Lubricating oil additive composition and lubricating oil composition

Abstract

To provide an additive agent composition for a lubricating oil which can provide excellent abrasion resistance to a lubricating oil composition while containing no sulfur and no phosphorus and exhibiting excellent solubility to a lubricating oil base oil.SOLUTION: An additive agent composition for a lubricating oil contains the following components (X) and (Y). The component (X) is an organozirconium compound, and the component (Y) is borate of polyolefin polyamine succinimide.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a lubricating oil additive composition and a lubricating oil composition containing the lubricating oil additive composition. [Background technology]

[0002] In order to impart various properties and performance to a lubricating oil composition, various additives are blended into the lubricating oil composition. For example, zinc dialkyldithiophosphate (hereinafter also referred to as "ZnDTP") has long been widely used as an anti-wear additive for lubricating oils (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-331270 [Patent Document 2] JP 2020-026447 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, ZnDTP contains sulfur and phosphorus, which are highly corrosive elements. In addition, additives used in applications such as anti-wear agents, including ZnDTP, often contain at least one of sulfur and phosphorus. Therefore, there is a demand for the development of a new anti-wear agent that does not contain sulfur or phosphorus.

[0005] An object of the present invention is to provide a lubricating oil additive composition that does not contain sulfur or phosphorus, exhibits excellent solubility in a lubricating base oil, and is capable of imparting excellent wear resistance to a lubricating oil composition, and a lubricating oil composition containing the lubricating oil additive composition. [Means for solving the problem]

[0006] According to the present invention, the following [1] to [4] are provided. [1] A lubricating oil additive composition comprising the following component (X) and the following component (Y): Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide [2] A method for using the lubricating oil additive composition according to [1] above as an anti-wear agent. [3] A lubricating oil composition comprising a lubricating base oil (Z) and the lubricating oil additive composition according to [1] above. [4] A method for producing a lubricating oil composition, comprising the step of mixing a lubricating base oil (Z), the following component (X), and the following component (Y): Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide Effect of the Invention

[0007] According to the present invention, it is possible to provide a lubricating oil additive composition that does not contain sulfur or phosphorus, exhibits excellent solubility in a lubricating base oil, and is capable of imparting excellent wear resistance to a lubricating oil composition, and a lubricating oil composition containing the lubricating oil additive composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The upper and lower limit values ​​of the numerical ranges described in this specification can be combined in any way. For example, when "A to B" and "C to D" are described as numerical ranges, the numerical ranges "A to D" and "C to B" are also included in the scope of the present invention. In addition, unless otherwise specified, a numerical range of "lower limit value to upper limit value" described in this specification means not less than the lower limit value and not more than the upper limit value. In this specification, the numerical values ​​in the examples are numerical values ​​that can be used as upper or lower limits.

[0009] [Embodiments of the lubricating oil additive composition] The lubricating oil additive composition of the present embodiment contains the following component (X) and component (Y). Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide

[0010] The present inventors have conducted extensive research to solve the above problems, and have found that the above problems can be solved by using an organic zirconium compound in combination with a boronized polyolefin polyamine succinimide. The reason why the lubricating oil additive composition of this embodiment exhibits excellent solubility in a lubricating base oil and can impart excellent wear resistance to a lubricating oil composition is presumed to be, for example, as follows (1) and (2). (1) The interaction between the organozirconium compound and the boronized polyolefin polyamine succinimide improves the solubility of the organozirconium compound in the lubricating base oil compared to when the organozirconium compound is used alone, and improves the solubility of the lubricating oil additive composition as a whole in the lubricating base oil. (2) The interaction between the organic zirconium compound and the boronized polyolefin polyamine succinimide makes it easier to form a zirconium-based thin film on the sliding surface more effectively than when the organic zirconium compound is used alone or when the boronized polyolefin polyamine succinimide is used alone, thereby providing an excellent effect in improving wear resistance. In addition, if non-boronized polyolefin polyamine succinimide and boron-containing compound (e.g., tributyl borate, etc.) are used in combination with organic zirconium compound instead of boronized polyolefin polyamine succinimide, the wear resistance is greatly reduced, and the effect of the present invention is not achieved.The reason for this is presumably that when non-boronized polyolefin polyamine succinimide and boron-containing compound are used in combination, the formation of zirconium-based thin film on the sliding surface is inhibited by the action of competitive adsorption, etc. Therefore, the effect of the present invention is believed to be a unique effect achieved by combining an organozirconium compound with a boronized polyolefin polyamine succinimide.

