less, based on the total amount of the composition, and in one embodiment, it may be 0.001 to 5.0% by mass, or 0.010 to 3.0% by mass, or 0.050 to 1.00% by mass.

[0083] In one embodiment, the total content of components (B1) and (B2) in the lubricating oil composition is preferably 0.001% by mass or more, or 0.010% by mass or more, or 0.050% by mass or more, on a basis of the total composition, in terms of compounds in a state where salts have not been formed, from the viewpoint of further improving storage stability and further improving friction reduction performance, particularly from the viewpoint of further improving friction reduction performance in mixed lubrication regions such as gear lubrication conditions. From the viewpoint of ease of manufacture, it is preferably 10.0% by mass or less, or 5.0% by mass or less, or 1.00% by mass or less, and in one embodiment, it may be 0.001 to 10.0% by mass, or 0.010 to 5.0% by mass, or 0.050 to 1.00% by mass.

[0084] <(B3) Third amide compound> In one embodiment, the lubricating oil composition may further contain (B3) a third amide compound (hereinafter sometimes referred to as "component (B3)" or "component (B3)") which is an amide of one or more alkanolamines (a3) ​​represented by the general formula (1) and the monounsaturated fatty acid (a1), and does not have an ester bond. The third amide compound has a structure represented by the following general formula (18a) or (18b). General formula (18a) shows a structure corresponding to a dialkanolamine, and general formula (18b) shows a structure corresponding to a monoalkanolamine. In one preferred embodiment, component (B3) has a structure in which the amino group and one or more hydroxyl groups of one or more dialkanolamines represented by the general formula (1) are acylated with the monounsaturated fatty acid (a1), and the structure is represented by general formula (18a).

[0085] [ka] (In general formulas (18a) and (18b), R 1 As defined above, R 13 This is as defined in general formulas (17a) to (17c).

[0086] <(B4) Fourth amide compound, and / or salt thereof> In one embodiment, the lubricating oil composition may further include a fourth amide compound and / or a salt thereof (hereinafter referred to as "component (B4)" or "component (B4)") having a structure in which one or more amino groups and one or more hydroxyl groups of the amine compound (a2) are acylated with the monounsaturated fatty acid (a1). The fourth amide compound differs from the first amide compound in that it has not only amide bonds but also ester bonds. The fourth amide compound may have one or more amino groups capable of forming a salt. Examples of acids that form a salt with the fourth amide compound include the various acids described above in relation to component (B1).

[0087] The lubricating oil composition may or may not contain component (B3). The lubricating oil composition may or may not contain component (B4). In one embodiment, the total content of components (B3) and (B4) in the lubricating oil composition may be, for example, 1.00% by mass or less, or 0.50% by mass or less, on a basis of the total composition, when calculated on a basis of compounds in a state where salts have not been formed. Furthermore, from the viewpoint of ease of manufacture, it is preferably 0.001% by mass or more, or 0.005% by mass or more, on a basis of the total composition, and in one embodiment, it may be 0.001 to 1.00% by mass, or 0.005 to 0.50% by mass. In this specification, the content of component (B4) "on a basis of the compound in a state that has not formed a salt" means the content as is if the fourth amide compound has not formed any salt, and if all or part of the fourth amide compound has formed a salt with the acid, it means the content converted to the mass in a state that has not been neutralized by the acid.

[0088] In one embodiment, the total content of components (B2) and (B3) in the lubricating oil composition is preferably 20% by mass or more, or 50% by mass or more, or more than 85% by mass or more, or 86% by mass or more, based on the total content of all acylated compounds by the monounsaturated fatty acid (a1) of the alkanolamine structure containing the hydroxyl group which may be etherified, in terms of compounds in which no salt has been formed, from the viewpoint of ease of manufacture and further improvement of storage stability, and may be 99% by mass or less, or 96% by mass or less, and may be 20-99% by mass, or 50-99% by mass, or more than 85% by mass and 99% by mass or less, or 86-99% by mass, in one embodiment. In this specification, "all acylated compounds of the above monounsaturated fatty acid (a1) of a compound containing an alkanolamine structure in which the hydroxyl group may be etherified" means any alkanolamine structure, i.e., HO-R 14 -NR 15 R 16 Structure (R 14 R represents any alkylene group; 15 and R 16 Each of these independently represents a hydrogen atom or any organic group, and R 15 and R 16 The concept encompasses any compound containing ) which may be bonded to each other to form a cyclic structure. Furthermore, the statement that "the hydroxyl group of the alkanolamine structure may be etherified" means that the alkanolamine structure (HO-R 14 -NR 15 R 16This means that the hydroxy(-OH) group of the structure may be converted into an ether bond. An example of an "alkanolamine structure with an etherified hydroxyl group" is a structure in which the hydroxyl group of an alkanolamine is converted into an ether bond by intermolecular or intramolecular dehydration condensation. For an alkanolamine to form an ether bond by intramolecular dehydration condensation, it is necessary to have two or more hydroxyl groups in a single molecule, and for example, dialkanolamine satisfies this requirement. The formation of an ether bond by intramolecular dehydration condensation of an alkanolamine is a cyclization reaction and can give an azaoxacycloalkane skeleton (e.g., a morpholine skeleton). Such intramolecular dehydration cyclization reactions will be described later. Furthermore, "all acylids by the above monounsaturated fatty acid (a1)" is a concept that encompasses any acylid by the above monounsaturated fatty acid (a1), for example, it may be an amide of fatty acid (a1), an ester of fatty acid (a1), or a compound that has undergone acylation by fatty acid (a1) at multiple locations in a single molecule. Furthermore, the "total content in terms of compounds that have not formed salts" can be calculated by summing the content of compounds that have not formed salts, and the content of compounds that have formed salts in whole or in part as compounds in their non-salt state (for example, for compounds in which all or part of the unacylated amino group has been neutralized with acid, the content is calculated by converting it to the mass of the compound in its unneutralized state).

[0089] (Manufacturing) The amine compound (a2), i.e., the alkanolamine oligomer, can be produced, for example, by the dehydration condensation of one or more alkanolamines (a3). The amine compound (a2) may be an oligomer having a single degree of polymerization, or it may be a combination of two or more oligomers having different degrees of polymerization (for example, a combination of oligomers having a successive number of different degrees of polymerization). In one embodiment, component (B1) can be produced by a dehydration condensation reaction between a fatty acid (a1) and an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by heating and refluxing the fatty acid (a1) and the amine compound (a2) in an organic solvent (e.g., toluene, xylene, cumene, cymene, etc.) that forms an azeotrope with water, in the presence of an acid catalyst (e.g., sulfuric acid, trifluoroacetic acid, etc.) or a base catalyst (e.g., sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, etc.), or without a catalyst, and removing the water produced as the condensation reaction progresses by azeotrope. Under catalyst-free conditions, the fatty acid (a1) itself can act as an acid catalyst. Similarly, in one embodiment, component (B2) can be produced by a dehydration condensation reaction between a fatty acid (a1) and an alkanolamine (a3). Such a dehydration condensation reaction can be carried out, for example, by heating the fatty acid (a1) and the alkanolamine (a3) ​​under reflux in the presence of an organic solvent that forms an azeotrope with water, and removing the water produced as the condensation reaction progresses by azeotrope. In another embodiment, component (B1) can be produced by reacting a fatty acid (a1), an amine compound (a2), and a condensing agent in a solvent. Similarly, in one embodiment, component (B2) can be produced by reacting a fatty acid (a1), an alkanolamine (a3), and a condensing agent in a solvent. The condensing agents include carbodiimide-based condensing agents such as N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC); imidazole-based condensing agents such as N,N'-carbonyldiimidazole (CDI) and 1,1'-carbonyldi(1,2,4-triazole) (CDT); triazine-based condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride hydrate (DMT-MM); and 2-chloro-1-methylpyridinium p-toluenesulfonate and 2-fluoro-1-methylpyridinium Any known condensing agent usable for esterification can be used without particular limitation, such as 2-halopyridinium salts such as p-toluenesulfonate; 2,4,6-trichlorobenzoyl chloride (TCBC); 2-methyl-6-nitrobenzoic anhydride (MNBA); a combination of diethyl azodicarboxylate (DEAD) and triphenylphosphine; a combination of phosphines such as chlorodiphenylphosphine and 2,2'-dipyridyl disulfide; a combination of p-benzoquinones such as 2,6-dimethyl-1,4-benzoquinone (DMBQ) and tetrafluoro-1,4-benzoquinone; and dimethylammonium pentafluorobenzenesulfonate. The condensing agent may also be used with catalysts such as 4-dimethylaminopyridine (DMAP), N-hydroxysuccinimide (NHS), 1-hydroxybenzotriazole (HOBt), and 1-hydroxy-7-azabenzotriazole (HOAt). In another embodiment, component (B1) can be produced by reacting an acylating agent derived from fatty acid (a1) with an amine compound (a2) in a solvent. Similarly, in another embodiment, component (B2) can be produced by reacting an acylating agent derived from fatty acid (a1) with an alkanolamine (a3) ​​in a solvent. Examples of acylating agents derived from fatty acid (a1) include acid halides of fatty acid (a1) (e.g., acid chlorides, acid bromides, etc.), active esters of fatty acid (a1) (e.g., esters of fatty acid (a1) with N-hydroxysuccinimide (NHS), esters of fatty acid (a1) with 1-hydroxybenzotriazole (HOBt), esters of fatty acid (a1) with 1-hydroxy-7-azabenzotriazole (HOAt), etc.), and acid anhydrides of fatty acid (a1). The acylating agent derived from fatty acid (a1) may be used together with a catalyst such as 4-dimethylaminopyridine (DMAP). As the solvent, any organic solvent that does not interfere with the condensation reaction (e.g., aliphatic hydrocarbon solvents such as hexane and petroleum ether, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene, pyridine, etc.) can be used without particular restriction. In addition, in the condensation reaction to produce component (B1) and / or (B2), a suitable base (e.g., amines such as triethylamine, pyridine, and 2,6-lutidine, organolithium reagents such as butyllithium, inorganic bases such as potassium carbonate, etc.) may be added to the reaction mixture as needed to promote the reaction or to capture acids generated as the reaction progresses (e.g., hydrogen halides are generated as the reaction progresses in reactions using acid halides). In another embodiment, component (B1) can be produced by a dehydration condensation reaction between component (B3) (a third amide compound, which is an amide of one or more alkanolamines (a3) ​​represented by the general formula (1) above and the monounsaturated fatty acid (a1), and which does not have an ester bond) and an alkanolamine (a3) ​​and / or an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by heating and refluxing component (B3) and an alkanolamine (a3) ​​or an amine compound (a2) or a mixture thereof in an organic solvent that forms an azeotrope with water in the presence of an acid catalyst, and removing the water generated as the condensation reaction progresses by azeotrope. It should be noted that the above-mentioned dehydration condensation reactions can also be carried out under solvent-free conditions. For example, it is possible to carry out a dehydration condensation reaction under solvent-free conditions and remove the water generated as the reaction progresses by distillation.

