Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/16—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/02—Well-defined hydrocarbons
  • C10M105/06—Well-defined hydrocarbons aromatic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
  • C10M2215/0806—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
  • C10M2215/082—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/047—Thioderivatives not containing metallic elements
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/02—Unspecified siloxanes; Silicones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/14—Electric or magnetic purposes
  • C10N2040/16—Dielectric; Insulating oil or insulators
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/29—Hybrid or electric engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/29—Hybrid or electric engines
  • C10N2040/292—Electric engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

• 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 gear lubrication.
• Lubricating oil is used in internal combustion engines, automatic transmissions, bearings, etc. to make their operations smooth. Generally, various additives are added to lubricating oil in order to provide the lubricating oil with the required performance.
• FM friction modifiers
• Generally used FMs can be classified into organic molybdenum-based FMs containing molybdenum and oil-based FMs (also referred to as ashless FMs) that reduce friction by improving oiliness.
• MoDTC molybdenum dithiocarbamate
• MoDTP molybdenum dithiophosphate
• Patent Document 1 As organic molybdenum-based FMs, MoDTC (molybdenum dithiocarbamate) and MoDTP (molybdenum dithiophosphate) are widely known (see, for example, Patent Document 1). Although these organic molybdenum-based FMs have an excellent friction reduction effect at the initial stage of use, there is a limit to how well the friction reduction effect can be maintained over a long period of time. Furthermore, since organic molybdenum-based FM contains ash, it becomes difficult to recycle used lubricating oil. Therefore, it is required to reduce the amount of organic molybdenum-based FM added.
• oily agent-based FM has a possibility of overcoming the above-mentioned problems of organic molybdenum-based FM, so the importance of oily agent-based FM is increasing (see, for example, Patent Documents 2 to 4).
• An object of the present invention is to provide a lubricating oil additive composition useful as an oil-based friction modifier, which has enhanced friction reduction performance and fatigue resistance improvement performance while maintaining solubility in base oil. . Also provided is a lubricating oil composition containing the lubricating oil additive composition.
• the present invention includes the embodiments [1] to [11] below.
• the amine compound (a2) is an alkanolamine oligomer having a degree of polymerization of 2 or more and having a structure in which one or more alkanolamines (a3) represented by the following general formula (1) are dehydrated and condensed without having an ester bond.
• One or more alkanolamines (a3) represented by the following general formula (1) have a structure in which the amino group and one or more hydroxy groups are acylated with the monovalent fatty acid (a1).
• a lubricating oil additive composition characterized in that the content is 8.0% by mass or more based on the total content in terms of conversion.
• n is 1 or 2; R 1 is a straight chain alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, and the number of carbon atoms in the main chain is represents a branched alkylene group in which is 2; when n is 2, multiple R 1s may be the same or different.
• a lubricating base oil comprising one or more mineral base oils or one or more synthetic base oils or a combination thereof;
• a lubricating oil composition comprising the lubricating oil additive composition according to any one of [1] to [6].
• component (A) does not form salts of all acylation products with the monovalent fatty acid (a1) of the compound containing an alkanolamine structure in which the hydroxyl group may be etherified.
• [9] Further contains one or more additives selected from a metal detergent, an ashless dispersant, a phosphorus-containing anti-wear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver, [7] or The lubricating oil composition according to [8].
• a metal detergent an ashless dispersant, a phosphorus-containing anti-wear agent, a sulfur-containing extreme pressure agent, an antioxidant, and a viscosity index improver, [7] or The lubricating oil composition according to [8].
• the lubricating oil additive composition according to the first aspect of the present invention has improved friction reduction performance and fatigue resistance improvement performance while maintaining solubility in base oil, and is useful as an oil-based friction modifier. It is.
• the lubricating oil composition according to the second aspect of the present invention contains the lubricating oil additive composition according to the first aspect of the present invention, thereby maintaining storage stability and exhibiting improved friction reduction performance and Can exhibit fatigue resistance.
• alkaline earth metal includes magnesium.
• the content of each element of calcium, magnesium, zinc, phosphorus, sulfur, boron, barium, and molybdenum in oil is determined by inductively coupled plasma emission spectroscopy in accordance with JIS K0116. It shall be measured by an analytical method (intensity ratio method (internal standard method)). Further, the content of nitrogen element in the oil shall be measured by chemiluminescence method in accordance with JIS K2609. Moreover, in this specification, "weight average molecular weight” means a weight average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The GPC measurement conditions are as follows.
• the lubricating oil additive composition according to the first aspect of the present invention (hereinafter sometimes simply referred to as "additive composition”) comprises (i) a linear or branched saturated or A monoamide of one or more unsaturated monovalent fatty acids (a1) and one or more amine compounds (a2), which does not have an ester bond, and the amine compound (a2) has the following general formula (1).
• the amino group and one or more hydroxy group are One or more second amide compounds (hereinafter sometimes referred to as "component (ii)") having a structure acylated with a monovalent fatty acid (a1), the component (ii)
• the content of is the total of all acylated products with the monovalent fatty acid (a1) of the compound containing an alkanolamine structure in which the hydroxyl group may be etherified, in terms of the compound in a non-salt state. Based on the content, it is 20% by mass or more.
• n is 1 or 2; R 1 is a straight chain alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, and the number of carbon atoms in the main chain is represents a branched alkylene group in which is 2; when n is 2, multiple R 1s may be the same or different.
• 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 be a straight chain fatty acid or a branched chain fatty acid.
• fatty acid (a1) may be a branched chain fatty acid.
• straight chain saturated fatty acids are 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.
• branched chain saturated fatty acids examples include branched chain isomers thereof.
• straight chain unsaturated fatty acids are 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, nonadecenic acid.
• branched chain unsaturated fatty acids include branched chain isomers of these fatty acids. can. Note that the arrangement of the C ⁇ C double bond in the unsaturated fatty acid is not particularly limited.
• the number of C ⁇ C double bonds in the unsaturated fatty acid may be one (i.e., monoenoic acid), two (i.e., dienoic acid), or three (i.e., trienoic acid). Often, there may be 4 or more (ie, tetraenoic acid).
• unsaturated fatty acids having 18 carbon atoms include oleic acid (cis-9-octadecenoic acid), paxenoic acid (11-octadecenoic acid), and linoleic acid (cis, cis-9,12-octadecadienoic acid).
• linolenic acid (9,12,15-octadecanetrienoic acid, 6,9,12-octadecanetrienoic acid), eleostearic acid (9,11,13-octadecanetrienoic acid), etc.
• eleostearic acid (9,11,13-octadecanetrienoic acid
• various analogous compounds that differ in number, arrangement, and/or geometric isomerism may be mentioned.
• unsaturated fatty acids having other carbon numbers there may be mentioned various related compounds having different numbers of C ⁇ C double bonds, arrangement, and/or geometric isomerism.
• 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 increasing the friction reduction effect in lubrication of gears, etc., and from the same viewpoint, 30 or less, preferably 24 or less. , or 22 or less, or 20 or less, or 18 or less, and in one embodiment, 6 to 30, or 8 to 24, or 8 to 22, or 10 to 22, or 12 to 20, or 12 to 18. obtain.
• fatty acid (a1) can be one or more straight chain fatty acids.
• 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, and elaidin.
• 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, nisic acid, nervonic acid, Examples include cerotic acid, montanic acid, melisic acid, and mixtures thereof. As a mixture containing two or more types of fatty acids, fatty acids derived from natural fats and oils or hydrogenated natural fats and oils may be used.
• fatty acids derived from natural 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, and rice bran oil fatty acids.
• examples include 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 oils and fats are usually a mixture containing two or more types of fatty acids having 6 to 24 carbon atoms.
• fatty acid (a1) can be one or more branched chain fatty acids.
• the branched chain fatty acid preferably has a tertiary or quaternary carbon atom (i.e., branching) at the alpha, beta, or gamma position of the carbonyl carbon; It is preferable to have a tertiary or quaternary carbon atom at the carbonyl carbon position, and it is particularly preferable to have a tertiary or quaternary carbon atom at the ⁇ position of the carbonyl carbon.
• a preferable example of such a branched chain fatty acid is a branched chain fatty acid represented by the following general formula (2).
• k is an integer of 0 to 2, preferably 0 or 1, more preferably 0; R 2 and R 3 are each independently a linear or branched alkyl group; R 4 is a hydrogen atom or a linear or branched alkyl group, preferably a hydrogen atom; (number of carbon atoms in R 2 ) ⁇ (number of carbon atoms in R 3 ) ⁇ (number of carbon atoms in R 4 ); (number of carbon atoms in R 3 ) + (number of carbon atoms in R 4 ) + k+2 is equal to the total number of carbon atoms in the branched chain fatty acid.)
• k is 0, R 2 is a straight chain or branched alkyl group having 3 to 19 carbon atoms, and R 3 is a straight chain or branched alkyl group having 1 to 10 carbon atoms.
• the group R 4 can be a hydrogen atom.
• Preferred examples of the branched chain fatty acid represented by the general formula (4) include 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-decyltetradecanoic acid, 5,7,7-trimethyl-2-(1,3 , 3-trimethylbutyl)octanoic acid, and the like.
• Such branched chain fatty acids can be prepared, if necessary, by the reaction of carbon dioxide with organometallic compounds such as Grignard reagents or alkyl lithiums prepared from secondary or tertiary alkyl halides, or by the reaction of hydroformylation catalysts.
• aldehyde and/or alcohol can be produced by synthesizing an aldehyde and/or alcohol through a reaction of an alkene, carbon monoxide, and hydrogen in the presence of the compound, and subjecting the obtained aldehyde and/or alcohol to a further oxidation reaction.
• Secondary or tertiary alkyl halides can be prepared if necessary, for example, by addition reaction of the corresponding alkenes with hydrogen halides (eg hydrogen chloride, hydrogen bromide, or hydrogen iodide).
• Secondary or tertiary alkyl halides derived from alkenes are usually obtained as isomer mixtures of secondary or tertiary alkyl halides with different positions to which the halogen atoms are attached;
• a branched chain fatty acid derived from a mixture of tertiary alkyl halide isomers is usually obtained as an isomer mixture of branched chain fatty acids having different combinations of carbon numbers in R 2 to R 4 in the general formula (2).
• Other preferred examples of branched chain fatty acids include branched chain fatty acids having a methyl branch at the end.
• a preferable example of such a branched chain fatty acid is a branched chain fatty acid represented by the following general formula (3).
• j+4 is equal to the total number of carbon atoms in the branched chain fatty acid.
• Preferred examples of such branched chain fatty acids include 16-methylheptadecanoic acid.
• the amine compound (a2) is an alkanolamine oligomer with a degree of polymerization of 2 or more and has a structure in which one or more alkanolamines (a3) represented by the following general formula (1) are dehydrated and condensed.
• n is 1 or 2; R 1 is a straight chain alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, and the number of carbon atoms in the main chain is represents a branched alkylene group in which is 2; when n is 2, multiple R 1s may be the same or different from each other.
• R 1 is a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms, in which the main chain has 2 carbon atoms. be.
• the number of carbon atoms in R 1 which is a linear alkylene group is preferably 2 to 4, or 2 to 3, and may be 2 in one embodiment.
• each side chain of R 1 which is a branched alkylene group is a methyl group or an ethyl group, and R 1 may have 3 to 6 carbon atoms, or 3 to 5 carbon atoms, or 3 to 4 carbon atoms.
• 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 bonded to R 1 and the oxygen atom, and the number of carbon atoms in the main chain used in the naming of R 1 is selected. It is determined regardless of.
• each side chain of R 1 is preferably a methyl group or an ethyl group, and in one embodiment may be a methyl group.
• an alkanolamine having a linear alkylene group R 1 having 2 carbon atoms can be produced by reacting an unsubstituted oxirane with ammonia.
• an alkanolamine having a linear alkylene group R 1 having 3 carbon atoms can be produced by reacting unsubstituted oxetane with ammonia.
• an alkanolamine having a linear alkylene group R 1 having 4 carbon atoms can be produced by reacting unsubstituted tetrahydrofuran with ammonia.
• an alkanolamine having a branched alkylene group R1 having 2 carbon atoms in the main chain can be produced by reacting a substituted oxirane with ammonia, and each substituent of the substituted oxirane has a branched alkylene group.
• Each side chain of R1 .