[0011] In this embodiment, the lubricating oil additive composition may be composed only of component (X) and component (Y), but may also contain components other than component (X) and component (Y) as long as the effects of the present invention are not impaired. In the lubricating oil additive composition of this embodiment, the total content of component (X) and component (Y) is, based on the total amount of the lubricating oil additive composition, preferably 50 mass% to 100 mass%, more preferably 60 mass% to 100 mass%, even more preferably 70 mass% to 100 mass%, still more preferably 80 mass% to 100 mass%, even more preferably 90 mass% to 100 mass%, and even more preferably 95 mass% to 100 mass%. The total content of components (X) and (Y) referred to here is the total content based on the total amount of active ingredients in the lubricating oil additive composition, and does not include diluent ingredients (e.g., diluent oil, etc.). Components (X) and (Y) will be described in detail below.

[0012] <Component (X): Organic zirconium compound> The lubricating oil additive composition of this embodiment contains an organic zirconium compound as component (X). If the lubricating oil additive composition does not contain an organic zirconium compound, it will not be possible to provide the lubricating oil composition with excellent wear resistance. The organic zirconium compound used in the present embodiment is not particularly limited as long as it is a compound having an organic group and zirconium, and examples thereof include zirconium chelate compounds, zirconium alkoxide compounds, and zirconium acylate compounds. The organozirconium compounds may be used alone or in combination of two or more.

[0013] An example of the zirconium chelate compound is a compound represented by the following general formula (x1). [ka]

[0014] In the above general formula (x1), m is an integer of 0 to 3, n is an integer of 1 to 4, and m+n=4. R 1 is a hydrogen atom or an alkyl group having a carbon number of 1 to 20. The alkyl group is preferably linear or branched. R when m is 2 or more 1 may be the same or different. L is a ligand. When n is 2 or more, L may be the same or different.

[0015] As the ligand that can be selected as L, any ligand commonly used as a ligand for a chelating compound can be used without particular limitation, except for ligands containing sulfur and ligands containing phosphorus. Examples of ligands that can be selected for L include β-diketones, β-ketoesters, and alkanolamines. Here, from the viewpoint of making it easier to exert the effects of the present invention, the ligand that can be selected as L is preferably a β-diketone. In addition, when n is 2 or more, the ligands that can be selected as L are preferably the same.

[0016] From the viewpoint of making it easier to exert the effects of the present invention, the value of m is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. Therefore, the value of n is preferably 2 to 4, more preferably 3 to 4, and even more preferably 4.

[0017] Specific examples of zirconium chelate compounds include β-diketone-zirconium chelate compounds such as tri-n-butoxyzirconium monoacetylacetonate, di-n-butoxyzirconium bisacetylacetonate, n-butoxyzirconium triacetylacetonate, triisopropoxyzirconium monoacetylacetonate, diisopropoxyzirconium bisacetylacetonate, isopropoxyzirconium triacetylacetonate, and zirconium tetraacetylacetonate; β-ketoester-zirconium chelate compounds such as tri-n-butoxyzirconium monoethylacetoacetate, di-n-butoxyzirconium bisethylacetoacetate, n-butoxyzirconium triethylacetoacetate, triisopropoxyzirconium monoethylacetoacetate, diisopropoxyzirconium bisethylacetoacetate, isopropoxyzirconium triethylacetoacetate, and zirconium tetraethylacetoacetate; Examples of alkanolamine-zirconium chelate compounds include zirconium tetrakis(diethanol aminate), isopropoxy zirconium tris(diethanol aminate), diisopropoxy zirconium bis(diethanol aminate), triisopropoxy zirconium mono(diethanol aminate), dibutoxy zirconium bis(diethanol aminate), zirconium tetrakis(triethanol aminate), dimethoxy zirconium bis(triethanol aminate), diethoxy zirconium bis(triethanol aminate), isopropoxy zirconium tris(triethanol aminate), diisopropoxy zirconium bis(triethanol aminate), triisopropoxy zirconium mono(triethanol aminate), and di-n-butoxy zirconium bis(triethanol aminate). Among these, β-diketone-zirconium chelate compounds are preferred, and zirconium tetraacetylacetonate is more preferred. The zirconium chelate compounds may be used alone or in combination of two or more.