[0090] In one preferred embodiment, a mixture containing components (B1) and (B2) can be produced by a dehydration condensation reaction between a fatty acid (a1) and an alkanolamine (a3). In one embodiment, such a dehydration condensation reaction can be carried out by heating the fatty acid (a1) and the alkanolamine (a3) ​​under reflux in the presence of an organic solvent that forms an azeotropic mixture with water, and removing the water generated as the condensation reaction progresses by azeotropy. In another embodiment, if the boiling point of the alkanolamine (a3) ​​is higher than the boiling point of water, such a dehydration condensation reaction can be carried out by gradually increasing the heating temperature while heating and stirring the fatty acid (a1) and alkanolamine (a3) ​​under solvent-free conditions, so that the water produced by the reaction continues to distill off, and continuing heating and stirring until no more water distills off even if the temperature is increased further. The above dehydration condensation reaction can also be carried out under solvent-free conditions. For example, while the dehydration condensation reaction is carried out under solvent-free conditions, the water produced as the reaction progresses can be removed by distillation. In the above dehydration condensation reaction, component (B3) and / or component (B4) may be produced as by-products. In this reaction, the molar ratio ((a3) / (a1)) of the fatty acid (a1) to the alkanolamine (a3) ​​used in the reaction may be, for example, 0.01 to 100, preferably 0.02 to 50, or 0.5 to 5, or 1.5 to 2.0. Furthermore, in the above dehydration condensation reaction, a disproportionation reaction (general formula (19) below) in which two molecules of dialkanolamine (a3d) are disproportionated into one molecule of monoalkanolamine (a3m) and one molecule of trialkanolamine (a3t) may proceed simultaneously as a side reaction.

[0091] [ka] This disproportionation reaction is thought to be accelerated by the action of a coexisting fatty acid (a1) in the system as an acid catalyst. The resulting monoalkanolamine (a3m) can further participate in dehydration condensation reactions with other alkanolamine molecules. Therefore, even if the alkanolamine used as a starting material consists of one or more dialkanolamines (a3d), the alkanolamine oligomer structure of the resulting amine compound (a2) may include structural units derived from the monoalkanolamine (a3m). Furthermore, such disproportionation reactions can proceed even after the formation of an alkanolamine oligomer structure. For example, a reaction between an alkanolamine dimer (e.g., dialkanolamine dimer (a2-dd)) and an alkanolamine (dialkanolamine (a3d) or monoalkanolamine (a3m)) can result in the formation of a hydroxyalkyl (-R 1 Alkanolamine dimers with one less -OH group (e.g., a2-dm or a2-md) and alkanolamines with one more hydroxyalkyl group (trialkanolamine (a3t) or dialkanolamine (a3d)) can be produced (see general formula (20) below).

[0092] [ka] Furthermore, in the above dehydration condensation reaction, a cyclization reaction of the alkanolamine oligomer structure may proceed as a side reaction. For example, two hydroxyalkyl (-R) bonded to the same nitrogen atom 1 If an -OH) group is present, an azaoxacycloalkane skeleton such as a morpholine skeleton can be formed by intramolecular dehydration cyclization. For example, an alkanolamine dimer (a2-dd) (see general formula (4)) in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a secondary amino group can give a cyclization product (cao-a2-dd) by intramolecular dehydration, and the cyclization product (cao-a2-dd) can further give a dehydration condensation product (acyl-cao-a2-dd) with a fatty acid (a1). Alternatively, a dehydration condensation reaction between the dialkanolamine dimer (a2-dd) and a fatty acid (a1) may proceed to give an amide compound (acyl-a2-dd), after which an intramolecular dehydration reaction may produce a cyclization product (acyl-cao-a2-dd) (see general formula (21) below).

[0093] [ka] Similarly, an alkanolamine dimer (a2-md) in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a primary amino group can also yield a cyclization product by intramolecular dehydration (see general formula (22) below).

[0094] [ka] The intramolecular dehydration cyclization reaction that forms such an azaoxacycloalkane skeleton involves the alkylene group R 1 This process is more likely to occur when the main chain has two carbon atoms, in which case a morpholine skeleton is formed. Furthermore, for example, in alkanolamine oligomers with a degree of polymerization of 2 or more, alkylene group R 1 The two free valencies of hydroxyalkyl (-R 1If a structure exists in which a nitrogen atom to which an -OH) group is bonded is bonded to a primary or secondary amino group, an intramolecular dehydration cyclization reaction that forms a diazacycloalkane skeleton may proceed as a side reaction. In other words, in alkanolamine oligomers with a degree of polymerization of 2 or more, the alkylene group R 1 One of the two nitrogen atoms bonded to it has one or more hydrogen atoms bonded to it, and the other has one or more hydroxyalkyl (-R) atoms bonded to it. 1 If a structure with a -OH) group attached exists, an intramolecular dehydration cyclization reaction that forms a diazacycloalkane skeleton may proceed as a side reaction. For example, an alkanolamine dimer (a2-md) in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a primary amino group can undergo an intramolecular dehydration reaction to give a cyclization product (caa-a2-md) having a diazacycloalkane skeleton, and the acylation reaction of this cyclization product (caa-a2-md) with a fatty acid (a1) may proceed further (see general formula (23) below).

[0095] [ka] For example, an alkanolamine dimer (a2-dm) in which both amino groups are secondary amino groups can undergo intramolecular dehydration to give a cyclization product (caa-a2-md) having a diazacycloalkane skeleton, and the acylation reaction of this cyclization product (caa-a2-md) with a fatty acid (a1) may proceed further. Alternatively, a dehydration condensation reaction between the dialkanolamine dimer (a2-dm) and the fatty acid (a1) may proceed to give an amide compound (acyl-a2-dm), after which an intramolecular dehydration reaction may produce a cyclization product (acyl-caa-a2-md) (see general formula (24) below).

[0096] [ka] For example, an alkanolamine dimer (a2-dd) in which one amino group is a secondary amino group and the other amino group is a tertiary amino group can undergo an intramolecular dehydration reaction to give a cyclization product (caa-a2-dd) having a diazacycloalkane skeleton, and the acylation reaction of this cyclization product (caa-a2-dd) with a fatty acid (a1) can proceed further (see general formula (25) below).

[0097] [ka] The intramolecular dehydration cyclization reaction that forms such a diazacycloalkane skeleton involves the alkylene group R 1 This process is more likely to occur when the main chain has two carbon atoms, in which case a piperazine skeleton is formed.

[0098] By-products having a cyclic structure and acylated with the monounsaturated fatty acid (a1) (hereinafter sometimes referred to as "component (B5)" or "component (B5)"), which are produced via an intramolecular dehydration cyclization reaction of an alkanolamine (a3) ​​or alkanolamine oligomer structure, are usually produced in small amounts, and their total content in the lubricating oil composition may be, for example, 0 to 2.0% by mass or 0 to 5.0% by mass, based on the total content of all acylated compounds by the monounsaturated fatty acid (a1) of the alkanolamine structure, which may have its hydroxyl group etherified, in terms of compounds in their unsalted state.

[0099] After the condensation reaction between fatty acid (a1) and dialkanolamine (a3) ​​is complete, unreacted starting materials can be removed by known methods such as washing with water, silica gel short-pass column chromatography, and Celite filtration. A solvent can be used as appropriate during such operations. Suitable solvents include pentane, hexane, cyclohexane, heptane, benzene, toluene, xylene, diethyl ether, ethyl acetate, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, dichloromethane, chloroform, and carbon tetrachloride. The content of each component (B1) to (B5) can be adjusted by further purification of the obtained product using known purification methods such as column chromatography. Washing with water here refers to washing with water or an aqueous solution. Suitable aqueous solutions for washing include acidic water such as dilute hydrochloric acid, alkaline water such as dilute sodium hydroxide aqueous solution, and salt aqueous solutions such as saturated brine.