• alkylene group R 1 include straight chain alkylene groups such as ethane-1,2-diyl group and propane-1,3-diyl group; propane-1,2-diyl group; butane-1,2-diyl group; group, butane-2,3-diyl group, C4 branched alkylene group such as 1-methylpropane-1,2-diyl group; pentane-1,2-diyl group, pentane-2,3-diyl group , 2-methylbutane-1,2-diyl group, 3-methylbutane-2,3-diyl group and other branched alkylene groups having 5 carbon atoms; hexane-1,2-diyl group, hexane-2,3-diyl group , hexane-3,4-diyl group, 2-methylpentane-2,3-diyl group, 3-methylpentane-2,3-diyl group,
• R 1 may be a single alkylene group or a combination of two or more alkylene groups.
• alkylene group R 1 is ethane-1,2-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, butane-1,2-diyl group, It can be a -1,4-diyl group or a butane-2,3-diyl group, or a combination thereof.
• R 1 is an asymmetric branched alkylene group, i.e. an alkylene group with different side chains attached to the two free valences (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.
• the reaction between propylene oxide and ammonia gives a propanolamine structure in which the 1-position of the propylene-1,2-diyl group is bonded to the nitrogen atom (i.e., the 2-hydroxypropyl group is bonded to the nitrogen atom).
• the reaction route provides a propanolamine structure in which the 2-position of the propylene-1,2-diyl group is bonded to the nitrogen atom (that is, the 1-hydroxypropan-2-yl group is bonded to the nitrogen atom).
• Competition can give a mixture of both products.
• two R 1 's may be the same or different from each other.
• the orientations of the two R 1s may be the same or different.
• the two HO-R 1 - groups may both be 2-hydroxypropyl groups, and both 1-hydroxypropane It may be a -2-yl group, or one may be a 2-hydroxypropyl group and the other may be a 1-hydroxypropan-2-yl group.
• dipropanolamine by reacting propylene oxide with ammonia, these compounds can 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 one or more alkanolamines. Although a combination of a monoalkanolamine and one or more dialkanolamines may be used, one or more dialkanolamines are particularly preferred.
• the amine compound (a2) forming a monoamide with the monohydric fatty acid (a1) in component (i) has a structure in which one or more alkanolamines (a3) represented by the general formula (1) are dehydrated and condensed. It is an alkanolamine oligomer, and its degree of polymerization is 2 or more.
• the following general formula (4) represents a reaction in which an alkanolamine dimer (a2-dd) with a degree of polymerization of 2 is produced by a dehydration condensation reaction of two molecules of dialkanolamine (a3d).
• the following general formula (5) represents a reaction in which an alkanolamine dimer (a2-mm) with a degree of polymerization of 2 is produced by a dehydration condensation reaction of two molecules of monoalkanolamine (a3m).
• the following general formula (6) is produced by a dehydration condensation reaction between one molecule of dialkanolamine (a3d) and one molecule of monoalkanolamine (a3m) to form an alkanolamine dimer (a2-2dm or a2-2md) with a degree of polymerization of 2.
• the product may contain structural isomers. Which structural isomer is produced depends on which molecule's hydroxyl group is eliminated.
• 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 dehydration condensation of three dialkanolamine molecules.
• general formula (4) is referred to regarding the production of dimer (a2-dd).
• the dialkanolamine trimer has structural isomers (a2-ddd1 and a2-ddd2) corresponding to the hydroxyl group released from the dialkanolamine dimer (2a-dd). ) may be included.
• alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers.
• the following general formula (8) 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.
• general formula (5) is referred to regarding the formation of dimer (a2-mm).
• the monoalkanolamine trimer has structural isomers (a2-mmm1 and a2-mmm2) corresponding to the hydroxyl group that leaves the monoalkanolamine dimer (2a-mm). ) may be included.
• alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers.
• general formulas (9a) to (9c) general formulas (4) and (6) are referred to regarding the formation of dimers (a2-dd, a2-dm, a2-md).
• the mixed alkanolamine trimer has structural isomers (a2-ddm1, a2-ddm2, a2-dmd, and a2- mdd).
• mixed alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers.
• the following general formulas (10a) to (10c) can be formed into mixed alkanolamine trimers (a2-mmd, a2-dmm1, or a2-dmm2) is generated.
• general formulas (10a) to (10c) general formulas (5) and (6) are referred to regarding the formation of dimers (a2-mm, a2-dm, a2-md).
• the mixed alkanolamine trimer contains structural isomers (a2-mmd, a2-dmm1, and a2-dmm2) corresponding to the hydroxy group to be eliminated. obtain.
• mixed alkanolamine oligomers with a degree of polymerization of 4 or higher may also contain multiple structural isomers.
• an alkanolamine oligomer having a structure in which one or more alkanolamines (a3) represented by the general formula (1) is dehydrated and condensed has the following general formula (11) when the degree of polymerization is 2 or 3. ) can be expressed as
• R 5 to R 9 each independently represent a hydrogen atom or a -R 1 -OH group; R 1 is as defined above; multiple R 1s may be the same or different from each other.
• m may be 0 or 1; when m is 0, at least one of R 5 to R 8 is a hydrogen atom, and at least one of R 5 to R 8 is -R 1 - is an OH group; when m is 1, at least one of R 5 to R 9 is a hydrogen atom, and at least one of R 5 to R 9 is a -R 1 -OH group.
• an alkanolamine oligomer having a structure in which one or more alkanolamines (a3) represented by the general formula (1) is dehydrated and condensed has a linear polyalkyleneamine skeleton when the degree of polymerization is 4 or more.
• isomers with a branched polyalkyleneamine skeleton and isomers with a branched polyalkyleneamine skeleton There are isomers with a branched polyalkyleneamine skeleton and isomers with a branched polyalkyleneamine skeleton.
• the isomer having a linear polyalkylene amine skeleton is bonded to the N atom of the unsubstituted linear polyalkylene amine represented by the following general formula (12a). It is a compound in which some of the hydrogen atoms are replaced with -R 1 -OH groups; its isomer having a branched polyalkylene amine skeleton is an unsubstituted branched polyalkylene represented by the following general formula (12b).
• R 1 is as defined above, and multiple R 1s may be the same or different from each other. good.
• the unsubstituted polyalkylene amine having m+2 (m ⁇ 1) N atoms is “linear” means that the unsubstituted polyalkylene amine has two primary amino groups and m This means that the alkylene group has a secondary amino group, and is determined regardless of whether the alkylene group is linear or branched.
• an unsubstituted polyalkylene amine is "branched" it means that the unsubstituted polyalkylene amine has at least one tertiary amino group, and the alkylene group is linear or branched. It is determined regardless of whether it is a chain or not.
• the unsubstituted branched polyalkyleneamine having m+2 (m ⁇ 2) N atoms has k (1 ⁇ k ⁇ m/2) tertiary amino groups
• the unsubstituted branched polyalkyleneamine has , has 2+k primary amino groups and m-2k secondary amino groups.
• the degree of polymerization m+2 of the alkanolamine oligomer is 4 or more
• the isomer having a linear polyalkylene amine skeleton is the N atom of the unsubstituted linear polyalkylene amine represented by the following general formula (13).
• R is as defined above, and a plurality of R 1 's may be the same or different from each other.
• m is m ⁇ 2, corresponding to the degree of polymerization m+2 of the alkanolamine oligomer.
• the degree of polymerization of the amine compound (a2) is 2 or more, preferably 2 to 15, or 2 to 10, and may be 2 to 4 or 2 to 3 in one embodiment.
• the alkanolamine oligomer (a2) may have a single degree of polymerization, or may be a combination of oligomers having a plurality of different degrees of polymerization. In one embodiment, the alkanolamine oligomer (a2) may be a combination of a plurality of consecutive oligomers having different degrees of polymerization.
• a certain oligomer is "a combination of a plurality of continuous oligomers having different degrees of polymerization", when the minimum and maximum values of the degrees of polymerization of the oligomer are d min and d MAX , respectively. This means that the oligomers contain oligomers with all degrees of polymerization from d min to d MAX .
• the first amide compound is a monoamide of the above one or more monovalent fatty acids (a1) and the above 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. Because the first amide compound has one or more amine nitrogen atoms that are not acylated, it can form a salt with an acid.
• the salt of the first amide compound may be a salt of the first amide compound and an organic acid (organic acid salt), or a salt of the first amide compound and an inorganic acid (inorganic acid salt). It may also be 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 types of organic acid salts.
• the inorganic acid salt may be one type of inorganic acid salt or a combination of two or more types of inorganic acid salts. Further, as described later, the organic acid constituting the organic acid salt may be the monovalent fatty acid (a1) described above.
• perchloric acid hypobromous acid, bromite, bromate, perbromate, hypoiodic acid, oxyhalogen acids such as iodic acid, iodic acid, periodic acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid , phosphoric acid (means a phosphorus oxoacid in which the formal oxidation number of the phosphorus atom is +V, and may be orthophosphoric acid or condensed phosphoric acid such as pyrophosphoric acid or polyphosphoric acid), phosphorous acid Acid, boric acid (means an oxoacid of boron whose formal oxidation number of the boron atom is +III, and may be orthoboric acid, or condensed boric acid such as tetraboric acid or metaboric acid), Examples include inorganic oxoacids such as carbonic acid; and inorganic Bronsted acids such as hydrocyanic acid.
• organic acids constituting the first amide compound and the organic acid salt include carboxylic acids, organic sulfonic acids, organic phosphonic acids and their monoesters, organic boronic acids and their monoesters, sulfuric acid monoesters, and phosphoric acid monoesters. , phosphoric acid diester, phosphorous acid monoester, phosphorous acid diester, boric acid monoester, boric acid diester, substituted or unsubstituted phenol, and other organic Bronsted acids.
• Examples of the carboxylic acid that forms a salt with the first amide compound include aliphatic carboxylic acids and aromatic carboxylic acids.
• Examples of aliphatic carboxylic acids include monovalent fatty acids with 1 to 5 carbon atoms, monovalent fatty acids with 6 to 30 carbon atoms, divalent aliphatic carboxylic acids with 2 to 10 carbon atoms and their monoesters, and aliphatic hydroxy acids. , etc.
• Examples of monovalent fatty acids having 1 to 5 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, and valeric acid, and preferably has 2 to 5 carbon atoms.
• Examples of monovalent fatty acids having 6 to 30 carbon atoms include the various monovalent fatty acids described above in relation to 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, sebacic acid, etc. can be mentioned.
• Examples of the monoester include the divalent aliphatic dicarboxylic acid and methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, etc. Mention may be made, for example, of monoesters with alcohols having from 1 to 12 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 8 carbon atoms.
• aliphatic hydroxy acids are 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, ricinelizin.
• examples include aliphatic hydroxy acids having 2 to 18 carbon atoms such as 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, 4,4,4-trifluorobutyric acid, etc.
• aromatic carboxylic acids include aromatic monocarboxylic acids, aromatic dicarboxylic acids and monoesters thereof, aromatic hydroxy acids, aromatic polycarboxylic acids, and the like.
• aromatic monocarboxylic acids include compounds having, for example, 7 to 10 carbon atoms, such as benzoic acid, o- or m- or p-toluic acid, phenylacetic acid, cinnamic acid, and the like.
• aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and the like.
• Examples of the monoester include monoesters of the aromatic dicarboxylic acid and the various alcohols described above in connection with monoesters of divalent aliphatic dicarboxylic acids.
• aromatic hydroxy acids include salicylic acid, (m- or p-)hydroxybenzoic acid, (o-, m-, or p-)hydroxymethylbenzoic acid, vanillic acid, syringic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-) dihydroxybenzoic acid, orceric acid, gallic acid, mandelic acid, hydroxydiphenylacetic acid (benzilic acid), atrolactic acid , fluoretic acid, (o-, m-, or p-)hydroxycinnamic acid, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5 -) Compounds having 7 to 14 carbon atoms, such as dihydroxycinnamic acid, ferulic acid, and sin
• organic sulfonic acids examples include compounds represented by the following general formula (14).
• R 10 represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms.
• R10 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• a straight or branched alkyl or alkenyl group having 1 to 18 carbon atoms such as a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an oleyl group; a phenyl group, a tolyl group, a xylyl group, Aromatic hydrocarbon groups having 6 to 10 carbon atoms such as mesityl group, cumyl group, naphthyl group; trifluoromethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, chlorophenyl group, dichlorophenyl group, Examples include halogenated hydrocarbon groups such as chlorophenyl group, camphor-10-yl group, and the like.
• 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. .
• organic phosphonic acids examples include compounds represented by the following general formula (15).
• R 11 represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms.
• R 11 include linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the like, as explained above in relation to R 10 .
• Examples of monoesters of organic phosphonic acids include monoesters of the organic phosphonic acid and various alcohols described above in connection with monoesters of divalent aliphatic dicarboxylic acids.
• organic boronic acids examples include compounds represented by the following general formula (16).
• R 12 represents an organic group having 1 or more carbon atoms, for example, 1 to 18 carbon atoms.