[0018] The zirconium alkoxide compound may be, for example, a compound in which four alkoxy groups having 1 to 20 carbon atoms are bonded to a zirconium element. The four alkoxy groups may be the same or different. The alkyl group constituting the alkoxy group may be linear or branched. Specific examples of the zirconium alkoxide compound include zirconium tetra-n-propoxide and zirconium tetra-n-butoxide. The zirconium alkoxide compounds may be used alone or in combination of two or more.

[0019] The zirconium acylate compound may be a compound having one or more groups represented by the following general formula (x2). [ka] In the general formula (x2) above, R 2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 20. The alkyl group is preferably linear or branched. In the above general formula (x2), the wavy line indicates the bond position with the zirconium element. When the zirconium acylate compound has two or more groups represented by the above general formula (x2), the multiple groups may be the same or different. Specific examples of the zirconium acylate compound include zirconium octylate, zirconium stearate, and zirconium(IV) oxide tetrakis(2-ethylhexanoate). The zirconium acylate compounds may be used alone or in combination of two or more.

[0020] In this embodiment, the organic zirconium compound, component (X), preferably contains one or more organic zirconium compounds (X1) selected from the group consisting of zirconium chelate compounds, zirconium alkoxide compounds, and zirconium acylate compounds, more preferably contains one or more organic zirconium compounds (X2) selected from the group consisting of zirconium chelate compounds and zirconium acylate compounds, and even more preferably contains one or more organic zirconium compounds (X3) selected from zirconium chelate compounds.

[0021] In the present embodiment, the content of the organic zirconium compound (X1), the organic zirconium compound (X2), or the organic zirconium compound (X3) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass, based on the total amount of the component (X).

[0022] (Zirconium content derived from component (X) (X Zr )) The zirconium content (X) derived from the organozirconium compound, which is component (X) Zr From the viewpoint of making it easier to exert the effects of the present invention, the amount of the organozirconium compound is preferably 10% by mass or more, more preferably 13% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the organozirconium compound. Also, the amount is preferably 30% by mass or less, more preferably 27% by mass or less, and even more preferably 25% by mass or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the content is preferably 10% by mass to 30% by mass, more preferably 13% by mass to 27% by mass, and even more preferably 15% by mass to 25% by mass.

[0023] <Component (Y): Boronized polyolefin polyamine succinimide> The lubricating oil additive composition of this embodiment contains a boronized polyolefin polyamine succinimide as component (Y). If the lubricating oil additive composition does not contain a boronized polyolefin polyamine succinimide, the solubility of the organozirconium compound in the lubricating oil base oil becomes insufficient. In addition, it is not possible to provide the lubricating oil additive composition with excellent wear resistance. The boronized polyolefin polyamine succinimide may be used alone or in combination of two or more kinds.

[0024] Examples of polyolefin polyamine succinimide constituting the boronized product of polyolefin polyamine succinimide include compounds represented by the following general formulae (y1) and (y2).

[0025] [ka]

[0026] In the above general formulas (y1) and (y2), R 11 , R 13 , and R 16 are each independently an alkenyl group or an alkyl group having a number average molecular weight (Mn) of 500 to 4,000. The number average molecular weight (Mn) of the alkenyl group or alkyl group is preferably 500 to 3,000, more preferably 700 to 2,000, and even more preferably 800 to 1,500. In this specification, the number average molecular weight (Mn) of the alkenyl group or alkyl group can be evaluated as the number average molecular weight (Mn) in terms of standard polystyrene by, for example, measuring a polyolefin that is a source of the alkenyl group or alkyl group using a GPC apparatus (apparatus name: HLC-8220, manufactured by Tosoh Corporation) equipped with columns (two columns with product name: TSKgel GMH-XL and one column with product name: G2000H-XL, manufactured by Tosoh Corporation) under the following conditions: detector: refractive index detector, measurement temperature: 40° C., mobile phase: tetrahydrofuran, flow rate: 1.0 mL / min, concentration: 0.5 mg / mL.

