Lubricating oil additive composition and lubricating oil composition

Abstract

A lubricating oil additive composition characterized by containing (i) one or more protonic acid salts of a first amide compound that is a salt of a first amide compound and a protonic acid, the first amide compound being a monoamide of one or more fatty acids (a1) and one or more amine compounds (a2); the amine compound (a2) is an oligomer of one or more alkanolamines (a3) represented by general formula (1). [Chemical Formula 1] # imgabs0 # (In the formula, n is 1 or 2; r1 represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms and having 2 carbon atoms in the main chain; when n is 2, the plurality of R1s may be the same as or different from each other. ).

Description

Technical Field

[0001] The present invention relates to a lubricating oil additive composition and a lubricating oil composition, and more particularly, to a lubricating oil additive composition and a lubricating oil composition which can be preferably used for lubrication of gears. Background Art

[0002] Lubricating oil is used in internal combustion engines, automatic transmissions, bearings, etc. to make them run smoothly. Generally, various additives are blended into the lubricating oil to obtain the required performance of the lubricating oil.

[0003] Among lubricating oil additives, additives that have the effect of reducing friction resistance (friction modifiers, hereinafter sometimes referred to as "FM") are important components for reducing energy loss caused by friction. Commonly used FMs can be classified into organic molybdenum-based FMs containing molybdenum and oiliness-based FMs (also called ashless FMs) that reduce friction by improving oiliness.

[0004] As organic molybdenum-based FM, MoDTC (molybdenum dithiocarbamate) and MoDTP (molybdenum dithiophosphate) are widely known (for example, refer to Patent Document 1). Although these organic molybdenum-based FMs have excellent friction reduction effects in the initial stage of use, there is a limit to maintaining their friction reduction effects well for a long time. In addition, since organic molybdenum-based FMs contain ash, it is difficult to reuse the used lubricating oil. Therefore, it is required to reduce the amount of organic molybdenum-based FMs added.

[0005] On the other hand, according to the oiliness agent type FM, since there is a possibility that the above-mentioned problems of the organic molybdenum type FM can be overcome, the importance of the oiliness agent type FM is increased (for example, refer to Patent Documents 2 to 4). [Prior art literature] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2013-133453 [Patent Document 2] Japanese Patent Application Publication No. 2009-235252 [Patent Document 3] Japanese Patent Application Publication No. 2006-257383 [Patent Document 4] International Publication No. 2019 / 129793 Summary of the invention [Problems to be solved by the invention]

[0007] However, the conventional oily agent-based FM still has room for improvement in terms of friction reducing performance.

[0008] An object of the present invention is to provide a lubricating oil additive composition which improves friction reduction performance and is useful as an oiliness agent-based friction modifier, and also to provide a lubricating oil composition containing the lubricating oil additive composition.

Methods to solve the problem

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

[19] .

[0010] [1] A lubricating oil additive composition characterized by containing (i) a Bronsted acid salt of at least one first amide compound, wherein the Bronsted acid salt of the first amide compound is a salt of the first amide compound and a Bronsted acid, wherein the first amide compound is a monoamide of at least one linear or branched saturated or unsaturated monobasic fatty acid (a1) having 6 to 30 carbon atoms and at least one amine compound (a2) and does not have an ester bond, and wherein the amine compound (a2) is an alkanolamine oligomer having a structure formed by dehydration condensation of at least one alkanolamine (a3) ​​represented by the following general formula (1) and having a degree of polymerization of at least 2.

[0011]

Chemical formula 1

[0012] [2] The lubricating oil additive composition according to [1], wherein the protonic acid comprises one or more inorganic acids selected from hydrogen halides, nitric acid, boric acid and carbonic acid, or one or more organic acids selected from carboxylic acids, organic sulfonic acids and substituted or unsubstituted phenols, or a combination thereof.

[0013] [3] The lubricating oil additive composition according to [2], wherein the carboxylic acid is a monobasic fatty acid having 1 to 5 carbon atoms, a monobasic fatty acid having 6 to 30 carbon atoms, an aliphatic hydroxy acid having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, an aromatic monocarboxylic acid having 7 to 10 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, mellitic acid or an aromatic hydroxy acid having 7 to 14 carbon atoms, and the monobasic fatty acid having 6 to 30 carbon atoms may also be the monobasic fatty acid (a1).

[0014] [4] The lubricating oil additive composition according to any one of [1] to [3], wherein the monovalent fatty acid contains one or more straight-chain fatty acids.

[0015] [5] The lubricating oil additive composition according to any one of [1] to [4], wherein the monovalent fatty acid contains one or more branched-chain fatty acids.

[0016] [6] The lubricating oil additive composition according to [5], wherein the branched fatty acid has a tertiary carbon or a quaternary carbon atom at the α-position, β-position or γ-position of the carbonyl carbon.

[0017] [7] A lubricating oil composition comprising 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; and (A) the lubricating oil additive composition according to any one of [1] to [6].

[0018] [8] The lubricating oil additive composition according to [7], wherein the content of the component (A) is 0.005 to 10.0% by mass based on the total amount of the lubricating oil composition.

[0019] [9] The lubricating oil composition according to [7] or [8], further comprising one or more additives selected from the group consisting of metallic detergents, ashless dispersants, phosphorus-containing antiwear agents, sulfur-containing extreme pressure agents, antioxidants and viscosity index improvers.

[0020]

[10] The lubricating oil composition according to any one of [7] to [9], wherein the kinematic viscosity at 40° C. is 2.0 to 50 mm 2 / s.

[0021]

[11] The lubricating oil composition according to any one of [7] to

[10] , which is used for lubrication of gears.

[0022]

[12] A method for producing a lubricating oil composition, comprising: a) a step of adding and mixing (i) a proton acid salt of at least one first amide compound to a lubricating base oil or a mixture containing the lubricating base oil and at least one additive other than the following component (i), wherein the proton acid salt of at least one first amide compound is a salt of the first amide compound and a protonic acid, wherein the first amide compound is a monoamide of at least one linear or branched saturated or unsaturated monobasic fatty acid (a1) having 6 to 30 carbon atoms and at least one amine compound (a2) having no ester bond, wherein the amine compound (a2) is an alkanolamine oligomer having a structure formed by dehydration condensation of at least one alkanolamine (a3) ​​represented by the following general formula (1) and having a polymerization degree of 2 or more, The lubricating base oil contains one or more mineral base oils or one or more synthetic base oils, or a combination thereof.

[0023]

[13] The production method according to

[12] , wherein in a), 0.005 to 11.1 parts by mass of the component (i) is added per 100 parts by mass of the lubricating base oil.

[0024]

[14] The production method according to

[12] or

[13] , wherein the protonic acid comprises one or more inorganic acids selected from hydrogen halides, nitric acid, boric acid and carbonic acid, or one or more organic acids selected from carboxylic acids, organic sulfonic acids and substituted or unsubstituted phenols, or a combination thereof.

[0025]

[15] The production method according to

[14] , wherein the carboxylic acid is a monobasic fatty acid having 1 to 5 carbon atoms, a monobasic fatty acid having 6 to 30 carbon atoms, an aliphatic hydroxy acid having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, an aromatic monocarboxylic acid having 7 to 10 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, mellitic acid or an aromatic hydroxy acid having 7 to 14 carbon atoms, and the monobasic fatty acid having 6 to 30 carbon atoms may also be the monobasic fatty acid (a1).

[0026]

[16] The production method according to any one of

[12] to

[15] , wherein the monovalent fatty acid contains one or more straight-chain fatty acids.

[0027]

[17] The production method according to any one of

[12] to

[15] , wherein the monovalent fatty acid contains one or more branched-chain fatty acids.

[0028]

[18] The production method according to

[17] , wherein the branched fatty acid has a tertiary carbon or a quaternary carbon atom at the α-position, β-position or γ-position of the carbonyl carbon.

[0029]

[19] The production method according to any one of

[12] to

[18] , which includes b) allowing one or more additives selected from metal detergents, ashless dispersants, phosphorus-containing antiwear agents, sulfur-containing extreme pressure agents, antioxidants and viscosity index improvers to be present in the lubricating oil composition. [Effects of the invention]

[0030] The lubricating oil additive composition according to the first aspect of the present invention has improved friction reducing performance and is useful as an oiliness agent-based friction modifier. The lubricating oil composition according to the second aspect of the present invention can exhibit improved friction reducing performance by containing the lubricating oil additive composition according to the first aspect of the present invention. The method for producing a lubricating oil composition according to the third aspect of the present invention makes it possible to produce a lubricating oil composition having improved friction reducing performance by allowing the lubricating oil additive composition according to the first aspect of the present invention to exist in the lubricating oil composition. Detailed Embodiments

[0031] The present invention will be described in detail below. In addition, in this specification, unless otherwise specified, for numerical values A and B, the expression "A to B" is equivalent to "A or more and B or less". In this expression, when a unit is attached only to the numerical value B, the unit is also assumed to apply to the numerical value A. In this specification, unless otherwise specified, the words "or" and "or" are assumed to represent a logical or. In this specification, for elements E1 and E2, the expression "E1 and / or E2" is 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 expression "E1, ..., and / or E N " is equivalent to "E1, ..., or E i 、…、or E N 、or a combination thereof" (i is a variable taking all integer values satisfying 1 < i < N). In addition, in this specification, "alkaline earth metal" is also assumed to include magnesium.

[0032] In addition, in this specification, unless otherwise specified, the content of each element of calcium, magnesium, zinc, phosphorus, sulfur, boron, barium, and molybdenum in the oil is assumed to be a value measured by inductively coupled plasma emission spectrometry (intensity ratio method (internal standard method)) according to JIS K0116. In addition, the content of nitrogen element in the oil is assumed to be a value measured by chemiluminescence method according to JIS K2609. In addition, in this specification, "weight average molecular weight" means: the weight average molecular weight converted to 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 Chromatographic column: Two ACQUITY (registered trademark) APC XT900A columns (gel particle size 2.5 μm, column size (inner diameter × length) 4.6 mm × 150 mm) and one ACQUITY (registered trademark) APC XT200A column (gel particle size 2.5 μm, column size (inner diameter × length) 4.6 mm × 150 mm) manufactured by Waters Corporation are connected in series from the upstream side Column temperature: 40 °C Sample solution: Tetrahydrofuran solution with a sample concentration of 1.0 mass% Eluent: Tetrahydrofuran Solution injection volume: 20.0 μL Detection device: Differential refractive index detector Reference material: 8 parts of standard polystyrene (Agilent EasiCal (registered trademark) PS-1 manufactured by Agilent Technologies) (molecular weight: 2698000, 597500, 290300, 133500, 70500, 30230, 9590, 2970) When the weight average molecular weight measured under the above conditions was less than 10,000, the column and the standard substance were changed to the following conditions and the measurement was repeated. Chromatographic columns: One Waters Corporation ACQUITY (registered trademark) APC XT125A (gel particle size 2.5 μm, column size (inner diameter × length) 4.6 mm × 150 mm) and two Waters Corporation ACQUITY (registered trademark) APC XT45A (gel particle size 1.7 μm, column size (inner diameter × length) 4.6 mm × 150 mm) connected in series from the upstream side Reference material: 10 parts of standard polystyrene (Agilent EasiCal (registered trademark) PS-1 manufactured by Agilent Technologies) (molecular weight: 30230, 9590, 2970, 890, 786, 682, 578, 474, 370, 266)

[0033] <1. Lubricating oil additive composition> The lubricating oil additive composition involved in the first embodiment of the present invention may be simply referred to as "additive composition" below.) contains one or more proton acid salts of a first amide compound (i) (hereinafter sometimes referred to as "(i) component" or "component (i)"). The proton acid salt of the first amide compound (i) is a salt of the first amide compound and a protonic acid, the first amide compound is a monoamide of one or more linear or branched saturated or unsaturated monobasic fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2) and does not have an ester bond, and the amine compound (a2) is an alkanolamine oligomer having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1) and having a polymerization degree of 2 or more.

[0034]

Chemical formula 2

[0035] Fatty acid (a1) can be one kind of fatty acid or a combination of two or more kinds of fatty acids. Fatty acid (a1) can be a saturated fatty acid or an unsaturated fatty acid. In addition, fatty acid (a1) can be a straight-chain fatty acid or a branched-chain fatty acid. In a preferred embodiment, fatty acid (a1) can be a branched-chain fatty acid. Examples of straight-chain saturated fatty acids include caproic 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., and examples of branched-chain saturated fatty acids include their branched-chain isomers. Examples of straight-chain unsaturated fatty acids include hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, 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, triacontadecenoic acid, and examples of branched unsaturated fatty acids include their branched isomers. In addition, there is no particular restriction on the configuration of the C=C double bond in the unsaturated fatty acid. The number of C=C double bonds in the unsaturated fatty acid may be 1 (i.e., monoenoic acid), 2 (i.e., dienoic acid), 3 (i.e., trienoic acid), or 4 (i.e., tetraenoic acid) or more. In addition, the C=C double bond in the unsaturated fatty acid may be a cis-type (Z-type) or a trans-type (E-type), and a cis-type (Z-type) C=C double bond and a trans-type (E-type) C=C double bond may coexist between different molecules or in the same molecule. For example, fatty acids derived from hydrogenated natural oils and fats may contain, in addition to saturated fatty acids produced by hydrogenation, unsaturated fatty acids having a cis-type C=C double bond and unsaturated fatty acids having a trans-type C=C double bond derived from a side reaction of the hydrogenation reaction. For example, as specific examples of unsaturated fatty acids having 18 carbon atoms, various similar compounds having different numbers, configurations and / or geometrical isomers of C=C double bonds, such as oleic acid (cis-9-octadecenoic acid), vaccenic acid (11-octadecenoic acid), linoleic acid (cis, cis-9,12-octadecadienoic acid), linolenic acid (9,12,15-octadecatrienoic acid, 6,9,12-octadecatrienoic acid), and eleostearic acid (9,11,13-octadecatrienoic acid) can be cited. Various similar compounds having different numbers, configurations and / or geometrical isomers of C=C double bonds can also be cited for unsaturated fatty acids having other carbon atoms.