• R 12 include the straight or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the like, which were explained above in relation to R 10 . Can be done.
• R12 examples include cycloalkyl groups having 5 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; arylalkyl groups such as phenylethyl group; fluorophenyl group, difluorophenyl group, trifluorophenyl group, Halogenated aromatic hydrocarbon groups (for example, having 6 to 7 carbon atoms) such as chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorotolyl group, chlorotolyl group; hydroxyphenyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, methoxytolyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group, nitrophenyl group, cyan
• Examples of monoesters of organic boronic acids include monoesters of the organic phosphonic acid and various alcohols described above in connection with monoesters of divalent aliphatic dicarboxylic acids.
• sulfuric acid monoesters, phosphoric acid monoesters, phosphorous acid monoesters, and boric acid monoesters include monoesters of sulfuric acid, orthophosphoric acid, phosphorous acid, or orthoboric acid, and divalent aliphatic dicarboxylic acids, respectively.
• Monoesters with the various alcohols described above can be mentioned in connection with this.
• Examples of phosphoric acid diesters and boric acid diesters include monoesters of orthophosphoric acid or orthoboric acid, respectively, and the various alcohols described above in connection with monoesters of divalent aliphatic dicarboxylic acids.
• substituted phenols include substituted phenols that have a smaller pKa than unsubstituted phenols.
• Such substituted phenols typically have one or more substituents on the aromatic ring that act as electron-withdrawing groups.
• electron-withdrawing groups include acyl groups such as acetyl groups, formyl groups, carboxy groups, alkoxycarbonyl groups, nitro groups, cyano groups, halogeno groups (e.g. fluoro groups, chloro groups, bromo groups, and iodo groups). ), etc.
• Examples of alcohols corresponding to the alkoxy group of the alkoxycarbonyl group include the various alcohols described above in connection with monoesters of divalent aliphatic dicarboxylic acids.
• Examples of such substituted phenols include acetylphenol, formylphenol, carboxyphenol, methoxycarbonylphenol, ethoxycarbonylphenol, nitrophenol, cyanophenol, fluorophenol, chlorophenol, bromophenol, iodophenol, etc. .
• the substituted phenol may preferably have 6 to 13 carbon atoms, or 6 to 11 carbon atoms, or 6 to 9 carbon atoms.
• Component (ii) has a structure in which the amino group and one or more hydroxyl groups of one or more alkanolamines (a3) represented by general formula (1) are acylated with the above monovalent fatty acid (a1).
• one or more second amide compounds having Component (ii) has a structure represented by the following general formula (17a), (17b), or (17c).
• General formulas (17a) and (17b) show structures corresponding to dialkanolamines
• general formula (17c) shows a structure corresponding to monoalkanolamines.
• component (ii) is such that the amino group and one or more hydroxy groups of one or more dialkanolamines represented by general formula (1) are the monohydric fatty acid (a1). It has an acylated structure, and the structure is represented by general formula (17a) or (17b).
• R 1 is as defined above; in general formulas (17a) and (17b), two R 1s in the same molecule may be the same or different from each other. Often represents two alkylene groups of the corresponding dialkanolamine; in the general formula (17c), R 1 represents the alkylene group of the corresponding monoalkanolamine; R 13 represents the carboxy group from the monohydric fatty acid (a1) above; is an aliphatic hydrocarbon group obtained by removing; when the monovalent fatty acid (a1) is one type of fatty acid, multiple R 13s in the same molecule are the same aliphatic hydrocarbon group; When the monovalent fatty acid (a1) is a combination of two or more different fatty acids, multiple R 13s in the same molecule are the same aliphatic acid corresponding to the combination of the two or more different fatty acids. (It is a hydrocarbon group or a combination of two or more different aliphatic hydrocarbon groups.)
• the content of component (ii) in the lubricating oil additive composition is determined from the viewpoint of improving storage stability, and from the viewpoint of improving friction reduction performance, especially in the mixed lubrication region such as gear lubrication conditions, and , from the viewpoint of improving fatigue resistance, all acylation products with the monohydric fatty acid (a1) of the compound containing an alkanolamine structure in which the hydroxyl group may be etherified, in terms of the compound in a non-salt state. It is 8.0% by mass or more based on the total content in .
• the content of component (ii) in the lubricating oil additive composition is determined from the viewpoint of improving storage stability, and from the viewpoint of improving friction reduction performance, especially in the mixed lubrication region such as gear lubrication conditions, and , from the viewpoint of improving fatigue resistance, all acylation products with the monohydric fatty acid (a1) of the compound containing an alkanolamine structure in which the hydroxyl group may be etherified, in terms of the compound in
• a compound containing an alkanolamine structure of "all acylation products with the above monovalent fatty acid (a1) of a compound containing an alkanolamine structure in which the hydroxyl group may be etherified” refers to any alkanolamine structure, that is, HO-R 14 -NR 15 R 16 structure (R 14 represents an arbitrary alkylene group; R 15 and R 16 each independently represent a hydrogen atom or an arbitrary organic group, and R 15 and R 16 The concept encompasses any compound containing the compound (which may be bonded to each other to form a cyclic structure).
• the fact that "the hydroxy group may be etherified" in the "alkanolamine structure” means that the hydroxy (-OH) group in the alkanolamine structure (HO-R 14 -NR 15 R 16 structure) is converted into an ether bond. This means that it may have been done.
• An example of "an alkanolamine structure in which a hydroxy group is etherified” includes a structure in which the hydroxy group of an alkanolamine is converted into an ether bond by intermolecular or intramolecular dehydration condensation. For alkanolamines to form ether bonds through intramolecular dehydration condensation, it is necessary that two or more hydroxy groups exist in a single molecule, and dialkanolamines, for example, satisfy this requirement.
• acylated products of the above monovalent fatty acid (a1) is a concept that includes any acylated products of the above monovalent fatty acid (a1), for example, it may be an amide of the fatty acid (a1), It may be an ester of fatty acid (a1), or it may be a compound that is acylated by fatty acid (a1) at multiple sites in one molecule.
• total content in terms of compounds that do not form salts refers to the content for compounds that do not form salts, and the content for compounds that partially or completely form salts.
• Content as a compound in a state that does not form a salt (for example, for compounds in which all or part of the non-acylated amino group is neutralized with an acid, the content in the state that is not neutralized with an acid) It can be calculated by summing up the converted content).
• the content of component (i) in the lubricating oil additive composition is determined from the viewpoint of further improving friction reduction performance, particularly in the mixed lubrication region such as gear lubrication conditions, and from the viewpoint of further improving fatigue resistance.
• the first amide compound has at least one amino group capable of forming a salt.
• the content of component (i) "in terms of a compound in a state in which no salt is formed” means the content as it is when the first amide compound does not form any salt. However, when all or part of the first amide compound forms a salt with an acid, it means the content in terms of mass without being neutralized with an acid.
• the total content of components (i) and (ii) in the lubricating oil additive composition is determined from the viewpoint of further enhancing storage stability and friction reduction performance, especially friction in the mixed lubrication area such as gear lubrication conditions.
• salts of all acylation products with the above monohydric fatty acid (a1) of a compound containing an alkanolamine structure in which the hydroxyl group may be etherified.
• the content is preferably 56% by mass or more, or 58% by mass or more in terms of the compound without forming a salt, based on the total content in terms of the compound without forming a salt. From this point of view, it is preferably 99% by weight or less, or 98% by weight or less, and in one embodiment may be 56 to 99% by weight, or 58 to 98% by weight, or 60 to 96% by weight.
• the lubricating oil additive composition includes, in addition to components (i) and (ii), (iii) one or more alkanolamines (a3) represented by the above general formula (1); It may further contain a third amide compound (hereinafter sometimes referred to as "component (iii)”) that is an amide with the monovalent fatty acid (a1) and does not have an ester bond.
• component (iii) has a structure represented by the following general formula (18a) or (18b).
• General formula (18a) shows a structure corresponding to dialkanolamine
• general formula (18b) shows a structure corresponding to monoalkanolamine.
• component (iii) is such that the amino group and one or more hydroxy group of one or more dialkanolamines represented by general formula (1) are the monohydric fatty acid (a1). It has an acylated structure, and the structure is represented by general formula (18a).
• R 1 is as defined above, and R 13 is as defined in general formulas (17a) to (17c).
• the lubricating oil additive composition comprises, in addition to components (i) and (ii), or in addition to components (i), (ii), and (iii), (iv) an amine compound as described above.
• a fourth amide compound and/or a salt thereof may further be referred to as "component (iv)").
• the fourth amide compound differs from the first amide compound in that it has not only an amide bond but also an ester bond.
• the fourth amide compound may have one or more amino groups capable of forming salts. Examples of acids that form salts with the fourth amide compound include the various acids described above in connection with component (B1).
• the total content of components (iii) and (iv) in the lubricating oil additive composition is the monovalent fatty acid of the compound containing an alkanolamine structure in which the hydroxy group may be etherified.
• the monovalent fatty acid of the compound containing an alkanolamine structure in which the hydroxy group may be etherified for example, 60% by mass or less, or 42% by mass in terms of compounds in a non-salt state, based on the total content of all acylated products according to (a1) in terms of compounds in a non-salt state. % or less.
• it is preferably 0.10% by mass or more, or 1.0% by mass or more based on the above criteria and the above conversion, and in one embodiment, 0.10 to 60% by mass, or 1. .0 to 42% by weight.
• the total content of components (ii) and (iii) in the lubricating oil additive composition is determined from the viewpoint of ease of manufacture and from the viewpoint of further improving storage stability.
• % or more, or more than 85% by weight, or 86% by weight or more and in one embodiment can be 99% by weight or less, or 96% by weight or less, and in one embodiment 20-99% by weight, or 50% by weight or less.
• the amine compound (a2) ie, the alkanolamine oligomer
• the amine compound (a2) 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 (for example, a combination of consecutive oligomers having a plurality of different degrees of polymerization). There may be.
• component (i) can be produced by a dehydration condensation reaction between fatty acid (a1) and amine compound (a2).
• Such a dehydration condensation reaction can be carried out, for example, by combining a fatty acid (a1) and an amine compound (a2) in an organic solvent that forms an azeotrope with water (such as toluene, xylene, cumene, cymene, etc.) using an acid catalyst (e.g., sulfuric acid, trifluoroacetic acid, etc.) or a basic catalyst (e.g., sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, triethylamine, pyridine, etc.) or without a catalyst while heating under reflux.
• an acid catalyst e.g., sulfuric acid, trifluoroacetic acid, etc.
• a basic catalyst e.g., sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, triethylamine, pyridine, etc.
• This can be carried out by azeotropically removing water produced as the
• component (ii) can be produced by a dehydration condensation reaction of fatty acid (a1) and alkanolamine (a3).
• a dehydration condensation reaction for example, a fatty acid (a1) and an alkanolamine (a3) are heated under reflux in the presence of an organic solvent that forms an azeotrope with water, and are produced as the condensation reaction progresses. This can be done by removing water azeotropically.
• component (i) can be produced by reacting fatty acid (a1), amine compound (a2), and condensing agent in a solvent.
• component (ii) can be produced by reacting fatty acid (a1), alkanolamine (a3), and condensing agent in a solvent.
• condensing agents include carbodiimide condensing agents such as N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC).
• Imidazole condensing agents such as N,N'-carbonyldiimidazole (CDI) and 1,1'-carbonyldi(1,2,4-triazole) (CDT); 4-(4,6-dimethoxy-1, Triazine condensing agents such as 3,5-triazin-2-yl)-4-methylmorpholinium chloride hydrate (DMT-MM); 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro- 2-halopyridinium salts such as 1-methylpyridinium p-toluenesulfonate; 2,4,6-trichlorobenzoyl chloride (TCBC); 2-methyl-6-nitrobenzoic anhydride (MNBA); diethyl azodicarboxylate (DEAD) ) and triphenylphosphine; phosphines such as chlorodiphenylphosphine and 2,2'-dipyridyl disulf
• component (i) can be produced by reacting an acylating agent derived from fatty acid (a1) with an amine compound (a2) in a solvent.
• component (ii) can be prepared by reacting an acylating agent derived from fatty acid (a1) with alkanolamine (a3) in a solvent.
• acylating agents derived from fatty acids (a1) include acid halides of fatty acids (a1) (e.g. acid chlorides, acid bromides, etc.), active esters of fatty acids (a1) (e.g. fatty acids (a1) and N -Ester with hydroxysuccinimide (NHS), ester with fatty acid (a1) and 1-hydroxybenzotriazole (HOBt), ester with fatty acid (a1) and 1-hydroxy-7-azabenzotriazole (HOAt), etc. ), acid anhydrides of fatty acids (a1), and the like.
