Lubricating oil additive composition, and lubricating oil composition

Abstract

This lubricating oil additive composition contains (i) one or more Brφnsted acid salts of a first amide compound, the Brφnsted acid salts being salts of a first amide compound and a Brφnsted acid. With respect to this lubricating oil additive composition, the first amide compound is a monoamide of one or more fatty acids (a1) and one or more amine compounds (a2); and the amine compounds (a2) are each an oligomer of one or more alkanolamines (a3) that are represented by general formula (1). (In the formula, n represents 1 or 2; R1 represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group which has 3 to 10 carbon atoms, while having 2 carbon atoms in the main chain; and in cases where n is 2, the plurality of R1 moieties may be the same as or different from each other.)

Description

Lubricating oil additive composition and lubricating oil composition

[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 that can be suitably used for lubricating gears.

[0002] Lubricating oils are used to smooth the operation of internal combustion engines, automatic transmissions, bearings, etc. Generally, various additives are blended into lubricating oils to give them the performance required.

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

[0004] Widely known organic molybdenum FMs include MoDTC (molybdenum dithiocarbamate) and MoDTP (molybdenum dithiophosphate) (see, for example, Patent Document 1). While these organic molybdenum FMs are excellent in reducing friction during the initial period of use, there are limitations to maintaining this friction-reducing effect over a long period of time. Furthermore, organic molybdenum FMs contain ash, which makes it difficult to reuse used lubricating oil. Therefore, there is a demand for reducing the amount of organic molybdenum FM added.

[0005] On the other hand, oil-based FMs have the potential to overcome the above-mentioned problems of organic molybdenum-based FMs, and therefore the importance of oil-based FMs is increasing (see, for example, Patent Documents 2 to 4).

[0006] JP 2013-133453 A JP 2009-235252 A JP 2006-257383 A International Publication No. 2019 / 129793

[0007] However, conventional oil-based FMs still have room for improvement in terms of friction-reducing performance.

[0008] An object of the present invention is to provide a lubricating oil additive composition useful as an oiliness-based friction modifier with improved friction-reducing properties, and to provide a lubricating oil composition containing the lubricating oil additive composition.

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

[19] .

[0010] [1] (i) A lubricating oil additive composition comprising one or more Bronsted acid salts of a first amide compound, wherein the first amide compound is a monoamide of one or more C6 to C30 linear or branched saturated or unsaturated monovalent fatty acids (a1) and one or more amine compounds (a2), and the monoamide has no ester bond, and the amine compound (a2) is an alkanolamine oligomer having a degree of polymerization of 2 or more and having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1):

[0011] (In the general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms and having 2 carbon atoms in the main chain; when n is 2, a plurality of R １ may be the same or different from each other.)

[0012] [2] The lubricating oil additive composition according to [1], wherein the Bronsted acid comprises 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 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 monovalent fatty acid having 1 to 5 carbon atoms, a monovalent fatty acid having 6 to 30 carbon atoms which may be the monovalent fatty acid (a1), 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.

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

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

[0017] [7] A lubricating oil composition comprising a lubricating base oil comprising one or more mineral 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 composition according to [7], wherein the content of the component (A) is 0.005 to 10.0 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 a metallic detergent, an ashless dispersant, a phosphorus-containing antiwear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver.

[0020]

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

[0021]

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

[10] , which is used for lubricating gears.

[0022]

[12] A method for producing a lubricating oil composition, comprising: a) adding and mixing one or more Brønsted acid salts (i) of a first amide compound with a Brønsted acid, wherein the first amide compound is a monoamide of one or more linear or branched, saturated or unsaturated monovalent fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2), the salt having no ester bond, and the amine compound (a2) is an alkanolamine oligomer having a degree of polymerization 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), to a lubricating oil base oil or a mixture containing the lubricating oil base oil and one or more additives other than component (i), wherein the lubricating oil base oil comprises one or more mineral base oils, one or more synthetic base oils, or a combination thereof:

[0023]

[13] In the a), 0.005 to 11.1 parts by mass of the (i) component is blended with respect to 100 parts by mass of the lubricating base oil. The manufacturing method according to

[12] .

[0024]

[14] The method according to

[12] or

[13] , wherein the Bronsted acid comprises 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.

[0025]

[15] The production method according to

[14] , wherein the carboxylic acid is a monovalent fatty acid having 1 to 5 carbon atoms, a monovalent fatty acid having 6 to 30 carbon atoms which may be the monovalent fatty acid (a1), 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.

[0026]

[16] The method according to any one of

[12] to

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

[0027]

[17] The method according to any one of

[12] to

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

[0028]

[18] The method according to

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

[0029]

[19] The method according to any one of

[12] to

[18] , comprising: b) adding one or more additives selected from a metallic detergent, an ashless dispersant, a phosphorus-containing antiwear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver to the lubricating oil composition.

[0030] The lubricating oil additive composition according to the first aspect of the present invention has enhanced friction-reducing properties and is useful as an oiliness-based friction modifier. The lubricating oil composition according to the second aspect of the present invention can exhibit improved friction-reducing properties 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 can produce a lubricating oil composition with improved friction-reducing properties by including the lubricating oil additive composition according to the first aspect of the present invention in the lubricating oil composition.

[0031] The present invention will be described in detail below. In this specification, unless otherwise specified, the expression "A to B" for numerical values ​​A and B is equivalent to "A or more and B or less." In such an expression, when a unit is assigned only to numerical value B, the unit is also applied to numerical value A. In this specification, the words "or" and "or" mean a logical sum unless otherwise specified. In this specification, element E １ and E ２ About "E １ and / or E ２ " is written as "E １ , or E ２ , or a combination thereof, and １ , ..., E ｉ , ..., E Ｎ (N is an integer of 3 or more.) １ , ..., and / or E Ｎ" is written as "E １ , ..., or E ｉ , ..., or E Ｎ , or a combination thereof (where i is a variable that takes on any integer value satisfying 1<i<N). In this specification, the term "alkaline earth metal" also includes magnesium.

[0032] In this specification, unless otherwise specified, the contents of calcium, magnesium, zinc, phosphorus, sulfur, boron, barium, and molybdenum in oil are measured by inductively coupled plasma atomic emission spectrometry (intensity ratio method (internal standard method)) in accordance with JIS K0116. The content of nitrogen in oil is measured by chemiluminescence in accordance with JIS K2609. In addition, in this specification, "weight average molecular weight" means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). The GPC measurement conditions are as follows: [GPC Measurement Conditions] Apparatus: ACQUITY (registered trademark) APC UV RI system manufactured by Waters Corporation Column: From the upstream side, two ACQUITY (registered trademark) APC XT900A manufactured by Waters Corporation (gel particle size 2.5 μm, column size (inner diameter × length) 4.6 mm × 150 mm) and one ACQUITY (registered trademark) APC XT200A manufactured by Waters Corporation (gel particle size 2.5 μm, column size (inner diameter × length) 4.6 mm × 150 mm) were connected in series. Column temperature: 40°C Sample solution: tetrahydrofuran solution with a sample concentration of 1.0 mass% Eluent: tetrahydrofuran Solution injection amount: 20.0 μL Detector: differential refractive index detector Reference material: standard polystyrene (Agilent Agilent EasiCal (registered trademark) PS-1 (manufactured by Agilent Technologies) 8 points (molecular weight: 2,698,000, 597,500, 290,300, 133,500, 70,500, 30,230, 9,590, 2,970) If the weight average molecular weight measured under the above conditions is less than 10,000, change the column and standard substance to the following conditions and perform the measurement again.Columns: From the upstream side, 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. Reference substance: 10 standard polystyrenes (Agilent Technologies Agilent EasiCal (registered trademark) PS-1) (molecular weights: 30230, 9590, 2970, 890, 786, 682, 578, 474, 370, 266).

[0033] <1. Lubricating Oil Additive Composition> The lubricating oil additive composition according to a first aspect of the present invention (hereinafter may be simply referred to as the "additive composition") contains one or more Brønsted acid salts (i) of the first amide compound (hereinafter may be referred to as "component (i)" or "component (i)"), which are salts of a first amide compound and a Brønsted acid, wherein the first amide compound is a monoamide of one or more linear or branched, saturated or unsaturated monovalent fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2), the monoamide having no ester bond, and the amine compound (a2) is an alkanolamine oligomer having a degree of polymerization 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):

[0034] (In the general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms and having 2 carbon atoms in the main chain; when n is 2, a plurality of R １ may be the same or different from each other.)

[0035] The fatty acid (a1) may be one type of fatty acid or a combination of two or more types of fatty acids. The fatty acid (a1) may be a saturated fatty acid or an unsaturated fatty acid. The fatty acid (a1) may also be a straight-chain fatty acid or a branched-chain fatty acid. In one preferred embodiment, the fatty acid (a1) may be a branched-chain fatty acid. Examples of straight-chain saturated fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, etc. Examples of branched-chain saturated fatty acids include branched-chain isomers of these. 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, and triacontenoic acid. Examples of branched-chain unsaturated fatty acids include branched-chain isomers thereof. The arrangement of the C=C double bond in unsaturated fatty acids is not particularly limited. The number of C=C double bonds in unsaturated fatty acids may be one (i.e., monoenoic acid), two (i.e., dienoic acid), three (i.e., trienoic acid), or four or more (i.e., tetraenoic acid). Furthermore, the C═C double bond in unsaturated fatty acids may be of the cis type (Z type) or the 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 within the same molecule. For example, fatty acids derived from hydrogenated natural fats and oils 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, which are derived from side reactions of the hydrogenation reaction.For example, specific examples of unsaturated fatty acids having 18 carbon atoms include various analogs differing in the number, arrangement, and / or geometric isomerism of C═C double bonds, such as oleic acid (cis-9-octadecenoic acid), paccenic acid (11-octadecenoic acid), linoleic acid (cis,cis-9,12-octadecadienoic acid), linolenic acid (9,12,15-octadecanetrienoic acid, 6,9,12-octadecanetrienoic acid), and eleostearic acid (9,11,13-octadecanetrienoic acid).Similarly, various analogs differing in the number, arrangement, and / or geometric isomerism of C═C double bonds can be mentioned for unsaturated fatty acids having other carbon numbers.

[0036] The number of carbon atoms in the fatty acid (a1) is 6 or more, preferably 8 or more, or 10 or more, or 12 or more, from the viewpoint of enhancing the friction-reducing effect in lubrication of gears and the like, and from the same viewpoint is 30 or less, preferably 24 or less, or 22 or less, or 20 or less, or 18 or less, and in one embodiment may be 6 to 30, or 8 to 24, or 8 to 22, or 10 to 22, or 12 to 20, or 12 to 18. In one embodiment, the fatty acid (a1) may be one or more types of straight-chain fatty acid. Preferred examples of straight-chain fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, vaccenic acid, elaidic acid, linoleic acid, linolenic acid, eleostearic acid, stearidonic acid, arachidic acid, gadoleic acid, eicosenoic acid, eicosapentaenoic acid, behenic acid, erucic acid, sardine acid, docosahexaenoic acid, lignoceric acid, nisinic acid, nervonic acid, cerotic acid, montanic acid, melissic acid, and mixtures thereof. Fatty acids derived from natural fats and oils or hydrogenated natural fats and oils may also be used as mixtures containing two or more fatty acids. Examples of fatty acids derived from natural fats and oils 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, beef tallow fatty acids, hydrogenated products thereof, and mixtures thereof. These fatty acids derived from natural fats and oils are typically mixtures containing two or more fatty acids having 6 to 24 carbon atoms. In one embodiment, the fatty acid (a1) can be one or more branched-chain fatty acids. In one embodiment, the branched-chain fatty acid preferably has a tertiary or quaternary carbon atom (i.e., branched) at the α-, β-, or γ-position relative to the carbonyl carbon, preferably a tertiary or quaternary carbon atom at the α- or β-position relative to the carbonyl carbon, and particularly preferably a tertiary or quaternary carbon atom at the α-position relative to the carbonyl carbon. A preferred example of such a branched chain fatty acid is a branched chain fatty acid represented by the following general formula (2).