[0027] R 11 , R 13 , and R 16 Examples of the alkenyl group that can be selected as include a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer. Examples of the alkyl group include a polybutenyl group, a polyisobutenyl group, and a group obtained by hydrogenating an ethylene-propylene copolymer. Among these, an alkenyl group is preferable. Among the alkenyl groups, a polybutenyl group or a polyisobutenyl group is preferable, and a polyisobutenyl group is more preferable.

[0028] In the above general formulas (y1) and (y2), R 12 , R 14 , and R 15 each independently represents an alkylene group having 2 to 5 carbon atoms. In the above general formulas (y1) and (y2), A 1 and A 2 are each independently -NH- or a heterocycloalkylene group having 5 to 10 ring members and having one or more nitrogen atoms as a ring-forming atom. q and r each independently represents an integer of 1 to 10. Here, from the viewpoint of making it easier to exert the effects of the present invention, q is preferably 1 to 5, more preferably 1 to 4. Furthermore, r is preferably 1 to 4, more preferably 1 to 3.

[0029] The boronized polyolefin polyamine succinimide can be obtained, for example, by reacting a polyolefin with maleic anhydride to obtain polyolefin succinic anhydride (a), further reacting a polyamine with a boron compound to obtain intermediate (b), and then reacting polyolefin succinic anhydride (a) with intermediate (b) to perform imidization. Alternatively, the boronized polyolefin polyamine succinimide can be obtained by reacting polyolefin polyamine succinimide with a boron compound. The polyolefin polyamine succinimide represented by the above general formula (y1) and the polyolefin polyamine succinimide represented by the above general formula (y2) can be produced by changing the reaction ratio of polyolefin succinic anhydride and polyamine.

[0030] As the olefin monomer forming the polyolefin, one or a mixture of two or more α-olefins having 2 to 8 carbon atoms can be used, and it is preferable to use a mixture of isobutene and 1-butene or isobutene. On the other hand, examples of the polyamines include single diamines such as ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine; polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, and pentapentylenehexamine; and piperazine derivatives such as aminoethylpiperazine. The polyamines may be used alone or in combination of two or more kinds.

[0031] The boron compound includes boric acid, borate salts, and borate esters. Examples of boric acid include orthoboric acid, metaboric acid, and paraboric acid. Examples of borate salts include ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, and ammonium octaborate. Examples of borate esters include monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, and tributyl borate. The boron compounds may be used alone or in combination of two or more.

[0032] (Boron content derived from component (Y) (Y B )) Boron content derived from component (Y) (Y B From the viewpoint of making it easier to exert the effects of the present invention, the content of component (Y) is preferably 1.0 mass% or more, more preferably 1.3 mass% or more, and even more preferably 1.5 mass% or more based on the total amount of component (Y). Also, it is preferably 3.0 mass% or less, more preferably 2.7 mass% or less, and even more preferably 2.5 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 1.0 mass % to 3.0 mass %, more preferably 1.3 mass % to 2.7 mass %, and even more preferably 1.5 mass % to 2.5 mass %.

[0033] (Nitrogen content derived from component (Y) (Y N )) Nitrogen content derived from component (Y) (Y N From the viewpoint of making it easier to exert the effects of the present invention, the content of component (Y) is preferably 1.0 mass% or more, more preferably 1.3 mass% or more, and even more preferably 1.5 mass% or more based on the total amount of component (Y). Also, it is preferably 3.0 mass% or less, more preferably 2.5 mass% or less, and even more preferably 2.0 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 1.0 mass % to 3.0 mass %, more preferably 1.3 mass % to 2.5 mass %, and even more preferably 1.5 mass % to 2.0 mass %.

[0034] (Content ratio [(Y B ) / (Y N )]) Boron content derived from component (Y) (Y B ) and the nitrogen content derived from component (Y) (Y N ) and its content ratio [(Y B ) / (Y N From the viewpoint of making it easier to exert the effects of the present invention, the mass ratio of (a) to (c) is preferably 0.33 or more, more preferably 0.60 or more, and even more preferably 0.80 or more, and is preferably 2.0 or less, more preferably 1.6 or less, and even more preferably 1.4 or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 0.33 to 2.0, more preferably 0.60 to 1.6, and even more preferably 0.80 to 1.4.