• Acylating agents derived from fatty acids (a1) may be used with catalysts such as 4-dimethylaminopyridine (DMAP).
• DMAP 4-dimethylaminopyridine
• organic solvents that do not interfere with the condensation reaction for example, aliphatic hydrocarbon solvents such as hexane and petroleum ether, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, dichloromethane, 1,2-dichloroethane, chlorobenzene, - halogenated hydrocarbon solvents such as dichlorobenzene, pyridine, etc.
• aliphatic hydrocarbon solvents such as hexane and petroleum ether
• aromatic hydrocarbon solvents such as benzene, toluene, and xylene
• dichloromethane 1,2-dichloroethane
• chlorobenzene chlorobenzene
• - halogenated hydrocarbon solvents such as dichlorobenzene, pyridine, etc.
• an appropriate base e.g., amines such as triethylamine, pyridine, 2,6-lutidine, organolithium reagents such as butyl lithium, carbonic acid, etc.
• An inorganic base such as potassium, etc.
• component (i) is an amide of component (iii) (one or more alkanolamines (a3) represented by the above general formula (1) and the above monovalent fatty acid (a1)). It can be produced by a dehydration condensation reaction between a third amide compound (which does not have an ester bond) and an alkanolamine (a3) and/or an amine compound (a2). Such a dehydration condensation reaction can be carried out, for example, by combining component (iii) with alkanolamine (a3) or amine compound (a2) or a mixture thereof in an organic solvent that forms an azeotrope with water in the presence of an acid catalyst.
• a mixture containing component (i) and component (ii) can be produced by a dehydration condensation reaction of fatty acid (a1) and alkanolamine (a3).
• a dehydration condensation reaction is carried out by heating the fatty acid (a1) and the alkanolamine (a3) under reflux in the presence of an organic solvent that forms an azeotrope with water, while the condensation reaction proceeds. This can be done by removing the water produced along with this by azeotropy.
• such dehydration condensation reaction involves combining the fatty acid (a1) and the alkanolamine (a3) under solvent-free conditions.
• dehydration condensation reaction can also be performed under solvent-free conditions.
• component (iii) and/or component (iv) may be produced as by-products.
• the reaction molar ratio ((a3)/(a1)) between fatty acid (a1) and alkanolamine (a3) is, for example, 0.01 to 100, preferably 0.02 to 50, or 0.5 to 5, or 1.5 to 2.0.
• a reaction in which two molecules of dialkanolamine (a3d) are disproportioned into one molecule of monoalkanolamine (a3m) and one molecule of trialkanolamine (a3t) (the following general formula (19)) may proceed simultaneously as a side reaction.
• This disproportionation reaction is thought to be promoted by the fatty acid (a1) coexisting in the system acting as an acid catalyst.
• the produced monoalkanolamine (a3m) can further participate in a dehydration condensation reaction with other alkanolamine molecules. Therefore, even if the alkanolamine used as a raw material consists of one or more dialkanolamines (a3d), the alkanolamine oligomer structure of the produced amine compound (a2) is a structure derived from monoalkanolamine (a3m). May contain units. Moreover, such a disproportionation reaction can proceed even after the alkanolamine oligomer structure is formed.
• hydroxyalkyl (-R 1 Alkanolamine dimers with one less -OH) group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• alkanolamines with one more hydroxyalkyl group e.g. a2-dm or a2-md
• the cyclization reaction of the alkanolamine oligomer structure may further proceed as a side reaction.
• an azaoxacycloalkane skeleton such as a morpholine skeleton can be formed by an intramolecular dehydration cyclization reaction.
• an alkanolamine dimer (a2-dd) in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a secondary amino group see general formula (4)
• the cyclization product (cao-a2-dd) can be obtained by an intramolecular dehydration reaction, and the cyclization product (cao-a2-dd) is a dehydration condensation product (acyl-cao-a2- dd) may further be given.
• dialkanolamine dimer (a2-dd) and fatty acid (a1) proceeds to give an amide compound (acyl-a2-dd)
• cyclization is produced by intramolecular dehydration reaction. (acyl-cao-a2-dd) (the following general formula (21)).
• an alkanolamine dimer (a2-md) in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a primary amino group is also cyclized by an intramolecular dehydration reaction.
• a product can be obtained (general formula (22) below).
• Such an intramolecular dehydration cyclization reaction that forms an azaoxacycloalkane skeleton tends to proceed when the main chain of the alkylene group R1 has 2 carbon atoms, and in such a case, a morpholine skeleton is formed.
• the two free valences of the alkylene group R 1 are a nitrogen atom to which a hydroxyalkyl (-R 1 -OH) group is bonded, and a primary or secondary amino
• an intramolecular dehydration cyclization reaction to form a diazacycloalkane skeleton may proceed as a side reaction.
• an intramolecular dehydration cyclization reaction to form a diazacycloalkane skeleton may proceed as a side reaction.
• an alkanolamine dimer (a2-md), in which one amino group is a bis(hydroxyalkyl)amino group and the other amino group is a primary amino group, undergoes an intramolecular dehydration reaction to form a diazacyclo A cyclization product (caa-a2-md) having an alkane skeleton is obtained, and the acylation reaction of the cyclization product (caa-a2-md) with fatty acid (a1) can further proceed (the following general formula (23) )).
• an alkanolamine dimer (a2-dm) in which both of the two amino groups are secondary amino groups is converted into a cyclized product (caa-a2-dm) having a diazacycloalkane skeleton by an intramolecular dehydration reaction. md), and the acylation reaction of the cyclized product (caa-a2-md) with fatty acid (a1) can further proceed.
• a dehydration condensation reaction between the dialkanolamine dimer (a2-dm) and the fatty acid (a1) proceeds to give an amide compound (acyl-a2-dm), and then a cyclization product is generated by an intramolecular dehydration reaction. (acyl-caa-a2-md) (the following general formula (24)).
• an alkanolamine dimer (a2-dd) in which one amino group is a secondary amino group and the other amino group is a tertiary amino group can be formed with a diazacycloalkane skeleton by an intramolecular dehydration reaction.
• Acylation reaction of the cyclization product (caa-a2-dd) with fatty acid (a1) can further proceed (general formula (25) below). .
• component (v ) A by-product (hereinafter referred to as “component (v )” or “component (v)”) is usually produced in a small amount even if it is produced, and the total content of them in the additive composition is determined by the amount of etherified hydroxy groups.
• component (v ) A by-product (hereinafter referred to as “component (v )” or “component (v)”) is usually produced in a small amount even if it is produced, and the total content of them in the additive composition is determined by the amount of etherified hydroxy groups.
• component (a1) Based on the total content of all acylated products with the monovalent fatty acid (a1) of a compound containing an alkanolamine structure that may contain an alkanolamine structure, in terms of the compound in a non-salt state, The content may be, for example, 0 to 2.0% by mass, or 0 to 5.0% by mass in terms of the content as a compound in the free state.
• a solvent can be used as appropriate.
• pentane, hexane, cyclohexane, heptane, benzene, toluene, xylene, diethyl ether, ethyl acetate, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, dichloromethane, chloroform, carbon tetrachloride, etc. can be used.
• washing with water means washing with water or an aqueous solution
• aqueous solution used for washing include acidic water such as dilute hydrochloric acid, alkaline water such as dilute aqueous sodium hydroxide solution, and salt aqueous solution such as saturated saline solution. be able to.
• HPLC high performance liquid chromatography
• Equipment Thermo Fisher Scientific UltiMate 3000 UHPLC Column: ACQUITY (registered trademark) UPLC BEH C18 1.7 ⁇ m 50 x 2.1 mm (ODS) manufactured by Waters Corporation
• Detection device combination of charged particle detector (CAD) and mass spectrometer (MS)
• MS Mass spectrometer
• MS JEOL JMS-T100LP AccuTOF (registered trademark) LC-plus 4G (ionization method: ESI+)
• Mobile phase Use a gradient elution method using ultrapure water, methanol, and isopropyl alcohol.
• Ammonium formate is added to each solvent so that the concentration is 10 mmol/L.
• the composition is continuously changed to 100% methanol, and then further continuously changed to 100% isopropyl alcohol.
• MS mass spectrometer
• each peak detected by the charged particle detector (CAD) can be assigned to a compound. If the analysis conditions are the same, a peak detected by CAD will show an area value that depends on the amount of compound flowing into the detector, regardless of the characteristics of the compound.
• the content of each component (mass % in terms of compound in a non-salt state) can be quantitatively measured.
• the area value of the detected peak of CAD is divided proportionally according to the ratio of the peak area values of the multiple compounds by MS, so that each component can be determined.
• the content (mass % in terms of compound in a non-salt state) can be calculated.
• the detected peaks of components (i), (ii), (iv), and (v) in the CAD chromatogram are separated from the detected peaks of the other components.
• the detected peak group of fatty acid acylated products of alkanolamine oligomers is separated from the detected peak group of fatty acid acylated products of alkanolamine monomers.
• the detected peak of component (ii) i.e., a compound in which the amino group and one or more hydroxy groups of the alkanolamine monomer are acylated with a fatty acid
• the detected peaks of component (iii) i.e.
• fatty acid amide of alkanolamine monomer which does not have an ester bond
• a solution was obtained by known pretreatment such as filtration. Afterwards, measurements can be taken. Before performing the measurement using the above-mentioned high performance liquid chromatography (C18 column, detector: CAD and MS), if necessary, perform silica gel column chromatography, preparative liquid chromatography (e.g. gel permeation chromatography (GPC), etc.). Pretreatment may be performed to remove all or part of components other than components (i) to (v) by known purification means such as .).
• pretreatment may be performed to remove all or part of components other than components (i) to (v) by known purification means such as .).
• 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 kind of component other than the base oil.
• the lubricating base oil includes one or more mineral base oils or one or more synthetic base oils, or a combination thereof.
• the lubricating base oil is used.
• the lubricating base oil includes Group I base oil of the API base oil classification (hereinafter sometimes referred to as "API Group I base oil”), Group II base oil (hereinafter referred to as “API Group II base oil”), ), Group III base oils (hereinafter sometimes referred to as “API Group III base oils”), Group IV base oils (hereinafter sometimes referred to as “API Group IV base oils”). ), Group V base oil (hereinafter sometimes referred to as "API Group V base oil”), or a mixed base oil thereof can be used.
• API Group I base oil Group I base oil
• API Group II base oil Group II base oil
• API Group III base oils Group III base oils
• API Group IV base oils hereinafter sometimes referred to as “API Group IV base oils”
• Group V base oil hereinafter sometimes referred to as "API Group V base oil”
• a mixed base oil thereof can be used.
• API Group I base oil is a mineral oil base oil with a sulfur content of more than 0.03% by mass and/or a saturated content of less than 90% by mass, and a viscosity index of 80 or more and less than 120.
• API Group II base oil is a mineral oil base oil 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 or more and less than 120.
• API Group III base oil is a mineral oil base oil 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 polyalpha-olefin base oils.
• API Group V base oils are base oils other than the above Groups I to IV, and preferred examples include ester base oils.
• component (A) includes 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 IV base oils.
• V base oils or combinations thereof can be preferably used.
• mineral oil base oils include lubricating oil fractions obtained by atmospheric distillation and/or vacuum distillation of crude oil, which can be subjected to solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrogen dewaxing.
• mineral oil base oils include paraffinic base oils refined by one or a combination of two or more selected from chemical refining, sulfuric acid washing, clay treatment, etc., normal paraffinic base oils, isoparaffinic base oils, and mixtures thereof. be able to.
• API Group II and Group III base oils are typically produced via a hydrocracking process.
• the % CP of the mineral base oil is preferably 60 or more, more preferably 65 or more from the viewpoint of further improving the viscosity-temperature characteristics and fuel efficiency of the composition, and is also preferably from the viewpoint of improving the solubility of additives. is 99 or less, more preferably 95 or less, even more preferably 94 or less, and in one embodiment may be 60-99, or 60-95, or 65-95, or 65-94.
• the % CA of the mineral base oil is preferably 2 or less, more preferably 1 or less, still more preferably 0.8 or less, particularly preferably 0. 5 or less.
• the % CN of the mineral base oil is preferably 1 or more, more preferably 4 or more from the viewpoint of increasing the solubility of additives, and is also preferably from the viewpoint of further improving the viscosity-temperature characteristics and fuel efficiency of the composition. is 40 or less, more preferably 35 or less, and in one embodiment may be 1-40, or 4-35.
• %C P , %C N and %C A are the percentages of the number of paraffin carbons to the total number of carbons, respectively, determined by a method based on ASTM D 3238-85 (ndM ring analysis). , means the percentage of naphthenic carbon number to total carbon number, and the percentage of aromatic carbon number to total carbon number.