[0100] In the lubricating oil composition of the present invention, components (B1) to (B5) act as oily friction modifiers. The total content of components (B1) to (B4) in the lubricating oil composition is preferably 0.005% by mass or more, or 0.010% by mass or more, or 0.030% by mass or more, or 0.050% by mass or more, on a basis of the total lubricating oil composition, in terms of compounds in a state where salts have not been formed, from the viewpoint of further improving friction reduction performance, particularly friction reduction performance on metal surfaces that are subject to high loads such as gears, while suppressing a decrease in the storage stability of the lubricating oil composition. From the viewpoint of storage stability, it is preferably 10.0% by mass or less, preferably 5.0% by mass or less, or 4.0% by mass or less, or 3.0% by mass or less. In one embodiment, it may be 0.005 to 10.0% by mass, or 0.010 to 5.0% by mass, or 0.030 to 4.0% by mass, or 0.050 to 3.0% by mass. In one embodiment, the total content of the above components (B1) to (B5) in the lubricating oil composition is preferably 0.005% by mass or more, or 0.010% by mass or more, or 0.030% by mass or more, or 0.050% by mass or more, on a basis of the total lubricating oil composition, in terms of compounds in a state where salts have not been formed, from the viewpoint of further improving friction reduction performance, particularly friction reduction performance on metal surfaces that are subject to high loads such as gears, while suppressing a decrease in the storage stability of the lubricating oil composition. From the viewpoint of storage stability, it is preferably 10.0% by mass or less, preferably 5.0% by mass or less, or 4.0% by mass or less, or 3.0% by mass or less. In one embodiment, it may be 0.005 to 10.0% by mass, or 0.010 to 5.0% by mass, or 0.030 to 4.0% by mass, or 0.050 to 3.0% by mass. According to the lubricating oil additive composition of the present invention, by including component (B1), it is possible to obtain improved friction reduction performance, particularly improved friction reduction performance in the mixed lubrication region, compared to when component (B3) is used alone as a friction modifier.

[0101] ((C): Metal-based cleaning agent) In one preferred embodiment, the lubricating oil composition may further contain one or more metal-based detergents (hereinafter sometimes referred to as "component (C)"). Examples of component (C) include salicylate detergents, sulfonate detergents, phenate detergents, etc. Furthermore, component (C) may contain only one metal-based detergent, or it may contain two or more metal-based detergents. Generally, in the field of lubricating oils, metal-based detergents used include organic acid metal salts capable of forming micelles in the base oil (e.g., alkali or alkaline earth metal alkyl salicylates, alkali or alkaline earth metal alkylbenzene sulfonates, and alkali or alkaline earth metal alkyl phenates, etc.), or mixtures of the organic acid metal salt and a basic metal salt (e.g., hydroxides, carbonates, borates, etc. of the alkali or alkaline earth metal constituting the organic acid metal salt). Such organic acids typically have in one molecule at least one polar group (e.g., a carboxyl group, a sulfo group, a phenolic hydroxyl group, etc.) that has Brønsted acidity and can form a salt with a metal base (typically a metal oxide and / or metal hydroxide), and at least one lipophilic group such as a linear or branched alkyl group (e.g., a linear or branched alkyl group having 6 or more carbon atoms, etc.).

[0102] Examples of salicylate-based cleaning agents include metal salicylates or their basic or overbasic salts. Preferred examples of metal salicylates include alkali or alkaline earth metal salicylates represented by the following general formula (26).

[0103] [ka]

[0104] In general formula (26), R 17Each of these independently represents an alkyl or alkenyl group having 14 to 30 carbon atoms, M represents an alkali metal or alkaline earth metal, a represents 1 or 2, and p represents 1 or 2 corresponding to the valency of M. When M is an alkali metal, p is 1, and when M is an alkaline earth metal, p is 2. M is preferably an alkaline earth metal. Sodium or potassium is preferred as the alkali metal, and calcium or magnesium is preferred as the alkaline earth metal. a is preferably 1. When a=2, R 17 This can be a combination of different bases.

[0105] A preferred form of salicylate-based cleaning agent is an alkaline earth metal salicylate or its basic or overbasic salt, where a=1 in the general formula (26) described above.

[0106] Preferred examples of sulfonate-based detergents include alkali or alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds, or their basic or overbasic salts, more preferably alkaline earth metal salts, or their basic or overbasic salts. The weight-average molecular weight of the alkyl aromatic compound is preferably 400 to 1500, more preferably 700 to 1300. Sodium or potassium are preferred as alkali metals, and calcium or magnesium are preferred as alkaline earth metals. Examples of alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids. Examples of petroleum sulfonic acids include alkyl aromatic compounds obtained by sulfonating the lubricating oil fraction of mineral oil, and so-called mahogany acid, which is a by-product during the production of white oil. An example of a synthetic sulfonic acid is obtained by sulfonating alkylbenzenes having linear or branched alkyl groups, which are obtained by recovering by-products in alkylbenzene production plants that are raw materials for detergents, or by alkylating benzene with polyolefins. Another example of a synthetic sulfonic acid is obtained by sulfonating alkylnaphthalenes such as dinonylnaphthalene. Furthermore, there are no particular restrictions on the sulfonating agent used when sulfonating these alkyl aromatic compounds; for example, fuming sulfuric acid or anhydrous sulfuric acid can be used.

[0107] Preferred examples of phenate-based cleaning agents include overbasic salts of alkali or alkaline earth metal salts of compounds having the structure shown in the following general formula (27), more preferably overbasic salts of alkaline earth metal salts. Sodium or potassium is preferred as the alkali metal, and calcium or magnesium is preferred as the alkaline earth metal.

[0108] [ka]

[0109] In general formula (27), R 18 R represents a linear or branched, saturated or unsaturated alkyl or alkenyl group with 6 to 21 carbon atoms, q represents an integer from 0 to 9, A represents a sulfide (-S-) group or a methylene (-CH2-) group, and x represents an integer from 1 to 3. 18x may be a combination of two or more different groups, and x may be a combination of multiple different integers. When A is a methylene group, x is preferably 1. -A in each aromatic ring x - The substitution site of the group is typically the orthogonal or para-position relative to the hydroxyl group, usually the orthogonal position.

[0110] R in general formula (27) 18 The carbon number is preferably 9 or more from the viewpoint of increasing solubility in the base oil, and preferably 18 or less, more preferably 15 or less from the viewpoint of ease of manufacture, and in one embodiment it may be 9 to 18 or 9 to 15.

[0111] In general formula (27), q is preferably between 0 and 3.

[0112] Metal-based cleaning agents may be over-basicated with carbonates (for example, alkali metal carbonates such as sodium carbonate or potassium carbonate, or alkaline earth metal carbonates such as calcium carbonate or magnesium carbonate), or they may be over-basicated with borates (for example, alkali metal borates such as sodium borate or potassium borate, or alkaline earth metal borates such as calcium borate or magnesium borate).

[0113] In one embodiment, component (C) comprises one or more overbasic calcium or magnesium sulfonate cleaning agents, one or more overbasic calcium or magnesium salicylate cleaning agents, and / or one or more overbasic calcium or magnesium phenate cleaning agents, preferably comprising one or more overbasic calcium sulfonate cleaning agents and / or one or more overbasic calcium salicylate cleaning agents. The calcium sulfonate cleaning agent, calcium salicylate cleaning agent, and calcium phenate cleaning agent are preferably overbasicated with calcium carbonate, and the magnesium sulfonate cleaning agent, magnesium salicylate cleaning agent, and magnesium phenate cleaning agent are preferably overbasicated with magnesium carbonate.

[0114] The base number of the metal-based detergent can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the base number of the metal-based detergent is preferably 200 mg KOH / g or more, more preferably 250 mg KOH / g or more, from the viewpoint of increasing wear resistance, seizure resistance, and the transmission torque capacity of wet clutches, and also preferably 600 mg KOH / g or less, more preferably 550 mg KOH / g or less, and in one embodiment it may be 200 to 600 mg KOH / g or 250 to 550 mg KOH / g. Furthermore, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the base number is preferably 0 mgKOH / g or more, more preferably 20 mgKOH / g or more, from the viewpoint of improving cleaning performance and base number maintenance, and preferably 500 mgKOH / g or less, more preferably 450 mgKOH / g or less, from the viewpoint of suppressing ash content in the composition and the lifespan of the exhaust gas aftertreatment device, and in one embodiment it may be 0 to 500 mgKOH / g or 20 to 450 mgKOH / g. In this specification, the base number refers to the base number measured by the perchloric acid method in accordance with JIS K2501.

[0115] If the lubricating oil composition contains component (C), its content can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (C) in the lubricating oil composition is preferably 200 ppm by mass or more, more preferably 250 ppm by mass or more, as a metal content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, seizure resistance, fatigue resistance, and the transmission torque capacity of wet clutches. Furthermore, from the viewpoint of improving fuel efficiency and fatigue resistance, it is preferably 600 ppm by mass or less, more preferably 550 ppm by mass or less, and in one embodiment it may be 200 to 600 ppm by mass or 250 to 550 ppm by mass. Furthermore, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the content of component (C) is preferably 500 ppm by mass or more, more preferably 1,000 ppm by mass or more, as a metal content based on the total amount of the lubricating oil composition, from the viewpoint of improving cleaning performance and base number maintenance, and preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, from the viewpoint of suppressing ash content in the composition and the lifespan of the exhaust gas aftertreatment device, and in one embodiment it may be 500 to 10,000 ppm by mass or 1,000 to 5,000 ppm by mass.

[0116] ((D) Nitrogen-containing dispersant) In one preferred embodiment, the lubricating oil composition may further contain one or more nitrogen-containing dispersants (hereinafter sometimes referred to as "component (D)"). Generally in the field of lubricating oils, nitrogen-containing dispersants used are nitrogen-containing compounds having at least one long-chain (e.g., 40 or more carbon atoms) straight-chain or branched-chain aliphatic hydrocarbon group and at least one polyamine chain (typically a polyethyleneamine chain) in one molecule, wherein some of the nitrogen atoms of the polyamine chain may be acylated, or modified versions (derivatives) thereof. Examples of modified versions will be described later.

[0117] (D) For example, one or more compounds selected from (D-1) to (D-3) below can be used as component (D). (D-1) Succinimide or a modified product (derivative) thereof having at least one alkyl group or alkenyl group in the molecule (hereinafter sometimes referred to as "component (D-1)"), (D-2) Benzylamine having at least one alkyl or alkenyl group in its molecule (for example, a Mannich base obtained by the reaction of an alkyl or alkenylphenol with formaldehyde and a polyamine) or a modified product (derivative) thereof (hereinafter sometimes referred to as "component (D-2)"), (D-3) N-alkyl or alkenylated polyamines or modified products (derivatives) thereof having at least one alkyl or alkenyl group in the molecule (hereinafter sometimes referred to as "component (D-3)").