[0036] From the viewpoint of improving the friction reduction effect in lubrication of gears, etc., the number of carbon atoms in the fatty acid (a1) is 6 or more, preferably 8 or more, 10 or more, or 12 or more. From the same viewpoint, it is 30 or less, preferably 24 or less, 22 or less, 20 or less, or 18 or less. In one embodiment, it can be 6 to 30, or 8 to 24, 8 to 22, 10 to 22, 12 to 20, or 12 to 18. In one embodiment, the fatty acid (a1) can be one or more straight-chain fatty acids. Preferred examples of straight-chain fatty acids include caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, myristic 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, clupanodonic acid, docosahexaenoic acid, lignoceric acid, nisinic acid, nervonic acid, cerotic acid, montanic acid, melissic acid, and mixtures thereof. As a mixture having two or more fatty acids, fatty acids derived from natural fats or hydrogenated natural fats may also 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, tung 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, tallow fatty acids, hydrogenated products 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, the fatty acid (a1) may be one or more branched fatty acids. In one embodiment, the branched fatty acid preferably has a tertiary carbon or a quaternary carbon atom (i.e., a branched chain) at the α, β, or γ position of the carbonyl carbon, preferably has a tertiary carbon or a quaternary carbon atom at the α or β position of the carbonyl carbon, and particularly preferably has a tertiary carbon or a quaternary carbon atom at the α position of the carbonyl carbon. As a preferred example of such a branched fatty acid, a branched fatty acid represented by the following general formula (2) may be mentioned.

[0037]

Chemical formula 3

[0038]

Chemical formula 4

[0039] The amine compound (a2) is an alkanolamine oligomer having a polymerization degree of 2 or more and having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1).

[0040]

Chemical formula 5

[0041] In a preferred embodiment, the alkylene group R 1 The radical may be ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,2-diyl, butane-1,4-diyl or butane-2,3-diyl, or a combination thereof.

[0042] The alkanolamine represented by the general formula (1) is a monoalkanolamine when n=1 and a dialkanolamine when n=2. 1In the case of an asymmetric branched alkylene group, that is, the side chains bonded to the two free atomic valences are different alkylene groups (e.g., propane-1,2-diyl, butane-2,3-diyl, pentane-2,3-diyl, etc.), any one of the two free atomic valences may be bonded to the nitrogen atom. For example, in the reaction of propylene oxide and ammonia, the reaction route to form a propanolamine structure in which the 1-position of propylene-1,2-diyl is bonded to the nitrogen atom (i.e., the nitrogen atom is bonded to the 2-hydroxypropyl group) competes with the reaction route to form a propanolamine structure in which the 2-position of propylene-1,2-diyl is bonded to the nitrogen atom (i.e., the nitrogen atom is bonded to the 1-hydroxypropane-2-yl group), and a mixture of the two products may be formed. In the general formula (1), in the dialkanolamine with n=2, the two R 1 They can be the same or different. 1 When the two R 1 The directions of the two R 1 In dipropanolamine, which is propane-1,2-diyl, the two HO-R 1 -yl may be both 2-hydroxypropyl, or both 1-hydroxypropane-2-yl, or one may be 2-hydroxypropyl and the other 1-hydroxypropane-2-yl. When dipropanolamine is produced by the reaction of propylene oxide and ammonia, these compounds are simultaneously generated and may form a mixture. The one or more alkanolamines (a3) ​​represented by the 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 one or more dialkanolamines are particularly preferred.

[0043] In component (i), the monovalent fatty acid (a1) and the amine compound (a2) forming a monoamide are alkanolamine oligomers having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by the general formula (1), and the degree of polymerization is 2 or more. For example, the following general formula (4) represents a reaction in which an alkanolamine dimer (a2-dd) having a degree of polymerization of 2 is generated by a dehydration condensation reaction of two molecules of dialkanolamine (a3d). In addition, for example, the following general formula (5) represents a reaction in which an alkanolamine dimer (a2-mm) having a degree of polymerization of 2 is generated by a dehydration condensation reaction of two molecules of monoalkanolamine (a3m). In addition, for example, the following general formula (6) represents a reaction in which an alkanolamine dimer (a2-2dm or a2-2md) having a degree of polymerization of 2 is generated by a dehydration condensation reaction of one molecule of dialkanolamine (a3d) and one molecule of monoalkanolamine (a3m). As shown in the general formula (6), in the dehydration condensation reaction of dialkanolamine and monoalkanolamine, the product may contain structural isomers. Which structural isomer is generated depends on which molecule's hydroxyl group is detached.

[0044]

Chemical formula 6

[0045]

Chemical formula 7

[0046]

Chemical formula 8

[0047]

Chemical formula 9

[0048]

Chemical formula 10

[0049]

Chemical formula 11

[0050]

Chemical formula 12

[0051]

Chemical formula 13

[0052] The degree of polymerization of the amine compound (a2), i.e., the alkanolamine oligomer, is 2 or more, preferably 2 to 15 or 2 to 10, and in one embodiment, may be 2 to 4 or 2 to 3. The alkanolamine oligomer (a2) may have a single degree of polymerization, or may be a combination of oligomers having a plurality of different degrees of polymerization. In one embodiment, the alkanolamine oligomer (a2) may be a combination of oligomers having a plurality of continuous different degrees of polymerization. In this specification, a certain oligomer is "a combination of oligomers having a plurality of continuous different degrees of polymerization" means: the minimum and maximum values ​​of the degree of polymerization of the oligomer are set to d min and d MAX When the oligomer contains d min Above, d MAX Oligomers with all the following degrees of polymerization.

[0053] The first amide compound is a monoamide of one or more monobasic fatty acids (a1) and one or more amine compounds (a2), and is a compound without an ester bond. Component (i) is the first amide compound and / or its salt. Since the first amide compound has one or more amine nitrogen atoms that are not acylated, it can form a salt with an acid. The salt of the first amide compound can be a salt of the first amide compound and an organic acid (organic acid salt), or a salt of the first amide compound and 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 can be one organic acid salt or a combination of two or more organic acid salts. The inorganic acid salt can be one inorganic acid salt or a combination of two or more inorganic acid salts. In addition, as described below, the organic acid constituting the organic acid salt can also be the above-mentioned monobasic fatty acid (a1).

[0054] Examples of the inorganic acid that forms the inorganic acid salt with the first amide compound include hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide; halogen oxygen acids such as hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, hypoiodine acid, iodous acid, iodic acid, and periodic acid; nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid (an oxygen acid of phosphorus in which the apparent oxidation number of the phosphorus atom is +V, which may be orthophosphoric acid or condensed phosphoric acid such as pyrophosphoric acid and polyphosphoric acid), phosphorous acid, boric acid (an oxygen acid of boron in which the apparent oxidation number of the boron atom is +III, which may be orthoboric acid or condensed boric acid such as tetraboric acid and metaboric acid), and carbonic acid; and inorganic protonic acids such as cyanic acid.

[0055] Examples of organic acids that form organic acid salts with the first amide compound include organic protonic acids such as carboxylic acids, organic sulfonic acids, organic phosphonic acids and their monoesters, organic boric acids and their monoesters, sulfuric acid monoesters, phosphoric acid monoesters, phosphoric acid diesters, phosphite monoesters, phosphorous acid diesters, boric acid monoesters, boric acid diesters, and substituted or unsubstituted phenols.

[0056] Examples of the carboxylic acid that forms a salt with the first amide compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monovalent fatty acids having 1 to 5 carbon atoms, monovalent fatty acids having 6 to 30 carbon atoms, divalent aliphatic carboxylic acids having 2 to 10 carbon atoms and monoesters thereof, and aliphatic hydroxy acids. Examples of the monovalent fatty acid having 1 to 5 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, and valeric acid. The monovalent fatty acid having 2 to 5 carbon atoms is preferred. Examples of the monovalent fatty acid having 6 to 30 carbon atoms include the various monovalent fatty acids described above with respect to the monovalent fatty acid (a1). Examples of dibasic 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 monoesters thereof include monoesters of the dibasic aliphatic dicarboxylic acids with alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, and for example, with alkanols having 1 to 12, 1 to 10, or 1 to 8 carbon atoms. Examples of aliphatic hydroxy acids include aliphatic hydroxy acids having 2 to 18 carbon atoms, such as glycolic acid, lactic acid, malonic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine, mevalonic acid, pantoic acid, ricinolic acid, ricinelaidic acid, quinic acid, and shikimic acid. Other examples of the aliphatic carboxylic acid include halogenated (for example, fluorinated) aliphatic carboxylic acids such as trifluoroacetic acid, 3,3,3-trifluoropropionic acid, and 4,4,4-trifluorobutyric acid. Examples of the aromatic carboxylic acid include aromatic monocarboxylic acids, aromatic dicarboxylic acids and monoesters thereof, aromatic hydroxy acids, and aromatic polycarboxylic acids. Examples of the aromatic monocarboxylic acid include compounds having 7 to 10 carbon atoms, such as benzoic acid, o-, m- or p-toluic acid, phenylacetic acid, and cinnamic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, etc. Examples of the monoesters thereof include monoesters of the aromatic dicarboxylic acid and the various alcohols described above with respect to the monoesters of the divalent aliphatic dicarboxylic acid. 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, orsellinic acid, gallic acid, mandelic acid, hydroxydiphenylacetic acid (benzyl alcoholic acid), atrolactic acid, phloretic acid, (o-, m- or p-)hydroxycinnamic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-)dihydroxycinnamic acid, ferulic acid, sinapic acid, and the like, for example, compounds having 7 to 14 carbon atoms. Examples of the aromatic polycarboxylic acid include compounds having a structure in which 3 to 6 hydrogen atoms on a benzene ring are substituted with carboxyl groups, such as trimellitic acid and mellitic acid.

[0057] Examples of the organic sulfonic acid include compounds represented by the following general formula (14).

[0058]

Chemical formula 14

[0059] Examples of the organic phosphonic acid include compounds represented by the following general formula (15).

[0060]

Chemical formula 15

[0061] Examples of organic boronic acids include compounds represented by the following general formula (16).

[0062]

Chemical formula 16

[0063] Examples of sulfuric acid monoesters, phosphoric acid 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 for the monoesters of divalent aliphatic dicarboxylic acids. Examples of phosphoric acid diesters and boric acid diesters include monoesters of orthophosphoric acid or orthoboric acid with the various alcohols described above with respect to the monoesters of divalent aliphatic dicarboxylic acids.

[0064] As a preferred example of substituted phenyl, substituted phenyl having a pKa smaller than that of unsubstituted phenyl can be cited. Such substituted phenyl usually has one or more substituents as electron-withdrawing groups on the aromatic ring. Examples of such electron-withdrawing groups include acyl groups such as acetyl, aldehyde groups, carboxyl groups, alkoxycarbonyl groups, nitro groups, cyano groups, halogen groups (such as fluoro groups, chloro groups, bromo groups and iodo groups), etc. As examples of alcohols corresponding to the alkoxy groups of the alkoxycarbonyl groups, various alcohols described above for divalent aliphatic dicarboxylic acids can be cited. As examples of such substituted phenyl, acetylphenyl, formylphenyl, carboxylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, nitrophenyl, cyanophenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, etc. can be cited. The number of carbon atoms of the substituted phenyl may preferably be 6 to 13, 6 to 11, or 6 to 9.

[0065] In one embodiment, the protonic acid may include one or more inorganic acids selected from hydrogen halide, nitric acid, boric acid and carbonic acid, or one or more organic acids selected from carboxylic acid, organic sulfonic acid and substituted or unsubstituted phenol, or a combination thereof. In one embodiment, the carboxylic acid may be a monobasic fatty acid having 1 to 5 carbon atoms, a monobasic fatty acid having 6 to 30 carbon atoms, an aliphatic hydroxy acid having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, an aromatic monocarboxylic acid having 7 to 10 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, mellitic acid or an aromatic hydroxy acid having 7 to 14 carbon atoms, and the monobasic fatty acid having 6 to 30 carbon atoms may also be the monobasic fatty acid (a1).