• the preferred ranges of %C P , %C N and %C A described above are based on the values determined by the above method. For example, even if the lubricant base oil does not contain naphthenes, %C N can have a value greater than zero.
• the content of saturated components in the mineral base oil is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass, based on the total amount of the base oil. % by mass or more.
• the saturated content means a value measured in accordance with ASTM D 2007-93.
• the aromatic content in the mineral base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, particularly preferably 0 to 1% by mass, based on the total amount of the base oil. In embodiments, it may be 0.1% by mass or more.
• Aromatic components usually include alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene, and their alkylated products, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols, naphthols, etc. This includes aromatic compounds having heteroatoms.
• API Group IV base oils include those having 2 to 32 carbon atoms, preferably 6 carbon atoms, such as ethylene-propylene copolymers, polybutenes, 1-octene oligomers, 1-decene oligomers, and hydrogenated products thereof. Mention may be made of oligomers and cooligomers of ⁇ -olefins of ⁇ 16 and their hydrogenation products.
• API Group V base oils include 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.); polycarboxylic acid esters (e.g. trimellitic acid ester, etc.); polyol esters (e.g.
• API Group V base oils include aromatic synthetic base oils such as alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, dialkyl diphenyl ethers, polyphenyl ethers, and the like.
• the kinematic viscosity at 40° C. of the lubricating base oil is 40 mm 2 /s or less, preferably 30 mm 2 /s or less, more preferably 20 mm from the viewpoint of energy saving and improving the low-temperature viscosity characteristics of the lubricating oil composition. 2 /s or less, and from the viewpoint of improving wear resistance and seizure resistance, preferably 5.0 mm 2 /s or more, more preferably 6.0 mm 2 /s or more, even more preferably 7.0 mm 2 /s or more. and in one embodiment may be from 5.0 to 40 mm 2 /s, or from 6.0 to 30 mm 2 /s, or from 7.0 to 20 mm 2 /s.
• kinematic viscosity at 40°C refers to a kinematic viscosity measured in accordance with JIS K 2283-2000 using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument Co., Ltd.) as a measuring device. Means kinematic viscosity at 40°C.
• the kinematic viscosity at 100° C. of the lubricating base oil is preferably 10.0 mm 2 /s or less, more preferably 7.0 mm 2 from the viewpoint of further improving energy saving and low-temperature viscosity characteristics of the lubricating oil composition.
• kinematic viscosity at 100°C refers to a kinematic viscosity measured in accordance with JIS K 2283-2000 using an automatic viscometer (trade name "CAV-2100", manufactured by Cannon Instrument) as a measuring device. Means kinematic viscosity at 100°C.
• the viscosity index of the lubricating 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.
• the viscosity index means the viscosity index measured in accordance with JIS K 2283-2000 using an automatic viscometer (product name "CAV-2100", manufactured by Cannon Instrument) as the measuring device.
• the pour point of the lubricating base oil is preferably -10°C or lower, more preferably -12.5°C or lower, and even more preferably -15°C or lower, from the viewpoint of low-temperature fluidity of the entire lubricating oil composition. , particularly preferably -17.5°C or lower, most preferably -20.0°C or lower.
• pour point means a pour point measured in accordance with JIS K 2269-1987.
• the sulfur content in the base oil depends on the sulfur content of its raw material.
• a substantially sulfur-free raw material such as a synthetic wax component obtained by Fischer-Tropsch reaction or the like
• a substantially sulfur-free base oil can be obtained.
• the sulfur content in the obtained base oil is usually 100 mass ppm 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.
• the sulfur content in the base oil means the amount of sulfur measured in accordance with JIS K 2541-2003.
• Lubricating base oils may consist of a single base oil component or may include multiple base oil components.
• the kinematic viscosity of the entire base oil (total base oil) at 40° C. may be 40 mm 2 /s or less.
• the lubricant base oil is 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.
• the base oil, or a combination thereof may comprise 80 to 100%, or 90 to 100%, or 90 to 99%, or 95 to 99% by weight based on the total amount of base oil.
• 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% by mass, based on the total amount of the lubricating oil composition. .5% by weight, and in one embodiment 75-97% by weight.
• the lubricating oil composition of the present invention contains the lubricating oil additive composition (hereinafter sometimes referred to as "component (A)") according to the first aspect of the present invention described above.
• component (A) lubricating oil additive composition according to the first aspect of the present invention acts as an oil-based friction modifier.
• the content of component (A) in the lubricating oil composition is such that the content of component (A) in the lubricating oil composition is determined to improve friction reduction performance, particularly for metals that are susceptible to high loads such as gears, while suppressing a decrease in storage stability of the lubricating oil composition.
• all acylations with the monohydric fatty acid (a1) of the compound containing an alkanolamine structure in which the hydroxyl group may be etherified Based on the total amount of the lubricating oil composition, preferably 0.005% by mass or more, or 0.010% by mass or more, or 0.030% by mass or more, or 0.
• .050% by mass or more preferably 10.0% by mass or less, or 5.0% by mass or less, or 4.0% by mass or less, or 3.0% by mass or less, from the viewpoint of storage stability, and In embodiments of 0.005 to 10.0% by weight, or 0.010 to 5.0% by weight, or 0.030 to 4.0% by weight, or 0.050 to 3.0% by weight.
• the total content of the components (i) to (iv) in the lubricating oil composition is such that the total content of the components (i) to (iv) in the lubricating oil composition improves friction reduction performance, particularly for gears, etc., while suppressing a decrease in storage stability of the lubricating oil composition. From the viewpoint of further increasing the friction reduction performance on metal surfaces that are susceptible to high loads, and from the viewpoint of further increasing fatigue resistance, preferably 0 in terms of compounds in a state without forming salts, based on the total amount of the lubricating oil composition.
• .005% by mass or more or 0.010% by mass or more, or 0.030% by mass or more, or 0.050% by mass or more, and preferably 10.0% by mass or less from the viewpoint of storage stability, or 5. 0% by mass or less, or 4.0% by mass or less, or 3.0% by mass or less, and in one embodiment, 0.005 to 10.0% by mass, or 0.010 to 5.0% by mass, or It can be from 0.030 to 4.0% by weight, or from 0.050 to 3.0% by weight.
• the total content of the components (i) to (v) in the lubricating oil composition is such that the total content of the components (i) to (v) in the lubricating oil composition improves friction reduction performance, particularly for gears, etc., while suppressing a decrease in storage stability of the lubricating oil composition. From the viewpoint of further increasing the friction reduction performance on metal surfaces that are susceptible to high loads, and from the viewpoint of further increasing fatigue resistance, preferably 0 in terms of compounds in a state without forming salts, based on the total amount of the lubricating oil composition.
• .005% by mass or more or 0.010% by mass or more, or 0.030% by mass or more, or 0.050% by mass or more, and preferably 10.0% by mass or less from the viewpoint of storage stability, or 5. 0% by mass or less, or 4.0% by mass or less, or 3.0% by mass or less, and in one embodiment, 0.005 to 10.0% by mass, or 0.010 to 5.0% by mass, or It can be from 0.030 to 4.0% by weight, or from 0.050 to 3.0% by weight.
• the lubricating oil composition may further contain one or more metal-based detergents (hereinafter sometimes referred to as "component (B)").
• component (B) include salicylate detergents, sulfonate detergents, phenate detergents, and the like.
• the component (B) may contain only one type of metal-based detergent, or may contain two or more types of metal-based detergents.
• metal detergents include organic acid metal salts that can form micelles in the base oil (for example, alkali or alkaline earth metal alkyl salicylates, alkali or alkaline earth metal alkylbenzene sulfonates, and alkali or alkaline earth metal alkyl phenates, etc.), or the organic acid metal salt and basic metal salt (for example, the hydroxide, carbonate, boron of the alkali or alkaline earth metal constituting the organic acid metal salt) (acid acid, etc.) is used.
• organic acid metal salts that can form micelles in the base oil
• the organic acid metal salt and basic metal salt for example, the hydroxide, carbonate, boron of the alkali or alkaline earth metal constituting the organic acid metal salt
• Such organic acids typically contain at least one polar group (e.g., a carboxy group, a sulfo group) with Br ⁇ nsted acidity capable of forming salts with metal bases (typically metal oxides and/or metal hydroxides). , phenolic hydroxy group, etc.) and at least one lipophilic group such as a linear or branched alkyl group (for example, a linear or branched alkyl group having 6 or more carbon atoms, etc.) in one molecule.
• polar group e.g., a carboxy group, a sulfo group
• metal bases typically metal oxides and/or metal hydroxides
• lipophilic group such as a linear or branched alkyl group (for example, a linear or branched alkyl group having 6 or more carbon atoms, etc.) in one molecule.
• salicylate-based detergents include metal salicylates or basic salts or overbased salts thereof.
• Preferred examples of metal salicylates include alkali or alkaline earth metal salicylates represented by the following general formula (26).
• R 17 each 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
• p represents M. It represents 1 or 2 depending on the valence.
• M is an alkali metal
• p is 1
• M is an alkaline earth metal
• M is preferably an alkaline earth metal.
• the alkali metal is preferably sodium or potassium
• the alkaline earth metal is preferably calcium or magnesium.
• sulfonate detergents include alkali or alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonating an alkyl aromatic compound, or basic salts or overbased salts thereof, more preferably alkali Mention may be made of earth metal salts or their basic or overbased salts.
• the weight average molecular weight of the alkyl aromatic compound is preferably 400 to 1,500, more preferably 700 to 1,300.
• the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium.
• alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids.
• Examples of petroleum sulfonic acids include those obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, and so-called mahogany acid, which is a by-product during the production of white oil.
• Examples of synthetic sulfonic acids include straight-chain or branched alkyls obtained by recovering by-products in alkylbenzene manufacturing plants, which are raw materials for detergents, or by alkylating benzene with polyolefins. Examples include sulfonated alkylbenzenes having groups.
• Other examples of synthetic sulfonic acids include sulfonated alkylnaphthalenes such as dinonylnaphthalene.
• the sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, and for example, fuming sulfuric acid or sulfuric anhydride can be used.
• Preferred examples of phenate-based detergents include overbased salts of alkali or alkaline earth metal salts of compounds having the structure represented by the following general formula (27), more preferably overbased salts of alkaline earth metal salts. can be mentioned.
• the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium.
• R 18 represents a linear or branched, saturated or unsaturated alkyl or alkenyl group having 6 to 21 carbon atoms
• q represents an integer of 0 to 9
• A represents sulfide (-S -) group or methylene (-CH 2 -) group
• x represents an integer of 1 to 3.
• R 18 may be a combination of two or more different groups, and x may be a combination of a plurality of different integers.
• x is preferably 1.
• the substitution position of the -A x - group in each aromatic ring is typically the o-position or the p-position relative to the hydroxy group, typically the o-position.
• the number of carbon atoms in R 18 in general formula (27) is preferably 9 or more from the viewpoint of increasing solubility in base oil, and preferably 18 or less, more preferably 15 or less from the viewpoint of ease of production. In embodiments of 9-18, or 9-15.
• q in general formula (27) is preferably 0 to 3.
• Metal-based detergents may be overbased with carbonates (e.g., alkali metal carbonates such as sodium carbonate or potassium carbonate, or alkaline earth metal carbonates such as calcium carbonate or magnesium carbonate), or may be overbased with boric acid. It may be overbased with a salt (eg, an alkali metal borate such as sodium borate or potassium borate, or an alkaline earth metal borate such as calcium borate or magnesium borate).
• carbonates e.g., alkali metal carbonates such as sodium carbonate or potassium carbonate, or alkaline earth metal carbonates such as calcium carbonate or magnesium carbonate
• boric acid e.g., calcium carbonate or magnesium carbonate
• a salt eg, an alkali metal borate such as sodium borate or potassium borate, or an alkaline earth metal borate such as calcium borate or magnesium borate.
• component (B) comprises 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 sulfonate detergents.
• a calcium or magnesium phenate detergent may be included, preferably one or more overbased calcium sulfonate detergents, and/or one or more overbased calcium salicylate detergents.
• Calcium sulfonate detergents, calcium salicylate detergents, and calcium phenate detergents are each preferably overbased with calcium carbonate
• magnesium sulfonate detergents, magnesium salicylate detergents, and magnesium phenate detergents are each preferably overbased with calcium carbonate. Preferably it is overbased with magnesium.
• the base number of the metal detergent can be appropriately determined depending on the use of the lubricating oil composition.
• the base number of the metal-based detergent is determined by the wear resistance.
• the base number of the metal-based detergent is determined by the wear resistance.