[0118] (D) Component (D-1) can be used as component (D-1) in particular preference. Examples of succinimides among component (D-1) that have at least one alkyl or alkenyl group in the molecule include condensation reaction products of alkyl or alkenyl succinic acid or its anhydride having an alkyl or alkenyl group with 40 to 400 carbon atoms and a polyamine. Such condensation reaction products (condensation products) can be represented, for example, by the following general formula (28a) or (28b).

[0119] [ka]

[0120] In general formula (28a), R 19 represents an alkyl or alkenyl group having 40 to 400 carbon atoms, and b represents an integer from 1 to 10, preferably from 2 to 6. In one typical embodiment, the compound represented by general formula (28a) is obtained as a mixture of compounds having different b. 19The carbon number is 40 or more, preferably 60 or more, from the viewpoint of solubility in the base oil, and 400 or less, preferably 350 or less, more preferably 250 or less, from the viewpoint of low-temperature fluidity of the composition, and in one embodiment it may be 40 to 400, 60 to 350, or 60 to 250.

[0121] In general formula (28b), R 20 and R 21 Each of these independently represents an alkyl or alkenyl group having 40 to 400 carbon atoms, and may be a combination of different groups. Furthermore, c represents an integer from 0 to 15, preferably 1 to 13, and more preferably 1 to 11. In one typical embodiment, the compound represented by general formula (28b) is obtained as a mixture of compounds having different c values. 20 and R 21 The carbon number is 40 or more, preferably 60 or more, from the viewpoint of solubility in the base oil, and 400 or less, preferably 350 or less, more preferably 250 or less, from the viewpoint of low-temperature fluidity of the composition, and in one embodiment it may be 40 to 400, 60 to 350, or 60 to 250.

[0122] The alkyl or alkenyl group (R) in general formulas (28a) and (28b) 19 ~R 21 The group may be linear or branched. Preferred examples include branched alkyl or branched alkenyl groups derived from olefin oligomers such as propylene, 1-butene, and isobutene, or from co-oligomers of ethylene and propylene. Among these, branched alkyl or alkenyl groups derived from isobutene oligomers, commonly called polyisobutylene, or polybutenyl groups are the most preferred. The alkyl or alkenyl group (R) in general formulas (28a) and (28b) 19 ~R 21 The preferred number-average molecular weight of ) is 800 to 3500, preferably 900 to 3500.

[0123] Succinimides having at least one alkyl or alkenyl group in the molecule include so-called monotype succinimides represented by general formula (28a), in which only one end of the polyamine chain is imidized, and so-called bistype succinimides represented by general formula (28b), in which both ends of the polyamine chain are imidized. The lubricating oil composition may contain either monotype succinimides or bistype succinimides, or both may be contained as a mixture. The content of bistype succinimides or their modified products in component (D-1) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount of component (D-1) (100% by mass).

[0124] The weight-average molecular weight of component (D-1) is preferably 1000 to 20000, more preferably 2000 to 20000, and even more preferably 3000 to 15000, and in one embodiment it may be 4000 to 15000.

[0125] Examples of modified products (modified compounds, derivatives) in components (D-1) to (D-3) include (i) modified products with oxygen-containing organic compounds, (ii) boric acid modified products, (iii) phosphoric acid modified products, (iv) sulfur modified products, and (v) modified products obtained by a combination of two or more of these modifications. (i) Modified products with oxygen-containing organic compounds are modified compounds in which some or all of the remaining amino groups and / or imino groups are neutralized or amidated by reacting succinimide, benzylamine, or polyamine (hereinafter referred to as "the above nitrogen-containing compound") having at least one alkyl group or alkenyl group in its molecule with a carbon-1 to carbon-30 monocarboxylic acid such as fatty acids, carbon-2 to carbon-30 polycarboxylic acid (e.g., oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.), anhydrides or ester compounds thereof, carbon-2 to carbon-6 alkylene oxide, or hydroxy(poly)oxyalkylene carbonate. (ii) Boric acid modified compounds are modified compounds in which some or all of the remaining amino groups and / or imino groups are neutralized or amidated by reacting the above-mentioned nitrogen-containing compound with boric acid. (iii) Phosphate-modified compounds are modified compounds in which some or all of the remaining amino groups and / or imino groups are neutralized or amidated by reacting the above-mentioned nitrogen-containing compound with phosphoric acid. (iv) Sulfur-modified compounds are modified compounds obtained by reacting the above-mentioned nitrogen-containing compounds with sulfur compounds. (v) Modified compounds obtained by a combination of two or more modification methods can be obtained by applying a combination of two or more modification methods selected from modification with an oxygen-containing organic compound, modification with borate, modification with phosphoric acid, and modification with sulfur to the nitrogen-containing compound described above. Among these modified products (derivatives) (i) to (v), boric acid modified compounds of alkenyl succinimide, particularly boric acid modified bis-type alkenyl succinimide, can be preferably used.

[0126] If the lubricating oil composition contains component (D), its content can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (D) in the lubricating oil composition is preferably 0.1% by mass or more on a basis of the total lubricating oil composition from the viewpoint of improving oxidation stability, and preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining energy efficiency. Also, for example, when the lubricating oil composition is used to lubricate internal combustion engines, the content of component (D) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more on a basis of the total lubricating oil composition from the viewpoint of improving coking resistance, and preferably 10.0% by mass or less, more preferably 5.0% by mass or less, from the viewpoint of maintaining fuel efficiency, and in one embodiment it may be 0.5% by mass to 10.0% by mass, or 1.0% by mass to 5.0% by mass.

[0127] Component (D) may preferably be component (D-1), and a boric acid modified product may preferably be used as the modified product of component (D). In one embodiment, component (D) may be one or more unmodified components (D-1) (unmodified succinimide dispersants), one or more boric acid modified products of component (D-1) (boric acid modified succinimide dispersants), or a combination of one or more unmodified succinimide dispersants and one or more boric acid modified succinimide dispersants. Component (D) may or may not contain a boric acid modified product, but from the viewpoint of sludge dispersibility, the ratio (B / N) of the boron content B of component (D) to the nitrogen content N of component (D) is preferably 0 to 1.0 in one embodiment.

[0128] ((E) Phosphorus-containing wear inhibitor) In one preferred embodiment, the lubricating oil composition may contain one or more phosphorus-containing anti-wear agents (hereinafter sometimes referred to as "component (E)"). Component (E) can be any phosphorus-containing anti-wear agent used in lubricating oils without particular limitation. Examples of phosphorus-containing anti-wear agents include compounds represented by the following general formula (29), compounds represented by the following general formula (30), and their metal salts and ammonium salts.

[0129] [ka] (In general formula (29), X 1 , X 2 , and X 3 Each represents either an oxygen atom or a sulfur atom independently; R 22 R represents a hydrocarbon group having 1 to 30 carbon atoms, which may contain a sulfur atom; 23 and R 24 Each of these independently represents a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, which may contain a sulfur atom; R 22 , R 23 , and R 24 They may be identical or mutually different. 23 and / or R 24When it is a hydrogen atom, the compound of general formula (29) shall include any tautomer thereof.)

[0130] [Chemical formula] (In general formula (30), X 4 , X 5 , X 6 , and X 7 each independently represents an oxygen atom or a sulfur atom; R 25 represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom; R 26 and R 27 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom or a hydrogen atom; R 25 , R 26 , and R<000019​​​​​​​​​​​​In one embodiment, a preferred example of a hydrocarbon group that does not contain a sulfur atom is a linear alkyl group having 4 to 18 carbon atoms. Examples of linear alkyl groups include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

[0134] Examples of hydrocarbon groups containing sulfur atoms include hydrocarbon groups functionalized by sulfide bonds. Preferred examples of hydrocarbon groups functionalized by sulfide bonds include groups having 4 to 20 carbon atoms represented by the following general formula (31).

[0135] [ka] In general formula (31), R 28 R is a linear hydrocarbon group having 2 to 17 carbon atoms, preferably an ethylene group or a propylene group, and in one embodiment it is an ethylene group. 29 The group is a linear hydrocarbon group having 2 to 17 carbon atoms, preferably a linear hydrocarbon group having 2 to 16 carbon atoms, and particularly preferably a linear hydrocarbon group having 6 to 10 carbon atoms.

[0136] Preferred examples of the group represented by general formula (31) include 3-thiapentyl group, 3-thiahexyl group, 3-thiaheptyl group, 3-thiaoctyl group, 3-thianonyl group, 3-thiadecyl group, 3-thiaundecyl group, 4-thiahexyl group, and the like.

[0137] Examples of metals that form metal salts with phosphorus compounds represented by general formula (29) or (30) include alkali metals such as lithium, sodium, potassium, and cesium; alkaline earth metals such as calcium, magnesium, and barium; and transition metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium, or zinc, or combinations thereof are preferred.

[0138] Examples of nitrogen-containing compounds that form ammonium salts with phosphorus compounds represented by general formula (29) or (30) include ammonia, monoamines, diamines, polyamines, and alkanolamines. More specifically, examples include nitrogen-containing compounds represented by the following general formula (32); alkylenediamines such as methylenediamine, ethylenediamine, propylenediamine, and butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; and combinations thereof.

[0139] [ka] (In general formula (32), R 30 ~R 32 Each of these independently represents a hydrogen atom, a C1-C8 hydrocarbyl group, or a C1-C8 hydrocarbyl group having a hydroxyl group; R 30 ~R 32 At least one of these is a hydroxyl group having 1 to 8 carbon atoms, or a hydroxyl group having 1 to 8 carbon atoms.