[0035] <Content ratio [(Y N ) / (X Zr )]> In the lubricating oil additive composition of this embodiment, the nitrogen content derived from the component (Y) (Y N ) and the zirconium content (X Zr ) and its content ratio [(Y N ) / (X Zr From the viewpoint of solubility in the lubricating base oil, the mass ratio is preferably 3.5 or more, more preferably 4.0 or more, even more preferably 4.5 or more, still more preferably 5.0 or more, even more preferably 5.5 or more, and even more preferably 6.0 or more. From the viewpoint of improving the wear resistance, the mass ratio is preferably 15.0 or less, more preferably 10.0 or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 3.5 to 15.0, more preferably 4.0 to 15.0, even more preferably 4.5 to 15.0, still more preferably 5.0 to 10.0, even more preferably 5.5 to 10.0, and even more preferably 6.0 to 10.0.

[0036] <Other additives> The lubricating oil additive composition of this embodiment may contain any additive other than component (X) and component (Y) to the extent that the effects of the present invention are not impaired. Such other additives include antioxidants, oiliness agents, detergents and dispersants, viscosity index improvers, rust inhibitors, metal deactivators, and antifoam agents. The other additives may be used alone or in combination of two or more.

[0037] (Antioxidants) As the antioxidant, amine-based antioxidants, phenol-based antioxidants, etc., which are used in conventional lubricating oil compositions, can be used. These antioxidants may be used alone or in combination of two or more. Examples of the amine-based antioxidant include monoalkyldiphenylamine-based compounds such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamine-based compounds such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; polyalkyldiphenylamine-based compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; and naphthylamine-based compounds such as α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, and nonylphenyl-α-naphthylamine. Examples of the phenol-based antioxidant include monophenol-based compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; and bisphenol-based compounds such as 4,4'-methylenebis(2,6-di-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol).

[0038] (Oil-based agent) Examples of oily agents include fatty alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; and amine compounds such as fatty amines.

[0039] (Detergent / dispersant) Detergent-dispersants include metal sulfonates, metal salicylates, and metal phenates.

[0040] (Viscosity index improver) Examples of viscosity index improvers include polymethacrylates, dispersion-type polymethacrylates, olefin copolymers (e.g., ethylene-propylene copolymers, etc.), dispersion-type olefin copolymers, and styrene copolymers (e.g., hydrogenated styrene-diene copolymers, etc.).

[0041] (rust inhibitor) Rust inhibitors include metal sulfonates, succinic acid esters, and alkanolamines such as alkylamines and monoisopropanolamine.

[0042] (Metal deactivator) Examples of metal deactivators include benzotriazole and thiadiazole.

[0043] (Antifoaming agent) Examples of the antifoaming agent include methylsilicone oil, fluorosilicone oil, and polyacrylate.

[0044] <Dilution mode of lubricating oil additive composition> The lubricating oil additive composition of this embodiment may be diluted with a diluent such as diluent oil, taking into consideration ease of handling and storage stability. The diluent oil may be appropriately selected from mineral oils and synthetic oils exemplified as the lubricating oil base oil (Z) used in the lubricating oil composition described later. Alternatively, an organic solvent or the like may be used.

[0045] <Uses of lubricating oil additive composition> The lubricating oil additive composition of the present embodiment has excellent solubility in lubricating base oils and excellent anti-wear properties, and is therefore useful as an anti-wear additive for lubricating oil compositions. Thus, in this embodiment, there is provided a method of using the lubricating oil additive composition as an anti-wear agent.

[0046] [Lubricating oil composition] The lubricating oil composition of this embodiment contains the above-mentioned lubricating oil additive containing component (X) and component (Y), and lubricating oil base oil (Z). In other words, the lubricating oil additive of this embodiment contains the following component (X) and component (Y), and the lubricating oil base oil (Z). Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide

[0047] In the lubricating oil composition of this embodiment, “preferable compounds as component (X) and component (Y)” and “zirconium content derived from component (X) (X Zr ) (based on the total amount of component (X)) and the boron content derived from component (Y) (Y B ) (based on the total amount of component (Y))" and "Nitrogen content derived from component (Y) (Y N ) (based on the total amount of component (Y))" and "Content ratio [(Y B ) / (Y N )]”, “Content ratio [(Y N ) / (X Zr )” is as explained in the above embodiment of the lubricating oil additive.