• the content when used to lubricate an internal combustion engine, the content is preferably 0 mgKOH/g or more, more preferably 20 mgKOH/g or more, from the viewpoint of improving cleaning performance and base number maintenance. From the viewpoint of suppressing the ash content and the life of the exhaust gas after-treatment device, it is preferably 500 mgKOH/g or less, more preferably 450 mgKOH/g or less, and in one embodiment, 0 to 500 mgKOH/g, or 20 to 450 mgKOH/g. It can be.
• the base number means the base number measured by the perchloric acid method in accordance with JIS K2501.
• the lubricating oil composition contains component (B), its content can be appropriately determined depending on the use of the lubricating oil composition.
• the content of component (B) in the lubricating oil composition is preferably 200 mass ppm or more, more preferably 250 mass ppm as a metal amount based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, seizure resistance, fatigue resistance, and transmission torque capacity of a wet clutch.
• the lubricating oil composition is used to lubricate an internal combustion engine, the content of component (C) is determined as the amount of metal based on the total amount of the lubricating oil composition, from the viewpoint of improving cleaning performance and base number maintenance.
• It is preferably 500 mass ppm or more, more preferably 1000 mass ppm or more, and preferably 10000 mass ppm or less, more preferably 5000 mass ppm from the viewpoint of suppressing the ash content in the composition and the life of the exhaust gas after-treatment device. or less, and in one embodiment may be from 500 to 10,000 ppm by mass, or from 1,000 to 5,000 ppm by mass.
• the lubricating oil composition may further contain one or more nitrogen-containing dispersants (hereinafter sometimes referred to as "component (C)").
• nitrogen-containing dispersants include at least one long chain (e.g., 40 or more carbon atoms), straight or branched aliphatic hydrocarbon group and at least one polyamine chain (typically polyethylene
• a nitrogen-containing compound having a polyamine chain (amine chain) in one molecule, and a portion of the nitrogen atoms of the polyamine chain may be acylated, or a modified product (derivative) thereof is used. Examples of modified products will be described later.
• component (C) for example, one or more compounds selected from the following (C-1) to (C-3) can be used.
• component (C-1) Succinimide or modified product (derivative) thereof having at least one alkyl group or alkenyl group in the molecule
• component (C-2) Benzylamine having at least one alkyl group or alkenyl group in the molecule (for example, Mannich base obtained by reacting an alkyl or alkenylphenol with formaldehyde and a polyamine) or a modified product thereof (derivative) )
• component (C-2) Benzylamine having at least one alkyl group or alkenyl group in the molecule
• component (C-2) for example, Mannich base obtained by reacting an alkyl or alkenylphenol with formaldehyde and a polyamine
• component (C-3) N-alkyl or alkenylated polyamine having at least one alkyl group or alkenyl group in the molecule or a modified product
• component (C) can be particularly preferably used.
• succinimides having at least one alkyl group or alkenyl group in the molecule include alkyl or alkenyl succinic acid having an alkyl or alkenyl group having 40 to 400 carbon atoms or anhydride thereof;
• condensation reaction products of polyamines and polyamines include condensation reaction products of polyamines and polyamines.
• condensation reaction product may be represented by the following general formula (28a) or (28b), for example.
• R 19 represents an alkyl or alkenyl group having 40 to 400 carbon atoms
• b represents an integer of 1 to 10, preferably 2 to 6.
• the compound represented by general formula (28a) is obtained as a mixture of compounds having different b.
• the carbon number of R19 is 40 or more, preferably 60 or more from the viewpoint of solubility in base oil, and 400 or less, preferably 350 or less, more preferably 250 or less from the viewpoint of low temperature fluidity of the composition. In one embodiment, it can be from 40 to 400, or from 60 to 350, or from 60 to 250.
• R 20 and R 21 each independently represent an alkyl group or alkenyl group having 40 to 400 carbon atoms, and may be a combination of different groups. Further, 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 (28b) is obtained as a mixture of compounds having different c.
• the number of carbon atoms in R 20 and R 21 is 40 or more, preferably 60 or more from the viewpoint of solubility in the base oil, and 400 or less, preferably 350 or less, more preferably 350 or less from the viewpoint of low temperature fluidity of the composition. 250 or less, and in one embodiment may be 40-400, or 60-350, or 60-250.
• the alkyl or alkenyl groups (R 19 to R 21 ) in general formulas (28a) and (28b) may be linear or branched.
• Preferred examples include branched alkyl groups and branched alkenyl groups derived from olefin oligomers such as propylene, 1-butene, and isobutene, and cooligomers of ethylene and propylene.
• branched alkyl or alkenyl groups derived from oligomers of isobutene commonly called polyisobutylene
• polybutenyl groups are most preferred.
• Suitable number average molecular weights of the alkyl or alkenyl groups (R 19 to R 21 ) in general formulas (28a) and (28b) are 800 to 3,500, preferably 900 to 3,500.
• Succinimide having at least one alkyl group or alkenyl group in the molecule includes a so-called monotype succinimide represented by the general formula (28a) in which only one end of the polyamine chain is imidized. and a so-called bis-type succinimide represented by the general formula (28b), in which both ends of the polyamine chain are imidized.
• the lubricating oil composition may contain either mono-type succinimide or bis-type succinimide, or may contain both as a mixture.
• the content of bis-type succinimide or its modified product in component (C-1) is preferably 50 to 100% by mass, more preferably 50 to 100% by mass based on the total amount of component (C-1) (100% by mass). It is 70 to 100% by mass.
• the weight average molecular weight of component (C-1) is preferably 1,000 to 20,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, and in one embodiment may be 4,000 to 15,000.
• modified products examples include (i) modified products with oxygen-containing organic compounds, (ii) boric acid modified products, (iii) phosphorus Examples include acid-modified products, (iv) sulfur-modified products, and (v) modified products resulting from a combination of two or more modifications among these.
• a modified product with an oxygen-containing organic compound is a succinimide, benzylamine, or polyamine (hereinafter referred to as "the above-mentioned nitrogen-containing compound") having at least one alkyl group or alkenyl group in the molecule, and a fatty acid.
• the phosphoric acid modified product is a modified compound in which some or all of the remaining amino groups and/or imino groups are neutralized or amidated by allowing phosphoric acid to act on the above-mentioned nitrogen-containing compound.
• the sulfur-modified compound is a modified compound obtained by allowing a sulfur compound to act on the above-mentioned nitrogen-containing compound.
• a modified compound resulting from a combination of two or more types of modification is a combination of the above-mentioned nitrogen-containing compound and two or more types of modification selected from modification with an oxygen-containing organic compound, boric acid modification, phosphoric acid modification, and sulfur modification.
• boric acid-modified compounds of alkenylsuccinimides particularly bis-type alkenylsuccinimides modified with boric acid, can be preferably used.
• the lubricating oil composition contains component (C), its content can be appropriately determined depending on the use of the lubricating oil composition.
• the content of component (C) in the lubricating oil composition is preferably 0.1% by mass or more based on the total amount of the lubricating oil composition from the viewpoint of increasing oxidation stability, and preferably 10% by mass or less, more preferably 5% by mass from the viewpoint of maintaining energy saving properties. It is as follows.
• the content of component (C) is preferably 0.5% by mass or more based on the total amount of the lubricating oil composition, from the viewpoint of improving coking resistance. , more preferably 1.0% by mass or more, and from the viewpoint of maintaining fuel efficiency, preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and in one embodiment, 0.0% by mass or less. It can be from 5% to 10.0% by weight, or from 1.0% to 5.0% by weight.
• the (C) component can be preferably used, and as the modified component (C), a boric acid modified product can be preferably used.
• the (C) component may be one or more unmodified (C-1) components (unmodified succinimide dispersant), and one or more unmodified (C-1) components. It may be a boric acid-modified product (boric acid-modified succinimide dispersant), or it may be a combination of one or more unmodified succinimide dispersants and one or more boric acid-modified succinimide dispersants. You can.
• Component (C) may or may not contain a boric acid modified product, but from the viewpoint of sludge dispersibility, the boron content B of component (C) is lower than that of component (C).
• the ratio (B/N) to the nitrogen content N may preferably be 0 to 1.0.
• the lubricating oil composition may contain one or more phosphorus-containing antiwear agents (hereinafter sometimes referred to as "component (D)").
• component (D) phosphorus-containing anti-wear agents used in lubricating oils can be used without particular limitation.
• the phosphorus-containing antiwear agent include compounds represented by the following general formula (29), compounds represented by the following general formula (30), and metal salts and ammonium salts thereof.
• X 1 , X 2 , and X 3 each independently represent an oxygen atom or a sulfur atom;
• R 22 is a hydrocarbon group having 1 to 30 carbon atoms that may contain a sulfur atom)
• R 23 and R 24 each independently represent a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom which may contain a sulfur atom;
• R 22 , R 23 and R 24 are the same or different;
• R 23 and/or R 24 are hydrogen atoms, the compound of general formula (29) shall include any tautomer thereof.
• X 4 , X 5 , X 6 , and X 7 each independently represent an oxygen atom or a sulfur atom; Represents a hydrocarbon group; R 26 and R 27 each independently represent a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom which may contain a sulfur atom; R 25 , R 26 and R 27 may be the same; (They may be different from each other.)
• hydrocarbon groups having 1 to 30 carbon atoms in general formulas (29) and (30) include alkyl groups, cycloalkyl groups, alkenyl groups, alkyl-substituted cycloalkyl groups, aryl groups, alkyl-substituted aryl groups, and aryl groups.
• alkyl groups include alkyl groups.
• the hydrocarbon group is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, and in one embodiment, an alkyl group having 3 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms. It is an aryl group or an alkylaryl group.
• the hydrocarbon group having 1 to 30 carbon atoms in general formulas (29) and (30) may be a hydrocarbon group containing a sulfur atom or may be a hydrocarbon group not containing a sulfur atom.
• a preferable example of the hydrocarbon group not containing a sulfur atom is a straight-chain alkyl group having 4 to 18 carbon atoms.
• straight-chain alkyl groups include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl. , octadecyl group.
• hydrocarbon group containing a sulfur atom is a hydrocarbon group functionalized with a sulfide bond.
• Preferred examples of the hydrocarbon group functionalized with a sulfide bond include a group having 4 to 20 carbon atoms represented by the following general formula (31).
• R 28 is a straight chain hydrocarbon group having 2 to 17 carbon atoms, preferably an ethylene group or a propylene group, and in one embodiment, an ethylene group.
• R 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.
• Preferred examples of the group represented by general formula (31) include 3-thiapentyl group, 3-thiahexyl group, 3-thiaheptyl group, 3-thiaoctyl group, 3-thianonyl group, 3-thiadecyl group, and 3-thiaundecyl group. , 4-thiahexyl group, and the like.
• Examples of metals that form metal salts with the phosphorus compound represented by general formula (29) or (30) include alkali metals such as lithium, sodium, potassium, and cesium, and alkaline earth metals such as calcium, magnesium, and barium. , zinc, copper, iron, lead, nickel, silver, manganese, and other transition metals. Among these, alkaline earth metals such as calcium and magnesium, zinc, or a combination thereof are preferred.
• nitrogen-containing compounds that form ammonium salts with the phosphorus compound represented by general formula (29) or (30) include ammonia, monoamines, diamines, polyamines, and alkanolamines. More specifically, nitrogen-containing compounds represented by the following general formula (32); alkylene diamines such as methylene diamine, ethylene diamine, propylene diamine, and butylene diamine; diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine; and combinations thereof.
• R 30 to R 32 each independently represent a hydrogen atom, a hydrocarbyl group having 1 to 8 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms having a hydroxyl group; R 30 to R 32 At least one of them is a hydrocarbyl group having 1 to 8 carbon atoms, or a hydrocarbyl group having 1 to 8 carbon atoms and having a hydroxyl group.
• a preferable example of the compound represented by the above general formula (29) is a compound in which in the above general formula (29), X 1 to X 3 are oxygen atoms, and R 22 to R 24 each independently contain a sulfur atom.
• a phosphite compound which is an alkyl group, an aryl group (for example, a phenyl group, etc.), or an alkylaryl group (for example, an alkylphenyl group, etc.) having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms);
• X 1 to X 3 are oxygen atoms
• R 22 and R 23 are each independently an alkyl group having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms), aryl, which may contain a sulfur atom.
• R 24 is hydrogen
• Two are oxygen atoms, the remaining one is a sulfur atom
• R 22 and R 23 are each independently an alkyl group having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms), an aryl group (e.g.
• R 22 and R 23 are each an alkyl group or an aryl group (for example, a phenyl group) having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms) that may independently contain a sulfur atom. etc.), or alkylaryl groups (for example, alkylphenyl groups, etc.), and hydrogen dithiophosphite compounds in which R 24 is hydrogen.