[0037] (In general formula (2), k is an integer of 0 to 2, preferably 0 or 1, and more preferably 0; R ２ and R ３ are each independently a straight-chain or branched-chain alkyl group; R ４ is a hydrogen atom or a linear or branched alkyl group, preferably a hydrogen atom; ２ (number of carbon atoms in R ３ (number of carbon atoms in R ４ (R ２ (number of carbon atoms in R ３ (number of carbon atoms in R ４ In one preferred embodiment, in the general formula (2), k is 0, R ２ is a linear or branched alkyl group having 3 to 19 carbon atoms; R ３ is a linear or branched alkyl group having 1 to 10 carbon atoms; R ４ may be a hydrogen atom. Preferred examples of branched-chain fatty acids represented by general formula (4) include 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-decyltetradecanoic acid, and 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanoic acid. If necessary, such branched-chain fatty acids can be produced by, for example, reacting a Grignard reagent prepared from a secondary or tertiary alkyl halide or an organometallic compound such as an alkyllithium with carbon dioxide, or by synthesizing an aldehyde and / or alcohol by reacting an alkene, carbon monoxide, and hydrogen in the presence of a hydroformylation catalyst, and then subjecting the resulting aldehyde and / or alcohol to a further oxidation reaction. If necessary, secondary or tertiary alkyl halides can be produced, for example, by the addition reaction of the corresponding alkene with a hydrogen halide (e.g., hydrogen chloride, hydrogen bromide, or hydrogen iodide). The secondary or tertiary alkyl halide derived from an alkene is usually obtained as an isomeric mixture of secondary or tertiary alkyl halides having different positions at which the halogen atom is bonded, and the branched chain fatty acid derived from such an isomeric mixture of secondary or tertiary alkyl halides is usually represented by the general formula (2) where R ２ ~R ４The branched-chain fatty acid is obtained as an isomer mixture of branched-chain fatty acids having different combinations of carbon numbers. Other preferred examples of branched-chain fatty acids include branched-chain fatty acids having a methyl branch at the terminal. Preferred examples of such branched-chain fatty acids include branched-chain fatty acids represented by the following general formula (3):

[0038] (In general formula (3), j+4 is equal to the total number of carbon atoms in the branched chain fatty acid.) A preferred example of such a branched chain fatty acid is 16-methylheptadecanoic acid.

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

[0040] (In the general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms and having 2 carbon atoms in the main chain; when n is 2, a plurality of R １ may be the same or different from each other.) In general formula (1), R １ is 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. １ The number of carbon atoms in R is preferably 2 to 4, or 2 to 3, and in one embodiment, may be 2. In one embodiment, R is a branched alkylene group. １ Each side chain of R is a methyl group or an ethyl group, １ The carbon number of R may be 3 to 6, or 3 to 5, or 3 to 4. １ The number of carbon atoms in the main chain of R １ means the number of carbon atoms in the shortest carbon chain connecting the nitrogen atom and oxygen atom bonded to R １ The designation is determined independently of the choice of backbone used in the naming of R. １ is a butane-1,2-diyl group, R １ The main chain of R has 2 carbon atoms. １is a linear alkylene group, R １ The number of carbon atoms in the main chain of R １ The number of carbon atoms is equal to R. １ is a branched alkylene group, R １ Each side chain of R is preferably a methyl group or an ethyl group, and in one embodiment may be a methyl group. For example, a linear alkylene group R １ can be produced by reacting an unsubstituted oxirane with ammonia. １ can be produced by reacting unsubstituted oxetane with ammonia. １ can be produced by reacting unsubstituted tetrahydrofuran with ammonia. １ can be prepared by the reaction of a substituted oxirane with ammonia, wherein each substituent of the substituted oxirane is a branched alkylene group R １ The alkylene group R １Preferred examples of the alkylene group include linear alkylene groups such as ethane-1,2-diyl and propane-1,3-diyl; propane-1,2-diyl; branched alkylene groups having 4 carbon atoms such as butane-1,2-diyl, butane-2,3-diyl, and 1-methylpropane-1,2-diyl; and branched alkylene groups having 4 carbon atoms such as pentane-1,2-diyl, pentane-2,3-diyl, 2-methylbutane-1,2-diyl, and 3-methylbutane-2,3-diyl. branched alkylene groups having 5 carbon atoms; branched alkylene groups having 6 carbon atoms such as a hexane-1,2-diyl group, a hexane-2,3-diyl group, a hexane-3,4-diyl group, a 2-methylpentane-2,3-diyl group, a 3-methylpentane-2,3-diyl group, or a 2,3-dimethylbutane-2,3-diyl group; a heptane-1,2-diyl group, a heptane-2,3-diyl group, a heptane-3,4-diyl group, or a 3-ethylpentane-2,3-diyl group, Branched-chain alkylene groups having 7 carbon atoms, such as 3-methylpentane-3,4-diyl group; branched-chain alkylene groups having 8 carbon atoms, such as octane-1,2-diyl group, octane-2,3-diyl group, octane-3,4-diyl group, octane-4,5-diyl group, 3-ethylhexane-3,4-diyl group, 3-ethyl-2-methylpentane-2,3-diyl group, and 3,4-dimethylhexane-3,4-diyl group; nonane-1,2-diyl group, nonane- branched alkylene groups having 9 carbon atoms such as a 2,3-diyl group, a nonane-3,4-diyl group, a nonane-4,5-diyl group, and a 2,3-diethylpentane-2,2-diyl group; and branched alkylene groups having 10 carbon atoms such as a decane-1,2-diyl group, a decane-2,3-diyl group, a decane-3,4-diyl group, a decane-4,5-diyl group, a decane-5,6-diyl group, and a 3,4-diethylhexane-3,4-diyl group. １ may be a single alkylene group or a combination of two or more alkylene groups.

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

[0042] The alkanolamine represented by general formula (1) is a monoalkanolamine when n=1, and a dialkanolamine when n=2. １ is an asymmetric branched alkylene group, i.e., when the side chains bonded to the two free valences are different alkylene groups (e.g., propane-1,2-diyl group, butane-2,3-diyl group, pentane-2,3-diyl group, etc.), either of the two free valences may be bonded to the nitrogen atom. For example, in the reaction of propylene oxide with ammonia, a reaction pathway giving a propanolamine structure in which the 1-position of the propylene-1,2-diyl group is bonded to the nitrogen atom (i.e., a 2-hydroxypropyl group is bonded to the nitrogen atom) competes with a reaction pathway giving a propanolamine structure in which the 2-position of the propylene-1,2-diyl group is bonded to the nitrogen atom (i.e., a 1-hydroxypropan-2-yl group is bonded to the nitrogen atom), and a mixture of both products may be obtained. In a dialkanolamine represented by general formula (1) where n=2, １ may be the same or different from each other. １ are the same asymmetric branched alkylene group, two R １ The orientations of the two R may be the same or different from each other. １ In dipropanolamine, where R is a propane-1,2-diyl group, two HO-R １ Both of the - groups may be 2-hydroxypropyl groups, or both may be 1-hydroxypropan-2-yl groups, or one may be a 2-hydroxypropyl group and the other a 1-hydroxypropan-2-yl group. When producing dipropanolamine by the reaction of propylene oxide with ammonia, these compounds may be produced simultaneously to give a mixture. The one or more alkanolamines (a3) ​​represented by general formula (1) may be one or more monoalkanolamines, one or more dialkanolamines, or a combination of one or more monoalkanolamines and one or more dialkanolamines, but one or more dialkanolamines are particularly preferred.

[0043] In component (i), the amine compound (a2) forming a monoamide with the monovalent fatty acid (a1) is an alkanolamine oligomer having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by general formula (1), and its degree of polymerization is 2 or greater. For example, the following general formula (4) represents a reaction in which two molecules of dialkanolamine (a3d) undergo a dehydration condensation reaction to produce an alkanolamine dimer (a2-dd) having a degree of polymerization of 2. Further, for example, the following general formula (5) represents a reaction in which two molecules of monoalkanolamine (a3m) undergo a dehydration condensation reaction to produce an alkanolamine dimer (a2-mm) having a degree of polymerization of 2. Further, for example, the following general formula (6) represents a reaction in which one molecule of dialkanolamine (a3d) undergoes a dehydration condensation reaction with one molecule of monoalkanolamine (a3m) to produce an alkanolamine dimer (a2-2dm or a2-2md) having a degree of polymerization of 2. As shown in general formula (6), the dehydration condensation reaction between a dialkanolamine and a monoalkanolamine can produce structural isomers, depending on which hydroxyl group is eliminated from which molecule.

[0044] As shown in general formulas (4) to (6), in the dehydration condensation of alkanolamine (a3), a hydroxy group is eliminated from one molecule, and a new C-N bond is formed between the carbon atom to which the eliminated hydroxy group was bonded (the α-carbon of the hydroxy group) and the primary or secondary amine nitrogen atom of the other molecule. Furthermore, for example, the following general formula (7) represents a reaction in which an alkanolamine trimer (a2-ddd1 or a2-ddd2) with a degree of polymerization of 3 is produced by the dehydration condensation of three molecules of dialkanolamine:

[0045] In general formula (7), the production of the dimer (a2-dd) is described with reference to general formula (4). As shown in general formula (7), the dialkanolamine trimer may contain structural isomers (a2-ddd1 and a2-ddd2) corresponding to the hydroxy group that leaves the dialkanolamine dimer (2a-dd). Similarly, alkanolamine oligomers with a degree of polymerization of 4 or more may also contain multiple structural isomers. For example, general formula (8) below represents a reaction in which an alkanolamine trimer (a2-mmm1 or a2-mmm2) with a degree of polymerization of 3 is produced by dehydration condensation of three monoalkanolamine molecules.

[0046] In general formula (8), the production of the dimer (a2-mm) is described with reference to general formula (5). As shown in general formula (8), the monoalkanolamine trimer may contain structural isomers (a2-mmm1 and a2-mmm2) corresponding to the hydroxy group that leaves the monoalkanolamine dimer (2a-mm). Similarly, alkanolamine oligomers with a degree of polymerization of 4 or more may also contain multiple structural isomers. Furthermore, for example, the following general formulas (9a) to (9c) represent a reaction in which a mixed alkanolamine trimer (a2-ddm1, a2-ddm2, a2-dmd, or a2-mdd) with a degree of polymerization of 3 is produced by dehydration condensation of two molecules of dialkanolamine and one molecule of monoalkanolamine.

[0047] In the general formulas (9a) to (9c), the production of dimers (a2-dd, a2-dm, a2-md) is described with reference to the general formulas (4) and (6). As shown in the general formulas (9a) to (9c), the mixed alkanolamine trimer may contain structural isomers (a2-ddm1, a2-ddm2, a2-dmd, and a2-mdd) corresponding to the hydroxy group that is eliminated. Similarly, a mixed alkanolamine oligomer having a degree of polymerization of 4 or more may contain multiple structural isomers. For example, the following general formulas (10a) to (10c) represent a reaction in which one molecule of dialkanolamine and two molecules of monoalkanolamine undergo dehydration condensation to produce a mixed alkanolamine trimer (a2-mmd, a2-dmm1, or a2-dmm2) having a degree of polymerization of 3.

[0048] In the general formulas (10a) to (10c), the production of dimers (a2-mm, a2-dm, a2-md) is described with reference to the general formulas (5) and (6). As shown in the general formulas (10a) to (10c), the mixed alkanolamine trimer may contain structural isomers (a2-mmd, a2-dmm1, and a2-dmm2) corresponding to the hydroxy group that is eliminated. Similarly, a mixed alkanolamine oligomer having a degree of polymerization of 4 or more may also contain multiple structural isomers. Thus, an alkanolamine oligomer having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by the general formula (1) can be represented by the following general formula (11) when its degree of polymerization is 2 or 3.

[0049] (In general formula (11), R ５ ~R ９ are each independently a hydrogen atom or -R １ represents an —OH group; R １ is as defined above; １ may be the same or different from each other; m is 0 or 1; when m is 0, R ５ ~R ８ At least one of R is a hydrogen atom, and ５ ~R ８ At least one of them is -R １ -OH group; when m is 1, R ５ ~R ９ At least one of R is a hydrogen atom, and ５ ~R ９ At least one of them is -R １ In one embodiment, in general formula (11), when m=0, R ５ ~R ８ One of them is a hydrogen atom, and the other three are -R １ When m=1, R ５ ~R ９ One of them is a hydrogen atom, and the other four are -R １The alkanolamine oligomer having a structure formed by dehydration condensation of one or more alkanolamines (a3) ​​represented by general formula (1) includes an isomer having a linear polyalkyleneamine skeleton and an isomer having a branched polyalkyleneamine skeleton when the degree of polymerization is 4 or more. For example, when the degree of polymerization of the alkanolamine oligomer is 4, the isomer having a linear polyalkyleneamine skeleton is an isomer in which some of the hydrogen atoms bonded to the N atom of the unsubstituted linear polyalkyleneamine represented by the following general formula (12a) are -R １ The isomer having a branched chain polyalkyleneamine skeleton is a compound in which some of the hydrogen atoms bonded to the N atom of the unsubstituted branched chain polyalkyleneamine represented by the following general formula (12b) are replaced with —R １ is a compound substituted with an —OH group; R １ is as defined above, and a plurality of R １ may be the same or different from each other.