[0066] (manufacture) The amine compound (a2), i.e., an alkanolamine oligomer, can be produced, for example, by dehydration condensation of one or more alkanolamines (a3). The amine compound (a2) can be an oligomer having a single degree of polymerization, or a combination of two or more oligomers having different degrees of polymerization (e.g., a combination of a plurality of oligomers having consecutive different degrees of polymerization). In one embodiment, the first amide compound can be manufactured by the dehydration condensation reaction of fatty acid (a1) and amine compound (a2). Such a dehydration condensation reaction, for example, can be carried out by the following method: fatty acid (a1) and amine compound (a2) are in an organic solvent (such as toluene, xylene, isopropylbenzene, methyl isopropylbenzene (cymene), etc.) that forms an azeotropic mixture with water, in the presence of an acid catalyst (such as sulfuric acid, trifluoroacetic acid, etc.) or a base catalyst (such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, triethylamine, pyridine, etc.) or in the absence of a catalyst, and the water generated by the condensation reaction is removed by azeotropy. In addition, under catalyst-free conditions, fatty acid (a1) and / or amine compound (a2) represent that they can act as catalysts. In another embodiment, the first amide compound is prepared by reacting a fatty acid (a1), an amine compound (a2) and a condensing agent in a solvent. As the condensing agent, carbodiimide condensing agents such as N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) can be used without particular limitation; imidazole condensing agents such as N,N'-carbonyldiimidazole (CDI), 1,1'-carbonylbis(1,2,4-triazole) (CDT); triazine condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholine hydrochloride hydrate (DMT-MM); 2- 2-halopyridinium salts such as chloro-1-methylpyridinium p-toluenesulfonate and 2-fluoro-1-methylpyridinium 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 diphenylphosphine chloride and 2,2'-bipyridine disulfide; a combination of p-benzoquinones such as 2,6-dimethyl-1,4-benzoquinone (DMBQ) and tetrafluoro-1,4-benzoquinone; pentafluorobenzenesulfonic acid di-mesitylenylammonium salt, etc. are known condensing agents that can be used for esterification. The condensing agent can also be used together with a catalyst such as 4-dimethylaminopyridine (DMAP), N-hydroxysuccinimide (NHS), 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), etc. In another embodiment, the first amide compound can be prepared by reacting an acylating agent derived from a fatty acid (a1) with an amine compound (a2) in a solvent. Examples of acylating agents derived from fatty acids (a1) include acyl halides (e.g., acyl chlorides, acyl bromides, etc.) of fatty acids (a1), active esters (e.g., esters of fatty acids (a1) and N-hydroxysuccinimide (NHS), esters of fatty acids (a1) and 1-hydroxybenzotriazole (HOBt), esters of fatty acids (a1) and 1-hydroxy-7-azabenzotriazole (HOAt), etc.), and anhydrides of fatty acids (a1). Acylating agents derived from fatty acids (a1) can also be used together with catalysts such as 4-dimethylaminopyridine (DMAP). As a solvent, an organic solvent that does not interfere with the condensation reaction can be used without particular limitation (for example, 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.). In addition, in the condensation reaction for producing the first amide compound, as required, a suitable base (for example, amines such as triethylamine, pyridine, and 2,6-lutidine, organic lithium reagents such as butyl lithium, inorganic bases such as potassium carbonate, etc.) can be added to the reaction mixture for the purpose of promoting the reaction or for the purpose of capturing the acid generated as the reaction proceeds (for example, in a reaction using an acid halide, hydrogen halide is generated as the reaction proceeds). In another embodiment, the first amide compound can be produced by a dehydration condensation reaction of an amide of one or more alkanolamines (a3) ​​represented by the general formula (1) and the monovalent fatty acid (a1) and having no ester bond (hereinafter sometimes referred to as the "second amide compound") with an alkanolamine (a3) ​​and / or an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by the following method: the second amide compound and the alkanolamine (a3) ​​or the amine compound (a2) or a mixture thereof are heated to reflux in an organic solvent that forms an azeotropic mixture with water in the presence of an acid catalyst or a base catalyst or in the absence of a catalyst, and water generated by the condensation reaction is removed by azeotropy. In addition, the above-mentioned various dehydration condensation reactions can also be carried out in the absence of a solvent. For example, the dehydration condensation reaction can be carried out in the absence of a solvent while distilling off the water generated as the reaction proceeds.

[0067] In a preferred embodiment, the composition containing the first amide compound can be produced by a dehydration condensation reaction of a fatty acid (a1) and an alkanolamine (a3). In one embodiment, such a dehydration condensation reaction can be carried out by the following method: while 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, water generated by the condensation reaction is removed by azeotropy. In another embodiment, when 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 the following method: while heating and stirring the fatty acid (a1) and the alkanolamine (a3) ​​in the absence of a solvent, slowly increase the heating temperature to continue to distill off the water produced by the reaction, and continue heating and stirring until no water is distilled off even if the temperature is further increased. In addition, the above-mentioned dehydration condensation reaction can also be carried out in the absence of a solvent. For example, the dehydration condensation reaction can be carried out in the absence of a solvent while distilling off the water generated as the reaction proceeds. In the above dehydration condensation reaction, a reaction in which two molecules of dialkanolamine (a3d) are disproportionated into one molecule of monoalkanolamine (a3m) and one molecule of trialkanolamine (a3t) (the following general formula (17)) may simultaneously proceed as a side reaction.

[0068]

Chemical formula 17

[0069]

Chemical formula 18

[0070] After the condensation reaction of fatty acid (a1) and dialkanolamine (a3) ​​is completed, the unreacted raw material can be removed by known methods such as water washing, silica gel short-range column chromatography, diatomaceous earth filtration, etc. During such operation, a solvent can be used appropriately. As a solvent, organic solvents such as pentane, hexane, cyclohexane, heptane, benzene, toluene, xylene, ether, ethyl acetate, tetrahydrofuran, methanol, ethanol, isopropanol, dichloromethane, chloroform, carbon tetrachloride, etc. can be used. It is also possible to further refine the obtained product by using known refining means such as column chromatography. In addition, the so-called water washing here refers to cleaning based on water or an aqueous solution. As the aqueous solution for water washing, an acidic aqueous solution such as dilute hydrochloric acid, an alkaline aqueous solution such as a dilute sodium hydroxide aqueous solution, an aqueous solution of salts such as saturated salt water, etc. can be used.

[0071] There is no particular limitation on the method for forming a salt between the first amide compound and the protonic acid to obtain component (i). In one embodiment, when the protonic acid is water-soluble (e.g., inorganic acids such as hydrogen halides and boric acid, or highly hydrophilic organic acids such as formic acid, acetic acid, and methanesulfonic acid), for example, by neutralizing an organic solvent solution of the first amide compound (or a composition containing the first amide compound) with an aqueous solution containing a protonic acid (e.g., dilute hydrochloric acid, dilute hydrobromic acid, dilute hydroiodic acid, an aqueous boric acid solution, an aqueous methanesulfonic acid solution, etc.), and distilling off the solvent from the neutralized organic layer (e.g., under reduced pressure), component (i) (or a composition containing component (i)) can be obtained. Before distilling off the solvent from the organic phase, an operation of removing water from the neutralized organic layer may also be further performed. For example, the solvent may be distilled off after drying the neutralized organic layer with a desiccant (e.g., anhydrous sodium sulfate, molecular sieves, etc.). The aqueous solution containing the above-mentioned protonic acid may further contain a water-soluble neutral salt (e.g., a neutral salt such as NaCl or sodium sulfate). For example, when the protonic acid is hydrogen chloride, a dilute hydrochloric acid-NaCl aqueous solution prepared from hydrochloric acid and saturated saline may be used as the aqueous solution containing the above-mentioned protonic acid. As the organic solvent for dissolving the first amide compound (or the composition containing the first amide compound), an organic solvent that can dissolve the first amide compound and is immiscible with water (for example, the organic solvents described above) can be used. In another embodiment, when the protonic acid is soluble in an organic solvent (e.g., fatty acids having more than 2 carbon atoms, aromatic carboxylic acids, etc.), the first amide compound and the protonic acid can be mixed in an organic solvent, dried with a desiccant (e.g., anhydrous sodium sulfate, molecular sieves, etc.), the desiccant is filtered out, and the solvent is distilled off (e.g., under reduced pressure) to obtain component (i) (or a composition containing component (i)). In another embodiment, when the first amide compound (or a composition containing the first amide compound) is an oily substance at room temperature and the protonic acid is soluble in an organic solvent, for example, component (i) (or a composition containing component (i)) can also be obtained by mixing the first amide compound and the protonic acid in the absence of a solvent. In another embodiment, when the first amide compound is produced by reacting the acyl halide of a monovalent fatty acid (a1) with an amine compound (a2), a salt of a byproduct of the reaction, namely a hydrogen halide, and the first amide compound can be obtained. In this reaction, the obtained product can also be used directly as component (i) (or a composition containing component (i)). In addition, for example, the obtained product can be further washed with water (for example, with an alkaline aqueous solution) to form a salt between the first amide compound and a protonic acid. In addition, for example, the obtained product can be further washed with an aqueous solution containing hydrogen halide (for example, a dilute hydrochloric acid-sodium chloride aqueous solution), the washed material can be dissolved in an organic solvent, dried with a desiccant, the desiccant can be filtered off, and the solvent can be distilled off (for example, under reduced pressure) to obtain a component (i) (or a composition containing component (i)) from which water has been removed. The first amide compound has n-1 amino groups that can form a salt with a protonic acid, corresponding to the degree of polymerization n of the alkanolamine oligomer (amine compound (a2)) that forms an amide with the monovalent fatty acid (a1). In one embodiment, the average degree of polymerization (number average degree of polymerization) of the alkanolamine oligomer corresponding to the first amide compound is set to n avr When the equivalent of the protonic acid to be reacted with the first amide compound is 1.0 to n avr Equivalent, or 1.0~n avr -1.0 equivalent. For example, when the average degree of polymerization of the alkanolamine oligomer corresponding to the first amide compound is 3, the equivalent of the protonic acid corresponding to the first amide compound can be set to, for example, 1.0 to 3.0 equivalents or 1.0 to 2.0 equivalents. In another embodiment, the equivalent of the protonic acid reacting with the first amide compound can be set to max(1.0, n avr -2.0)~n avr Equivalent or max(1.0, n avr -2.0)~n avr -1.0 equivalent. Among them, for real numbers x1, x2, ..., the function max(x1, x2, ...) is a function that returns the maximum value of the given independent variables x1, x2, ...

[0072] In the present specification, the content of component (i) in a sample can be measured using a high performance liquid chromatography (HPLC) apparatus. The measurement conditions of HPLC are as follows. [HPLC measurement conditions] Apparatus: UltiMate 3000 UHPLC manufactured by Thermo Fisher Scientific Column: ACQUITY (registered trademark) UPLC BEH C18 1.7 μm 50×2.1 mm (ODS) manufactured by Waters Corporation Detection device: Combination of charged particle detector (CAD) and mass spectrometer (MS) Charged particle detector (CAD): Corona (registered trademark) Veo (registered trademark) RS manufactured by Thermo Fisher Scientific, drying tube temperature: 35°C Mass spectrometer (MS): JMS-T100LP AccuTOF (registered trademark) LC-plus 4G manufactured by JEOL Ltd. (ionization method: ESI+) Mobile phase: A gradient elution method based on ultrapure water, methanol, and isopropanol was used. Ammonium formate was added to each solvent to a concentration of 10 mmol / L. Starting from a water / methanol mixing volume ratio of 20 / 80, the composition was continuously changed until methanol was 100%, and then the composition was further continuously changed until isopropanol was 100%. Column temperature: 40°C Sample solution: Methanol solution with a sample concentration of about 100 ppm by mass Sample injection volume: 1.0 μL Based on the detection results of the mass spectrometer (MS), each detection peak of the charged particle detector (CAD) can be attributed to a compound. As long as the analysis conditions are the same, the detection peak of CAD is independent of the characteristics of the compound and represents the area value corresponding to the amount of compound flowing into the detector. Therefore, by using the peak area value of CAD, the content of each component (converted to the mass % of the compound in the state where no salt is formed) can be quantitatively determined. In addition, when one detection peak of CAD contains multiple compounds, the content of each component (converted to the mass % of the compound in the state where no salt is formed) can be calculated by proportionally allocating the area value of the detection peak of CAD according to the ratio of the peak area values ​​of the multiple compounds based on MS. In the above-mentioned measurement method, the detection peak of the component (i) in the chromatogram of CAD is separated from the detection peaks of other components (for example, by-products generated in the production process of the component (i)). When the sample to be measured for the content of component (i) is not a complete solution (contains insoluble matter or is a suspension), the measurement can be performed after obtaining a solution by known pretreatment such as filtration. Before the measurement based on the above-mentioned high performance liquid chromatography (C18 column, detector: CAD and MS), it is also possible to perform a pretreatment to remove all or part of the components other than component (i) by known purification methods such as silica gel column chromatography, preparative liquid chromatography separation (e.g., gel permeation chromatography (GPC), etc.) as needed.

[0073] <2. Lubricating oil composition and method for producing the same> The lubricating oil composition according to the second embodiment of the present invention (hereinafter sometimes referred to as "lubricating oil composition" or "composition") comprises a lubricating base oil and one or more additives other than the base oil. The lubricating oil composition comprises a lubricating base oil and the lubricating oil additive composition according to the first embodiment of the present invention described above. A method for producing a lubricating oil composition according to a third aspect of the present invention (hereinafter sometimes referred to as "the method for producing a lubricating oil composition" or "the production method") comprises: a) (A) adding and mixing the component (i) to a lubricating base oil or a mixture containing the lubricating base oil and one or more additives other than the component (i) (hereinafter sometimes referred to as "the step (a)"). In the lubricating oil composition and the production method of the present invention, as the lubricating base oil, a lubricating base oil comprising one or more mineral base oils or one or more synthetic base oils, or a combination thereof can be used.

[0074] As the lubricating oil base oil, one or more mineral oil base oils or one or more synthetic base oils or their mixed base oils can be used. In one embodiment, as the lubricating oil base oil, the Class I base oil (hereinafter sometimes referred to as "API Class I base oil"), the Class II base oil (hereinafter sometimes referred to as "API Class II base oil"), the Class III base oil (hereinafter sometimes referred to as "API Class III base oil"), the Class IV base oil (hereinafter sometimes referred to as "API Class IV base oil") or the Class V base oil (hereinafter sometimes referred to as "API Class V base oil"), or their mixed base oils can be used. API Class I base oil is a mineral oil base oil with a sulfur content greater than 0.03% by mass and / or a saturated content less than 90% by mass, and a viscosity index of 80 or more and less than 120. API Class II base oil is a mineral oil base oil with a sulfur content of less than 0.03% by mass, a saturated content of more than 90% by mass, and a viscosity index of more than 80 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 the above-mentioned Groups I to IV, and ester base oils can be cited as preferred examples thereof.