• two of X 4 to X 7 are sulfur atoms, the remaining two are oxygen atoms, and R 25 to R 27 are Examples include dithiophosphate compounds which are alkyl groups, aryl groups, or alkylaryl groups having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms), each of which may independently contain a sulfur atom. These compounds may be used alone or in combination of two or more.
• component (D) is zinc dialkyldithiophosphate (ZnDTP).
• ZnDTP zinc dialkyldithiophosphate
• Examples of zinc dialkyldithiophosphate include compounds represented by the following general formula (33).
• R 33 to R 36 each independently represent a straight or branched alkyl group having 3 to 18 carbon atoms, and may be a combination of different groups. Further, the number of carbon atoms in R 33 to R 36 is preferably 3 to 12, more preferably 3 to 8. Furthermore, R 33 to R 36 may be any of a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group, and may be a primary alkyl group, a secondary alkyl group, or their A combination is preferred.
• the lubricating oil composition contains component (D), its content can be appropriately determined depending on the use of the lubricating oil composition.
• the content of component (D) in the lubricating oil composition is preferably 50 mass ppm or more, more preferably 100 mass ppm or more as a phosphorus content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance, seizure resistance, bearing fatigue life, and transmission shock prevention property.
• the content of component (D) is preferably 400 mass ppm as a phosphorus content based on the total amount of the lubricating oil composition, from the viewpoint of improving wear resistance.
• the above is more preferably 500 mass ppm or more, and from the viewpoint of reducing catalyst poisoning of the exhaust gas after-treatment device, preferably 5000 mass ppm or less, more preferably 3000 mass ppm or less, and in one embodiment, 400 to 5000 mass ppm. It can be ppm by weight, or from 500 to 3000 ppm by weight.
• the lubricating oil composition may further include one or more sulfur-containing extreme pressure agents other than component (D) (hereinafter sometimes referred to as "component (E)").
• component (E) include thiadiazole compounds, dihydrocarbyl (poly)sulfides, sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkylthiodipropionate compounds, and sulfurized
• component (E) include thiadiazole compounds, dihydrocarbyl (poly)sulfides, sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkylthiodipropionate compounds, and sulfurized
• sulfur-containing extreme pressure agents such as mineral oil
• thiadiazole compounds include 1,3,4-thiadiazole compounds represented by the following general formula (34), 1,2,4-thiadiazole compounds represented by the following general formula (35), and the following general formula.
• a 1,2,3-thiadiazole compound represented by (36) can be mentioned.
• R 37 and R 38 may be the same or different and each independently represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms; d and e are the same or different , and each independently represents an integer from 0 to 8.
• Dihydrocarbyl (poly)sulfide is a compound represented by the following general formula (37).
• R 31 and R 32 are alkyl groups, they may be referred to as alkyl sulfide.
• R 39 and R 40 may be the same or different, each independently an alkyl group having 1 to 20 carbon atoms (which may be linear or branched, or may have a cyclic structure) ) represents 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.
• the lubricating oil composition contains component (E), its content can be appropriately determined depending on the use of the lubricating oil composition.
• the content of component (E) in the lubricating oil composition is preferably 200 mass ppm or more, more preferably 300 mass ppm or more based on the total amount of the lubricating oil composition, and also has wear resistance, fatigue resistance, And from the viewpoint of increasing oxidation stability, it is preferably 3000 mass ppm or less, more preferably 2500 mass ppm or less, and in one embodiment, it may be 200 to 3000 mass ppm, or 300 to 2500 mass ppm.
• the content of component (E) is preferably set as the sulfur content based on the total amount of the lubricating oil composition, from the viewpoint of improving extreme pressure properties and fatigue resistance. It is 10 mass ppm or more, more preferably 30 mass ppm or more, and from the viewpoint of reducing catalyst poisoning of the exhaust gas after-treatment device, it is preferably 200 mass ppm or less, more preferably 100 mass ppm or less, and one embodiment may be 10 to 200 ppm by weight, or 30 to 100 ppm by weight.
• the lubricating oil composition contains one or more amine antioxidants and/or one or more antioxidants (hereinafter sometimes referred to as “component (F)"). It may further include a phenolic antioxidant.
• amine-based antioxidants include aromatic amine-based antioxidants and hindered amine-based antioxidants.
• aromatic amine antioxidants include primary aromatic amine compounds such as alkylated ⁇ -naphthylamine; and alkylated diphenylamine, phenyl- ⁇ -naphthylamine, alkylated phenyl- ⁇ -naphthylamine, and phenyl- ⁇ .
• Secondary aromatic amine compounds such as naphthylamine;
• alkylated diphenylamine, alkylated phenyl- ⁇ -naphthylamine, or a combination thereof can be preferably used.
• hindered amine antioxidants include compounds having a 2,2,6,6-tetraalkylpiperidine skeleton (2,2,6,6-tetraalkylpiperidine derivatives).
• a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position is preferred.
• two 2,2,6,6-tetraalkylpiperidine skeletons may be bonded via a substituent at each 4-position.
• the N-position of the 2,2,6,6-tetraalkylpiperidine skeleton may be unsubstituted, or the N-position may be substituted with an alkyl group having 1 to 4 carbon atoms.
• the 2,2,6,6-tetraalkylpiperidine skeleton is preferably a 2,2,6,6-tetramethylpiperidine skeleton.
• Examples of the substituent at the 4-position of the 2,2,6,6-tetraalkylpiperidine skeleton include an acyloxy group (R 41 COO-), an alkoxy group (R 41 O-), an alkylamino group (R 41 NH-), Examples include acylamino group (R 41 CONH-), and the like.
• R 41 is preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, even more preferably 1 to 20 carbon atoms.
• hydrocarbon group examples include an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.
• the substituent is a hydrocarbylene bis(carbonyloxy) group (-OOC- R 42 -COO-), a hydrocarbylene diamino group (-HN-R 42 -NH-), a hydrocarbylene bis(carbonylamino) group (-HNCO-R 42 -CONH-), and the like.
• R 42 is preferably a hydrocarbylene group having 1 to 30 carbon atoms, more preferably an alkylene group.
• an acyloxy group is preferable.
• 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 and a carboxylic acid.
• the carboxylic acid include linear or branched aliphatic carboxylic acids having 8 to 20 carbon atoms.
• phenolic antioxidants examples include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); -bis(2-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 4,4'-butylidenebis(3-methyl-6-tert-butylphenol); 4,4'-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6 -nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4 -Methylphenol; 2,6-di-tert-but
• the lubricating oil composition contains component (F), its content can be appropriately determined depending on the use of the lubricating oil composition.
• the content of component (F) in the lubricating oil composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2.0% by mass from the same viewpoint, based on the total amount of the lubricating oil composition, from the viewpoint of increasing thermo-oxidative stability.
• the content is more preferably 1.0% by mass or less, and in one embodiment may be 0.1 to 2.0% by mass, or 0.2 to 1.0% by mass.
• the content of component (F) in the lubricating oil composition is preferably based on the total amount of the lubricating oil composition from the viewpoint of improving thermo-oxidative stability. is 0.1% by mass or more, more preferably 0.5% by mass or more, and from the same point of view, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and in one embodiment, 0. .1 to 5.0% by weight, or 0.5 to 3.0% by weight.
• the lubricating oil composition further contains one or more polymers having a viscosity index improving effect (hereinafter sometimes referred to as “viscosity index improver” or “component (G)”). obtain.
• component (G) examples include non-dispersed or dispersed poly(meth)acrylates, (meth)acrylate-olefin copolymers, non-dispersed or dispersed ethylene- ⁇ -olefin copolymers, or hydrides thereof; Examples include polyisobutylene or its hydride, styrene-diene hydrogenated copolymer, styrene-maleic anhydride copolymer, and polyalkylstyrene.
• “(meth)acrylate” means "acrylate and/or methacrylate.”
• component (G) one type of polymer may be used alone, or two or more types of polymers may be used in combination.
• dispersed poly(meth)acrylate as component (G), dispersed poly(meth)acrylate, non-dispersed poly(meth)acrylate, or a combination thereof can be preferably used.
• dispersed poly(meth)acrylate can be preferably used.
• the dispersed poly(meth)acrylate compound has a functional group containing a nitrogen atom, whereas the non-dispersed poly(meth)acrylate compound does not have a functional group containing a nitrogen atom.
• the poly(meth)acrylate-based viscosity index improver has a structural unit represented by the following general formula (38) in a proportion of 10 to 90 mol% of all monomer units in the polymer.
• Poly(meth)acrylate hereinafter sometimes referred to as "poly(meth)acrylate (G1)” or simply “component (G1)" can be preferably used.
• R 43 represents hydrogen or a methyl group
• R 44 represents a straight or branched hydrocarbon group having 1 to 36 carbon atoms, preferably an alkyl group.
• the weight average molecular weight of component (G) can be appropriately determined depending on the use of the lubricating oil composition. For example, when the lubricating oil composition is used to lubricate a gear device such as a transmission (for example, a manual transmission, an automatic transmission, a continuously variable transmission, etc.), the weight average molecular weight of the component (G) is determined by the viscosity index.
• the lubricating oil composition is used to lubricate an internal combustion engine, the weight average molecular weight of component (G) is preferably 100% from the viewpoint of increasing the viscosity index improvement effect and improving low temperature viscosity characteristics and fuel efficiency.
• ,000 or more more preferably 200,000 or more, and from the viewpoint of improving solubility in oil, storage stability, and shear stability, preferably 1,000,000 or less, more preferably 700,000 or less. 100,000 to 1,000,000, or 200,000 to 700,000 in one embodiment.
• 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.
• the viscosity index is an index for evaluating viscosity-temperature characteristics.
• the content of component (G) in the lubricating oil composition is, for example, 0.1% by mass or more, or 0.5% by mass or more as a resin content based on the total amount of the lubricating oil composition, from the viewpoint of improving viscosity-temperature characteristics and increasing energy saving, and also improving shear stability. From this point of view, it may be, for example, 22% by weight or less, or 12% by weight or less, and in one embodiment, 0.1 to 22% by weight, or 0.5 to 12% by weight.
• the content of component (G) in the lubricating oil composition is determined based on the resin content based on the total amount of the lubricating oil composition, from the viewpoint of improving fuel efficiency. For example, 0.1% by mass or more, or 0.5% by mass or more, and from the viewpoint of increasing shear stability, for example, 20% by mass or less, or 15% by mass or less, in one embodiment, 0.1 to 20% by mass, or 0.5 to 15% by mass.
• the resin component means a polymer component having a molecular weight of 1,000 or more.
• the lubricating oil composition of the present invention comprises (H) a friction modifier other than the above-mentioned (A) component and (E) component, (I) a pour point depressant other than the above-mentioned (G) component, (J) the above-mentioned (E) Corrosion inhibitor other than component (K) metal deactivator other than component (E) above, (L) rust preventive agent other than component (A) above, (M) demulsifier, (N) antifoaming agent, and (O) one or more additives selected from colorants.
• component (H) Friction modifiers other than the above components (A) and (E) (hereinafter sometimes referred to as "component (H)”) include oil-soluble organic molybdenum compounds used as friction modifiers in lubricating oils. Or, it is an oil-based friction modifier, and compounds other than the above-mentioned components (A) and (E) can be used. Examples of such compounds include oil-soluble organic molybdenum compounds other than molybdenum dithiocarbamate explained above as an example of component (E), and oil-based friction modifiers other than component (A) above. .
• component (H) When the lubricating oil composition contains component (H), its content may be, for example, 0.1 to 1.0% by mass based on the total amount of the lubricating oil composition.
• pour point depressants other than component (G) above may include, for example, ethylene vinyl acetate, etc., depending on the properties of the lubricant base oil used. Known pour point depressants can be used.
• component (I) When the lubricating oil composition contains component (I), its content may be, for example, 0.01 to 1.0% by mass based on the total amount of the lubricating oil composition.
• component (J) Corrosion inhibitors other than component (E) above (hereinafter sometimes referred to as “component (J)”) include known corrosion inhibitors such as benzotriazole compounds, tolyltriazole compounds, and imidazole compounds. Inhibitors can be used.
• component (K) When the lubricating oil composition contains component (K), its content may be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.
• component (K) Metal deactivators other than the above component (E) (hereinafter sometimes referred to as “component (K)”) include, for example, imidazolines, pyrimidine derivatives, mercaptobenzothiazole, benzotriazole and their derivatives, Known metal deactivators such as 2-(alkyldithio)benzimidazole and ⁇ -(o-carboxybenzylthio)propionitrile can be used.
• component (K) its content may be, for example, 0.005 to 1.0% by mass based on the total amount of the lubricating oil composition.