[0050] As used herein, when an unsubstituted polyalkyleneamine having m+2 (m≧1) N atoms is described as "linear," it means that the unsubstituted polyalkyleneamine has two primary amino groups and m secondary amino groups, regardless of whether the alkylene group is linear or branched. In contrast, when an unsubstituted polyalkyleneamine is described as "branched," it means that the unsubstituted polyalkyleneamine has at least one tertiary amino group, regardless of whether the alkylene group is linear or branched. When an unsubstituted branched polyalkyleneamine having m+2 (m≧2) N atoms has k (1≦k≦m / 2) tertiary amino groups, the unsubstituted branched polyalkyleneamine has 2+k primary amino groups and m−2k secondary amino groups. Generally, when the degree of polymerization m+2 of the alkanolamine oligomer is 4 or more, the isomer having a linear polyalkyleneamine skeleton is an isomer in which some (for example, m+3) of the hydrogen atoms bonded to the N atom of the unsubstituted linear polyalkyleneamine represented by the following general formula (13) are -R １The isomer having a branched chain polyalkyleneamine skeleton is a compound in which some (for example, m+3) of the hydrogen atoms bonded to the N atom of the unsubstituted branched chain polyalkyleneamine isomer of the unsubstituted linear polyalkyleneamine represented by general formula (13) are replaced with -R １ is a compound substituted with an —OH group; R １ is as defined above, and a plurality of R １ may be the same or different from each other.

[0051] (In general formula (13), m corresponds to the degree of polymerization of the alkanolamine oligomer (m+2), and m≧2.)

[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 multiple different degrees of polymerization. In one embodiment, the alkanolamine oligomer (a2) may be a combination of oligomers having multiple different consecutive degrees of polymerization. In this specification, when a certain oligomer is "a combination of oligomers having multiple different consecutive degrees of polymerization," the minimum and maximum values ​​of the degrees of polymerization of the oligomers are d ｍｉｎ and d ＭＡＸ When the oligomer is d ｍｉｎ more than d ＭＡＸ This means that oligomers of all the following polymerization degrees are included.

[0053] The first amide compound is a monoamide of one or more monovalent fatty acids (a1) and one or more amine compounds (a2), and is a compound that does not have an ester bond. Component (i) is the first amide compound and / or a salt thereof. The first amide compound has one or more unacylated amine nitrogen atoms, and therefore can form a salt with an acid. The salt of the first amide compound may be a salt of the first amide compound and an organic acid (organic acid salt), 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 may be one type of organic acid salt or a combination of two or more organic acid salts. The inorganic acid salt may be one type of inorganic acid salt or a combination of two or more inorganic acid salts. As described below, the organic acid constituting the organic acid salt may be the monovalent fatty acid (a1).

[0054] Examples of the inorganic acid that constitutes the first amide compound and the inorganic acid salt include hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide; oxyhalogen acids such as hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, hypoiodous acid, iodous acid, iodic acid, and periodic acid; inorganic oxoacids such as nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid (meaning an oxoacid of phosphorus in which the formal oxidation state of the phosphorus atom is +V, which may be orthophosphoric acid or a condensed phosphoric acid such as pyrophosphoric acid or polyphosphoric acid), phosphorous acid, boric acid (meaning an oxoacid of boron in which the formal oxidation state of the boron atom is +III, which may be orthoboric acid or a condensed boric acid such as tetraboric acid or metaboric acid), and carbonic acid; and inorganic Brønsted acids such as hydrocyanic acid.

[0055] Examples of the organic acid that constitutes the first amide compound and the organic acid salt include organic Bronsted acids such as carboxylic acids, organic sulfonic acids, organic phosphonic acids and monoesters thereof, organic boronic acids and monoesters thereof, sulfuric acid monoesters, phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid monoesters, phosphorous acid diesters, boric acid monoesters, boric acid diesters, and substituted or unsubstituted phenols.

[0056] Examples of carboxylic acids that form salts 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 and monoesters thereof having 2 to 10 carbon atoms, and aliphatic hydroxy acids. Examples of monovalent fatty acids having 1 to 5 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, etc., and the number of carbon atoms is preferably 2 to 5. Examples of monovalent fatty acids having 6 to 30 carbon atoms include the various monovalent fatty acids described above in relation to the monovalent fatty acid (a1). Examples of divalent aliphatic dicarboxylic acids having 2 to 10 carbon atoms include oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples of the monoester include monoesters of the divalent aliphatic dicarboxylic acid with alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, and dodecanol, for example, alkyl alcohols having 1 to 12, 1 to 10, or 1 to 8 carbon atoms. Examples of the aliphatic hydroxy acids include aliphatic hydroxy acids having 2 to 18 carbon atoms, such as glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinelaideic acid, quinic acid, and shikimic acid. Other examples of aliphatic carboxylic acids include halogenated (e.g., fluorinated) aliphatic carboxylic acids such as trifluoroacetic acid, 3,3,3-trifluoropropionic acid, and 4,4,4-trifluorobutyric acid. Examples of aromatic carboxylic acids include aromatic monocarboxylic acids, aromatic dicarboxylic acids and their monoesters, aromatic hydroxy acids, and aromatic polycarboxylic acids. Examples of aromatic monocarboxylic acids 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 aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, etc. Examples of monoesters thereof include monoesters of the aromatic dicarboxylic acids with the various alcohols described above in relation to the monoesters of divalent aliphatic dicarboxylic acids. Examples of aromatic hydroxy acids include salicylic acid, (m- or p-)hydroxybenzoic acid, (o-, m-, or p-)hydroxymethylbenzoic acid, vanillic acid, syringic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dihydroxybenzoic acid, orsellitic acid, gallic acid, mandelic acid, hydroxydiphenylacetic acid (benzilic 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, and sinapic acid, and other compounds having 7 to 14 carbon atoms. Examples of aromatic polycarboxylic acids include trimellitic acid, mellitic acid, and other compounds having a structure in which 3 to 6 hydrogen atoms of a benzene are substituted with carboxy groups.

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

[0058] (In general formula (14), R １０ represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms. １０Examples of the alkyl group include linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and oleyl; aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenyl, tolyl, xylyl, mesityl, cumyl, and naphthyl; halogenated hydrocarbon groups, such as trifluoromethyl, 2,2,2-trifluoroethyl, fluorophenyl, chlorophenyl, dichlorophenyl, and trichlorophenyl; and camphor-10-yl. Preferred examples of organic sulfonic acids include compounds having 1 to 10 carbon atoms, such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 10-camphorsulfonic acid.

[0059] An example of the organic phosphonic acid is a compound represented by the following general formula (15).

[0060] (In general formula (15), R １１ represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms. １１ Examples of １０ Examples of the monoester of an organic phosphonic acid include the linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms and the aromatic hydrocarbon groups having 6 to 10 carbon atoms, which are described above in relation to the monoester of a divalent aliphatic dicarboxylic acid.

[0061] An example of the organic boronic acid is a compound represented by the following general formula (16):

[0062] (In general formula (16), R １２ represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms. １２ Examples of １０Examples of the alkyl or alkenyl groups include linear or branched alkyl groups having 1 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 10 carbon atoms, as explained above in relation to R. １２ Other examples include cycloalkyl groups having 5 to 6 carbon atoms, such as a cyclopentyl group or a cyclohexyl group; arylalkyl groups, such as a phenylethyl group; halogenated aromatic hydrocarbon groups (having 6 to 7 carbon atoms, for example), such as a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a dibromophenyl group, an iodophenyl group, a fluorotolyl group, or a chlorotolyl group; hydroxyphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, a trimethoxyphenyl group, a ... Examples of the monoester of an organic boronic acid include hydroxy-, alkoxy-, cyano-, formyl-, or nitro-substituted or acylated aromatic hydrocarbon groups (e.g., having 6 to 10 carbon atoms), such as phenyl, methoxytolyl, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, butoxyphenyl, nitrophenyl, cyanophenyl, formylphenyl, and acetylphenyl; and heterocyclic groups, such as furan-2-yl, thiophen-3-yl, thiophen-2-yl, benzofuran-2-yl, and benzo[b]thiophen-2-yl. Examples of the monoester of an organic boronic acid include monoesters of the organic phosphonic acid and the various alcohols described above in connection with the monoesters of divalent aliphatic dicarboxylic acids.

[0063] Examples of the sulfuric acid monoester, phosphoric acid monoester, phosphorous acid monoester, and boric acid monoester include the monoesters of sulfuric acid, orthophosphoric acid, phosphorous acid, or orthoboric acid with the various alcohols described above in relation to the monoesters of divalent aliphatic dicarboxylic acids, respectively. Examples of the phosphoric acid diester and boric acid diester include the monoesters of orthophosphoric acid or orthoboric acid with the various alcohols described above in relation to the monoesters of divalent aliphatic dicarboxylic acids, respectively.

[0064] Preferred examples of substituted phenols include substituted phenols having a lower pKa than unsubstituted phenol. Such substituted phenols typically have one or more substituents that act as electron-withdrawing groups for the aromatic ring. Examples of such electron-withdrawing groups include acyl groups such as acetyl, formyl, carboxy, alkoxycarbonyl, nitro, cyano, and halogeno groups (e.g., fluoro, chloro, bromo, and iodo). Examples of alcohols corresponding to the alkoxy groups of the alkoxycarbonyl groups include the various alcohols described above in relation to the monoesters of divalent aliphatic dicarboxylic acids. Examples of such substituted phenols include acetylphenol, formylphenol, carboxyphenol, methoxycarbonylphenol, ethoxycarbonylphenol, nitrophenol, cyanophenol, fluorophenol, chlorophenol, bromophenol, and iodophenol. The number of carbon atoms in the substituted phenol may preferably be 6 to 13, 6 to 11, or 6 to 9.

[0065] In one embodiment, the Bronsted 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 acids, organic sulfonic acids, and substituted or unsubstituted phenols, or a combination thereof. In one embodiment, the carboxylic acid may be a monovalent fatty acid having 1 to 5 carbon atoms, a monovalent fatty acid having 6 to 30 carbon atoms which may be the monovalent fatty acid (a1), 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.

[0066] (Production) The amine compound (a2), i.e., the alkanolamine oligomer, can be produced, for example, by dehydration condensation of one or more alkanolamines (a3). The amine compound (a2) may 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 oligomers having consecutively different degrees of polymerization). In one embodiment, the first amide compound can be produced by a dehydration condensation reaction between a fatty acid (a1) and an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by heating the fatty acid (a1) and the amine compound (a2) under reflux in an organic solvent that forms an azeotrope with water (e.g., toluene, xylene, cumene, cymene, etc.) in the presence of an acid catalyst (e.g., sulfuric acid, trifluoroacetic acid, etc.) or a base catalyst (e.g., sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, triethylamine, pyridine, etc.) or in the absence of a catalyst, while azeotropically removing the water produced as the condensation reaction proceeds. In addition, under catalyst-free conditions, the fatty acid (a1) and / or the amine compound (a2) themselves can act as a catalyst. In another embodiment, the first amide compound can be produced by reacting the fatty acid (a1), the amine compound (a2), and a condensing agent in a solvent.Examples of condensing agents include carbodiimide-based condensing agents such as N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC); imidazole-based condensing agents such as N,N'-carbonyldiimidazole (CDI) and 1,1'-carbonyldi(1,2,4-triazole) (CDT); triazine-based condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride hydrate (DMT-MM); 2-chloro-1-methylpyridinium p-toluenesulfonate, and 2-fluoro-1-methylpyridinium Any known condensing agent that can be used for esterification can be used without particular limitation, including 2-halopyridinium salts such as p-toluenesulfonate; 2,4,6-trichlorobenzoyl chloride (TCBC); 2-methyl-6-nitrobenzoic anhydride (MNBA); a combination of diethyl azodicarboxylate (DEAD) and triphenylphosphine; a combination of phosphines such as chlorodiphenylphosphine and 2,2'-dipyridyl disulfide; a combination of p-benzoquinones such as 2,6-dimethyl-1,4-benzoquinone (DMBQ) or tetrafluoro-1,4-benzoquinone; and dimesitylammonium pentafluorobenzenesulfonate. The condensing agent may be used together with a catalyst such as 4-dimethylaminopyridine (DMAP), N-hydroxysuccinimide (NHS), 1-hydroxybenzotriazole (HOBt), or 1-hydroxy-7-azabenzotriazole (HOAt). In another embodiment, the first amide compound can be produced by reacting an acylating agent derived from a fatty acid (a1) with an amine compound (a2) in a solvent. Examples of the acylating agent derived from a fatty acid (a1) include acid halides of the fatty acid (a1) (e.g., acid chlorides, acid bromides, etc.), activated esters of the fatty acid (a1) (e.g., esters of the fatty acid (a1) and N-hydroxysuccinimide (NHS), esters of the fatty acid (a1) and 1-hydroxybenzotriazole (HOBt), esters of the fatty acid (a1) and 1-hydroxy-7-azabenzotriazole (HOAt), etc.), and acid anhydrides of the fatty acid (a1).The acylating agent derived from the fatty acid (a1) may be used together with a catalyst such as 4-dimethylaminopyridine (DMAP). The solvent may be any organic solvent that does not interfere with the condensation reaction (e.g., aliphatic hydrocarbon solvents such as hexane and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; pyridine, etc.). Furthermore, in the condensation reaction to produce the first amide compound, if necessary, a suitable base (e.g., amines such as triethylamine, pyridine, and 2,6-lutidine; organolithium reagents such as butyllithium; inorganic bases such as potassium carbonate) may be added to the reaction mixture for the purpose of promoting the reaction or capturing the acid generated as the reaction proceeds (e.g., 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 between one or more alkanolamines (a3) ​​represented by the general formula (1) above and an amide of the monovalent fatty acid (a1) above, which does not have an ester bond (hereinafter sometimes referred to as the "second amide compound"), and an alkanolamine (a3) ​​and / or an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by heating the second amide compound and the alkanolamine (a3) ​​or the amine compound (a2), or a mixture thereof, under reflux in an organic solvent that forms an azeotrope with water, in the presence of an acid catalyst or a base catalyst, or under catalyst-free conditions, while azeotropically removing the water generated as the condensation reaction proceeds. The above-mentioned various dehydration condensation reactions can also be carried out under solvent-free conditions. For example, the water generated as the reaction proceeds can be removed by distillation while the dehydration condensation reaction is carried out under solvent-free conditions.