[0075] In one embodiment, as component (A), one or more API Group II base oils, one or more API Group III base oils, one or more API Group IV base oils, one or more API Group V base oils, or a combination thereof can be preferably used.

[0076] Examples of mineral oil-based base oils include lubricating oil fractions obtained by atmospheric distillation and / or vacuum distillation of crude oil, paraffinic base oils refined by one or a combination of two or more of the refining treatments selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid cleaning, clay treatment, etc., normal paraffinic base oils, isoparaffinic base oils, and mixtures thereof, etc. API Group II base oils and Group III base oils are usually produced by a hydrocracking process.

[0077] From the viewpoint of further improving the viscosity-temperature characteristics and fuel economy of the composition, the %C of the mineral oil-based base oil is PIt is preferably 60 or more, more preferably 65 or more. In addition, from the viewpoint of improving the solubility of the additive, it is preferably 99 or less, more preferably 95 or less, further preferably 94 or less. In one embodiment, it can be 60-99 or 60-95, 65-95, 65-94.

[0078] From the viewpoint of further improving the viscosity-temperature characteristics and fuel economy of the composition, the %C of the mineral oil-based base oil is A It is preferably 2 or less, more preferably 1 or less, further preferably 0.8 or less, and particularly preferably 0.5 or less.

[0079] From the viewpoint of improving the solubility of additives, the %C of mineral oil base oil is N It is preferably 1 or more, more preferably 4 or more, and from the viewpoint of further improving the viscosity-temperature characteristics and fuel economy 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.

[0080] In this specification, %C P 、%C N and %C A They refer to the percentage of paraffin carbon atoms relative to the total carbon atoms, the percentage of cycloalkane carbon atoms relative to the total carbon atoms, and the percentage of aromatic carbon atoms relative to the total carbon atoms, respectively, as determined by the method of ASTM D 3238-85 (ndM ring analysis). P 、%C N and %C A The preferred range of %C is based on the range of values ​​obtained by the above method. For example, even for a lubricating base oil containing no cycloparaffin, the %C N Values ​​greater than 0 can also be displayed.

[0081] From the viewpoint of improving the viscosity-temperature characteristics of the composition, the content of saturated fractions 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 the base oil. In addition, in this specification, the saturated fraction refers to a value measured according to ASTM D 2007-93.

[0082] Based on the total amount of base oil, the content of aromatic components in the mineral oil base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass. In one embodiment, it can be 0.1% by mass or more. By making the content of aromatic components below the above upper limit, in addition to improving the low-temperature viscosity characteristics and viscosity-temperature characteristics in the new oil state, it can also further improve fuel economy while reducing the evaporation loss of the lubricating oil and reducing the consumption of the lubricating oil. In addition, when additives are blended in the lubricating base oil, the role of the additive can be effectively exerted. In addition, the lubricating base oil may not contain aromatic components, but by making the content of aromatic components above the above lower limit, the solubility of the additive can be improved.

[0083] In addition, in this specification, the aromatic fraction refers to the value measured according to ASTM D 2007-93. The aromatic fraction generally includes anthracene, phenanthrene and their alkylated products in addition to alkylbenzenes and alkylnaphthalenes, and further includes compounds having four or more benzene rings condensed, pyridines, quinolines, phenols, naphthols and other aromatic compounds having heteroatoms.

[0084] Examples of API Group IV base oils include oligomers and cooligomers 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 hydrogenated products thereof, and hydrogenated products thereof.

[0085] Preferred examples of API Group V base oils include monoesters (e.g., butyl stearate, octyl laurate, 2-ethylhexyl oleate, etc.); diesters (e.g., di(tridecyl glutarate), di-2-ethylhexyl adipate, diisodecyl adipate, di(tridecyl adipate), di-2-ethylhexyl sebacate, etc.); polyesters (e.g., trimellitic acid esters, etc.); polyol esters (e.g., trimethylolpropane octanoate, trimethylolpropane nonanoate, pentaerythritol-2-ethylhexanoate, pentaerythritol nonanoate, etc.) and other ester base oils. Other examples of API Group V base oils include aromatic synthetic base oils such as alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, dialkyldiphenyl ethers, and polyphenylene ethers.

[0086] From the viewpoint of improving energy saving and low temperature viscosity characteristics of the lubricating oil composition, the kinematic viscosity of the lubricating oil base oil (all base oils) at 40° C. is preferably 40 mm 2 / s or less or 30mm 2 / s or less, 20mm 2 / s or less, and preferably 2.0 mm from the viewpoint of improving wear resistance and seizure resistance. 2 / s or above or 5.0mm 2 / s or more, 8.0mm 2 / s or more, and in one embodiment, may be 2.0 to 40 mm 2 / s or 5.0~30mm 2 / s, 8.0~20mm 2 In addition, in this specification, "40 degreeC kinematic viscosity" means the kinematic viscosity at 40 degreeC measured using the automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument Co., Ltd.) as a measuring device according to JIS K 2283-2000.

[0087] From the viewpoint of further improving the energy economy and the low-temperature viscosity characteristics of the lubricating oil composition, the kinematic viscosity of the lubricating base oil (all base oils) at 100° C. is preferably 10.0 mm 2 / s or less or 7.0mm 2 / s or less, 4.0mm 2 / s or less, and preferably 0.8 mm from the viewpoint of improving abrasion resistance and galling resistance. 2 / s or above or 1.2mm 2 / s or more, 1.4mm 2 / s or more, 1.6mm 2 / s or more, and in one embodiment, may be 0.8 to 10.0 mm 2 / s or 1.2~10.0mm 2 / s, 1.4~7.0mm 2 / s, 1.6~4.0mm 2 In addition, in this specification, "kinematic viscosity at 100° C." means the kinematic viscosity at 100° C. measured using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument Co., Ltd.) as a measuring device in accordance with JIS K 2283-2000.

[0088] From the viewpoint of improving the viscosity-temperature characteristics of the composition and further improving fuel economy and wear resistance, the viscosity index of the lubricating base oil (total base oil) is preferably 100 or more, more preferably 105 or more, further preferably 110 or more, particularly preferably 115 or more, and most preferably 120 or more. In this specification, the viscosity index refers to a viscosity index measured using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument Co., Ltd.) as a measuring device in accordance with JIS K 2283-2000.

[0089] From the viewpoint of the low-temperature fluidity of the entire lubricating oil composition, the pour point of the lubricating base oil (all base oils) is preferably -10°C or lower, more preferably -12.5°C or lower, further preferably -15°C or lower, particularly preferably -17.5°C or lower, and most preferably -20.0°C or lower. In this specification, the pour point means the pour point measured in accordance with JIS K 2269-1987.

[0090] The content of sulfur in the base oil is related to the content of sulfur in its raw material. For example, when using a substantially sulfur-free raw material such as a synthetic wax component obtained by a Fischer-Tropsch reaction, a substantially sulfur-free base oil can be obtained. In addition, when using sulfur-containing raw materials such as slack wax obtained in the refining process of the base oil or microwax obtained in the refined wax process, the sulfur content in the obtained base oil is usually more than 100 mass ppm. The content of sulfur in the lubricating base oil (all base oils) is usually less than 0.03 mass %, and from the viewpoint of oxidation stability, it is preferably less than 0.01 mass %. In addition, in this specification, the content of sulfur in the base oil refers to: the sulfur amount measured according to JIS K 2541-2003.

[0091] The lubricating oil base oil may be composed of a single base oil component or may contain a plurality of base oil components. In a preferred embodiment, the kinematic viscosity of the base oil as a whole (the entire base oil) at 40° C. may be 40 mm 2 / s or less.

[0092] In one embodiment, the lubricating base oil may contain 80-100 mass %, or 90-100 mass %, 90-99 mass %, or 95-99 mass %, based on the total amount of the base oil, 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.

[0093] The content of the lubricating base oil (total base oil) in the lubricating oil composition is 60% by mass or more, preferably 60 to 98.5% by mass, more preferably 70 to 98.5% by mass, and in one embodiment, 75 to 97% by mass, based on the total amount of the lubricating oil composition.

[0094] ((A) Lubricating Oil Additive Composition / Component (i)) The lubricating oil composition of the present invention contains the lubricating oil additive composition according to the first embodiment of the present invention described above (hereinafter sometimes referred to as "component (A)"). The lubricating oil additive composition according to the first embodiment of the present invention functions as an oiliness agent-based friction modifier. From the viewpoint of further improving the friction reduction performance, especially the friction reduction performance on metal surfaces such as gears that are easily subjected to high loads, the content of component (i) in the lubricating oil composition is preferably 0.005% by mass or more, 0.010% by mass or more, 0.030% by mass or more, 0.050% by mass or more based on the total amount of the lubricating oil composition, and from the viewpoint of storage stability, it is preferably 10.0% by mass or less, preferably 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, and in one embodiment, it can be 0.005 to 10.0% by mass, 0.010 to 5.0% by mass, 0.030 to 4.0% by mass, 0.050 to 3.0% by mass.

[0095] In the method for producing a lubricating oil composition of the present invention, from the viewpoint of further improving the friction reducing performance, particularly the friction reducing performance on metal surfaces such as gears that are susceptible to high loads, the amount of the component (i) added in step (a) is preferably 0.005 parts by mass or more, 0.010 parts by mass or more, 0.030 parts by mass or more, or 0.050 parts by mass or more per 100 parts by mass of the lubricating base oil, and from the viewpoint of the storage stability of the lubricating oil composition produced, it is preferably 11.1 parts by mass or less, 5.3 parts by mass or less, 4.2 parts by mass or less, or 3.1 parts by mass or less, and in one embodiment, it may be 0.005 to 11.1 parts by mass, 0.010 to 5.3 parts by mass, 0.030 to 4.2 parts by mass, or 0.050 to 3.1 parts by mass. In step (a), the component (i) may be added and mixed with the lubricating base oil, or may be added and mixed with a mixture containing the lubricating base oil and one or more additives other than the component (i). In addition, the production method of the present invention may further include the step of making one or more additives other than the above-mentioned component (i) present in the lubricating oil composition. The additives other than the component (i) may be added to the lubricating oil composition before or after the component (i) is added. The details of additives other than the component (i) that can be added to the lubricating oil composition produced by the production method of the present invention are the same as those of the lubricating oil composition of the present invention. In one embodiment, the production method of the present invention may include: b) making one or more additives selected from the group consisting of metallic detergents, ashless dispersants, phosphorus-containing antiwear agents, sulfur-containing extreme pressure agents, antioxidants, and viscosity index improvers present in the lubricating oil composition (hereinafter sometimes referred to as "step (b)").

[0096] ((B): Metal-based detergent) In a preferred embodiment, the lubricating oil composition may further contain one or more metal detergents (hereinafter sometimes referred to as "(B) component".). Examples of the (B) component include salicylate detergents, sulfonate detergents, phenate detergents, and the like. In addition, the (B) component may contain only one metal detergent, or may contain two or more metal detergents. In addition, generally, in the field of lubricating oils, as metal detergents, organic acid metal salts that can form micelles in base oils (e.g., alkali metal or alkaline earth metal alkyl salicylates, alkali metal or alkaline earth metal alkylbenzene sulfonates, and alkali metal or alkaline earth metal alkylphenol salts, etc.), or mixtures of the organic acid metal salts and alkaline metal salts (e.g., hydroxides, carbonates, borates, etc. of alkali metals or alkaline earth metals constituting the organic acid metal salts) may be used. Such an organic acid usually has in one molecule at least one polar group with protonic acidity (e.g., carboxyl group, sulfonic acid group, phenolic hydroxyl group, etc.) that can form a salt with a metal base (typically a metal oxide and / or a metal hydroxide), and at least one lipophilic group such as a straight-chain or branched alkyl group (e.g., a straight-chain or branched alkyl group having more than 6 carbon atoms, etc.).

[0097] Examples of salicylate detergents include metal salicylates or basic salts thereof or overbased salts thereof. Preferred examples of metal salicylates include alkali metal or alkaline earth metal salicylates represented by the following general formula (19).

[0098]

Chemical formula 19

[0099] In the general formula (19), R 17 Each independently represents an alkyl or alkenyl group having 14 to 30 carbon atoms, M represents an alkali metal or an alkaline earth metal, a represents 1 or 2, and p represents 1 or 2 corresponding to the valence 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. As the alkali metal, sodium or potassium is preferred, and as the alkaline earth metal, calcium or magnesium is preferred. As a, 1 is preferred. In addition, when a=2, R 17 It can also be a combination of different groups.

[0100] As a preferred embodiment of the salicylate-based detergent, there can be mentioned an alkaline earth metal salicylate or a basic salt or a high-base salt thereof, wherein a=1 in the above general formula (19).