[0140] A preferred example of a compound represented by the above general formula (29) is one in which X 1 ~X 3 is an oxygen atom, and R 22 ~R 24 A phosphite ester compound in which each of the C3-C18 (preferably 4-C12) alkyl group, aryl group (e.g., phenyl group), or alkylaryl group (e.g., alkylphenyl group) may independently contain a sulfur atom; in the above general formula (29), X 1 ~X 3 is an oxygen atom, and R 22 and R 23 Each of these is an alkyl group, aryl group (e.g., phenyl group), or alkylaryl group (e.g., alkylphenyl group), each independently containing a sulfur atom, and R 24A hydrogen phosphite compound in which X is hydrogen; in the above general formula (29), X 1 ~X 3 Two of them are oxygen atoms, and the remaining one is a sulfur atom, R 22 and R 23 Each of these is an alkyl group, aryl group (e.g., phenyl group), or alkylaryl group (e.g., alkylphenyl group), each independently containing a sulfur atom, and R 24 Hydrogenthiophosphite compounds in which is hydrogen; and in the above general formula (29), X 1 ~X 3 One of them is an oxygen atom, and the remaining two are sulfur atoms, R 22 and R 23 Each of these is an alkyl group, aryl group (e.g., phenyl group), or alkylaryl group (e.g., alkylphenyl group), each independently containing a sulfur atom, and R 24 Examples include hydrogen dithiophosphine compounds in which hydrogen is present. A preferred example of a compound represented by the above general formula (30) is one in which X 4 ~X 7 Two of them are sulfur atoms, and the remaining two are oxygen atoms, R 25 ~R 27 Examples of dithiophosphate compounds in which each of the three C3-18 (preferably 4-12) alkyl groups, aryl groups, or alkylaryl groups may independently contain a sulfur atom. These compounds may be used individually or in combination of two or more.

[0141] (E) One example of component is zinc dialkyldithiophosphate (ZnDTP). An example of zinc dialkyldithiophosphate is the compound represented by the following general formula (33).

[0142] [ka] In general formula (33), R 33 ~R 36 Each of these independently represents a linear or branched alkyl group having 3 to 18 carbon atoms, and may be a combination of different groups. Also, R 33 ~R 36 The number of carbon atoms is preferably 3 to 12, more preferably 3 to 8. Also, R 33 ~R 36 This may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, but it is preferably a primary alkyl group, a secondary alkyl group, or a combination thereof.

[0143] If the lubricating oil composition contains component (E), its content can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (E) in the lubricating oil composition is preferably 50 ppm by mass or more, more preferably 100 ppm by mass or more, as phosphorus content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, seizure resistance, bearing fatigue life, and transmission shock prevention, and also preferably 800 ppm by mass or less, more preferably 700 ppm by mass or less, and in one embodiment it may be 50 to 800 ppm by mass or 100 to 700 ppm by mass. Furthermore, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the content of component (E) is preferably 400 ppm by mass or more, more preferably 500 ppm by mass or more, as phosphorus content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, and preferably 5000 ppm by mass or less, more preferably 3000 ppm by mass or less, from the viewpoint of reducing catalyst poisoning of the exhaust gas aftertreatment device, and in one embodiment it may be 400 to 5000 ppm by mass or 500 to 3000 ppm by mass.

[0144] ((F) Sulfur-containing extreme pressure agent) In one preferred embodiment, the lubricating oil composition may further contain one or more sulfur-containing extreme pressure agents other than the component (E) (hereinafter sometimes referred to as the "component (F)"). Examples of the component (F) include known sulfur-containing extreme pressure agents such as thiadiazole compounds, dihydrocarbyl (poly) sulfides, sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpenoid compounds, dialkylthiodipropionate compounds, sulfurized mineral oils, zinc dithiocarbamate compounds, molybdenum dithiocarbamate compounds, and the like.

[0145] Preferred examples of the thiadiazole compound include 1,3,4-thiadiazole compounds represented by the following general formula (34), 1,2,4-thiadiazole compounds represented by the following general formula (35), and 1,2,3-thiadiazole compounds represented by the following general formula (36).

[0146]

Chemical formula

[0147]

Chemical formula

[0148]

Chemical formula

[0149] The dihydrocarbyl (poly) sulfide is a compound represented by the following general formula (37). Here, when R 31 and R 32 are alkyl groups, it may be referred to as an alkyl sulfide.

[0150] [ka] (In general formula (37), R 39 and R 40 The elements may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms (which may be linear or branched, and may have a cyclic structure), an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, where f represents an integer from 1 to 8.

[0151] If the lubricating oil composition contains component (F), its content can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (F) in the lubricating oil composition is preferably 200 ppm by mass or more, more preferably 300 ppm by mass or more, as a sulfur content based on the total amount of the lubricating oil composition, from the viewpoint of improving extreme pressure resistance and fatigue resistance, and preferably 3000 ppm by mass or less, more preferably 2500 ppm by mass or less, from the viewpoint of improving wear resistance, fatigue resistance, and oxidation stability, and in one embodiment it may be 200 to 3000 ppm by mass or 300 to 2500 ppm by mass. Furthermore, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the content of component (F) is preferably 10 ppm by mass or more, more preferably 30 ppm by mass or more, as a sulfur content based on the total amount of the lubricating oil composition, from the viewpoint of improving extreme pressure properties and fatigue resistance, and preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, from the viewpoint of reducing catalyst poisoning of the exhaust gas aftertreatment device, and in one embodiment it may be 10 to 200 ppm by mass or 30 to 100 ppm by mass.

[0152] ((G) Antioxidant) In one preferred embodiment, the lubricating oil composition may further contain, as an antioxidant (hereinafter sometimes referred to as "component (G)"), one or more amine-based antioxidants and / or one or more phenol-based antioxidants.

[0153] Examples of amine-based antioxidants include aromatic amine-based antioxidants and hindered amine-based antioxidants. Examples of aromatic amine-based antioxidants include primary aromatic amine compounds such as alkylated α-naphthylamine; and secondary aromatic amine compounds such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, and phenyl-β-naphthylamine. As aromatic amine-based antioxidants, alkylated diphenylamine, alkylated phenyl-α-naphthylamine, or combinations thereof can be preferably used.

[0154] Examples of hindered amine antioxidants include compounds having a 2,2,6,6-tetraalkylpiperidine skeleton (2,2,6,6-tetraalkylpiperidine derivatives). Preferred 2,2,6,6-tetraalkylpiperidine derivatives have a substituent at the 4-position. Furthermore, two 2,2,6,6-tetraalkylpiperidine skeletons may be bonded via their respective 4-position substituents. The N-position of the 2,2,6,6-tetraalkylpiperidine skeleton may be unsubstituted, or it may be substituted with an alkyl group having 1 to 4 carbon atoms. The 2,2,6,6-tetraalkylpiperidine skeleton is preferably a 2,2,6,6-tetramethylpiperidine skeleton.

[0155] The substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton is an acyloxy group (R 41 COO-), alkoxy group (R 41 O-), alkylamino group (R 41 NH-), acylamino group (R 41 Examples include CONH-), etc. 41The hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and even more preferably 1 to 20 carbon atoms. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, alkylcycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and the like.

[0156] When two 2,2,6,6-tetraalkylpiperidine skeletons are bonded via substituents at their respective 4-positions, the substituents include hydrocarbylenebis(carbonyloxy) groups (-OOC-R 42 -COO-), hydrocarbylenediamino group (-HN-R 42 -NH-), hydrocarbylenebis(carbonylamino) group (-HNCO-R 42 Examples include -CONH-), etc. 42 Preferably, it is a hydrocarbylene group having 1 to 30 carbon atoms, and more preferably an alkylene group.

[0157] An acyloxy group is preferred as the substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton. An example of a compound having an acyloxy group at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton is an ester of 2,2,6,6-tetramethyl-4-piperidinol with a carboxylic acid. Examples of the carboxylic acid include linear or branched aliphatic carboxylic acids having 8 to 20 carbon atoms.

[0158] Examples of phenolic antioxidants include: 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 4,4'-bis(2-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 4,4'-butylidenebis(3-methyl-6-tert-butylphenol); 4,4'-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4-methylphenol; 2,6- Examples of hindered phenol compounds and bisphenol compounds include di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-butyl-4-(N,N'-dimethylaminomethyl)phenol; 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide; 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters; and 3-methyl-5-tert-butyl-4-hydroxyphenol fatty acid esters.

[0159] If the lubricating oil composition contains component (G), its content can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (G) in the lubricating oil composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total amount of the lubricating oil composition, from the viewpoint of improving thermal oxidation stability, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and in one embodiment it may be 0.1 to 2.0% by mass, or 0.2 to 1.0% by mass. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (G) in the lubricating oil composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the lubricating oil composition, from the viewpoint of improving thermal oxidation stability, and similarly preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and in one embodiment it may be 0.1 to 5.0% by mass, or 0.5 to 3.0% by mass.

[0160] ((H) Viscosity index improver) In one preferred embodiment, the lubricating oil composition may further contain one or more polymers having a viscosity index improving effect (hereinafter referred to as "viscosity index improver" or "component (H)"). Examples of component (H) include non-dispersible or dispersed poly(meth)acrylate, (meth)acrylate-olefin copolymer, non-dispersible or dispersed ethylene-α-olefin copolymer or its hydride, polyisobutylene or its hydride, styrene-diene hydrogenated copolymer, styrene-maleic anhydride copolymer, and polyalkylstyrene. In this specification, "(meth)acrylate" means "acrylate and / or methacrylate". Component (H) may be a single polymer or a combination of two or more polymers.

[0161] In one embodiment, the (H) component may preferably be a dispersed poly(meth)acrylate, a non-dispersed poly(meth)acrylate, or a combination thereof. In one embodiment, a dispersed poly(meth)acrylate may preferably be used. In this specification, dispersed poly(meth)acrylate compounds have a functional group containing a nitrogen atom, while non-dispersed poly(meth)acrylate compounds do not have a functional group containing a nitrogen atom.