[0067] In one preferred embodiment, a composition containing a first amide compound can be produced by a dehydration condensation reaction between a fatty acid (a1) and an alkanolamine (a3). In one embodiment, such a dehydration condensation reaction can be carried out by heating and refluxing the fatty acid (a1) and the alkanolamine (a3) ​​in the presence of an organic solvent that forms an azeotropic mixture with water, while azeotropically removing the water generated as the condensation reaction proceeds. 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 heating and stirring the fatty acid (a1) and the alkanolamine (a3) ​​under solvent-free conditions, gradually increasing the heating temperature so that the water generated by the reaction continues to distill off, and continuing the heating and stirring until further temperature increases no longer cause water to distill off. The above dehydration condensation reaction can also be carried out under solvent-free conditions. For example, it is possible to carry out the dehydration condensation reaction under solvent-free conditions, while distilling off the water generated as the reaction proceeds. Furthermore, in the above dehydration condensation reaction, a disproportionation reaction (general formula (17) below) of two molecules of dialkanolamine (a3d) into one molecule of monoalkanolamine (a3m) and one molecule of trialkanolamine (a3t) can proceed simultaneously as a side reaction.

[0068] This disproportionation reaction is thought to be promoted by the action of the fatty acid (a1) coexisting in the system as an acid catalyst. The produced monoalkanolamine (a3m) can further participate in a dehydration condensation reaction with other alkanolamine molecules. Therefore, even when the alkanolamine used as a raw material consists of one or more dialkanolamines (a3d), the alkanolamine oligomer structure of the produced amine compound (a2) can contain structural units derived from the monoalkanolamine (a3m). Furthermore, such a disproportionation reaction can proceed even after the alkanolamine oligomer structure is formed. For example, the reaction of an alkanolamine dimer (e.g., dialkanolamine dimer (a2-dd)) with an alkanolamine (dialkanolamine (a3d) or monoalkanolamine (a3m)) can produce a hydroxyalkyl (-R １This can produce an alkanolamine dimer (e.g., a2-dm or a2-md) in which one —OH group is lost, and an alkanolamine in which one hydroxyalkyl group is increased (trialkanolamine (a3t) or dialkanolamine (a3d)) (see general formula (18) below).

[0069]

[0070] After the condensation reaction between the fatty acid (a1) and the dialkanolamine (a3) ​​is completed, unreacted raw materials can be removed by known methods such as water washing, silica gel short-path column chromatography, and Celite filtration. A suitable solvent can be used during such operations. Examples of suitable solvents include organic solvents such as pentane, hexane, cyclohexane, heptane, benzene, toluene, xylene, diethyl ether, ethyl acetate, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, dichloromethane, chloroform, and carbon tetrachloride. The resulting product can also be purified by known purification methods such as column chromatography. The term "water washing" used here refers to washing with water or an aqueous solution. Examples of suitable aqueous solutions for washing include acidic water such as dilute hydrochloric acid, alkaline water such as dilute sodium hydroxide aqueous solution, and salt solutions such as saturated saline.

[0071] The method for obtaining component (i) by forming a salt with a first amide compound and a Brønsted acid is not particularly limited. In one embodiment, when the Brønsted acid is water-soluble (e.g., an inorganic acid such as hydrogen halide or boric acid, or a highly hydrophilic organic acid such as formic acid, acetic acid, or methanesulfonic acid), for example, an organic solvent solution of the first amide compound (or a composition containing the first amide compound) can be neutralized with an aqueous solution containing a Brønsted acid (e.g., dilute hydrochloric acid, dilute hydrobromic acid, dilute hydroiodic acid, an aqueous boric acid solution, an aqueous methanesulfonic acid solution, etc.), and the solvent can be distilled off (e.g., under reduced pressure) from the organic layer after neutralization to obtain component (i) (or a composition containing component (i)). Before distilling off the solvent from the organic phase, an operation of removing water from the organic layer after neutralization may be further performed. For example, the organic layer after neutralization may be dried using a desiccant (e.g., anhydrous sodium sulfate, molecular sieves, etc.), and then the solvent may be distilled off. The aqueous solution containing a Brønsted acid may further contain a water-soluble neutral salt (e.g., a neutral salt such as NaCl or sodium sulfate). For example, when the Brønsted acid is hydrogen chloride, a dilute hydrochloric acid-NaCl aqueous solution prepared using hydrochloric acid and saturated saline may be used as the aqueous solution containing a Brønsted acid. As the organic solvent for dissolving the first amide compound (or a composition containing the first amide compound), an organic solvent that is capable of dissolving the first amide compound and is immiscible with water (e.g., the organic solvents described above) can be used. In another embodiment, when the Brønsted acid is soluble in an organic solvent (e.g., a fatty acid having two or more carbon atoms, an aromatic carboxylic acid, etc.), the first amide compound and the Brønsted acid may be mixed in an organic solvent, dried using a desiccant (e.g., anhydrous sodium sulfate, molecular sieves, etc.), the desiccant is filtered off, 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 Brønsted acid is soluble in an organic solvent, for example, the first amide compound and the Brønsted acid may be mixed without a solvent to obtain component (i) (or a composition containing component (i)).In another embodiment, when the first amide compound is produced by reacting an acid halide of a monovalent fatty acid (a1) with an amine compound (a2), a salt of the first amide compound and hydrogen halide, which is a by-product of the reaction, is obtained. In this reaction, the resulting product may be used as component (i) (or a composition containing component (i)) as is. Alternatively, for example, the resulting product may be further washed with water (e.g., with a basic aqueous solution), and then a separate operation may be performed to cause the first amide compound to form a salt with a Brønsted acid. Alternatively, for example, the resulting product may be further washed with an aqueous solution containing hydrogen halide (e.g., a dilute hydrochloric acid-sodium chloride aqueous solution), and the washed material may be dissolved in an organic solvent and dried using a desiccant. The desiccant may then be filtered off, and the solvent may be distilled off (e.g., under reduced pressure) to obtain component (i) (or a composition containing component (i)) from which water has been removed. The first amide compound has n-1 amino groups capable of forming a salt with a Brønsted acid, where n corresponds to the degree of polymerization of the alkanolamine oligomer (amine compound (a2)) that forms an amide with the monovalent fatty acid (a1). In one embodiment, n is the average degree of polymerization (number average degree of polymerization) of the alkanolamine oligomer corresponding to the first amide compound. ａｖｒ In this case, the equivalent of the Bronsted acid to be reacted with the first amide compound is 1.0 to n ａｖｒ Equivalent, or 1.0 to n ａｖｒ For example, when the average degree of polymerization of the alkanolamine oligomer corresponding to the first amide compound is 3, the equivalent of the Bronsted acid relative to the first amide compound can be, for example, 1.0 to 3.0 equivalents, or 1.0 to 2.0 equivalents. In another embodiment, the equivalent of the Bronsted acid reacted with the first amide compound is max(1.0,n ａｖｒ -2.0) to n ａｖｒ Equivalent, or max(1.0,n ａｖｒ -2.0) to n ａｖｒ -1.0 equivalents, where x is a real number １ , x ２ , ..., the function max(x １ , x ２, ...) is a function of the given argument x １ , x ２ , ... is a function that returns the maximum value of

[0072] In this specification, the content of component (i) in a sample can be measured using a high performance liquid chromatography (HPLC) device. The HPLC measurement conditions 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 Detector: Combination of charged aerosol detector (CAD) and mass spectrometer (MS) Charged aerosol detector (CAD): Corona (registered trademark) Veo (registered trademark) RS manufactured by Thermo Fisher Scientific, drying tube temperature: 35 ° C. Mass spectrometer (MS): JEOL JMS-T100LP AccuTOF (registered trademark) LC-plus 4G (ionization method: ESI +) Mobile phase: Gradient elution with ultrapure water, methanol, and isopropyl alcohol was used. Ammonium formate was added to each solvent to a concentration of 10 mmol / L. The composition was continuously changed from a water / methanol volume ratio of 20 / 80 to 100% methanol, and then further changed to 100% isopropyl alcohol. Column temperature: 40°C. Sample solution: Methanol solution with a sample concentration of approximately 100 ppm by mass. Sample injection volume: 1.0 μL. Based on the detection results from the mass spectrometer (MS), each detected peak from the charged aerosol detector (CAD) can be assigned to a compound. Under the same analytical conditions, the CAD detected peak exhibits an area value corresponding to the amount of compound flowing into the detector, regardless of the compound's characteristics. Therefore, the content of each component (mass % of the compound in its unsalted state) can be quantitatively measured using the CAD peak area value. In addition, when one detection peak of CAD contains multiple compounds, the content of each component (mass % in terms of the compound in a state where no salt is formed) can be calculated by proportionally dividing the area value of the detection peak of CAD according to the ratio of the peak area values ​​of the multiple compounds by MS. In the above measurement method, the detection peak of component (i) in the CAD chromatogram may be divided by the content of other components (for example, by-products generated in the manufacturing process of component (i)).) is separated from the detection peak of (i). When the sample for which the content of component (i) is to be measured is not a complete solution (it contains insoluble matter or is a suspension), measurement can be performed after obtaining a solution by known pretreatment such as filtration. Before performing the measurement by the above-mentioned high-performance liquid chromatography (C18 column, detectors: CAD and MS), pretreatment may be performed, as necessary, to remove all or part of the components other than component (i) by known purification means such as silica gel column chromatography or preparative liquid chromatography (e.g., gel permeation chromatography (GPC)).

[0073] 2. Lubricating Oil Composition and Production Method Thereof The lubricating oil composition according to the second aspect of the present invention (hereinafter sometimes referred to as the "lubricating oil composition" or "composition") comprises a major amount of 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 aspect of the present invention described above. A production method for a lubricating oil composition according to the third aspect of the present invention (hereinafter sometimes referred to as the "production method for a lubricating oil composition" or "production method") comprises: a) (A) adding and mixing component (i) above to a lubricating base oil or a mixture containing the lubricating base oil and one or more additives other than component (i) (hereinafter sometimes referred to as "step (a)"). In the lubricating oil composition and production method of the present invention, the lubricating base oil is a lubricating base oil comprising one or more mineral base oils, one or more synthetic base oils, or a combination thereof.