[0101] Preferred examples of sulfonate-based detergents include alkali metal or alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds, or basic or overbased salts thereof, and more preferably alkaline earth metal salts, or basic or overbased salts thereof. The weight average molecular weight of the alkyl aromatic compound is preferably 400 to 1500, and more preferably 700 to 1300. As the alkali metal, sodium or potassium is preferred, and as the alkaline earth metal, calcium or magnesium is preferred. As examples of alkyl aromatic sulfonic acids, so-called petroleum sulfonic acids and synthetic sulfonic acids can be cited. As examples of petroleum sulfonic acids, products of sulfonation of alkyl aromatic compounds of lubricating oil fractions of mineral oil, by-products of manufacturing white oil (white oil), i.e., so-called mahogany acid, etc. can be cited. In addition, as an example of synthetic sulfonic acids, by-products in alkylbenzene manufacturing plants that are recovered as raw materials for detergents can be cited, or products of sulfonation of alkylbenzenes with linear or branched alkyl groups obtained by alkylating benzene with polyolefins. As another example of synthetic sulfonic acids, products of sulfonation of alkylnaphthalenes such as dinonylnaphthalene can be cited. In addition, as sulfonating agents when these alkyl aromatic compounds are sulfonated, there is no particular restriction, for example, oleum and sulfuric anhydride can be used.

[0102] Preferred examples of phenate-based detergents include high-based salts of alkali metal or alkaline earth metal salts of compounds having a structure represented by the following general formula (20), and more preferably high-based salts of alkaline earth metal salts. The alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium.

[0103]

Chemical formula 20

[0104] In the general formula (20), R 18 represents a linear or branched, saturated or unsaturated alkyl or alkenyl group having 6 to 21 carbon atoms, q represents an integer of 0 to 9, A represents a thio (-S-) group or a methylene (-CH2-) group, and x represents an integer of 1 to 3. In addition, R 18 It can also be a combination of two or more different groups, and x can also be a combination of multiple different integers. When A is a methylene group, x is preferably 1. x The substitution position of the - group is typically the ortho or para position relative to the hydroxy group, and typically the ortho position.

[0105] From the viewpoint of improving solubility in the base oil, R in the general formula (20) 18 The number of carbon atoms in the moiety is preferably 9 or more, and is preferably 18 or less, more preferably 15 or less, from the viewpoint of ease of production. In one embodiment, it may be 9 to 18 or 9 to 15.

[0106] In the general formula (20), q is preferably 0-3.

[0107] The metal detergent can be overbased with a carbonate (e.g., an alkali metal carbonate such as sodium carbonate, potassium carbonate, or an alkaline earth metal carbonate such as calcium carbonate, magnesium carbonate, etc.) or a borate (e.g., an alkali metal borate such as sodium borate, potassium borate, or an alkaline earth metal borate such as calcium borate, magnesium borate, etc.).

[0108] In one embodiment, component (B) contains one or more strongly basic calcium or magnesium sulfonate detergents, one or more strongly basic calcium or magnesium salicylate detergents and / or one or more strongly basic calcium or magnesium phenate detergents, and preferably contains one or more strongly basic calcium sulfonate detergents and / or one or more strongly basic calcium salicylate detergents. The calcium sulfonate detergent, calcium salicylate detergent and calcium phenate detergent are preferably overbased with calcium carbonate, and the magnesium sulfonate detergent, magnesium salicylate detergent and magnesium phenate detergent are preferably overbased with magnesium carbonate.

[0109] The base value of the metal-based detergent can be appropriately determined according to the use of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), the base value of the metal-based detergent is preferably 200 mgKOH / g or more, more preferably 250 mgKOH / g or more, from the viewpoint of improving wear resistance, anti-picking properties, and the transmission torque capacity of a wet clutch. In addition, from the same viewpoint, it is preferably 600 mgKOH / g or less, more preferably 550 mgKOH / g or less, and in one embodiment, it can be 200 to 600 mgKOH / g or 250 to 550 mgKOH / g. In addition, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, from the viewpoint of improving detergency and base number maintenance, it is preferably 0 mgKOH / g or more, more preferably 20 mgKOH / g or more, and from the viewpoint of suppressing the ash content in the composition and the life of the exhaust gas after-treatment device, it is preferably 500 mgKOH / g or less, more preferably 450 mgKOH / g or less, and in one embodiment, it may be 0 to 500 mgKOH / g or 20 to 450 mgKOH / g. In addition, in this specification, the base number refers to the base number measured by the perchloric acid method according to JIS K2501.

[0110] When the lubricating oil composition contains component (B), its content can be appropriately determined according to the purpose of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving wear resistance, pick resistance, fatigue resistance, and the transmission torque capacity of a wet clutch, the content of component (B) in the lubricating oil composition is preferably 200 mass ppm or more, more preferably 250 mass ppm or more, based on the total amount of the lubricating oil composition, in terms of metal amount. Furthermore, from the viewpoint of improving fuel economy and fatigue resistance, it is preferably 600 mass ppm or less, more preferably 550 mass ppm or less. In one embodiment, it can be 200 to 600 mass ppm or 250 to 550 mass ppm. Furthermore, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the content of the component (C) is preferably 500 ppm by mass or more, more preferably 1000 ppm by mass or more, in terms of metal amount, based on the total amount of the lubricating oil composition, from the viewpoint of improving cleaning performance and base number maintenance. Furthermore, from the viewpoint of suppressing ash content in the composition and from the viewpoint of the life of an exhaust gas after-treatment device, it is preferably 10000 ppm by mass or less, more preferably 5000 ppm by mass or less, and in one embodiment, it may be 500 to 10000 ppm by mass or 1000 to 5000 ppm by mass.

[0111] ((C) Nitrogen-containing dispersant) In a preferred embodiment, the lubricating oil composition may further contain one or more nitrogen-containing dispersants (hereinafter sometimes referred to as "component (C)"). In the field of lubricating oils, nitrogen-containing dispersants generally include nitrogen-containing compounds having at least one long-chain (e.g., 40 or more carbon atoms) straight or branched aliphatic hydrocarbon group and at least one polyamine chain (typically, polyethyleneamine chain) in one molecule, or modified products (derivatives) thereof, wherein some nitrogen atoms of the polyamine chain may be acylated. Examples of modified products are as follows.

[0112] As the component (C), for example, one or more compounds selected from the following (C-1) to (C-3) can be used. (C-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 (C-1)"), (C-2) a benzylamine having at least one alkyl or alkenyl group in the molecule (e.g., a Mannich base obtained by reaction of an alkyl or alkenylbenzene with formaldehyde or a polyamine) or a modified product (derivative) thereof (hereinafter sometimes referred to as "component (C-2)"), (C-3) N-alkyl or alkenylated polyamine having at least one alkyl or alkenyl group in the molecule, or a modified product (derivative) thereof (hereinafter sometimes referred to as "component (C-3)").

[0113] As the component (C), the component (C-1) can be particularly preferably used. In component (C-1), examples of succinimide having at least one alkyl or alkenyl group in the molecule include condensation reaction products of alkyl or alkenyl succinic acid or its anhydride and polyamine having an alkyl or alkenyl group having 40 to 400 carbon atoms. Such condensation reaction products (condensation products) can be represented by the following general formula (21a) or (21b), for example.

[0114]

Chemical formula 21

[0115] In the general formula (21a), R 19 represents an alkyl or alkenyl group having 40 to 400 carbon atoms, and b represents an integer of 1 to 10, preferably 2 to 6. In a typical embodiment, the compound represented by the general formula (21a) is obtained as a mixture of compounds having different b. From the viewpoint of solubility in the base oil, R 19 The number of carbon atoms is 40 or more, preferably 60 or more, and from the viewpoint of low temperature fluidity of the composition, it is 400 or less, preferably 350 or less, further preferably 250 or less, and in one embodiment it can be 40-400 or 60-350, 60-250.

[0116] In the general formula (21b), R 20 and R 21 Each independently represents an alkyl or alkenyl group having 40 to 400 carbon atoms, and may be a combination of different groups. In addition, c represents an integer of 0 to 15, preferably 1 to 13, and more preferably 1 to 11. In a typical embodiment, the compound represented by the general formula (21b) is obtained as a mixture of compounds having different c. From the viewpoint of solubility in the base oil, R 20 and R 21 The number of carbon atoms is 40 or more, preferably 60 or more, and from the viewpoint of low temperature fluidity of the composition, it is 400 or less, preferably 350 or less, further preferably 250 or less, and in one embodiment it can be 40-400 or 60-350, 60-250.

[0117] The alkyl or alkenyl group (R 19 ~R 21) may be straight-chain or branched. Preferred examples thereof include branched alkyl and alkenyl groups derived from oligomers of olefins such as propylene, 1-butene, and isobutylene, and co-oligomers of ethylene and propylene. Among them, branched alkyl or alkenyl groups derived from oligomers of isobutylene, which are conventionally referred to as polyisobutylene, and polybutenyl groups are most preferred. The alkyl or alkenyl group (R 19 ~R 21 ) has a preferred number average molecular weight of 800 to 3500, preferably 900 to 3500.

[0118] The succinimides having at least one alkyl or alkenyl group in the molecule include so-called mono-succinimides represented by the general formula (21a) in which only one end of the polyamine chain is imidized, and so-called bis-succinimides represented by the general formula (21b) in which both ends of the polyamine chain are imidized. The lubricating oil composition may contain either mono-succinimides or bis-succinimides, or may contain both of them as a mixture. The content of bis-succinimides or modified products thereof in the component (C-1) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount of the component (C-1) (100% by mass).

[0119] The weight average molecular weight of the component (C-1) is preferably 1,000 to 20,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and in one embodiment, may be 4,000 to 15,000.

[0120] Examples of modified products (modified compounds, derivatives) in components (C-1) to (C-3) include (i) modified products based on oxygen-containing organic compounds, (ii) boric acid modified products, (iii) phosphoric acid modified products, (iv) sulfur modified products, and (v) combined modified products of two or more of these. (i) Modified products based on oxygen-containing organic compounds are: modified compounds in which part or all of the remaining amino groups and / or imino groups are neutralized or amidated by allowing the above-mentioned succinimide, benzylamine or polyamine having at least one alkyl or alkenyl group in the molecule (hereinafter referred to as "the above-mentioned nitrogen-containing compound") to act with monocarboxylic acids having 1 to 30 carbon atoms such as fatty acids, polycarboxylic acids having 2 to 30 carbon atoms (for example, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.), their anhydrides or ester compounds, oxyalkylenes having 2 to 6 carbon atoms or hydroxy (poly)oxyalkylene carbonates. (ii) The boric acid-modified product is a modified compound in which a part or all of the remaining amino groups and / or imino groups are neutralized or amidated by reacting boric acid with the above-mentioned nitrogen-containing compound. (iii) The phosphoric acid-modified product is a modified compound in which a part or all of the remaining amino groups and / or imino groups are neutralized or amidated by reacting phosphoric acid with the above-mentioned nitrogen-containing compound. (iv) The sulfur-modified product is a modified compound obtained by reacting a sulfur compound with the above-mentioned nitrogen-containing compound. (v) Combination of Two or More Modifications The modified compound can be obtained by subjecting the above-mentioned nitrogen-containing compound to a combination of two or more modifications selected from the group consisting of modification with an oxygen-containing organic compound, boric acid modification, phosphoric acid modification, and sulfur modification. Among these modified products (derivatives) (i) to (v), boric acid-modified compounds of alkenyl succinimide, particularly bis-type boric acid-modified products of alkenyl succinimide, are preferably used.

[0121] When the lubricating oil composition contains component (C), its content can be appropriately determined according to the purpose of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving oxidation stability, the content of component (C) in the lubricating oil composition is preferably 0.1% by mass or more based on the total amount of the lubricating oil composition, and from the viewpoint of maintaining energy saving, it is preferably 10% by mass or less, and more preferably 5% by mass or less. In addition, for example, from the viewpoint of improving coking resistance, when the lubricating oil composition is used for lubrication of an internal combustion engine, the content of component (C) is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, and from the viewpoint of maintaining fuel economy, it is preferably 10.0% by mass or less, and more preferably 5.0% by mass or less, and in one embodiment, it can be 0.5% by mass to 10.0% by mass or 1.0% by mass to 5.0% by mass.

[0122] As the (C) component, the (C-1) component can be preferably used, and as the modified substance in the (C) component, a boric acid modified substance can be preferably used. In one embodiment, the (C) component can be one or more unmodified (C-1) components (unmodified succinimide dispersants), can be one or more boric acid modified substances of the (C-1) components (boric acid modified succinimide dispersants), or can be a combination of one or more unmodified succinimide dispersants and one or more boric acid modified succinimide dispersants. The (C) component may or may not contain a boric acid modified substance, but from the viewpoint of sludge dispersibility, the ratio (B / N) of the content B of the boron content as the (C) component to the content N of the nitrogen content as the (C) component can be preferably 0 to 1.0 in one embodiment.

[0123] ((D) Phosphorus-containing antiwear agent) In a preferred embodiment, the lubricating oil composition may contain one or more phosphorus-containing antiwear agents (hereinafter sometimes referred to as "component (D)"). As component (D), any phosphorus-containing antiwear agent that can be used in lubricating oils can be used without particular limitation. Examples of the phosphorus-containing antiwear agent include compounds represented by the following general formula (22), compounds represented by the following general formula (23), and metal salts and ammonium salts thereof.

[0124]

Chemical formula 22

[0125]

Chemical formula 23

[0126] Examples of the hydrocarbon group having 1 to 30 carbon atoms in the general formulae (22) and (23) include alkyl, cycloalkyl, alkenyl, alkyl-substituted cycloalkyl, aryl, alkyl-substituted aryl, and aralkyl. The hydrocarbon group is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, and in one embodiment, an alkyl group having 3 to 18 carbon atoms, and more preferably an alkyl group, aryl group, or alkylaryl group having 4 to 12 carbon atoms.