[0048] <Lubricant base oil (Z)> The lubricating base oil (Z) may be any base oil commonly used in lubricating oil compositions without any particular limitations.Specific examples of the base oil include one or more selected from the group consisting of mineral oils and synthetic oils. The kinetic viscosity of the lubricating base oil (Z) at 100°C is 1mm 2 / s~50mm 2 / s, and preferably in the range of 2 mm 2 / s~30mm 2 / s, and more preferably in the range of 3 mm 2 / s~20mm 2 The viscosity index of the lubricating base oil is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more. The kinematic viscosity and viscosity index of the lubricating base oil (Z) are values ​​measured or calculated in accordance with JIS K2283:2000.

[0049] Specific examples of the lubricating base oil (Z) are listed below. Examples of mineral oils include distillate oils obtained by distilling paraffin-based crude oil, intermediate-based crude oil, or naphthene-based crude oil under atmospheric pressure and / or reduced pressure, refined oils obtained by refining the distillate oils according to conventional methods, etc. Refining methods for obtaining refined oils include, for example, solvent dewaxing, hydroisomerization, hydrofinishing, clay treatment, etc. Examples of synthetic oils include hydrocarbon oils, aromatic oils, ester oils, ether oils, etc. In addition, as synthetic oils, GTL (Gas To Liquids) obtained by isomerizing wax (GTL wax, Gas To Liquids WAX) produced from natural gas by the Fischer-Tropsch process or the like may be used.

[0050] <Zirconium derived from component (X) (X Zr ) content> In the lubricating oil composition of the present embodiment, from the viewpoint of making it easier to improve wear resistance, zirconium (X Zr The content of component (X) is preferably 100 ppm by mass or more, more preferably 150 ppm by mass or more, and even more preferably 180 ppm by mass or more, based on the total amount of the lubricating oil composition. From the viewpoint of the solubility of component (X) in the lubricating base oil, the content is preferably 1,000 ppm by mass or less, more preferably 800 ppm by mass or less, and even more preferably 500 ppm by mass or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 100 ppm by mass to 1,000 ppm by mass, more preferably 150 ppm by mass to 800 ppm by mass, and even more preferably 180 ppm by mass to 500 ppm by mass. In addition, when the lubricating oil composition does not contain any zirconium-containing compound other than component (X), the zirconium (X Zr) is equal to the zirconium content in the lubricating oil composition. The zirconium content can be measured, for example, by high-frequency inductively coupled plasma (ICP) emission spectrometry. In the lubricating oil composition of this embodiment, the content of component (X) is zirconium (X Zr ) is satisfied. Specifically, the content of component (X) is preferably 0.05 mass% or more, more preferably 0.08 mass% or more, and even more preferably 0.09 mass% or more, based on the total amount of the lubricating oil composition. Also, it is preferably 0.50 mass% or less, more preferably 0.40 mass% or less, and even more preferably 0.25 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 0.05 mass % to 0.50 mass %, more preferably 0.08 mass % to 0.40 mass %, and even more preferably 0.09 mass % to 0.25 mass %.

[0051] Boron derived from component (Y) B ) content> In the lubricating oil composition of this embodiment, in order to more easily exert the effects of the present invention, boron (Y B The content of ) is preferably 350 ppm by mass or more, more preferably 500 ppm by mass or more, and even more preferably 700 ppm by mass or more, based on the total amount of the lubricating oil composition, and is preferably 3,000 ppm by mass or less, more preferably 2,500 ppm by mass or less, and even more preferably 2,000 ppm by mass or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 350 ppm by mass to 3,000 ppm by mass, more preferably 500 ppm by mass to 2,500 ppm by mass, and even more preferably 700 ppm by mass to 2,000 ppm by mass. In addition, when the lubricating oil composition does not contain any boron-containing compound other than component (Y), the boron (Y B ) is equal to the boron content in the lubricating oil composition. The boron content can be measured by inductively coupled plasma (ICP) optical emission spectrometry.