[0074] The lubricant base oil may be one or more mineral base oils, one or more synthetic base oils, or a mixture thereof. In one embodiment, the lubricant base oil may be a Group I base oil (hereinafter sometimes referred to as "API Group I base oil"), a Group II base oil (hereinafter sometimes referred to as "API Group II base oil"), a Group III base oil (hereinafter sometimes referred to as "API Group III base oil"), a Group IV base oil (hereinafter sometimes referred to as "API Group IV base oil"), or a Group V base oil (hereinafter sometimes referred to as "API Group V base oil"), or a mixture thereof, according to the API base oil classification. API Group I base oil is a mineral base oil having a sulfur content of more than 0.03 mass % and / or a saturates content of less than 90 mass %, and a viscosity index of 80 or greater but less than 120. API Group II base oils are mineral base oils having a sulfur content of 0.03% by mass or less, a saturated content of 90% by mass or more, and a viscosity index of 80 to less than 120. API Group III base oils are mineral base oils having a sulfur content of 0.03% by mass or less, a saturated content of 90% by mass or more, and a viscosity index of 120 or more. API Group IV base oils are poly-α-olefin base oils. API Group V base oils are base oils other than those in Groups I to IV, and preferred examples thereof include ester-based base oils.

[0075] In one embodiment, component (A) can be preferably 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.

[0076] Examples of mineral base oils include paraffinic base oils obtained by refining a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of crude oil through one or a combination of two or more refining processes selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc., as well as normal paraffinic base oils, isoparaffinic base oils, and mixtures thereof. API Group II base oils and Group III base oils are usually produced through a hydrocracking process.

[0077] %C of mineral base oil Ｐ is preferably 60 or more, more preferably 65 or more, from the viewpoint of further improving the viscosity-temperature characteristics and fuel economy of the composition, and is preferably 99 or less, more preferably 95 or less, even more preferably 94 or less, from the viewpoint of improving the solubility of the additives, and in one embodiment, may be 60 to 99, or 60 to 95, or 65 to 95, or 65 to 94.

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

[0079] %C of mineral base oil Ｎ is preferably 1 or more, more preferably 4 or more, from the viewpoint of enhancing the solubility of the additive, and is preferably 40 or less, more preferably 35 or less, from the viewpoint of further enhancing the viscosity-temperature characteristics and fuel economy of the composition, and in one embodiment, may be 1 to 40, or 4 to 35.

[0080] In this specification, %C Ｐ , %C Ｎ and %C Ａ The above percentages of paraffin carbon number, naphthenic carbon number, and aromatic carbon number are determined by a method (ndM ring analysis) in accordance with ASTM D 3238-85, respectively. Ｐ , %C Ｎ and %C Ａ The preferred range of % C is based on the value determined by the above method. For example, even in the case of a lubricating base oil that does not contain naphthenes, the % C determined by the above method is Ｎ can have a value greater than 0.

[0081] From the viewpoint of improving the viscosity-temperature characteristics of the composition, the content of saturated components in the mineral base oil is preferably 90 mass % or more, more preferably 95 mass % or more, and even more preferably 99 mass % or more, based on the total amount of the base oil. In this specification, saturated components refer to values ​​measured in accordance with ASTM D 2007-93.

[0082] The aromatic content of the mineral base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, based on the total amount of the base oil, and in one embodiment, may be 0.1% by mass or more. By having the aromatic content be equal to or less than the above upper limit, it is possible to improve the low-temperature viscosity characteristics and viscosity-temperature characteristics in a fresh oil state, further improve fuel economy, and reduce evaporation loss of the lubricating oil, thereby reducing lubricating oil consumption. Furthermore, when an additive is blended into the lubricating base oil, the effect of the additive can be effectively exerted. Furthermore, although the lubricating base oil may not contain aromatics, by having the aromatic content be equal to or greater than the above lower limit, the solubility of the additive can be increased.

[0083] In this specification, the aromatic content refers to a value measured in accordance with ASTM D 2007-93. The aromatic content typically includes alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene, and alkylated products thereof, as well as compounds having four or more fused benzene rings, pyridines, quinolines, phenols, naphthols, and other aromatic compounds having heteroatoms.

[0084] Examples of API Group IV base oils include oligomers and co-oligomers of α-olefins having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and hydrogenated products thereof, such as ethylene-propylene copolymers, polybutene, 1-octene oligomers, 1-decene oligomers, and hydrogenated products thereof.

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

[0086] The kinematic viscosity of the lubricating base oil (total base oil) at 40°C is preferably 40 mm from the viewpoint of energy saving and enhancing the low temperature viscosity characteristics of the lubricating oil composition. ２ / s or less, or 30 mm ２ / s or less, or 20 mm ２ / s or less, and from the viewpoint of improving the wear resistance and seizure resistance, it is preferably 2.0 mm ２ / s or more, or 5.0 mm ２ / s or more, or 8.0 mm ２ / s or more, and in one embodiment, 2.0 to 40 mm ２ / s, or 5.0 to 30 mm ２ / s, or 8.0 to 20 mm ２ In this specification, the term "kinematic viscosity at 40°C" refers to the kinematic viscosity at 40°C measured in accordance with JIS K 2283-2000 using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument) as the measuring device.

[0087] The kinematic viscosity at 100°C of the lubricating base oil (all base oils) is preferably 10.0 mm from the viewpoint of further improving the energy saving properties and the low temperature viscosity characteristics of the lubricating oil composition. ２ / s or less, or 7.0 mm ２ / s or less, or 4.0 mm ２ / s or less, and from the viewpoint of improving the wear resistance and seizure resistance, it is preferably 0.8 mm ２ / s or more, or 1.2 mm ２ / s or more, or 1.4 mm ２ / s or more, or 1.6 mm ２ / s or more, and in one embodiment, 0.8 to 10.0 mm ２ / s, or 1.2 to 10.0 mm ２ / s, or 1.4 to 7.0 mm ２ / s, or 1.6 to 4.0 mm ２ In this specification, the term "kinematic viscosity at 100°C" refers to the kinematic viscosity at 100°C measured in accordance with JIS K 2283-2000 using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument) as the measuring device.

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

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

[0090] The sulfur content in the base oil depends on the sulfur content of the raw material. For example, when using a raw material that is substantially free of sulfur, such as a synthetic wax component obtained by the Fischer-Tropsch reaction, a base oil that is substantially free of sulfur can be obtained. Furthermore, when using a raw material that contains sulfur, such as slack wax obtained during the base oil refining process or microwax obtained during the refined wax process, the sulfur content in the resulting base oil is usually 100 ppm by mass or more. The sulfur content in the lubricating base oil (total base oil) is usually 0.03% by mass or less, and preferably 0.01% by mass or less from the viewpoint of oxidation stability. In this specification, the sulfur content in the base oil means the amount of sulfur measured in accordance with JIS K 2541-2003.

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

[0092] In one embodiment, the lubricant base oil may comprise 80 to 100 mass %, or 90 to 100 mass %, or 90 to 99 mass %, or 95 to 99 mass %, based on total 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 combinations 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 aspect of the present invention (hereinafter may be referred to as "Component (A)"). The lubricating oil additive composition according to the first aspect of the present invention acts as an oiliness-based friction modifier. From the viewpoint of further enhancing friction-reducing performance, particularly friction-reducing performance on metal surfaces that are prone to high loads such as gears, the content of Component (i) in the lubricating oil composition is preferably 0.005 mass % or more, or 0.010 mass % or more, or 0.030 mass % or more, or 0.050 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 mass % or less, preferably 5.0 mass % or less, or 4.0 mass % or less, or 3.0 mass % or less; and in one embodiment, it may be 0.005 to 10.0 mass %, or 0.010 to 5.0 mass %, or 0.030 to 4.0 mass %, or 0.050 to 3.0 mass %.

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

[0096] (B): Metal-Based Detergent In one preferred embodiment, the lubricating oil composition may further contain one or more metal-based detergents (hereinafter sometimes referred to as "component (B)"). Examples of component (B) include salicylate-based detergents, sulfonate-based detergents, and phenate-based detergents. Component (B) may contain only one type of metal-based detergent, or may contain two or more types of metal-based detergents. In the field of lubricating oils, the metal-based detergent generally used is an organic acid metal salt capable of forming micelles in a base oil (e.g., alkali or alkaline earth metal alkyl salicylates, alkali or alkaline earth metal alkyl benzene sulfonates, and alkali or alkaline earth metal alkyl phenates), or a mixture of such an organic acid metal salt with a basic metal salt (e.g., hydroxides, carbonates, borates, etc. of the alkali or alkaline earth metals that constitute the organic acid metal salt). Such organic acids usually have, in one molecule, at least one polar group (e.g., a carboxy group, a sulfo group, a phenolic hydroxy group, etc.) having Bronsted acidity capable of forming a salt with a metal base (typically a metal oxide and / or a metal hydroxide), and at least one lipophilic group such as a linear or branched alkyl group (e.g., a linear or branched alkyl group having 6 or more carbon atoms, etc.).

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

[0098]

[0099] In general formula (19), R １７each independently represents an alkyl or alkenyl group having 14 to 30 carbon atoms, M represents an alkali metal or alkaline earth metal, a represents 1 or 2, and p represents 1 or 2 corresponding to the 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. a is preferably 1. When a=2, R １７ may be a combination of different groups.

[0100] A preferred embodiment of the salicylate detergent is an alkaline earth metal salicylate, or a basic salt or overbased salt thereof, in which a=1 in the above general formula (19).

[0101] Preferred examples of sulfonate detergents include alkali or alkaline earth metal salts of alkylaromatic sulfonic acids, or their basic salts or overbased salts, obtained by sulfonating alkylaromatic compounds, more preferably alkaline earth metal salts or their basic salts or overbased salts. The weight-average molecular weight of the alkylaromatic compounds is preferably 400 to 1500, more preferably 700 to 1300. The alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. Examples of alkylaromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids. Examples of petroleum sulfonic acids include those obtained by sulfonating alkylaromatic compounds from the lubricating oil fraction of mineral oil, and so-called mahogany acid, which is a by-product produced during the production of white oil. Furthermore, examples of synthetic sulfonic acids include those obtained by sulfonating alkylbenzenes with linear or branched alkyl groups, which are obtained by recovering by-products from alkylbenzene production plants, which are used as detergent raw materials, or by alkylating benzene with polyolefins. Other examples of synthetic sulfonic acids include those obtained by sulfonating alkylnaphthalenes such as dinonylnaphthalene. The sulfonating agent used to sulfonate these alkyl aromatic compounds is not particularly limited, and examples thereof include fuming sulfuric acid and sulfuric anhydride.

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

[0103]

[0104] In general formula (20), R １８represents 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 sulfide (—S—) group or a methylene (—CH ２ -) group, and x represents an integer of 1 to 3. １８ may be a combination of two or more different groups, and x may be a combination of multiple different integers. When A is a methylene group, x is preferably 1. -A in each aromatic ring ｘ The substitution position of the - group is typically the o- or p-position relative to the hydroxy group, typically the o-position.

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

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

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

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

[0109] The base number of the metallic detergent can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the base number of the metallic detergent is preferably 200 mgKOH / g or more, more preferably 250 mgKOH / g or more, from the viewpoint of enhancing wear resistance, seizure resistance, and transmission torque capacity of a wet clutch, and from the same viewpoint, is preferably 600 mgKOH / g or less, more preferably 550 mgKOH / g or less, and in one embodiment, may be 200 to 600 mgKOH / g, or 250 to 550 mgKOH / g. Furthermore, for example, when the lubricating oil composition is used for lubrication of an internal combustion engine, the base number is preferably 0 mgKOH / g or more, more preferably 20 mgKOH / g or more, from the viewpoint of enhancing detergency performance and base number retention, and is preferably 500 mgKOH / g or less, more preferably 450 mgKOH / g or less, from the viewpoint of suppressing ash content in the composition and extending the life of an exhaust gas aftertreatment device, and in one embodiment may be 0 to 500 mgKOH / g, or 20 to 450 mgKOH / g. In this specification, the base number refers to the base number measured by the perchloric acid method in accordance with JIS K2501.

[0110] When the lubricating oil composition contains component (B), the content thereof can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (B) in the lubricating oil composition is preferably 200 ppm by mass or more, more preferably 250 ppm by mass or more, in terms of the metal amount based on the total amount of the lubricating oil composition, from the viewpoints of improving wear resistance, seizure resistance, fatigue resistance, and the transmission torque capacity of a wet clutch, and is preferably 600 ppm by mass or less, more preferably 550 ppm by mass or less, from the viewpoints of improving fuel economy and fatigue resistance, and in one embodiment, may be 200 to 600 ppm by mass, or 250 to 550 ppm by mass. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (C) is preferably 500 ppm by mass or more, more preferably 1000 ppm by mass or more, in terms of the metal amount based on the total amount of the lubricating oil composition, from the viewpoint of enhancing cleaning performance and base number retention, and is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, from the viewpoint of suppressing ash content in the composition and from the viewpoint of the life of an exhaust gas aftertreatment device, and in one embodiment may be 500 to 10,000 ppm by mass, or 1,000 to 5,000 ppm by mass.