[0127] The hydrocarbon group having 1 to 30 carbon atoms in the general formulae (22) and (23) may be a hydrocarbon group containing a sulfur atom or may be a hydrocarbon group not containing a sulfur atom.

[0128] In one embodiment, preferred examples of the hydrocarbon group not containing a sulfur atom include linear alkyl groups having 4 to 18 carbon atoms. Examples of the linear alkyl group include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.

[0129] Examples of the hydrocarbon group containing a sulfur atom include hydrocarbon groups functionalized with a sulfur bond. Preferred examples of the hydrocarbon group functionalized with a sulfur bond include groups having 4 to 20 carbon atoms represented by the following general formula (24).

[0130]

Chemical formula 24

[0131] Preferred examples of the group represented by the general formula (24) include 3-thiopentyl, 3-thiohexyl, 3-thioheptyl, 3-thiooctyl, 3-thiononyl, 3-thiodecyl, 3-thioundecyl and 4-thiohexyl.

[0132] Examples of metals that form metal salts with the phosphorus compound represented by the general formula (22) or (23) 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 them, alkaline earth metals such as calcium and magnesium or zinc, or a combination thereof, are preferred.

[0133] Examples of nitrogen-containing compounds that form ammonium salts with the phosphorus compound represented by the general formula (22) or (23) include ammonia, monoamines, diamines, polyamines, and alkanolamines. More specifically, examples include nitrogen-containing compounds represented by the following general formula (25); alkylenediamines such as methylenediamine, ethylenediamine, propylenediamine, and butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; and combinations thereof.

[0134]

Chemical formula 25

[0135] Preferred examples of the compound represented by the general formula (22) include phosphite compounds, wherein in the general formula (22), X 1 ~X 3 is an oxygen atom, R 22 ~R 24 are independently an alkyl group, an aryl group (such as a phenyl group) or an alkylaryl group (such as an alkylphenyl group) having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms) and may contain a sulfur atom; a hydrogen phosphite compound, wherein in the above general formula (22), X 1 ~X 3 is an oxygen atom, R 22 and R 23 Each of them is independently an alkyl group having 3 to 18 (preferably 4 to 12) carbon atoms, an aryl group (such as a phenyl group) or an alkylaryl group (such as an alkylphenyl group) which may contain a sulfur atom. 24 is hydrogen; a thiophosphite compound, wherein in the above general formula (22), X 1 ~X 3 Two of them are oxygen atoms and the other one is a sulfur atom. 22 and R 23 Each of them is independently an alkyl group having 3 to 18 (preferably 4 to 12) carbon atoms, an aryl group (such as a phenyl group) or an alkylaryl group (such as an alkylphenyl group) which may contain a sulfur atom. 24 is hydrogen; and dithiophosphite compounds, wherein in the above general formula (22), X 1 ~X 3 One of them is oxygen atom and the other two are sulfur atoms. 22 and R 23 Each of them is independently an alkyl group having 3 to 18 (preferably 4 to 12) carbon atoms, an aryl group (such as a phenyl group) or an alkylaryl group (such as an alkylphenyl group) which may contain a sulfur atom. 24 For hydrogen; etc. Preferred examples of the compound represented by the general formula (23) include dithiophosphate compounds, wherein in the general formula (23), X 4 ~X 7 Two of them are sulfur atoms and the other two are oxygen atoms. 25 ~R 27Each independently represents an alkyl group, an aryl group or an alkylaryl group having 3 to 18 (preferably 4 to 12) carbon atoms which may contain a sulfur atom. These compounds may be used alone or in combination of two or more.

[0136] An example of the component (D) is zinc dialkyl dithiophosphate (ZnDTP). An example of zinc dialkyl dithiophosphate is a compound represented by the following general formula (26).

[0137]

Chemical formula 26

[0138] When the lubricating oil composition contains component (D), its content can be appropriately determined according to the purpose of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving wear resistance, anti-picking, bearing fatigue life, and prevention of speed change shock, the content of component (D) in the lubricating oil composition is preferably 50 mass ppm or more, more preferably 100 mass ppm or more, based on the total amount of the lubricating oil composition, in terms of phosphorus content. In addition, from the same viewpoint, it is preferably 800 mass ppm or less, more preferably 700 mass ppm or less, and in one embodiment, it can be 50 to 800 mass ppm or 100 to 700 mass ppm. Furthermore, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the content of the component (D) is preferably 400 ppm by mass or more, more preferably 500 ppm by mass or more, in terms of phosphorus content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, and is preferably 5000 ppm by mass or less, more preferably 3000 ppm by mass or less, from the viewpoint of reducing catalyst poisoning of an exhaust gas after-treatment device, and in one embodiment may be 400 to 5000 ppm by mass or 500 to 3000 ppm by mass.

[0139] ((E) Sulfur-containing extreme pressure agent) In a preferred embodiment, the lubricating oil composition may further contain one or more sulfur-containing extreme pressure agents other than the component (D) (hereinafter referred to as "component (E)"). Examples of component (E) include known sulfur-containing extreme pressure agents such as thiadiazole compounds, dialkyl (poly)sulfides, sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkylthiodipropionate compounds, sulfurized mineral oils, zinc dithiocarbamate compounds, and molybdenum dithiocarbamate compounds.

[0140] Preferred examples of the thiadiazole compound include 1,3,4-thiadiazole compounds represented by the following general formula (27), 1,2,4-thiadiazole compounds represented by the following general formula (28), and 1,2,3-thiadiazole compounds represented by the following general formula (29).

[0141]

Chemical formula 27

[0142]

Chemical formula 28

[0143]

Chemical formula 29

[0144] The dialkyl (poly)sulfide is a compound represented by the following general formula (30). 31 and R 32 When it is an alkyl group, it is sometimes called an alkyl sulfide.

[0145]

Chemical formula 30

[0146] When the lubricating oil composition contains component (E), its content can be appropriately determined according to the purpose of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving extreme pressure resistance and fatigue resistance, the content of component (E) in the lubricating oil composition is preferably 200 mass ppm or more, more preferably 300 mass ppm or more, based on the total amount of the lubricating oil composition, in terms of sulfur content. Furthermore, from the viewpoint of improving wear resistance, fatigue resistance and oxidation stability, it is preferably 3000 mass ppm or less, more preferably 2500 mass ppm or less, and in one embodiment, it can be 200 to 3000 mass ppm or 300 to 2500 mass ppm. Furthermore, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the content of the component (E) is preferably 10 ppm by mass or more, more preferably 30 ppm by mass or more, in terms of sulfur content, based on the total amount of the lubricating oil composition, from the viewpoint of improving extreme pressure resistance and fatigue resistance. Furthermore, from the viewpoint of reducing catalyst poisoning of an exhaust gas after-treatment device, it is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, and in one embodiment, it may be 10 to 200 ppm by mass or 30 to 100 ppm by mass.

[0147] ((F) Antioxidant) In a preferred embodiment, the lubricating oil composition may further contain one or more amine antioxidants and / or one or more phenolic antioxidants as antioxidants (hereinafter sometimes referred to as "component (F)").

[0148] Examples of amine antioxidants include aromatic amine antioxidants and hindered amine antioxidants. Examples of aromatic amine antioxidants include aromatic primary amine compounds such as alkylated α-naphthylamine, and aromatic secondary amine compounds such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, and phenyl-β-naphthylamine. As aromatic amine antioxidants, alkylated diphenylamine or alkylated phenyl-α-naphthylamine, or a combination thereof, can be preferably used.

[0149] Examples of hindered amine antioxidants include compounds having a 2,2,6,6-tetraalkylpiperidine skeleton (2,2,6,6-tetraalkylpiperidine derivatives). As 2,2,6,6-tetraalkylpiperidine derivatives, 2,2,6,6-tetraalkylpiperidine derivatives having a substituent at the 4-position are preferred. In addition, two 2,2,6,6-tetraalkylpiperidine skeletons may be bonded via a substituent at the 4-position, respectively. In addition, the N-position of the 2,2,6,6-tetraalkylpiperidine skeleton may be unsubstituted, or the N-position 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.

[0150] Examples of the substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton include an acyloxy group (R 41 COO-), alkoxy (R 41 O-), alkylamino (R 41 NH-), acylamino (R 41 CONH-) etc. 41 The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and still more preferably 1 to 20 carbon atoms. Examples of the hydrocarbon group include alkyl, alkenyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, and aralkyl groups.

[0151] Examples of the substituent when two 2,2,6,6-tetraalkylpiperidine skeletons are bonded via a substituent at the 4-position include an alkylenebis(carbonyloxy) group (-OOC-R 42 -COO-), alkylene diamino (-HN-R 42 -NH-), alkylenebis(carbonylamino) (-HNCO-R 42 -CONH-) etc. 42 A hydrocarbylene group having 1 to 30 carbon atoms is preferred, and an alkylene group is more preferred.

[0152] As the substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton, an acyloxy group is preferred. As an example of a compound having an acyloxy group at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton, an ester of 2,2,6,6-tetramethyl-4-piperidinol and a carboxylic acid can be cited. As an example of the carboxylic acid, a linear or branched aliphatic carboxylic acid having 8 to 20 carbon atoms can be cited.

[0153] 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'-butylenebis(3-methyl-6-tert-butylphenol); 4,4'-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butylphenol; Butyl-4-methylphenol; 2,6-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) propionate; 3-methyl-5-tert-butyl-4-hydroxyphenol fatty acid esters and other hindered phenol compounds and bisphenol compounds.

[0154] When the lubricating oil composition contains the component (F), the content thereof can be appropriately determined according to the use of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving thermal oxidation stability, the content of the component (F) 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 same viewpoint, it is 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 for lubrication of an internal combustion engine, from the viewpoint of improving thermal oxidation stability, the content of the component (F) 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 same viewpoint, it is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and in one embodiment, it is 0.1 to 5.0% by mass or 0.5 to 3.0% by mass.

[0155] ((G) Viscosity index improver) In a preferred embodiment, the lubricating oil composition may further contain one or more polymers having a viscosity index improving effect (hereinafter sometimes referred to as "viscosity index improver" or "(G) component".). Examples of the (G) component include non-dispersed or dispersed poly(meth)acrylates, (meth)acrylate-olefin copolymers, non-dispersed or dispersed ethylene-α-olefin copolymers or their hydrogenates, polyisobutylene or their hydrogenates, styrene-diene hydrogenated copolymers, styrene-maleic anhydride ester copolymers, and polyalkylstyrene. In addition, in this specification, "(meth)acrylate" means "acrylate and / or methacrylate". As the (G) component, one polymer may be used alone, or two or more polymers may be used in combination.

[0156] In one embodiment, as component (G), a dispersed poly(meth)acrylate or a non-dispersed poly(meth)acrylate, or a combination thereof, may be preferably used. In one embodiment, a dispersed poly(meth)acrylate may be preferably used. In addition, in this specification, the dispersed poly(meth)acrylate compound has a functional group containing a nitrogen atom, while the non-dispersed poly(meth)acrylate compound does not have a functional group containing a nitrogen atom.

[0157] In one embodiment, as a poly(meth)acrylate-based viscosity index improver, a poly(meth)acrylate in which the structural unit represented by the following general formula (31) accounts for 10 to 90 mol% of all monomer units in the polymer (hereinafter sometimes referred to as "poly(meth)acrylate (G1)" or simply "(G1) component") can be preferably used.

[0158]

Chemical formula 31

[0159] The weight average molecular weight of the component (G) can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), the weight average molecular weight of the component (G) is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 30,000 or more from the viewpoint of improving the viscosity index improvement effect and improving the low-temperature viscosity characteristics. In addition, from the viewpoint of improving the solubility in the base oil, storage stability, and shear stability, it is preferably 200,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less. In one embodiment, it can be 10,000 to 200,000, 20,000 to 150,000, or 30,000 to 100,000. Furthermore, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the weight average molecular weight of the component (G) is preferably 100,000 or more, more preferably 200,000 or more, from the viewpoint of improving the viscosity index improvement effect, improving the low-temperature viscosity characteristics and the fuel economy, and is preferably 1,000,000 or less, more preferably 700,000 or less, from the viewpoint of improving the solubility in oil, storage stability and shear stability, and in one embodiment, may be 100,000 to 1,000,000 or 200,000 to 700,000.

[0160] When the lubricating oil composition contains component (G), its content can be appropriately determined according to the amount that can obtain the desired kinematic viscosity and viscosity-temperature characteristics as the lubricating oil composition as a whole. For example, the viscosity index is an index for evaluating the viscosity-temperature characteristics. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), from the viewpoint of improving the viscosity-temperature characteristics and improving energy saving, the content of component (G) in the lubricating oil composition is, for example, 0.1% by mass or more or 0.5% by mass or more in terms of resin content based on the total amount of the lubricating oil composition. In addition, from the viewpoint of improving shear stability, it is, for example, 22% by mass or less or 12% by mass or less. In one embodiment, it can be 0.1 to 22% by mass or 0.5 to 12% by mass. In addition, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the content of the component (G) in the lubricating oil composition is, for example, 0.1% by mass or more or 0.5% by mass or more in terms of resin content based on the total amount of the lubricating oil composition from the viewpoint of improving fuel economy, and is, for example, 20% by mass or less or 15% by mass or less from the viewpoint of improving shear stability, and in one embodiment may be 0.1 to 20% by mass or 0.5 to 15% by mass. In addition, in this specification, the resin content refers to a polymer component having a molecular weight of 1,000 or more.