[0162] In one embodiment, as the poly(meth)acrylate viscosity index improver, a poly(meth)acrylate (hereinafter sometimes referred to as "poly(meth)acrylate (H1)" or simply "(H1) component") in which the proportion of structural units represented by the following general formula (38) to the total monomer units in the polymer is 10 to 90 mol% can be preferably used.

[0163] [ka] (In general formula (38), R 43 R represents a hydrogen or methyl group. 44 (This represents a linear or branched hydrocarbon group having 1 to 36 carbon atoms, preferably an alkyl group.)

[0164] The weight-average molecular weight of component (H) can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the weight-average molecular weight of component (H) is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, from the viewpoint of enhancing the viscosity index improvement effect and improving low-temperature viscosity characteristics, and is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less, from the viewpoint of improving solubility in the base oil, storage stability, and shear stability, and may be 10,000 to 200,000, or 20,000 to 150,000, or 30,000 to 100,000 in one embodiment. Furthermore, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the weight-average molecular weight of component (H) is preferably 100,000 or more, more preferably 200,000 or more, from the viewpoint of enhancing the viscosity index improvement effect and improving low-temperature viscosity characteristics and fuel efficiency, and is preferably 1,000,000 or less, more preferably 700,000 or less, from the viewpoint of improving solubility in oil, storage stability and shear stability, and may be 100,000 to 1,000,000 or 200,000 to 700,000 in one embodiment.

[0165] When a lubricating oil composition contains component (H), its content can be appropriately determined as an amount that yields the desired kinematic viscosity and viscosity-temperature characteristics for the lubricating oil composition as a whole. For example, the viscosity index is an index for evaluating viscosity-temperature characteristics. For example, when a lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (H) in the lubricating oil composition may be, for example, 0.1% by mass or more, or 0.5% by mass or more, as resin content on a basis of the total lubricating oil composition, from the viewpoint of improving viscosity-temperature characteristics and increasing energy efficiency, and for example, 22% by mass or less, or 12% by mass or less, or in one embodiment, 0.1 to 22% by mass, or 0.5 to 12% by mass, from the viewpoint of improving shear stability. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (H) in the lubricating oil composition may be, from the viewpoint of improving fuel efficiency, for example, 0.1% by mass or more, or 0.5% by mass or more, as resin content on a basis of the total lubricating oil composition, and from the viewpoint of improving shear stability, for example, 20% by mass or less, or 15% by mass or less, or in one embodiment, 0.1 to 20% by mass, or 0.5 to 15% by mass. In this specification, resin content means polymer components with a molecular weight of 1,000 or more.

[0166] (Other additives) The lubricating oil composition of the present invention may further contain one or more additives selected from (I) friction modifiers other than the above components (B1) to (B5) and (F), (J) pour point depressants other than the above component (H), (K) corrosion inhibitors other than the above component (F), (L) metal deactivators other than the above component (F), (M) rust inhibitors other than the above components (B1) to (B5), (N) anti-emulsifiers, (O) defoaming agents, and (P) colorants.

[0167] (I) Friction modifiers other than the above components (B1) to (B5) and (F) (hereinafter sometimes referred to as "component (I)") include oil-soluble organic molybdenum compounds or oily friction modifiers used as friction modifiers in lubricating oils, and compounds other than the above components (B1) to (B5) and (F) can be used. Examples of such compounds include oil-soluble organic molybdenum compounds other than the above-described molybdenum dithiocarbamate as an example of component (F), and oily friction modifiers other than the above components (B1) to (B5). If the lubricating oil composition contains component (I), its content may be, for example, 0.1 to 1.0% by mass based on the total amount of the lubricating oil composition.

[0168] (J) As a pour point depressant other than the component (H) above (hereinafter sometimes referred to as "component (J)"), known pour point depressants such as ethylene vinyl acetate can be used depending on the properties of the lubricating oil base oil used. If the lubricating oil composition contains component (J), its content may be, for example, 0.01 to 1.0% by mass on a basis of the total amount of the lubricating oil composition.

[0169] (K) As a corrosion inhibitor other than the above-mentioned (F) component (hereinafter sometimes referred to as "component (K)"), known corrosion inhibitors such as benzotriazole compounds, tolyltriazole compounds, and imidazole compounds can be used. If the lubricating oil composition contains component (K), its content may be, for example, 0.005 to 5.0% by mass on a basis of the total amount of the lubricating oil composition.

[0170] (L) Other metal deactivators besides the above-mentioned (F) component (hereinafter sometimes referred to as "component (L)") may be known metal deactivators such as imidazoline, pyrimidine derivatives, mercaptobenzothiazole, benzotriazole and its derivatives, 2-(alkyldithio)benzimidazole, and β-(o-carboxybenzylthio)propionnitrile. If the lubricating oil composition contains component (L), its content may be, for example, 0.005 to 1.0% by mass on a basis of the total amount of the lubricating oil composition.

[0171] (M) As a rust inhibitor other than the above components (B1) to (B5) (hereinafter sometimes referred to as "component (M)"), known rust inhibitors such as petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl succinates, and polyhydric alcohol esters (excluding those corresponding to components (B1) to (B5) above) can be used. If the lubricating oil composition contains component (M), its content may be, for example, 0.005 to 5.0% by mass on a basis of the total amount of the lubricating oil composition.

[0172] (N) As an anti-emulsifier, known anti-emulsifiers such as polyalkylene glycol-based nonionic surfactants can be used. If the lubricating oil composition contains an anti-emulsifier, its content may be, for example, 0.005 to 5.0% by mass on a basis of the total amount of the lubricating oil composition.

[0173] (O) As the defoaming agent, known defoaming agents such as silicones, fluorosilicones, and fluoroalkyl ethers can be used. If the lubricating oil composition contains a defoaming agent, the content may be, for example, 0.0005 to 1.0% by mass on a basis of the total amount of the lubricating oil composition.

[0174] (P) As a coloring agent, known coloring agents such as azo compounds can be used.

[0175] (Properties of lubricating oil composition) The kinematic viscosity of a lubricating oil composition at 100°C can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the kinematic viscosity of the lubricating oil composition at 100°C is preferably 1.0 mm from the viewpoint of improving wear resistance. 2 / s or more, more preferably 2.5m 2 The value should be 1 / s or more, and preferably 6.9 mm from the viewpoint of improving energy efficiency and significantly reducing the friction effect of component (B1). 2 Less than / s, more preferably 5.0 mm 2 It is less than or equal to / s, and in one embodiment, 1.0 to 6.9 mm 2 / s, or 1.0~5.0mm 2 / s, or 2.5-6.9mm 2 / s, or 2.5~5.0mm 2 It may be / s. Also, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the kinematic viscosity of the lubricating oil composition at 100°C is preferably 2.0 mm from the viewpoint of improving wear resistance. 2 / s or more, more preferably 4.0 mm 2 The value should be 1 / s or more, and preferably 6.9 mm from the viewpoint of improving energy efficiency and significantly reducing the friction effect of component (B1). 2 / s or less, more preferably 5.0 mm 2 / s or less, and in one embodiment, 2.0 to 6.9 mm 2 / s, or 4.0~6.9mm 2 / s, or 2.0~5.0mm 2 / s, or 4.0~5.0mm 2 It could be / s.

[0176] The kinematic viscosity of a lubricating oil composition at 40°C can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubricating gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the kinematic viscosity of the lubricating oil composition at 40°C is preferably 2.0 mm from the viewpoint of improving wear resistance. 2 / s or more, more preferably 5.0 mm 2The speed should be 1 / s or more, and preferably 50mm from the viewpoint of improving energy efficiency. 2 / s or less, more preferably 45mm 2 / s or less, and in one embodiment, 2.0~50mm 2 / s, or 2.0~45mm 2 / s, or 5.0~50mm 2 / s, or 5.0~45mm 2 It may be / s. Also, for example, when the lubricating oil composition is used for lubricating an internal combustion engine, the kinematic viscosity of the lubricating oil composition at 40°C is preferably 4.0 mm from the viewpoint of improving wear resistance. 2 / s or more, more preferably 6.0 mm 2 The speed should be 1 / s or more, and preferably 50mm from the viewpoint of improving energy efficiency. 2 / s or less, more preferably 35mm 2 / s or less, and in one embodiment, 4.0~50mm 2 / s, or 6.0~50mm 2 / s, or 4.0~35mm 2 / s, or 6.0~35mm 2 It could be / s.

[0177] The viscosity index of the lubricating oil composition is preferably 100 or higher, more preferably 110 or higher, and in one embodiment may be 115 or higher, or 120 or higher, from the viewpoint of further improving energy efficiency and wear resistance.

[0178] (Application) The additive composition and lubricating oil composition of the present invention can be widely used in the field of lubrication. The additive composition of the present invention maintains solubility in base oil while enhancing friction reduction performance, particularly friction reduction effect in mixed lubrication regions (e.g., gear lubrication conditions). The lubricating oil composition of the present invention contains component (B1), thereby enhancing friction reduction performance, particularly friction reduction effect in mixed lubrication regions (e.g., gear lubrication conditions). The additive composition and lubricating oil composition of the present invention exhibit an improved friction reduction effect in lubrication of metal surfaces that are susceptible to high loads, such as gears. Therefore, they can be suitably used for lubricating various mechanical devices equipped with metal surfaces that are susceptible to high loads, such as gear mechanisms, pistons, and connecting rod bearings. They can be particularly suitable for lubrication of transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, reduction gears for electric vehicles, speed increasers for wind turbines, etc.) and internal combustion engines, as well as for lubrication in various industrial applications (e.g., hydraulic fluids, turbine oils, compressor oils). [Examples]

[0179] The present invention will be described in more detail below based on examples and comparative examples. The following examples are intended to illustrate the present invention and are not intended to limit it.