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

[0112] The component (C) can be, for example, one or more compounds selected from the following (C-1) to (C-3): (C-1) a succinimide having at least one alkyl or alkenyl group in the molecule or a modified product (derivative) thereof (hereinafter sometimes referred to as "component (C-1)"), (C-2) a benzylamine having at least one alkyl or alkenyl group in the molecule (for example, a Mannich base obtained by reacting an alkyl- or alkenylphenol with formaldehyde and a polyamine) or a modified product (derivative) thereof (hereinafter sometimes referred to as "component (C-2)"), and (C-3) an 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] Component (C-1) is particularly preferably used as component (C). Among component (C-1), examples of succinimides having at least one alkyl or alkenyl group in the molecule include condensation reaction products of polyamines with alkyl or alkenyl succinic acids or anhydrides thereof having an alkyl or alkenyl group having 40 to 400 carbon atoms. Such condensation reaction products (condensation products) can be represented, for example, by the following general formula (21a) or (21b):

[0114]

[0115] In 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 one typical embodiment, the compound represented by general formula (21a) is obtained as a mixture of compounds having different b's. １９ The number of carbon atoms in the alkyl group is 40 or more, preferably 60 or more, from the viewpoint of solubility in the base oil, and is 400 or less, preferably 350 or less, more preferably 250 or less, from the viewpoint of low-temperature fluidity of the composition, and in one embodiment, may be 40 to 400, or 60 to 350, or 60 to 250.

[0116] In general formula (21b), R２０ and R ２１ R each independently represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, and may be a combination of different groups. Furthermore, c represents an integer of 0 to 15, preferably 1 to 13, more preferably 1 to 11. In one typical embodiment, the compound represented by general formula (21b) is obtained as a mixture of compounds having different c's. ２０ and R ２１ The number of carbon atoms in the alkyl group is 40 or more, preferably 60 or more, from the viewpoint of solubility in the base oil, and is 400 or less, preferably 350 or less, more preferably 250 or less, from the viewpoint of low-temperature fluidity of the composition, and in one embodiment, may be 40 to 400, or 60 to 350, or 60 to 250.

[0117] The alkyl or alkenyl group (R １９ ~R ２１ ) may be linear or branched. Preferred examples thereof include branched alkyl groups and branched alkenyl groups derived from olefin oligomers such as propylene, 1-butene, and isobutene, and from ethylene-propylene co-oligomers. Among these, branched alkyl or alkenyl groups derived from isobutene oligomers commonly called polyisobutylene, and polybutenyl groups are most preferred. The alkyl or alkenyl groups (R １９ ~R ２１ The number average molecular weight of the copolymer is preferably 800 to 3,500, more preferably 900 to 3,500.

[0118] Succinimides having at least one alkyl or alkenyl group in the molecule include so-called mono-type succinimides represented by general formula (21a), in which only one end of the polyamine chain is imidized, and so-called bis-type succinimides represented by general formula (21b), in which both ends of the polyamine chain are imidized. The lubricating oil composition may contain either a mono-type succinimide or a bis-type succinimide, or may contain both as a mixture. The content of the bis-type succinimide or modified product thereof in component (C-1) is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, based on the total amount of component (C-1) (100 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, and even more preferably 3,000 to 15,000, and in one embodiment, it can 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 with an oxygen-containing organic compound, (ii) boric acid modified products, (iii) phosphoric acid modified products, (iv) sulfur modified products, and (v) modified products obtained by combining two or more of these modifications. (i) The modified product with an oxygen-containing organic compound is a succinimide, benzylamine, or polyamine (hereinafter referred to as the "nitrogen-containing compound") having at least one alkyl or alkenyl group in the molecule, such as a fatty acid, a monocarboxylic acid having 1 to 30 carbon atoms, a polycarboxylic acid having 2 to 30 carbon atoms (e.g., oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.), an anhydride or ester compound thereof, an alkylene oxide having 2 to 6 carbon atoms, or a hydroxy (poly) oxyalkylene carbonate, in which some or all of the remaining amino groups and / or imino groups are neutralized or amidated modified compounds. (ii) The boric acid-modified compound is a modified compound obtained by reacting the above-mentioned nitrogen-containing compound with boric acid, thereby neutralizing or amidating some or all of the remaining amino and / or imino groups. (iii) The phosphoric acid-modified compound is a modified compound obtained by reacting the above-mentioned nitrogen-containing compound with phosphoric acid, thereby neutralizing or amidating some or all of the remaining amino and / or imino groups. (iv) The sulfur-modified compound is a modified compound obtained by reacting the above-mentioned nitrogen-containing compound with a sulfur compound. (v) The modified compound obtained by combining two or more types of modifications can be obtained by combining two or more types of modifications selected from modification with an oxygen-containing organic compound, boric acid modification, phosphoric acid modification, and sulfur modification to the above-mentioned nitrogen-containing compound. Among these modified compounds (derivatives) (i) to (v), boric acid-modified compounds of alkenyl succinimides, particularly boric acid-modified bis-type alkenyl succinimides, are preferably used.

[0121] When the lubricating oil composition contains component (C), its content can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (C) in the lubricating oil composition is preferably 0.1 mass% or more based on the total amount of the lubricating oil composition from the viewpoint of improving oxidation stability, and is preferably 10 mass% or less, more preferably 5 mass% or less from the viewpoint of maintaining energy saving properties. Furthermore, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (C) is preferably 0.5 mass% or more, more preferably 1.0 mass% or more based on the total amount of the lubricating oil composition from the viewpoint of improving coking resistance, and is preferably 10.0 mass% or less, more preferably 5.0 mass% or less from the viewpoint of maintaining fuel saving properties, and in one embodiment, it may be 0.5 to 10.0 mass%, or 1.0 to 5.0 mass%.

[0122] As the (C) component, a (C-1) component can be preferably used, and as the modified product of the (C) component, a boric acid modified product can be preferably used. In one embodiment, the (C) component may be one or more unmodified (C-1) components (unmodified succinimide dispersants), one or more boric acid modified products of the (C-1) component (boric acid modified succinimide dispersants), or 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 product, but from the viewpoint of sludge dispersibility, the ratio (B / N) of the content B as boron content of the (C) component to the content N as nitrogen content of the (C) component can be preferably 0 to 1.0 in one embodiment.

[0123] ((D) Phosphorus-Containing Antiwear Agent) In one 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 used in lubricating oils can be used without particular limitation. Examples of phosphorus-containing antiwear agents 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] (In general formula (22), X １ , X ２ , and X ３ each independently represents an oxygen atom or a sulfur atom; R ２２ represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom; R ２３ and R ２４ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom or a hydrogen atom; R ２２ , R ２３ , and R ２４ may be the same or different from each other. ２３ and / or R ２４ is a hydrogen atom, the compound of general formula (22) is intended to include any tautomer thereof.

[0125] (In general formula (23), X ４ , X ５ , X ６ , and X ７ each independently represents an oxygen atom or a sulfur atom; R ２５ represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom; R ２６ and R ２７ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a sulfur atom or a hydrogen atom; R ２５ , R ２６ , and R ２７ may be the same or different from each other.)

[0126] Examples of the hydrocarbon group having 1 to 30 carbon atoms in general formulas (22) and (23) include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group, etc. 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, is an alkyl group, aryl group, or alkylaryl group having 3 to 18 carbon atoms, more preferably 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 a hydrocarbon group containing no sulfur atom.

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

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

[0130] In general formula (24), R ２８ R is a linear hydrocarbon group having 2 to 17 carbon atoms, preferably an ethylene group or a propylene group, and in one embodiment is an ethylene group. ２９ is a straight chain hydrocarbon group having 2 to 17 carbon atoms, preferably a straight chain hydrocarbon group having 2 to 16 carbon atoms, and particularly preferably a straight chain hydrocarbon group having 6 to 10 carbon atoms.

[0131] Preferred examples of the group represented by formula (24) include a 3-thiapentyl group, a 3-thiahexyl group, a 3-thiaheptyl group, a 3-thiaoctyl group, a 3-thianonyl group, a 3-thiadecyl group, a 3-thiaundecyl group, and a 4-thiahexyl group.

[0132] Examples of metals that form metal salts with the phosphorus compounds represented by 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 these, alkaline earth metals such as calcium and magnesium, zinc, or a combination thereof is preferred.

[0133] Examples of the nitrogen-containing compound that forms an ammonium salt with the phosphorus compound represented by 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] (In general formula (25), R ３０ ~R ３２ each independently represents a hydrogen atom, a hydrocarbyl group having 1 to 8 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms and a hydroxyl group; R ３０ ~R ３２ At least one of the groups is a hydrocarbyl group having 1 to 8 carbon atoms or a hydrocarbyl group having 1 to 8 carbon atoms and a hydroxyl group.

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

[0136] One example of component (D) is zinc dialkyldithiophosphate (ZnDTP), which is a compound represented by the following general formula (26):

[0137] In general formula (26), R ３３ ~R ３６ Each independently represents a linear or branched alkyl group having 3 to 18 carbon atoms, and may be a combination of different groups. ３３ ~R ３６ The number of carbon atoms in R is preferably 3 to 12, more preferably 3 to 8. ３３ ~R ３６ may be any of a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group, but is preferably a primary alkyl group, a secondary alkyl group, or a combination thereof.

[0138] When the lubricating oil composition contains component (D), its content can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (D) in the lubricating oil composition is, from the viewpoint of improving wear resistance, seizure resistance, bearing fatigue life, and prevention of gear shift shock, preferably 50 ppm by mass or more, more preferably 100 ppm by mass or more, in terms of phosphorus content, based on the total amount of the lubricating oil composition, and from the same viewpoint, preferably 800 ppm by mass or less, more preferably 700 ppm by mass or less, and in one embodiment may be 50 to 800 ppm by mass, or 100 to 700 ppm by mass. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of 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 in exhaust gas aftertreatment devices, 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 one preferred embodiment, the lubricating oil composition may further contain one or more sulfur-containing extreme pressure agents other than component (D) (hereinafter sometimes referred to as "component (E)"). Examples of component (E) include known sulfur-containing extreme pressure agents such as thiadiazole compounds, dihydrocarbyl (poly)sulfides, sulfurized fats and oils, 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 a 1,3,4-thiadiazole compound represented by the following general formula (27), a 1,2,4-thiadiazole compound represented by the following general formula (28), and a 1,2,3-thiadiazole compound represented by the following general formula (29).

[0141]

[0142]

[0143] (In general formulas (27) to (29), R ３７ and R ３８ may be the same or different and each independently represent a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms; d and e may be the same or different and each independently represent an integer of 0 to 8.

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

[0145] (In general formula (30), R ３９ and R ４０ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms (which may be linear or branched, and may have a cyclic structure), an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and f represents an integer of 1 to 8.

[0146] When the lubricating oil composition contains component (E), its content can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (E) in the lubricating oil composition is preferably 200 ppm by mass or more, more preferably 300 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 properties and fatigue resistance, and is preferably 3000 ppm by mass or less, more preferably 2500 ppm by mass or less, from the viewpoint of improving wear resistance, fatigue resistance, and oxidation stability, and in one embodiment, it may be 200 to 3000 ppm by mass, or 300 to 2500 ppm by mass. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of 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 properties and fatigue resistance, and is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, from the viewpoint of reducing catalyst poisoning in exhaust gas aftertreatment devices, and in one embodiment may be 10 to 200 ppm by mass, or 30 to 100 ppm by mass.

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

[0148] Examples of the amine antioxidant include aromatic amine antioxidants and hindered amine antioxidants. Examples of the aromatic amine antioxidant include primary aromatic amine compounds such as alkylated α-naphthylamine; and secondary aromatic amine compounds such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, and phenyl-β-naphthylamine. As the aromatic amine antioxidant, alkylated diphenylamine, 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 the 2,2,6,6-tetraalkylpiperidine derivative, a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position is preferred. Furthermore, two 2,2,6,6-tetraalkylpiperidine skeletons may be bonded via a substituent at the respective 4-positions. Furthermore, the N-position of the 2,2,6,6-tetraalkylpiperidine skeleton may be unsubstituted, or may be substituted with an alkyl group having 1 to 4 carbon atoms at the N-position. The 2,2,6,6-tetraalkylpiperidine skeleton is preferably a 2,2,6,6-tetramethylpiperidine skeleton.