[0161] (Other additives) The lubricating oil composition of the present invention may further contain one or more additives selected from the group consisting of (H) a friction modifier other than the above-mentioned components (A) and (E), (I) a pour point depressant other than the above-mentioned component (G), (J) a corrosion inhibitor other than the above-mentioned component (E), (K) a metal deactivator other than the above-mentioned component (E), (L) a rust inhibitor other than the above-mentioned component (A), (M) an anti-emulsifier, (N) a defoaming agent, and (O) a colorant.

[0162] As the friction modifier (H) other than the above-mentioned components (A) and (E) (hereinafter sometimes referred to as "component (H)"), an oil-soluble organic molybdenum compound or an oiliness agent-based friction modifier used as a friction modifier in the lubricating oil can be used, and compounds other than the above-mentioned components (A) and (E) can be used. Examples of such compounds include oil-soluble organic molybdenum compounds other than the molybdenum dithiocarbamate described above as an example of component (E), and oiliness agent-based friction modifiers other than the above-mentioned component (A). When the lubricating oil composition contains the component (H), the content thereof may be, for example, 0.1 to 1.0% by mass based on the total amount of the lubricating oil composition.

[0163] As the pour point depressant (I) other than the above-mentioned component (G) (hereinafter sometimes referred to as "component (I)"), for example, a known pour point depressant such as ethylene-vinyl acetate copolymer can be used depending on the properties of the lubricating base oil used. When the lubricating oil composition contains component (I), its content can be, for example, 0.01 to 1.0% by mass based on the total amount of the lubricating oil composition.

[0164] As the anticorrosive agent (J) other than the above-mentioned component (E) (hereinafter sometimes referred to as "component (J)"), for example, a benzotriazole compound, a tolyltriazole compound, an imidazole compound or the like known anticorrosive agent can be used. When the lubricating oil composition contains the component (K), the content thereof can be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.

[0165] As the metal deactivator (K) other than the above-mentioned component (E) (hereinafter sometimes referred to as "component (K)"), for example, known metal deactivators such as imidazoline, pyrimidine derivatives, mercaptobenzothiazole, benzotriazole and its derivatives, 2-(alkyldithio)benzimidazole and β-(o-carboxybenzylthio)propionitrile can be used. When the lubricating oil composition contains component (K), its content can be, for example, 0.005 to 1.0% by mass based on the total amount of the lubricating oil composition.

[0166] As the rust inhibitor (L) other than the above-mentioned component (A) (hereinafter sometimes referred to as "component (L)"), for example, known rust inhibitors such as petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl succinates, and polyol esters (excluding the components belonging to the above-mentioned component (A)) can be used. When the lubricating oil composition contains the component (L), its content can be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.

[0167] As the demulsifier (M), for example, a known demulsifier such as a polyalkylene glycol nonionic surfactant can be used. When the lubricating oil composition contains a demulsifier, the content thereof can be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.

[0168] As the (N) defoaming agent, for example, known defoaming agents such as silicone, fluorosilicone and fluoroalkyl ether can be used. When the lubricating oil composition contains the defoaming agent, the content thereof can be, for example, 0.0005 to 1.0 mass % based on the total amount of the lubricating oil composition.

[0169] As the (O) colorant, for example, a known colorant such as an azo compound can be used.

[0170] (Properties of Lubricating Oil Composition) The kinematic viscosity of the lubricating oil composition at 100°C can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), the kinematic viscosity of the lubricating oil composition at 100°C is preferably 1.0 mm / s from the viewpoint of improving wear resistance. 2 / s or more, more preferably 2.5 mm 2 / s or more, and preferably 10.0 mm from the viewpoint of improving energy saving 2 / s or less, more preferably 7.0 mm 2 / s or less, and in one embodiment, may be 1.0 to 10.0 mm 2 / s or 1.0~7.0mm 2 / s, 2.5~10.0mm 2 / s, 2.5~7.0mm 2 In addition, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the kinematic viscosity of the lubricating oil composition at 100° C. is preferably 2.0 mm / s from the viewpoint of improving wear resistance. 2 / s or more, more preferably 4.0 mm 2 / s or more, and preferably 12.5 mm from the viewpoint of improving energy saving 2 / s or less, more preferably 9.3 mm 2 / s or less, and in one embodiment, may be 2.0 to 12.5 mm 2 / s or 4.0~12.5mm 2 / s, 2.0~9.3mm 2 / s, 4.0~9.3mm 2 / s.

[0171] The kinematic viscosity of the lubricating oil composition at 40°C can be appropriately determined according to the application of the lubricating oil composition. For example, when the lubricating oil composition is used for lubrication of a gear device such as a transmission (e.g., a manual transmission, an automatic transmission, a continuously variable transmission, etc.), the kinematic viscosity of the lubricating oil composition at 40°C is preferably 2.0 mm / s from the viewpoint of improving wear resistance. 2 / s or more, more preferably 5.0 mm 2 / s or more, and from the viewpoint of improving energy saving, 50 mm is preferred 2 / s or less, more preferably 45mm 2 / s or less, and in one embodiment, may be 2.0 to 50 mm 2 / s or 2.0~45mm 2 / s, 5.0~50mm 2 / s, 5.0~45mm 2 / s. For example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the kinematic viscosity of the lubricating oil composition at 40° C. is preferably 4.0 mm / s from the viewpoint of improving wear resistance. 2 / s or more, more preferably 6.0 mm 2 / s or more, and from the viewpoint of improving energy saving, 50 mm is preferred 2 / s or less, more preferably 35mm 2 / s or less, and in one embodiment, may be 4.0 to 50 mm 2 / s or 6.0~50mm 2 / s, 4.0~35mm 2 / s, 6.0~35mm 2 / s.

[0172] From the viewpoint of further improving energy saving performance and wear resistance, the viscosity index of the lubricating oil composition is preferably 100 or more, more preferably 110 or more, and in one embodiment, may be 115 or more or 120 or more.

[0173] (use) 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 improves friction reduction performance, especially the friction reduction effect in the mixed lubrication area (such as the lubrication conditions of gears, etc.). The lubricating oil composition of the present invention improves friction reduction performance, especially the friction reduction effect in the mixed lubrication area (such as the lubrication conditions of gears, etc.) by containing the (A) component. The additive composition and lubricating oil composition of the present invention play an improved friction reduction effect in the lubrication of metal surfaces that are easily subjected to high loads, such as gears. In addition to being preferably used for the lubrication of various mechanical devices with metal surfaces that are easily subjected to high loads, such as gear mechanisms, pistons, and connecting rod bearings, it can be preferably used for the lubrication of transmissions (such as manual transmissions, automatic transmissions, continuously variable transmissions, reducers of electric vehicles, speed increasers of wind turbines, etc.), and internal combustion engines. In addition, it can also be preferably used for lubrication of various industrial uses (such as hydraulic working oil, turbine oil, compressor oil). [Example]

[0174] The present invention will be described in further detail below based on Examples and Comparative Examples. In addition, the following Examples are intended to illustrate the present invention and are not intended to limit the present invention.

[0175] <Production Examples 1 to 9> The lubricating oil additive composition was produced according to the following procedure. (Measurement method) For the measurement of IR (infrared spectroscopy) spectrum, FT / IR-4100 manufactured by JASCO Corporation was used. A sample that was solid at room temperature was heated and melted, and a small amount was applied on a KBr plate for measurement. A sample that was liquid at room temperature was directly applied on a KBr plate for measurement.

[0176] The content of component (i) in the composition can be measured by high performance liquid chromatography (HPLC). The measurement conditions of HPLC analysis are as follows. [HPLC measurement conditions] Apparatus: UltiMate 3000 UHPLC manufactured by Thermo Fisher Scientific Column: ACQUITY (registered trademark) UPLC BEH C18 1.7 μm 50×2.1 mm (ODS) manufactured by Waters Corporation Detection device: Combination of charged particle detector (CAD) and mass spectrometer (MS) Charged particle detector (CAD): Corona (registered trademark) Veo (registered trademark) RS manufactured by Thermo Fisher Scientific, drying tube temperature: 35°C Mass spectrometer (MS): JMS-T100LP AccuTOF (registered trademark) LC-plus 4G manufactured by JEOL Ltd. (ionization method: ESI+) Mobile phase: A gradient elution method based on ultrapure water, methanol, and isopropanol was used. Ammonium formate was added to each solvent to a concentration of 10 mmol / L. Starting from a water / methanol mixing volume ratio of 20 / 80, the composition was continuously changed until methanol was 100%, and then the composition was further continuously changed until isopropanol was 100%. Column temperature: 40°C Sample solution: Methanol solution with a sample concentration of about 100 ppm by mass Sample injection volume: 1.0 μL Based on the detection results of the mass spectrometer (MS), each detection peak of the charged particle detector (CAD) is attributed to a compound. By using the peak area value of CAD, the content of each component (converted to the mass % of the compound in a state where no salt is formed) is quantified. When one detection peak of CAD contains multiple compounds, the content of each component (converted to the mass % of the compound in a state where no salt is formed) can be calculated by proportionally allocating the area value of the detection peak of CAD according to the ratio of the peak area values ​​of the multiple compounds based on MS.

[0177] (Production Example 1) 5.0 mol of lauric acid and 7.5 mol of diethanolamine (hereinafter sometimes referred to as "DEA") were added to a 5L three-necked flask equipped with a distillation tube together with a magnetic stirrer, the inside of the flask was replaced with nitrogen, and the contents of the flask were stirred with a magnetic stirrer to make a uniform mixture. While stirring the mixture in the flask with a magnetic stirrer, the flask was heated in an oil bath. The heating temperature of the oil bath was slowly increased to allow water to continue to distill out. The reaction was tracked with IR spectroscopy, and the end of the reaction was confirmed by IR spectroscopy after 24 hours from the start of the reaction. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the cooled flask were dried under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain DEA trimer lauramide (first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA trimer lauramide was mixed with 2.0 equivalents of lauric acid in the absence of a solvent and stirred at room temperature for 1 hour to produce lauric acid salt of DEA trimer lauramide.

[0178] (Production Example 2) Add 5.0 mol of oleic acid and 7.5 mol of DEA to a 5L three-necked flask equipped with a distillation tube together with a magnetic stirrer, replace the interior of the flask with nitrogen, and stir the contents of the flask with a magnetic stirrer to make a uniform mixture. While stirring the mixture in the flask with a magnetic stirrer, heat the flask in an oil bath. Slowly increase the heating temperature of the oil bath to allow water to continue to distill. Track the reaction with IR spectroscopy, and confirm the end of the reaction by IR spectroscopy after 24 hours from the start of the reaction. The heating temperature of the oil bath at the end of the reaction is 180°C. Place the contents of the cooled flask and dry under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain DEA trimer oleamide (first amide compound) as an oily substance. The oleate of DEA trimer oleamide was prepared by mixing 1.0 equivalent of the obtained DEA trimer oleamide with 2.0 equivalent of oleic acid without solvent and stirring at room temperature for 1 hour.

[0179] (Manufacturing Example 3 * ) 5.0 mol of 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanoic acid (in the general formula (4), k=0, R 6 =3,5,5-trimethylhexyl, R 7 =1,3,3-trimethylbutyl, R 8 = A branched fatty acid with a hydrogen atom. It is sometimes referred to as "multi-branched isostearic acid" below. ) and 7.5 mol DEA, replace the inside of the flask with nitrogen, and stir the contents of the flask with a magnetic stirrer to make a uniform mixture. While stirring the mixture in the flask with a magnetic stirrer, heat the flask in an oil bath. Slowly increase the heating temperature of the oil bath to allow water to continue to distill off. Track the reaction with IR spectroscopy, and confirm the end of the reaction by IR spectroscopy 24 hours after the start of the reaction. The heating temperature of the oil bath at the end of the reaction is 180°C. Place the contents of the cooled flask and dry under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain multi-branched isostearylamide (first amide compound) of DEA trimer as an oily substance.

[0180] (Production Example 4) A multi-branched isostearic acid salt of DEA trimer multi-branched isostearic acid amide was prepared by mixing 1.0 equivalent of the DEA trimer multi-branched isostearic acid amide and 2.0 equivalent of multi-branched isostearic acid without solvent and stirring at room temperature for 1 hour.

[0181] (Production Example 5) The DEA trimer multi-branched isostearamide (first amide compound) obtained in Preparation Example 3 was dissolved in toluene, and the toluene solution was washed with dilute hydrochloric acid (dilute hydrochloric acid-NaCl aqueous solution; 0.5 mol / L in terms of HCl) prepared with saturated saline. The washed organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation to prepare the hydrochloride of DEA trimer multi-branched isostearamide.

[0182] (Production Example 6) The DEA trimer multi-branched isostearamide (first amide compound) obtained in Preparation Example 3 was dissolved in toluene, and the toluene solution was neutralized with a boric acid aqueous solution (boric acid-NaCl aqueous solution; 0.8 mol / L in terms of boric acid) prepared from saturated saline. The neutralized organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure to prepare a borate salt of DEA trimer multi-branched isostearamide.

[0183] (Production Example 7) The toluenesulfonate of DEA trimer multi-branched isostearamide (first amide compound) was prepared by mixing 1.0 equivalent of the DEA trimer multi-branched isostearamide obtained in Preparation Example 3 with 2.0 equivalent of toluenesulfonic acid without solvent and stirring at room temperature for 1 hour.

[0184] (Manufacturing Example 8 * ) The DEA trimer multi-branched isostearamide (first amide compound) obtained in Preparation Example 3 was dissolved in toluene, and the toluene solution was neutralized with an aqueous sodium hydroxide solution (NaOH-NaCl aqueous solution; 0.5 mol / L as NaOH) prepared from saturated saline. The neutralized organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure to prepare a sodium salt of the DEA trimer multi-branched isostearamide.