[0180] <Manufacturing Examples 1-10> Friction modifier compositions having the compositions listed in Tables 1 to 5 were prepared according to the following procedure. (Measurement method) For IR (infrared spectroscopy) spectrum measurements, a JASCO FT / IR-4100 was used. For solid samples at room temperature, a small amount was heated and melted, then applied to a KBr plate for measurement. For liquid samples at room temperature, a small amount was applied directly to a KBr plate for measurement. The measurement conditions for LC-MS analysis were as follows. Equipment: Waters Corporation ACQUITY® UPLC H-Class liquid chromatography system Column: Waters Corporation ACQUITY® UPLC BEH C18 1.7μm 50×2.1mm (ODS) Mass spectrometer: Synapt (registered trademark) G2-S manufactured by Waters Corporation (ionization method: ESI+) A gradient elution method using ultrapure water, methanol, and isopropyl alcohol was employed as the mobile phase. Ammonium formate was added to each solvent to a concentration of 10 mmol / L. Starting with a water / methanol mixed volume ratio of 50 / 50, the composition was continuously varied up to 100% methanol, and then further continuously varied up to 100% isopropyl alcohol. Column temperature: 40℃ Sample solution: Methanol solution with a sample concentration of approximately 20 ppm by mass. Sample injection volume: 1.0 μL

[0181] (Manufacturing Example 1) 5.0 mol of lauric acid and 7.5 mol of diethanolamine (hereinafter sometimes referred to as "DEA") were placed in a 5 L three-necked flask fitted with a distillation tube, along with a magnetic stirrer. The flask was purged with nitrogen, and the contents were stirred with a magnetic stirrer to obtain a homogeneous mixture. The flask was heated in an oil bath while stirring the mixture with a magnetic stirrer. The oil bath temperature was gradually increased so that water would continue to distill. The reaction was monitored by IR spectroscopy, and the completion of the reaction was confirmed by IR spectroscopy 24 hours after the start of the reaction. The oil bath temperature at the end of the reaction was 180°C. The contents of the flask were allowed to cool, and the crude product was obtained by drying under reduced pressure. The crude product obtained was purified by preparative HPLC to prepare a friction modifier composition. The composition, as analyzed by LC-MS, is shown in Table 1.

[0182] [Table 1]

[0183] (Manufacturing example 2) The crude product obtained in Production Example 1 was purified by preparative HPLC to obtain DEA triper lauric acid amide (the first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA triper lauric acid amide and 2.0 equivalents of lauric acid were mixed without solvent and stirred at room temperature for 1 hour to produce the laurate salt of DEA triper lauric acid amide.

[0184] (Manufacturing Example 3) The crude product obtained in Production Example 1 was purified by preparative HPLC to produce diethanolamine monomer lauric acid amide (the third amide compound). Its composition is shown in Table 1.

[0185] (Manufacturing example 4) 2.5 mol of lauric acid, 2.5 mol of myristic acid, and 10.0 mol of DEA were placed in a 5 L three-necked flask fitted with a distillation tube, along with a magnetic stirrer. The flask was then purged with nitrogen, and the substances in the flask were stirred with a magnetic stirrer to obtain a homogeneous mixture. While stirring the mixture in the flask with a magnetic stirrer, the flask was heated to 150°C in an oil bath, and the pressure inside the flask was reduced using a rotary pump to maintain a pressure of 20,000 Pa. After 10 hours from the start of the reaction, the pressure in the system was further reduced to 2,000 Pa and maintained at that pressure. After 24 hours from the start of the reaction, the completion of the reaction was confirmed by IR spectroscopy. The contents of the flask were allowed to cool and dried under reduced pressure to obtain the friction modifier composition as a mixture of condensation products. The composition, as analyzed by LC-MS, is shown in Table 2.

[0186] [Table 2]

[0187] (Manufacturing example 5) 5.0 mol of oleic acid and 7.5 mol of DEA were placed in a 5 L three-necked flask fitted with a distillation tube, along with a magnetic stirrer. The flask was then purged with nitrogen, and the contents were stirred with a magnetic stirrer to obtain a homogeneous mixture. The flask was heated in an oil bath while stirring the mixture with a magnetic stirrer. The oil bath temperature was gradually increased to ensure continuous distillation of water. The reaction was monitored using IR spectroscopy, and the completion of the reaction was confirmed by IR spectroscopy 24 hours after the start of the reaction. The oil bath temperature at the end of the reaction was 180°C. The contents of the flask were allowed to cool, and the crude product was obtained by drying under reduced pressure. The crude product obtained was purified by preparative HPLC to prepare a friction modifier composition. The composition, as analyzed by LC-MS, is shown in Table 3.

[0188] [Table 3]

[0189] (Manufacturing example 6) The crude product obtained in Production Example 5 was purified by preparative HPLC to obtain the DEA triper oleamide (first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA triper oleamide was mixed with 2.0 equivalents of oleic acid without a solvent and stirred at room temperature for 1 hour to produce the oleate of the DEA triper oleamide.

[0190] (Manufacturing example 7) In a 5L three-necked flask fitted with a distillation tube, 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanoic acid (in general formula (4), k=0, R 6 =3,5,5-trimethylhexyl group, R 7 = 1,3,3-trimethylbutyl group, R 85.0 mol of branched-chain fatty acid (which is a hydrogen atom; hereafter referred to as "highly branched isostearic acid") and 7.5 mol of DEA were placed in the flask along with a magnetic stirrer, the inside of the flask was purged with nitrogen, and the substances in the flask were stirred with a magnetic stirrer to obtain a homogeneous mixture. The flask was heated in an oil bath while stirring the mixture in the flask with a magnetic stirrer. The heating temperature of the oil bath was gradually increased so that water would continue to distill off. The reaction was tracked by IR spectroscopy, and after 24 hours from the start of the reaction, the completion of the reaction was confirmed by IR spectroscopy. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the flask were allowed to cool and dried under reduced pressure to obtain the crude product. The crude product obtained was purified by preparative HPLC to prepare a friction modifier composition. The composition, as analyzed by LC-MS, is shown in Table 4.

[0191] [Table 4]

[0192] (Manufacturing example 8) The crude product obtained in Production Example 7 was purified by preparative HPLC to obtain a diethanolamine trimer polybranched isostearate (first amide compound). The obtained DEA trimer polybranched isostearate was dissolved in toluene, and the toluene solution was washed with dilute hydrochloric acid (dilute hydrochloric acid-NaCl aqueous solution; 0.5 mol / L as HCl) prepared with saturated saline. The organic layer after washing was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation to produce the hydrochloride salt of the DEA trimer polybranched isostearate. Its composition is shown in Table 4.

[0193] (Manufacturing example 9) In a 5L three-necked flask fitted with a distillation tube, 2-decyltetradecanoic acid (where k=0 and R in general formula (4)) is added. 6 = dodecyl group, R 7 = Decyl group, R 85.0 mol of branched-chain fatty acids (which contain hydrogen atoms) and 7.5 mol of DEA were placed in the flask along with a magnetic stirrer. The flask was then purged with nitrogen, and the contents were stirred with a magnetic stirrer to obtain a homogeneous mixture. The flask was heated in an oil bath while stirring the mixture with a magnetic stirrer. The oil bath temperature was gradually increased to ensure continuous distillation of water. The reaction was monitored using IR spectroscopy, and the completion of the reaction was confirmed by IR spectroscopy 24 hours after the start of the reaction. The oil bath temperature at the end of the reaction was 180°C. The contents of the flask were allowed to cool, and the crude product was obtained by drying under reduced pressure. The crude product obtained was purified by preparative HPLC to prepare a friction modifier composition. The composition, as analyzed by LC-MS, is shown in Table 5.

[0194] [Table 5]

[0195] (Manufacturing example 10) The crude product obtained in Production Example 9 was purified by preparative HPLC to obtain DEA triper 2-decyltetradecanoic acid amide (first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA triper 2-decyltetradecanoic acid amide and 2.0 equivalents of 2-decyltetradecanoic acid were mixed without solvent and stirred at room temperature for 1 hour to produce 2-decyltetradecanoate of DEA triper 2-decyltetradecanoic acid amide.

[0196] <Examples 1-29 and Comparative Examples 1-14> As shown in Tables 6-13, lubricating oil compositions of the present invention (Examples 1-29) and comparative lubricating oil compositions (Comparative Examples 1-14) were prepared. In the tables, "mass%" means mass% based on the total amount of the lubricating oil composition (100 mass%). Also, "mass ppm" means mass ppm based on the total amount of the lubricating oil composition, and for element X, the notation "mass ppm / X" means the amount of element X in mass ppm based on the total amount of the lubricating oil composition. Details of each component are as follows.

[0197] ((A) Lubricant base oil) O-1: API Group II base oil (hydrocracked mineral oil base oil), kinematic viscosity (40℃): 9.3 mm 2 / s, kinematic viscosity (100℃): 2.5mm 2 / s, viscosity index: 98, saturated content: 99.9% by mass, sulfur content: less than 1 mass ppm O-2: API Group III base oil (hydrocracking mineral oil base oil), kinematic viscosity (40°C): 19.4 mm 2 / s, kinematic viscosity (100℃): 4.2mm 2 / s, viscosity index: 125, saturated content: 99.9% by mass, sulfur content: less than 1 mass ppm O-3: API Group II base oil (hydrocracked mineral oil base oil), kinematic viscosity (40°C): 2.4 mm 2 / s, kinematic viscosity (100℃): 1.0mm 2 / s, Viscosity index: (Outside the definition range of viscosity index), Saturation content: 99.8% by mass, Sulfur content: Less than 1 ppm by mass O-4: API Group V base oil (diester base oil), kinematic viscosity (40°C): 10.3 mm 2 / s, kinematic viscosity (100℃): 2.9mm 2 Viscosity index: 138, Sulfur content: Less than 1 ppm by mass, viscosity index: 138, Sulfur content: Less than 1 ppm by mass.