[0052] Nitrogen derived from component (Y) N ) content> In the lubricating oil composition of this embodiment, from the viewpoint of making it easier to exert the effects of the present invention, the nitrogen (Y N The content of ) is preferably 340 ppm by mass or more, more preferably 500 ppm by mass or more, and even more preferably 700 ppm by mass or more, based on the total amount of the lubricating oil composition, and is preferably 2,300 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 1,800 ppm by mass or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the range is preferably 340 ppm by mass to 2,300 ppm by mass, more preferably 500 ppm by mass to 2,000 ppm by mass, and even more preferably 700 ppm by mass to 1,800 ppm by mass. The nitrogen content can be measured in accordance with JIS K2609:1998. In the lubricating oil composition of this embodiment, the content of component (Y) is the nitrogen (Y N ) is satisfied. Specifically, the content of component (Y) is preferably 1.9 mass% or more, more preferably 2.8 mass% or more, and even more preferably 3.9 mass% or more, based on the total amount of the lubricating oil composition. Also, it is preferably 13 mass% or less, more preferably 11 mass% or less, and even more preferably 10 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the content is preferably 1.9 mass % to 13 mass %, more preferably 2.8 mass % to 11 mass %, and even more preferably 3.9 mass % to 10 mass %.

[0053] <Other additives> The lubricating oil composition of this embodiment may contain additives other than component (X) and component (Y) to the extent that the effect of the lubricating oil additive composition is not impaired. Examples of such additives include the same additives as those exemplified as the additives that may be optionally contained in the lubricating oil additive composition. The other additives may be contained in the lubricating oil additive composition as described above. In this case, the lubricating oil composition containing the other additives can be prepared by blending the lubricating oil additive composition with the lubricating oil base oil (Z). When the other additives are not contained in the lubricating oil additive composition, the lubricating oil additive composition may be blended with the lubricating oil base oil (Z) and the other additives may be blended with the lubricating oil base oil (Z) to prepare a lubricating oil composition. Furthermore, even when the other additives are contained in the lubricating oil additive composition as described above, the lubricating oil additive composition may be blended with the lubricating oil base oil (Z) and the other additives may be blended with the lubricating oil base oil (Z) to prepare a lubricating oil composition.

[0054] [Method of manufacturing lubricating oil composition] The method for producing the lubricating oil composition of this embodiment is not particularly limited. For example, the method for producing the lubricating oil composition of this embodiment includes the step of mixing the lubricating base oil (Z), the following component (X), and the following component (Y). Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide The production method may further include a step of blending one or more kinds selected from the other additives described above, as necessary. The method for mixing the components is not particularly limited, but may be, for example, a method in which each component (one or more selected from component (X), component (Y), and the other additives described above) is blended with the lubricating base oil (Z). Incidentally, component (X) and component (Y) may be blended into the lubricating base oil (Z) simultaneously (that is, in the form of a lubricating oil additive composition) or may be blended separately. In addition, each component may be mixed after being made into a solution (dispersion) by adding a diluent oil or the like. After mixing each component, it is preferable to mix them together and disperse them uniformly by a known method. In the method for producing the lubricating oil composition of this embodiment, the “compounds preferred as component (X) and component (Y)” and the “zirconium content derived from component (X) (X Zr ) (based on the total amount of component (X)) and the boron content derived from component (Y) (Y B ) (based on the total amount of component (Y))" and "Nitrogen content derived from component (Y) (Y N ) (based on the total amount of component (Y))" and "Content ratio [(Y B ) / (Y N )]”, “Content ratio [(Y N ) / (X Zr )” is as explained in the above embodiment of the lubricating oil additive. In addition, the zirconium content derived from component (X) Zr ) (based on the total amount of the lubricating oil composition) and "boron content derived from component (Y) (Y B ) (based on the total amount of the lubricating oil composition) and "nitrogen content derived from component (Y) (Y N ) (based on the total amount of the lubricating oil composition) is also as explained in the above embodiment of the lubricating oil composition.

[0055] [Grease composition] The lubricating oil additive composition of the present embodiment can also be used by blending it with grease. That is, in this embodiment, a grease composition containing the lubricating oil additive composition, a thickener, and a lubricating oil base oil can be provided.

[0056] <Physical properties of lubricating oil composition> (Kinematic viscosity) The lubricating oil composition of this embodiment preferably has a kinematic viscosity at 100°C of 1.0 mm 2 / s~50mm 2 / s, more preferably 2.0 mm 2 / s~30mm 2 / s, more preferably 3.0 mm 2 / s~20mm 2 / s. The kinematic viscosity and viscosity index of the lubricating oil composition are values ​​measured or calculated in accordance with JIS K2283:2000.