[0185] (Production Example 9) 5.0 mol of 2-decyltetradecanoic acid (in the general formula (4), k=0, R 6 = dodecyl, R 7 =Decyl, R 8 = Branched chain fatty acid with hydrogen atom. ) and 7.5 mol DEA, replace the inside of the flask with nitrogen, and stir the contents of the flask with a magnetic stirrer to make a uniform mixture. While stirring the mixture in the flask with a magnetic stirrer, heat the flask in an oil bath. Slowly increase the heating temperature of the oil bath to allow water to continue to distill. Track the reaction with IR spectroscopy, and confirm the end of the reaction by IR spectroscopy after 24 hours from the start of the reaction. The heating temperature of the oil bath at the end of the reaction is 180°C. Cool the contents of the flask and dry under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain 2-decyltetradecylamide of DEA trimer (first amide compound) as an oily substance. 2-Decyltetradecanoic acid salt of DEA trimer 2-decyltetradecylamide was prepared by mixing 1.0 equivalent of the obtained DEA trimer 2-decyltetradecylamide with 2.0 equivalent of 2-decyltetradecanoic acid in the absence of a solvent and stirring at room temperature for 1 hour.

[0186] <Examples 1 to 22 and Comparative Examples 1 to 6> As shown in Tables 1 to 5, lubricating oil compositions of the present invention (Examples 1 to 22) and comparative lubricating oil compositions (Comparative Examples 1 to 6) were prepared. In the tables, "mass %" represents mass % based on the total amount of the lubricating oil composition (100 mass %). In addition, "mass ppm" represents mass ppm based on the total amount of the lubricating oil composition, and for element X, "mass ppm / X" represents mass ppm of the amount of element X based on the total amount of the lubricating oil composition. The details of each component are as follows.

[0187] Lubricating oil base oil: API Group II base oil (hydrocracked mineral oil base oil), kinematic viscosity (40°C): 9.3mm 2 / s, kinematic viscosity (100℃): 2.5mm 2 / s, viscosity index: 98, saturation content: 99.9% by mass, sulfur content: less than 1 mass ppm

[0188] ((A) Friction modifier) 1~2,3 in the table * , 4~7, 8 * , 9 are the lubricating oil additive compositions prepared in Preparation Examples 1 to 9, and the numbers correspond to the numbers of the Preparation Examples. 1: DEA trimer lauramide laurate 2: DEA trimer oleylamide oleate 3 * :Multi-branched isostearamide of DEA trimer (first amide compound) 4: DEA trimer multi-branched isostearamide multi-branched isostearate 5: DEA trimer multi-branched isostearamide hydrochloride 6: DEA trimer multi-branched isostearamide borate 7: DEA trimer multi-branched isostearamide toluenesulfonate 8 * :Sodium salt of DEA trimer multi-branched isostearamide 9: 2-Decylmtradecanoate of DEA trimer 2-decylmyristoylamide. 1-2, 4-7, 9 are lubricating oil additive compositions of the present invention, 3 * and 8 * This is a lubricating oil additive composition outside the scope of the present invention.

[0189] (B) Metal-based detergent: calcium carbonate-overbased calcium salicylate detergent, base value 300 mgKOH / g, Ca: 12.9 mass% (C) Dispersant: Boron-containing polybutenyl succinimide dispersant, N: 1.6 mass %, B: 0.35 mass %

[0190] ((D) Anti-wear agent) D-1: Tridecyl tetrathiophosphate D-2: Bis(3-thioundecyl) hydrogen phosphite

[0191] (E) Extreme pressure agent: thiadiazole compound, S: 36 mass % (F) Antioxidant: diphenylamine antioxidant (G) Viscosity index improver: non-dispersible polymethacrylate, weight average molecular weight 20,000 Defoamer: dimethyl silicone

[0192]

Table 1

[0193]

Table 2

[0194]

Table 3

[0195]

Table 4

[0196]

Table 5

[0197] (MTM test) For each lubricating oil composition, a ball-on-disk friction test was performed using an MTM traction tester (manufactured by PCS Instruments) to measure the friction coefficient (μ) under conditions simulating gear lubrication (mixed lubrication region). The measurement conditions are as follows. Ball and disc: Standard test piece (AISI52100 specification) Oil temperature: 90℃ Load: 60N Circumferential speed: 0.8m / s Slide rate: 10% The results are shown in Tables 1 to 5. The reduction rates (%) of the friction coefficients of Examples 1 to 15 and Comparative Examples 2 to 3 relative to Comparative Example 1, and the reduction rates (%) of the friction coefficients of Examples 16 to 22 and Comparative Examples 5 to 6 relative to Comparative Example 4 are shown in the tables.

[0198] (Evaluation results) The lubricating oil compositions of Examples 1 to 15 (Tables 1 to 3) containing the lubricating oil additive composition of the present invention as an oiliness-based friction modifier can sufficiently reduce the friction coefficient under conditions simulating gear lubrication, compared with the lubricating oil composition of Comparative Example 1 (Table 3) not containing an oiliness-based friction modifier.

[0199] The lubricating oil composition of Comparative Example 2 is a lubricating oil composition in which the first amide compound in a non-salt state is blended as an oiliness agent-based friction modifier. The lubricating oil composition of Comparative Example 3 is a lubricating oil composition in which a salt of a protonic base (not a protonic acid) and the first amide compound is blended as an oiliness agent-based friction modifier. The lubricating oil compositions of Comparative Examples 2 and 3 showed poor results in the effect of reducing the friction coefficient under conditions simulating the lubrication of gears.

[0200] The lubricating oil compositions of Examples 16 to 22 (Tables 4 and 5) are compositions obtained by removing additives other than the oiliness-based friction modifier from the lubricating oil compositions of Examples 2, 5, 7, 9, 11, 12, and 14, respectively. The lubricating oil compositions of Comparative Examples 4 to 6 (Table 5) are compositions obtained by removing additives other than the oiliness-based friction modifier from the lubricating oil compositions of Comparative Examples 1 to 3 (Table 3), respectively. The lubricating oil compositions of Examples 16 to 22 (Tables 4 and 5) containing the lubricating oil additive composition of the present invention as the oiliness-based friction modifier can sufficiently reduce the friction coefficient under conditions simulating the lubrication of gears, compared with the lubricating oil composition of Comparative Example 4 (Table 5) not containing the oiliness-based friction modifier.

[0201] The lubricating oil composition of Comparative Example 4 is a lubricating oil composition in which the first amide compound in a non-salt state is blended as an oiliness agent-based friction modifier. The lubricating oil composition of Comparative Example 5 is a lubricating oil composition in which a salt of a protonic base (not a protonic acid) and the first amide compound is blended as an oiliness agent-based friction modifier. The lubricating oil compositions of Comparative Examples 4 and 5 showed poor results in the effect of reducing the friction coefficient under conditions simulating the lubrication of gears.

[0202] The above test results show that the lubricating oil composition containing the lubricating oil additive composition of the present invention can improve friction reducing performance, particularly friction reducing performance in the mixed lubrication region (eg, lubrication of gears).

Industrial Applicability

[0203] 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 improves friction reduction performance, especially the friction reduction effect in the mixed lubrication area (such as the lubrication conditions of gears, etc.). The lubricating oil composition of the present invention improves friction reduction performance, especially the friction reduction effect in the mixed lubrication area (such as the lubrication conditions of gears, etc.). The additive composition and lubricating oil composition of the present invention exert an improved friction reduction effect in the lubrication of metal surfaces that are easily subjected to high loads, such as gears. Therefore, in addition to being preferably used for the lubrication of various mechanical devices such as gear mechanisms, pistons, connecting rod bearings, etc. that have metal surfaces that are easily subjected to high loads, it can be preferably used for transmissions (such as manual transmissions, automatic transmissions, continuously variable transmissions, reducers of electric vehicles, speed increasers of wind turbines, etc.), lubrication of internal combustion engines, and can also be preferably used for lubrication of various industrial uses (such as hydraulic working oil, turbine oil, compressor oil).

Claims

1. A lubricating oil additive composition, characterized in that: contain: (i) a proton acid salt of at least one first amide compound, wherein the proton acid salt of the first amide compound is a salt of the first amide compound and a proton acid, wherein the first amide compound is a monoamide of at least one linear or branched saturated or unsaturated monovalent fatty acid (a1) having 6 to 30 carbon atoms and at least one amine compound (a2) and does not have an ester bond, wherein the amine compound (a2) is an alkanolamine oligomer having a structure formed by dehydration condensation of at least one alkanolamine (a3) ​​represented by the following general formula (1) and having a degree of polymerization of at least 2, In the general formula (1), n ​​is 1 or 2; R 1 represents a straight-chain alkylene group having 1 to 4 carbon atoms, or a branched-chain alkylene group having 3 to 10 carbon atoms and 2 carbon atoms in the main chain; when n is 2, multiple R 1 They may be the same or different from each other.

2. The lubricating oil additive composition according to claim 1, wherein: The protonic acid includes one or more inorganic acids selected from hydrogen halide, nitric acid, boric acid and carbonic acid, or one or more organic acids selected from carboxylic acid, organic sulfonic acid and substituted or unsubstituted phenol, or a combination thereof.

3. The lubricating oil additive composition according to claim 2, wherein: The carboxylic acid is a monobasic fatty acid having 1 to 5 carbon atoms, a monobasic fatty acid having 6 to 30 carbon atoms, an aliphatic hydroxy acid having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, an aromatic monocarboxylic acid having 7 to 10 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, mellitic acid or an aromatic hydroxy acid having 7 to 14 carbon atoms, and the monobasic fatty acid having 6 to 30 carbon atoms can also be the monobasic fatty acid (a1).

4. The lubricating oil additive composition according to any one of claims 1 to 3, wherein The monovalent fatty acid includes one or more straight-chain fatty acids.

5. The lubricating oil additive composition according to any one of claims 1 to 3, wherein The monovalent fatty acid includes one or more branched-chain fatty acids.

6. The lubricating oil additive composition according to claim 5, wherein: The branched fatty acid has a tertiary carbon or a quaternary carbon atom at the alpha, beta or gamma position to the carbonyl carbon.

7. A lubricating oil composition, characterized in that: contain 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, and (A) The lubricating oil additive composition according to any one of claims 1 to 3.

8. The lubricating oil composition according to claim 7, wherein The content of the component (i) is 0.005 to 10.0% by mass based on the total amount of the lubricating oil composition.

9. The lubricating oil composition according to claim 7, wherein The invention further contains one or more additives selected from the group consisting of metal detergents, ashless dispersants, phosphorus-containing antiwear agents, sulfur-containing extreme pressure agents, antioxidants and viscosity index improvers.

10. The lubricating oil composition according to claim 7, wherein Its kinematic viscosity at 40°C is 2.0-50 mm 2 / s.

11. The lubricating oil composition according to claim 7, which is used for lubrication of gears.

12. A method for producing a lubricating oil composition, characterized in that: The invention relates to a method for producing a lubricating oil composition, comprising: a) a step of adding and mixing (i) a proton acid salt of at least one first amide compound to a lubricating base oil or a mixture containing the lubricating base oil and at least one additive other than the following component (i), wherein the proton acid salt of the first amide compound is a salt of the first amide compound and a protonic acid, wherein the first amide compound is a monoamide of at least one linear or branched saturated or unsaturated monobasic fatty acid (a1) having 6 to 30 carbon atoms and having no ester bond and at least one amine compound (a2), wherein the amine compound (a2) is an alkanolamine oligomer having a structure formed by dehydration condensation of at least one alkanolamine (a3) ​​represented by the following general formula (1) and having a polymerization degree of 2 or more, The lubricating base oil contains one or more mineral base oils or one or more synthetic base oils, or a combination thereof.

13. The manufacturing method according to claim 12, wherein: In the step a), 0.005 to 11.1 parts by mass of the component (i) is added to 100 parts by mass of the lubricating base oil.

14. The manufacturing method according to claim 12 or 13, wherein: The protonic acid includes one or more inorganic acids selected from hydrogen halide, nitric acid, boric acid and carbonic acid, or one or more organic acids selected from carboxylic acid, organic sulfonic acid and substituted or unsubstituted phenol, or a combination thereof.

15. The manufacturing method according to claim 14, wherein: The carboxylic acid is a monobasic fatty acid having 1 to 5 carbon atoms, a monobasic fatty acid having 6 to 30 carbon atoms, an aliphatic hydroxy acid having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, an aromatic monocarboxylic acid having 7 to 10 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, mellitic acid or an aromatic hydroxy acid having 7 to 14 carbon atoms, and the monobasic fatty acid having 6 to 30 carbon atoms can also be the monobasic fatty acid (a1).

16. The manufacturing method according to claim 12 or 13, wherein: The monovalent fatty acid includes one or more straight-chain fatty acids.

17. The manufacturing method according to claim 12 or 13, wherein: The monovalent fatty acid includes one or more branched-chain fatty acids.

18. The manufacturing method according to claim 17, wherein: The branched fatty acid has a tertiary carbon or a quaternary carbon atom at the alpha, beta or gamma position to the carbonyl carbon.

19. The manufacturing method according to claim 12 or 13, wherein: Include: b) at least one additive selected from the group consisting of metallic detergents, ashless dispersants, phosphorus-containing antiwear agents, sulfur-containing extreme pressure agents, antioxidants and viscosity index improvers is present in the lubricating oil composition.

Images