• component (L) Rust inhibitors other than the above component (A) (hereinafter sometimes referred to as “component (L)”) include petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl succinates, and polyesters.
• Known rust preventives such as alcohol esters (excluding those falling under component (A) above) can be used.
• component (L) When the lubricating oil composition contains component (L), its content may be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.
• demulsifier a known demulsifier such as a polyalkylene glycol nonionic surfactant can be used.
• its content may be, for example, 0.005 to 5.0% by mass based on the total amount of the lubricating oil composition.
• the antifoaming agent (N) for example, known antifoaming agents such as silicone, fluorosilicone, and fluoroalkyl ether can be used.
• the content thereof may be, for example, 0.0005 to 1.0% by mass based on the total amount of the lubricating oil composition.
• colorant for example, a known colorant such as an azo compound can be used.
• the kinematic viscosity at 100° C. of the lubricating oil composition can be appropriately determined depending on the use of the lubricating oil composition.
• the kinematic viscosity at 100°C of the lubricating oil composition is From the viewpoint of increasing wear resistance, it is preferably 1.0 mm 2 /s or more, more preferably 2.5 mm 2 /s or more, and from the viewpoint of increasing 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 mm 2 /s.
• the kinematic viscosity at 100°C of the lubricating oil composition is preferably 2.0 mm 2 /s or more, more preferably 2.0 mm 2 /s or more from the viewpoint of improving wear resistance.
• 4.0 mm 2 /s or more and from the viewpoint of improving energy saving, 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.
• the kinematic viscosity at 40°C of the lubricating oil composition can be appropriately determined depending on the use of the lubricating oil composition.
• the kinematic viscosity at 40°C of the lubricating oil composition is From the viewpoint of increasing wear resistance, it is preferably 5.0 mm 2 /s or more, more preferably 8.0 mm 2 /s or more, and from the viewpoint of increasing energy saving, it is preferably 50 mm 2 /s or less, more preferably 45 mm 2 /s or less, and in one embodiment, 5.0 to 50 mm 2 /s, or 5.0 to 45 mm 2 /s, or 8.0 to 50 mm 2 /s, or 8.0 to 45 mm 2 /s.
• the kinematic viscosity at 40°C of the lubricating oil composition is preferably 4.0 mm 2 /s or more, more preferably 6.0 mm 2 /s or more, and from the viewpoint of improving energy saving, 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.
• the viscosity index of the lubricating oil composition is preferably 100 or more, more preferably 110 or more, and in one embodiment, 115 or more, or 120 or more, from the viewpoint of further improving energy saving and wear resistance.
• 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 enhanced friction reduction performance, particularly in the mixed lubrication region (for example, gear lubrication conditions) while maintaining solubility in base oil.
• the lubricating oil composition of the present invention can enhance friction reduction performance, particularly friction reduction effect in mixed lubrication areas (for example, gear lubrication conditions, etc.) while maintaining storage stability.
• the additive composition and lubricating oil composition of the present invention exhibit an improved friction-reducing effect in the lubrication of metal surfaces that are subject to high loads, such as gears.
• transmissions e.g. manual transmissions, automatic transmissions, continuously variable transmissions, reduction gears for electric vehicles, speed increasers for wind turbines, etc.
• various industrial applications for example, hydraulic oil, turbine oil, compressor oil.
• Lubricating oil additive compositions having the compositions listed in Tables 1 to 5 were produced by the following procedure.
• FT/IR-4100 manufactured by JASCO Corporation.For samples that are solid at room temperature, we melt them by heating and apply a small amount to a KBr plate. Regarding the sample, a small amount was applied as it was on a KBr plate and measurements were performed.
• HPLC high performance liquid chromatography
• Equipment Thermo Fisher Scientific UltiMate 3000 UHPLC Column: ACQUITY (registered trademark) UPLC BEH C18 1.7 ⁇ m 50 x 2.1 mm (ODS) manufactured by Waters Corporation
• Detection device combination of charged particle detector (CAD) and mass spectrometer (MS)
• MS Mass spectrometer
• MS JEOL JMS-T100LP AccuTOF (registered trademark) LC-plus 4G (ionization method: ESI+)
• Mobile phase A gradient elution method using ultrapure water, methanol, and isopropyl alcohol was used.
• Ammonium formate was added to each solvent at a concentration of 10 mmol/L. Starting from a water/methanol mixed volume ratio of 20/80, the composition was continuously changed to 100% methanol, and then further continuously changed to 100% isopropyl alcohol. Column temperature: 40°C Sample solution: Methanol solution with sample concentration of approximately 100 mass ppm Sample injection amount: 1.0 ⁇ L Based on the detection results of the mass spectrometer (MS), each peak detected by the charged particle detector (CAD) was assigned to a compound. By using the peak area value of CAD, the content of each component (mass % in terms of compound in a state in which no salt is formed) was quantified.
• MS mass spectrometer
• the content of each component is determined by dividing the area value of the detected peak of CAD according to the ratio of the peak area values of the multiple compounds by MS. The amount (mass % in terms of compound without salt formation) was calculated.
• Manufacturing example 1 5.0 mol of lauric acid and 7.5 mol of diethanolamine (hereinafter sometimes referred to as "DEA") were placed in a 5L three-necked flask equipped with a distillation tube, together with a magnetic stirrer, and the inside of the flask was replaced with nitrogen. The materials were stirred with a magnetic stirrer to form a homogeneous mixture. The flask was heated in an oil bath while stirring the mixture in the flask with a magnetic stirrer. The heating temperature of the oil bath was gradually increased so that water continued to distill out. The reaction was followed by an IR spectrum, and 24 hours after the start of the reaction, completion of the reaction was confirmed by the IR spectrum.
• DEA diethanolamine
• compositions 1a, 1b, and 1c are lubricating oil additive compositions of the present invention
• composition 1d * is a lubricating oil additive composition outside the scope of the present invention.
• compositions 2a, 2b, 2c, and 2d * having different composition ratios of each component. Their compositions analyzed by LC-MS are shown in Table 2. Compositions 2a, 2b, and 2c are lubricating oil additive compositions of the invention, and composition 2d * is a lubricating oil additive composition outside the scope of the invention.
• compositions 3a, 3b, 3c, and 3d * having different composition ratios of each component. Their compositions analyzed by LC-MS are shown in Table 3. Compositions 3a, 3b, and 3c are lubricating oil additive compositions of the invention, and composition 3d * is a lubricating oil additive composition outside the scope of the invention.
• the flask was heated in an oil bath while stirring the mixture in the flask with a magnetic stirrer.
• the heating temperature of the oil bath was gradually increased so that water continued to distill.
• the reaction was followed by an IR spectrum, and 24 hours after the start of the reaction, the completion of the reaction was confirmed by the IR spectrum.
• 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 produce lubricating oil additive compositions 4a, 4b, 4c, 4d, and 4e * having different composition ratios of each component. Their compositions analyzed by LC-MS are shown in Table 4.
• Compositions 4a, 4b, 4c, and 4d are lubricating oil additive compositions of the present invention, and composition 4e * is a lubricating oil additive composition outside the scope of the present invention.
• composition 5 * is a lubricating oil additive composition outside the scope of this invention.
• lubricating oil compositions of the present invention (Examples 1 to 29) and comparative lubricating oil compositions (Comparative Examples 1 to 9) were prepared, respectively.
• “mass %” means mass % based on the total amount of the lubricating oil composition (100 mass %).
• “mass ppm” means mass ppm based on the total amount of the lubricating oil composition, and the expression “mass ppm/X" for element means. Details of each component are as follows.
• O-1 API Group II base oil (hydrocracked mineral oil base oil), kinematic viscosity (40°C): 9.3 mm 2 /s, kinematic viscosity (100°C): 2.5 mm 2 /s, viscosity index: 98, saturated content: 99.9% by mass, sulfur content: less than 1 mass ppm
• O-2 API Group V base oil (bis(2-ethylhexyl) azelaate), kinematic viscosity (40°C): 11.0 mm 2 / s, kinematic viscosity (100°C): 3.1 mm 2 /s, viscosity index: 146
• MTM test For each lubricating oil composition, a ball-on-disc friction test was conducted using an MTM traction measuring instrument (manufactured by PCS Instruments) to determine the friction coefficient ( ⁇ ) under conditions simulating gear lubrication (mixed lubrication region). was measured. The measurement conditions are as follows. Ball and disc: standard test piece (AISI52100 standard) Oil temperature: 80°C Load: 40N Circumferential speed: 0.3m/s Slip rate: 5% The results are shown in Tables 6-12. For Examples 1 to 21 and Comparative Examples 4 to 9, the reduction rate (%) of the friction coefficient relative to Comparative Example 1, and for Examples 23 to 25, the reduction rate (%) of the friction coefficient relative to Comparative Example 2. For Nos. 26 to 29, the reduction rate (%) of the friction coefficient relative to Comparative Example 3 is listed in the table.
• the lubricating oil compositions of Comparative Examples 4 to 8 contained a lubricating oil additive composition 1d outside the scope of the present invention as an oil-based friction modifier in place of the lubricating oil additive composition of the present invention * (Table 1 ), 2d * (Table 2), 3d * (Table 3), 4e * (Table 4), or 5 * (Table 5).
• the lubricating oil composition of Comparative Example 8 was not only unsuitable for practical use in terms of storage stability, but also showed poor results in reducing the coefficient of friction under conditions simulating gear lubrication. , and also showed poor results in fatigue resistance.
• the lubricating oil composition of Comparative Example 9 contained oleic acid amide (R 13 -CO in general formula (18a)) of diethanolamine monomer in place of the lubricating oil additive composition of the present invention as an oil-based friction modifier.
• This is a lubricating oil composition containing only an amide compound in which - is an oleoyl group.
• the lubricating oil composition of Comparative Example 9 had good storage stability, it showed almost no effect in reducing the coefficient of friction under conditions simulating gear lubrication, and also showed no effect in improving fatigue resistance. I could't see it.
• the lubricating oil compositions of Examples 22 to 25 are based on the lubricating oil compositions of Examples 3, 8, 13, and 19, in which base oil O-1 (hydrocracked mineral oil) is used as the lubricating oil base oil.
• This is a lubricating oil composition modified by replacing base oil O-2 (ester base oil, API base oil classification group V) with base oil O-2 (ester base oil, API base oil classification group V).
• the lubricating oil compositions of Examples 22 to 25 have lower friction coefficients under conditions simulating gear lubrication than the lubricating oil composition of Comparative Example 2 (Table 11), which does not contain an oil-based friction modifier. In addition to sufficiently reducing the amount of carbon dioxide, it exhibited sufficient storage stability and also sufficiently improved fatigue resistance.
• the lubricating oil compositions of Examples 26 to 29 were obtained by removing all lubricating oil additives other than the oil-based friction modifier from the lubricating oil compositions of Examples 3, 8, 13, and 19, respectively. It is a modified composition (that is, consisting of base oil O-1 and an oil-based friction modifier).
• the lubricating oil compositions of Examples 26 to 29 have lower friction coefficients under conditions simulating gear lubrication than the lubricating oil composition of Comparative Example 3 (Table 12), which does not contain an oil-based friction modifier. In addition to sufficiently reducing the amount of carbon dioxide, it exhibited sufficient storage stability and also sufficiently improved fatigue resistance.
• the lubricating oil composition containing the lubricating oil additive composition of the present invention can obtain sufficient storage stability and improve friction reduction performance, especially in mixed lubrication areas (for example, gear lubrication). It has been shown that it is possible to improve the friction reduction performance and further improve the fatigue resistance.
• 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 reduction performance, particularly in mixed lubrication areas (e.g. gear lubrication conditions, etc.), while maintaining solubility in base oil, and has improved fatigue resistance. sex is enhanced.
• the lubricating oil composition of the present invention has enhanced friction reduction performance, particularly in mixed lubrication areas (e.g. gear lubrication conditions, etc.), while maintaining storage stability, and also has enhanced fatigue resistance.
• the additive composition and lubricating oil composition of the present invention exhibit improved friction reduction effects and fatigue resistance when lubricating metal surfaces that are subject to high loads, such as gears, so they can be used for gear mechanisms, pistons, connecting rod bearings, etc. It can be suitably used to lubricate various mechanical devices with metal surfaces that are susceptible to high loads, especially transmissions (e.g. manual transmissions, automatic transmissions, continuously variable transmissions, electric vehicle reduction gears, wind turbine extensions). It can be suitably used for lubrication of internal combustion engines (speed engines, etc.) and internal combustion engines, and can also be suitably used for lubrication of various industrial applications (for example, hydraulic oil, turbine oil, compressor oil).

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