[0198] ((B) Friction modifier) The table shows the production example numbers (1-10) in which each friction modifier was manufactured. The table also shows the content of component (B1) in terms of the first amide compound (compound in its unsalted state).

[0199] (Other additives) (C) Metal-based cleaning agent: Calcium carbonate overbasicated calcium salicylate cleaning agent, base number 220 mg KOH / g, Ca: 8.1% by mass (D) Dispersant: Boron-containing polybutenyl succinimide dispersant, N: 1.6% by mass, B: 0.35% by mass (E) Anti-wear agent: Bis(3-thiaundecyl)hydrogen phosphite (F) Extreme pressure agent: Thiadianazole compound, S: 36% by mass (G) Antioxidant: Diphenylamine-based antioxidant (H) Viscosity index improver: Non-dispersible polymethacrylate, weight-average molecular weight 35,000 Antifoaming agent: Dimethyl silicone

[0200] [Table 6]

[0201] [Table 7]

[0202] [Table 8]

[0203] [Table 9]

[0204] [Table 10]

[0205] [Table 11]

[0206] [Table 12]

[0207] [Table 13]

[0208] [Table 14]

[0209] (MTM test) For each lubricating oil composition, a ball-on-disk friction test was performed using an MTM traction meter (PCS Instruments), and the coefficient of friction (μ) was measured under conditions simulating gear lubrication (mixed lubrication region). The measurement conditions were as follows: Balls and discs: Standard test specimens (AISI 52100 standard) Oil temperature: 90℃ Load: 35N Peripheral speed: 0.4m / s Slip ratio: 15% The results are shown in Tables 6-13. For Examples 1-9 and Comparative Example 2, the reduction rate of the coefficient of friction compared to Comparative Example 1 (%) is shown in the table; for Examples 10-13, the reduction rate of the coefficient of friction compared to Comparative Example 3 (%) is shown; for Examples 14-17, the reduction rate of the coefficient of friction compared to Comparative Example 4 (%) is shown; for Examples 18-21, the reduction rate of the coefficient of friction compared to Comparative Example 5 (%) is shown; for Examples 22-25, the reduction rate of the coefficient of friction compared to Comparative Example 6 (%) is shown; for Examples 26-29, the reduction rate of the coefficient of friction compared to Comparative Example 7 (%) is shown; and for Comparative Examples 9-14, the reduction rate of the coefficient of friction compared to Comparative Example 8 (%) is shown in the table.

[0210] (Evaluation results) The lubricating oil compositions of Examples 1-9 (Tables 6-7) were able to significantly reduce the coefficient of friction under conditions simulating gear lubrication compared to the lubricating oil composition of Comparative Example 1 (Table 7), which did not contain an oil-based friction modifier.

[0211] Comparative Example 2, a lubricating oil composition (Table 7) containing only component (B3) as an oil-based friction modifier and not component (B1), showed inferior results in reducing the coefficient of friction under conditions simulating gear lubrication.

[0212] The lubricating oil compositions of Examples 10-13 (Table 8) were obtained by increasing the content of the (H) viscosity index improver compared to the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, resulting in a kinematic viscosity of 3.7 mm at 100°C for the lubricating oil compositions. 2This composition has been modified to have a coefficient of friction of / s. Compared to the lubricating oil composition of Comparative Example 3 (Table 8), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 10 to 13 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0213] The lubricating oil compositions of Examples 14-17 (Table 9) were obtained by increasing the content of the (H) viscosity index improver compared to the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, resulting in a kinematic viscosity of 3.9 mm at 100°C for the lubricating oil compositions. 2 This composition was modified to have a coefficient of friction of / s. Compared to the lubricating oil composition of Comparative Example 4 (Table 9), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 14 to 17 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0214] The lubricating oil compositions of Examples 18-21 (Table 10) were obtained by increasing the content of the (H) viscosity index improver compared to the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, resulting in a kinematic viscosity of 6.8 mm at 100°C for the lubricating oil compositions. 2 This is a modified composition to have a coefficient of friction of / s. Compared to the lubricating oil composition of Comparative Example 5 (Table 10), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 18 to 21 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0215] The lubricating oil compositions of Examples 22-25 (Table 11) are modified versions of the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, by replacing base oil O-1 with base oil O-2 as the lubricating oil base oil. Compared to the lubricating oil composition of Comparative Example 6 (Table 11), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 22-25 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0216] The compositions of Examples 26-29 (Table 12) are modified versions of the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, by replacing base oil O-1 with base oil O-3 as the lubricating oil base oil. Compared to the lubricating oil composition of Comparative Example 7 (Table 12), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 26-29 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0217] The compositions of Examples 30-33 (Table 13) are modified versions of the lubricating oil compositions of Examples 1, 4, 6, and 8, respectively, by replacing base oil O-1 with base oil O-4 as the lubricating oil base oil. Compared to the lubricating oil composition of Comparative Example 8 (Table 13), which does not contain an oily friction modifier, the lubricating oil compositions of Examples 30-33 were able to sufficiently reduce the coefficient of friction under conditions simulating gear lubrication.

[0218] The lubricating oil compositions of Comparative Examples 10-15 (Table 14) were obtained by increasing the content of the (H) viscosity index improver compared to the lubricating oil compositions of Example 1, Comparative Example 2, Examples 3-4, 6, and 8 (Tables 6-7), respectively, resulting in a kinematic viscosity of 8.3 mm at 100°C for the lubricating oil compositions. 2 This is a modified composition to have a coefficient of / s. The lubricating oil compositions of Comparative Examples 10 to 15 showed almost no reduction in the coefficient of friction under conditions simulating gear lubrication compared to the lubricating oil composition of Comparative Example 9 (Table 14), which did not contain an oil-based friction modifier. There was no significant difference in the reduction rate of the coefficient of friction under conditions simulating gear lubrication between the lubricating oil compositions of Comparative Examples 10, 12 to 15, which contain component (B1) as an oil-based friction modifier, and the lubricating oil composition of Comparative Example 11, which contains only component (B3) as an oil-based friction modifier and does not contain component (B1).

[0219] The above test results demonstrate that the lubricating oil composition of the present invention can enhance friction reduction performance, particularly in mixed lubrication areas (e.g., gear lubrication). [Industrial applicability]

[0220] The lubricating oil composition of the present invention can be widely used in the field of lubrication. The lubricating oil composition of the present invention has enhanced friction reduction performance, particularly in mixed lubrication areas (e.g., gear lubrication conditions). Since the lubricating oil composition of the present invention exhibits an improved friction reduction effect when lubricating metal surfaces that are subject to high loads, such as gears, it can be suitably used for lubricating various mechanical devices equipped with metal surfaces that are subject to high loads, such as gear mechanisms, pistons, and connecting rod bearings. In particular, it can be suitably used for lubricating transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, reduction gears for electric vehicles, speed increasers for wind turbines, etc.) and internal combustion engines, and can also be suitably used for lubrication in various industrial applications (e.g., hydraulic fluids, turbine oils, compressor oils).

Claims

1. (A) A lubricating oil base oil comprising one or more mineral oil-based base oils or one or more synthetic base oils or a combination thereof, (B1) A monoamide comprising one or more monounsaturated or unsaturated monounsaturated fatty acids (a1) having 6 to 30 carbon atoms in a straight or branched chain, and one or more amine compounds (a2), wherein there are no ester bonds, and the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1), one or more first amide compounds, and / or a salt thereof, It contains, The kinematic viscosity at 100°C is 6.9 mm². ２ A lubricating oil composition characterized by having a ratio of less than / s. 【Chemistry 1】 (In general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R １ They may be identical or mutually different.

2. The lubricating oil composition according to claim 1, wherein the content of component (B1) is 0.005 to 10.0% by mass on a basis of the total lubricating oil composition, when converted to the content of the compound in a state that has not formed a salt.

3. (B2) One or more second amide compounds having a structure in which the amino group and one or more hydroxyl groups of one or more alkanolamines (a3) ​​represented by the following general formula (1) are acylated with the monounsaturated fatty acid (a1). The lubricating oil composition according to claim 1 or 2, further comprising the above.

4. (B3) One or more third amide compounds which are amides of the alkanolamine (a3) ​​and the monounsaturated fatty acid (a1) and do not have an ester bond. The lubricating oil composition according to claim 1 or 2, further comprising the above.

5. (B4) One or more fourth amide compounds and / or salts thereof, having a structure in which one or more amino groups and one or more hydroxyl groups of the amine compound (a2) are acylated with the monounsaturated fatty acid (a1). The lubricating oil composition according to claim 3, further containing the above.

6. The lubricating oil composition according to claim 1 or 2, wherein the monounsaturated fatty acid comprises one or more straight-chain fatty acids.

7. The lubricating oil composition according to claim 1 or 2, wherein the monounsaturated fatty acid comprises one or more branched-chain fatty acids.

8. The lubricating oil composition according to claim 7, wherein the branched-chain fatty acid has a tertiary or quaternary carbon atom at the α, β, or γ position of the carbonyl carbon.

9. The lubricating oil composition according to claim 1 or 2, further comprising one or more additives selected from a metal-based detergent, an ashless dispersant, a phosphorus-containing anti-wear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver.

10. The kinematic viscosity of the lubricating oil base oil (A) at 40°C is 40 mm ２ The lubricating oil composition according to claim 1 or 2, wherein the value is less than or equal to / s.

11. The kinematic viscosity at 40°C is 2.0 to 50 mm². ２ The lubricating oil composition according to claim 1 or 2, wherein the ratio is / s.

12. A lubricating oil composition according to claim 1 or 2, used for lubricating gears.

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