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

[0151] When two 2,2,6,6-tetraalkylpiperidine skeletons are bonded via a substituent at each 4-position, examples of the substituent include a hydrocarbylene bis(carbonyloxy) group (—OOC—R ４２ -COO-), hydrocarbylenediamino group (-HN-R ４２ -NH-), hydrocarbylene bis(carbonylamino) group (-HNCO-R ４２ -CONH-), etc. ４２ is preferably a hydrocarbylene group having 1 to 30 carbon atoms, more preferably an alkylene group.

[0152] The substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton is preferably an acyloxy group. An example of a compound having an acyloxy group at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton is an ester of 2,2,6,6-tetramethyl-4-piperidinol with a carboxylic acid. Examples of the carboxylic acid include linear or branched aliphatic carboxylic acids having 8 to 20 carbon atoms.

[0153] Examples of the phenolic antioxidant 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'-butyl 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4-methylphenol; 2,6- Examples of the phenol compound include hindered phenol compounds and bisphenol compounds such as di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-butyl-4-(N,N'-dimethylaminomethyl)phenol; 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters; and 3-methyl-5-tert-butyl-4-hydroxyphenol fatty acid esters.

[0154] When the lubricating oil composition contains component (F), the content thereof can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (F) in the lubricating oil composition is, from the viewpoint of improving thermal oxidation stability, preferably 0.1 mass % or more, more preferably 0.2 mass % or more, based on the total amount of the lubricating oil composition, and from the same viewpoint, preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and in one embodiment, may be 0.1 to 2.0 mass %, or 0.2 to 1.0 mass %. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (F) in the lubricating oil composition is, from the viewpoint of enhancing thermal oxidation stability, preferably 0.1 mass % or more, more preferably 0.5 mass % or more, based on the total amount of the lubricating oil composition, and from the same viewpoint, preferably 5.0 mass % or less, more preferably 3.0 mass % or less, and in one embodiment may be 0.1 to 5.0 mass %, or 0.5 to 3.0 mass %.

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

[0156] In one embodiment, the component (G) can be preferably a dispersion-type poly(meth)acrylate, a non-dispersion-type poly(meth)acrylate, or a combination thereof. In one embodiment, a dispersion-type poly(meth)acrylate can be preferably used. In this specification, the dispersion-type poly(meth)acrylate compound has a functional group containing a nitrogen atom, whereas the non-dispersion-type poly(meth)acrylate compound does not have a functional group containing a nitrogen atom.

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

[0158] (In general formula (31), R ４３ represents hydrogen or a methyl group, R ４４ represents a linear or branched hydrocarbon group having 1 to 36 carbon atoms, preferably an alkyl group.

[0159] The weight average molecular weight of component (G) can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the weight average molecular weight of component (G) is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, from the viewpoint of enhancing the viscosity index improving effect and improving low-temperature viscosity characteristics, and is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less, from the viewpoint of enhancing solubility in base oil, storage stability, and shear stability, and in one embodiment may be 10,000 to 200,000, or 20,000 to 150,000, or 30,000 to 100,000. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the weight average molecular weight of component (G) is preferably 100,000 or more, more preferably 200,000 or more, from the viewpoint of enhancing the viscosity index improving effect and improving low-temperature viscosity characteristics and fuel economy, and is preferably 1,000,000 or less, more preferably 700,000 or less, from the viewpoint of enhancing 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 as an amount that provides the desired kinematic viscosity and viscosity-temperature characteristics for the lubricating oil composition as a whole. For example, the viscosity index is an index for evaluating viscosity-temperature characteristics. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the content of component (G) in the lubricating oil composition may be, for example, 0.1 mass % or more, or 0.5 mass % or more, as resin content based on the total amount of the lubricating oil composition, from the viewpoint of improving the viscosity-temperature characteristics and enhancing energy saving, and may be, for example, 22 mass % or less, or 12 mass % or less, and in one embodiment, 0.1 to 22 mass %, or 0.5 to 12 mass %, from the viewpoint of enhancing shear stability. Furthermore, for example, when the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (G) in the lubricating oil composition may be, for example, 0.1 mass % or more, or 0.5 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 may be, for example, 20 mass % or less, or 15 mass % or less, and in one embodiment, 0.1 to 20 mass %, or 0.5 to 15 mass %, in terms of improving shear stability. In this specification, resin content means 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 (H) friction modifiers other than the above-mentioned components (A) and (E), (I) pour point depressants other than the above-mentioned component (G), (J) corrosion inhibitors other than the above-mentioned component (E), (K) metal deactivators other than the above-mentioned component (E), (L) rust inhibitors other than the above-mentioned component (A), (M) demulsifiers, (N) antifoaming agents, and (O) colorants.

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

[0163] (I) As a pour point depressant other than the above component (G) (hereinafter sometimes referred to as "component (I)"), known pour point depressants such as ethylene vinyl acetate 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 mass% based on the total amount of the lubricating oil composition.

[0164] (J) As a corrosion inhibitor other than the above component (E) (hereinafter sometimes referred to as "component (J)"), for example, known corrosion inhibitors such as benzotriazole-based compounds, tolyltriazole-based compounds, imidazole-based compounds, etc. When the lubricating oil composition contains component (K), its content may be, for example, 0.005 to 5.0 mass% based on the total amount of the lubricating oil composition.

[0165] (K) As a metal deactivator other than the above 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 mass% based on the total amount of the lubricating oil composition.

[0166] (L) Rust inhibitors other than component (A) (hereinafter sometimes referred to as "component (L)") may be known rust inhibitors such as petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl succinic acid esters, and polyhydric alcohol esters (excluding those corresponding to component (A)). When the lubricating oil composition contains component (L), its content may be, for example, 0.005 to 5.0 mass% based on the total amount of the lubricating oil composition.

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

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

[0169] As the colorant (O), known colorants such as azo compounds can be used.

[0170] (Properties of Lubricating Oil Composition) The kinematic viscosity at 100°C of the lubricating oil composition can be appropriately determined depending on the application of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate gear devices such as transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, etc.), the kinematic viscosity at 100°C of the lubricating oil composition is preferably 1.0 mmHg or less from the viewpoint of improving wear resistance. ２ / s or more, more preferably 2.5 mm ２ / s or more, and from the viewpoint of enhancing energy saving, it is preferably 10.0 mm ２ / s or less, more preferably 7.0 mm ２ / s or less, and in one embodiment, 1.0 to 10.0 mm ２ / s, or 1.0 to 7.0 mm ２ / s, or 2.5 to 10.0 mm ２ / s, or 2.5 to 7.0 mm２ For example, when the lubricating oil composition is used for lubricating an internal combustion engine, the kinematic viscosity at 100°C of the lubricating oil composition is preferably 2.0 mm / s from the viewpoint of enhancing wear resistance. ２ / s or more, more preferably 4.0 mm ２ / s or more, and from the viewpoint of enhancing energy saving, it is preferably 12.5 mm ２ / s or less, more preferably 9.3 mm ２ / s or less, and in one embodiment, 2.0 to 12.5 mm ２ / s, or 4.0 to 12.5 mm ２ / s, or 2.0 to 9.3 mm ２ / s, or 4.0 to 9.3 mm ２ / s.

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

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

[0173] (Applications) 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 has improved friction-reducing performance, particularly in the mixed lubrication region (e.g., gear lubrication conditions, etc.). The lubricating oil composition of the present invention contains component (A), thereby improving friction-reducing performance, particularly in the mixed lubrication region (e.g., gear lubrication conditions, etc.). The additive composition and lubricating oil composition of the present invention exhibit improved friction-reducing effect in the lubrication of metal surfaces that are prone to high loads, such as gears, and can therefore be suitably used for lubricating various mechanical devices that have metal surfaces that are prone to high loads, such as gear mechanisms, pistons, and connecting rod bearings. In particular, they can be preferably used for lubricating transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, reducers for electric vehicles, speed increasers for wind turbines, etc.) and internal combustion engines, as well as for lubricating various industrial applications (e.g., hydraulic oils, turbine oils, compressor oils).

[0174] The present invention will be described in more detail below with reference to examples and comparative examples. Note that the following examples are intended to illustrate the present invention, but are not intended to limit the present invention.

[0175] <Production Examples 1 to 9> Lubricating oil additive compositions were produced according to the following procedure: (Measurement Method) IR (infrared spectroscopy) spectra were measured using an FT / IR-4100 manufactured by JASCO Corporation, and for samples that were solid at room temperature, the sample was heated to melt and a small amount was applied to a KBr plate for measurement, while for samples that were liquid at room temperature, a small amount was applied directly to a KBr plate for measurement.

[0176] The content of component (i) in the composition was measured using high performance liquid chromatography (HPLC). The measurement conditions for HPLC analysis were 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 Detector: Combination of charged aerosol detector (CAD) and mass spectrometer (MS) Charged aerosol detector (CAD): Corona (registered trademark) Veo (registered trademark) RS manufactured by Thermo Fisher Scientific, drying tube temperature: 35 ° C. Mass spectrometer (MS): JEOL JMS-T100LP AccuTOF (registered trademark) LC-plus 4G (ionization method: ESI +) Mobile phase: Gradient elution with ultrapure water, methanol, and isopropyl alcohol was used. Ammonium formate was added to each solvent to a concentration of 10 mmol / L. The composition was continuously changed from a water / methanol volume ratio of 20 / 80 to 100% methanol, and then further changed to 100% isopropyl alcohol. Column temperature: 40°C. Sample solution: Methanol solution with a sample concentration of approximately 100 ppm by mass. Sample injection volume: 1.0 μL. Each detected peak by charged aerosol detector (CAD) was assigned to a compound based on the detection results from a mass spectrometer (MS). The CAD peak area values ​​were used to quantify the content of each component (mass % equivalent to the compound in a state where no salts were formed). When multiple compounds were contained in a single CAD detection peak, the area value of the CAD detection peak was proportionally divided according to the ratio of the peak area values ​​measured by MS for the multiple compounds, thereby calculating the content of each component (mass % equivalent to the compound in a state where no salts were formed).

[0177] (Production Example 1) 5.0 mol of lauric acid and 7.5 mol of diethanolamine (hereinafter sometimes referred to as "DEA") were placed in a 5 L three-neck flask equipped with a distillation tube, along with a magnetic stirrer. The atmosphere inside the flask was replaced with nitrogen, and the contents in the flask were stirred with a magnetic stirrer to form a homogeneous mixture. While stirring the mixture in the flask with the magnetic stirrer, the flask was heated in an oil bath. The heating temperature of the oil bath was gradually increased so that water continued to distill off. The reaction was monitored by IR spectroscopy, and completion of the reaction was confirmed 24 hours after the start of the reaction by IR spectroscopy. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the flask were allowed to cool and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain lauric acid amide of DEA trimer (first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA trimer lauric acid amide and 2.0 equivalents of lauric acid were mixed without a solvent and stirred at room temperature for 1 hour to produce a laurate salt of DEA trimer lauric acid amide.

[0178] (Preparation Example 2) 5.0 mol of oleic acid and 7.5 mol of DEA were placed in a 5 L three-neck flask equipped with a distillation tube, along with a magnetic stirrer. The atmosphere inside the flask was replaced with nitrogen, and the contents of the flask were stirred with a magnetic stirrer to obtain a homogeneous mixture. While stirring the mixture with the magnetic stirrer, the flask was heated in an oil bath. The temperature of the oil bath was gradually increased so that water continued to distill off. The reaction was monitored by IR spectroscopy, and completion of the reaction was confirmed 24 hours after the start of the reaction by IR spectroscopy. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the flask were allowed to cool and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain oleic acid amide of DEA trimer (first amide compound) as an oily substance. 1.0 equivalent of the obtained DEA trimer oleic acid amide and 2.0 equivalents of oleic acid were mixed without a solvent and stirred at room temperature for 1 hour to produce an oleate salt of DEA trimer oleic acid amide.

[0179] (Production Example 3 ＊ ) 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanoic acid (in general formula (4), k = 0, R ６ = 3,5,5-trimethylhexyl group, R ７ = 1,3,3-trimethylbutyl group, R ８ = hydrogen atom. Hereinafter, this may be referred to as "multiple-branched isostearic acid." 5.0 mol of PEG-100 (H) and 7.5 mol of DEA were placed in a flask along with a magnetic stirrer, the atmosphere inside the flask was replaced with nitrogen, and the contents in the flask were stirred with a magnetic stirrer to form 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 gradually increased so that water continued to distill off. The reaction was monitored by IR spectroscopy, and the completion of the reaction was confirmed 24 hours after the start of the reaction by IR spectroscopy. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the flask were allowed to cool and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain a multi-branched isostearic acid amide of DEA trimer (first amide compound) as an oily substance.

[0180] (Production Example 4) 1.0 equivalent of the DEA trimer multi-branched isostearic acid amide obtained in Production Example 3 and 2.0 equivalents of multi-branched isostearic acid were mixed without a solvent and stirred at room temperature for 1 hour to produce a multi-branched isostearic acid salt of DEA trimer multi-branched isostearic acid amide.

[0181] (Production Example 5) The DEA trimer hyperbranched isostearic acid amide (first amide compound) obtained in Production Example 3 was dissolved in toluene, and the toluene solution was washed with dilute hydrochloric acid prepared with saturated saline (dilute hydrochloric acid-NaCl aqueous solution; 0.5 mol / L as HCl). The organic layer after washing was dried over anhydrous sodium sulfate, and the solvent was then distilled off under reduced pressure to produce hydrochloride of DEA trimer hyperbranched isostearic acid amide.

[0182] (Production Example 6) The DEA trimer hyperbranched isostearic acid amide (first amide compound) obtained in Production Example 3 was dissolved in toluene, and the toluene solution was neutralized with an aqueous boric acid solution (boric acid-NaCl aqueous solution; 0.8 mol / L as boric acid) prepared with saturated saline. The neutralized organic layer was dried over anhydrous sodium sulfate, and the solvent was then distilled off under reduced pressure to produce a borate salt of DEA trimer hyperbranched isostearic acid amide.

[0183] (Production Example 7) 1.0 equivalent of the DEA trimer multi-branched isostearic acid amide (first amide compound) obtained in Production Example 3 and 2.0 equivalents of toluenesulfonic acid were mixed without a solvent and stirred at room temperature for 1 hour to produce a toluenesulfonate salt of DEA trimer multi-branched isostearic acid amide.

[0184] (Production Example 8 ＊ The DEA trimer multi-branched isostearic acid amide (first amide compound) obtained in Production 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 with saturated saline. The neutralized organic layer was dried over anhydrous sodium sulfate, and the solvent was then distilled off under reduced pressure to produce a sodium salt of DEA trimer multi-branched isostearic acid amide.

[0185] (Production Example 9) 2-decyltetradecanoic acid (in general formula (4), k = 0, R ６ = dodecyl group, R ７ = decyl group, R ８= hydrogen atom. 5.0 mol of branched-chain fatty acid (C = 0.05) and 7.5 mol of DEA were placed in the flask along with a magnetic stirrer, the atmosphere inside the flask was replaced with nitrogen, and the contents in the flask were stirred with a magnetic stirrer to form a homogeneous 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 gradually increased so that water continued to distill off. The reaction was monitored by IR spectroscopy, and the completion of the reaction was confirmed 24 hours after the start of the reaction by IR spectroscopy. The heating temperature of the oil bath at the end of the reaction was 180°C. The contents of the flask were allowed to cool and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by preparative HPLC to obtain 2-decyltetradecanoic acid amide (first amide compound), a DEA trimer, as an oily substance. 1.0 equivalent of the obtained DEA trimer 2-decyltetradecanoic acid amide and 2.0 equivalents of 2-decyltetradecanoic acid were mixed without a solvent and stirred at room temperature for 1 hour to produce 2-decyltetradecanoic acid salt of DEA trimer 2-decyltetradecanoic acid amide.

[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 %" means mass % based on the total amount of the lubricating oil composition (100 mass %). Furthermore, "ppm by mass" means ppm by mass based on the total amount of the lubricating oil composition, and the notation "ppm by mass / X" for element X means ppm by mass as the amount of element X based on the total amount of the lubricating oil composition. Details of each component are as follows:

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

[0188] ((A) Friction modifier) ​​1 to 2 and 3 in the table ＊ , 4-7, 8 ＊, 9 are the lubricating oil additive compositions produced in Production Examples 1 to 9, and the numbers correspond to the numbers of the Production Examples. That is, 1: laurate of DEA trimer lauric acid amide 2: oleate of DEA trimer oleic acid amide 3 ＊ : DEA trimer multi-branched isostearic acid amide (first amide compound) 4: DEA trimer multi-branched isostearic acid salt 5: DEA trimer multi-branched isostearic acid amide hydrochloride 6: DEA trimer multi-branched isostearic acid amide borate 7: DEA trimer multi-branched isostearic acid amide toluenesulfonate 8 ＊ 1: Sodium salt of DEA trimer multi-branched isostearic acid amide 9: 2-decyltetradecanoic acid salt of DEA trimer 2-decyltetradecanoic acid amide. 1 to 2, 4 to 7, and 9 are lubricating oil additive compositions of the present invention, and 3 is a 2-decyltetradecanoic acid salt of DEA trimer multi-branched isostearic acid amide. ＊ and 8 ＊ are lubricating oil additive compositions outside the scope of the present invention.

[0189] (B) Metallic detergent: calcium carbonate overbased calcium sulfonate detergent, base number 300 mg KOH / g, Ca: 12.9 mass% (C) Dispersant: boron-containing polybutenyl succinimide dispersant, N: 1.6 mass%, B: 0.35 mass%

[0190] ((D) Antiwear Agent) D-1: Tridecyl tetrathiophosphate D-2: Bis(3-thiaundecyl)hydrogen phosphite

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

[0192]

[0193]

[0194]

[0195]

[0196]

[0197] (MTM Test) A ball-on-disk friction test was performed on each of the lubricating oil compositions using an MTM traction measuring instrument (manufactured by PCS Instruments) to measure the coefficient of friction (μ) under conditions simulating gear lubrication (mixed lubrication region). The measurement conditions were as follows: Ball and disk: Standard test piece (AISI 52100 standard) Oil temperature: 90°C Load: 60 N Peripheral speed: 0.8 m / s Slide ratio: 10% The results are shown in Tables 1 to 5. The reduction rates (%) of the friction coefficient relative to Comparative Example 1 are shown for Examples 1 to 15 and Comparative Examples 2 and 3, and the reduction rates (%) of the friction coefficient relative to Comparative Example 4 are shown for Examples 16 to 22 and Comparative Examples 5 and 6.

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

[0199] The lubricating oil composition of Comparative Example 2 is a lubricating oil composition in which a first amide compound in a non-salt state is blended as an oiliness-based friction modifier. The lubricating oil composition of Comparative Example 3 is a lubricating oil composition in which a salt of a first amide compound and a Brønsted base, rather than a Brønsted acid, is blended as an oiliness-based friction modifier. The lubricating oil compositions of Comparative Examples 2 and 3 showed poor results in terms of the effect of reducing the friction coefficient under conditions simulating gear lubrication.

[0200] The lubricating oil compositions of Examples 16 to 22 (Tables 4 and 5) were modified 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) were modified 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), which contained the lubricating oil additive composition of the present invention as an oiliness-based friction modifier, were able to sufficiently reduce the friction coefficient under conditions simulating gear lubrication, compared to the lubricating oil composition of Comparative Example 4 (Table 5), which did not contain an oiliness-based friction modifier.

[0201] The lubricating oil composition of Comparative Example 4 is a lubricating oil composition in which a first amide compound in a non-salt state is blended as an oiliness-based friction modifier. The lubricating oil composition of Comparative Example 5 is a lubricating oil composition in which a salt of a first amide compound and a Brønsted base, rather than a Brønsted acid, is blended as an oiliness-based friction modifier. The lubricating oil compositions of Comparative Examples 4 and 5 showed poor results in terms of the effect of reducing the friction coefficient under conditions simulating gear lubrication.

[0202] The above test results demonstrate that lubricating oil compositions containing the lubricating oil additive composition of the present invention can enhance friction-reducing performance, particularly in the mixed lubrication region (e.g., gear lubrication).

[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 has improved friction-reducing performance, particularly in the mixed lubrication region (e.g., gear lubrication conditions, etc.). The lubricating oil composition of the present invention has improved friction-reducing performance, particularly in the mixed lubrication region (e.g., gear lubrication conditions, etc.). The additive composition and lubricating oil composition of the present invention exhibit improved friction-reducing effect in the lubrication of metal surfaces that are prone to high loads, such as gears, and can therefore be suitably used for lubricating various mechanical devices that have metal surfaces that are prone to high loads, such as gear mechanisms, pistons, and connecting rod bearings. In particular, they can be suitably used for lubricating transmissions (e.g., manual transmissions, automatic transmissions, continuously variable transmissions, reducers for electric vehicles, speed increasers for wind turbines, etc.) and internal combustion engines, as well as for lubricating various industrial applications (e.g., hydraulic oils, turbine oils, compressor oils).

Claims

1. (i) A salt of a first amide compound and a Brønsted acid, wherein the first amide compound is a monoamide of one or more linear or branched saturated or unsaturated monounsaturated fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2), which does not have an ester bond, and the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1), wherein the Brønsted salt of one or more first amide compounds A lubricating oil additive composition characterized by containing [the specified ingredient]. 【Chemistry 1】 (In general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R １ They may be identical or mutually different.

2. The lubricating oil additive composition according to claim 1, wherein the Brønsted 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 and substituted or unsubstituted phenols, or a combination thereof.

3. The lubricating oil additive composition according to claim 2, wherein the carboxylic acid is a monounsaturated fatty acid having 1 to 5 carbon atoms, a monounsaturated fatty acid having 6 to 30 carbon atoms which may be the monounsaturated fatty acid (a1), 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, a phthalic acid, an isophthalic acid, a terephthalic acid, a trimellitic acid, a mellitic acid, or an aromatic hydroxy acid having 7 to 14 carbon atoms.

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

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

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

7. 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, (A) The lubricating oil additive composition according to any one of claims 1 to 3 A lubricating oil composition containing the following:

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

9. The lubricating oil composition according to claim 7, further comprising one or more additives selected from a metal-based detergent, an ashless dispersant, a phosphorus-containing anti-wear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver.

10. The kinematic viscosity at 40°C is 2.0 to 50 mm². ２ The lubricating oil composition according to claim 7, wherein the ratio is / s.

11. A lubricating oil composition according to claim 7, used for lubricating gears.

12. A method for producing a lubricating oil composition, a) A step of adding and mixing a Brønsted salt (i) of one or more first amide compounds to a lubricating oil base oil or a mixture containing the lubricating oil base oil and one or more additives other than component (i), wherein the first amide compound is a monoamide of one or more monounsaturated or monounsaturated linear or branched fatty acids (a1) having 6 to 30 carbon atoms and one or more amine compounds (a2), without ester bonds, and the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more having a structure obtained by dehydration condensation of one or more alkanolamines (a3) ​​represented by the following general formula (1), to a lubricating oil base oil or a mixture containing the lubricating oil base oil and one or more additives other than component (i). Includes, A method for producing a lubricating oil composition, wherein the lubricating oil base oil comprises one or more mineral oil-based base oils, one or more synthetic base oils, or a combination thereof. 【Chemistry 2】 (In general formula (1), n ​​is 1 or 2; R １ represents a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms with 2 carbon atoms in the main chain; when n is 2, multiple R １ They may be identical or mutually different.

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

14. The method for producing the product according to claim 12 or 13, wherein the Brønsted 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 and substituted or unsubstituted phenols, or a combination thereof.

15. The method for producing a food product according to claim 14, wherein the carboxylic acid is a monounsaturated fatty acid having 1 to 5 carbon atoms, a monounsaturated fatty acid having 6 to 30 carbon atoms which may be the monounsaturated fatty acid (a1), 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, a phthalic acid, an isophthalic acid, a terephthalic acid, a trimellitic acid, a mellitic acid, or an aromatic hydroxy acid having 7 to 14 carbon atoms.

16. The manufacturing method according to claim 12 or 13, wherein the monounsaturated fatty acid comprises one or more straight-chain fatty acids.

17. The manufacturing method according to claim 12 or 13, wherein the monounsaturated fatty acid comprises one or more branched-chain fatty acids.

18. The manufacturing method according to claim 17, wherein the branched-chain fatty acid has a tertiary or quaternary carbon atom at the α, β, or γ position of the carbonyl carbon.

19. b) The lubricating oil composition contains one or more additives selected from metal-based detergents, ashless dispersants, phosphorus-containing anti-wear agents, sulfur-containing extreme pressure agents, antioxidants, and viscosity index improvers. A manufacturing method according to claim 12 or 13, including the method described in claim 12 or 13.

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