[0057] (Phosphorus content) The lubricating oil composition of this embodiment preferably has a low phosphorus content, specifically, preferably less than 1.0 mass %, more preferably less than 0.1 mass %, even more preferably less than 0.01 mass %, based on the total amount of the lubricating oil composition, and most preferably contains no phosphorus. In this specification, the phosphorus content of a lubricating oil composition means the value measured in accordance with JIS-5S-38-03.

[0058] (Sulfur content) The lubricating oil composition of this embodiment preferably has a low sulfur content, specifically, preferably less than 1.0 mass %, more preferably less than 0.1 mass %, even more preferably less than 0.01 mass %, based on the total amount of the lubricating oil composition, and most preferably contains no sulfur. In this specification, the sulfur content of the lubricating oil composition means the value measured in accordance with JIS K2541-6:2013 (ultraviolet fluorescence method).

[0059] (Wear resistance) The lubricating oil composition of this embodiment preferably has a wear scar diameter of 460 μm or less, more preferably 450 μm or less, and even more preferably 440 μm or less, as determined by a ball-on-disk test described in the Examples section below.

[0060] [Uses of lubricating oil composition] The lubricating oil composition of the present embodiment has excellent wear resistance because it contains the lubricating oil additive composition containing the component (X) and the component (Y). For this reason, the lubricating oil composition of the present embodiment can be suitably used for a variety of applications, including drive system oils such as gear oils (manual transmission oil, differential oil, etc.), automatic transmission oils (automatic transmission oil, etc.), continuously variable transmission oils (belt CVT oil, toroidal CVT oil, etc.), power steering oil, shock absorber oil, and electric motor oil; internal combustion engine (engine) oils such as for gasoline engines, diesel engines, and gas engines; hydraulic oils; turbine oils; compressor oils; fluid bearing oils; and rolling bearing oils; and can be suitably used as a lubricating oil composition that is filled into equipment used in each of these applications and lubricates the various parts associated with the equipment.

[0061] [Lubrication method using lubricating oil composition] A preferred example of a lubrication method using the lubricating oil composition of the present embodiment is a method in which the lubricating oil composition is filled into equipment used for each of the above-mentioned applications and lubricates the components associated with each of the equipment.

[0062] [One aspect of the present invention provided] According to one aspect of the present invention, the following [1] to

[13] are provided. [1] A lubricating oil additive composition comprising the following component (X) and the following component (Y): Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide [2] The lubricating oil additive composition according to the above [1], wherein the component (X) comprises at least one compound selected from the group consisting of a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. [3] Boron (Y B ) and nitrogen (Y N ) and its content ratio [(Y B ) / (Y N The lubricating oil additive composition according to the above [1] or [2], wherein the mass ratio of [4] Nitrogen derived from the component (Y) N) and zirconium (X) derived from the component (X) Zr ) and its content ratio [(Y N ) / (X Zr The lubricating oil additive composition according to any one of the above [1] to [3], wherein the mass ratio of [5] The lubricating oil additive composition according to any one of the above [1] to [4], which is used as an anti-wear agent. [6] A method for using the lubricating oil additive composition according to any one of the above [1] to [4] as an anti-wear agent. [7] A lubricating oil composition comprising a lubricating base oil (Z) and the lubricating oil additive composition according to any one of the above [1] to [5]. [8] Zirconium (X) derived from the component (X) Zr The lubricating oil composition according to [7] above, wherein the content of said component (I) is 100 ppm by mass or more based on the total amount of said lubricating oil composition. [9] Boron (Y) derived from the component (Y) B The lubricating oil composition according to the above [7] or [8], wherein the content of said component (I) is 350 ppm by mass or more based on the total amount of said lubricating oil composition.

[10] Nitrogen derived from the component (Y) N The lubricating oil composition according to any one of the above [7] to [9], wherein the content of said component (a) is 340 ppm by mass or more based on the total amount of said lubricating oil composition.

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

[10] , having a phosphorus content of less than 0.01 mass % based on the total amount of the lubricating oil composition.

[12] The lubricating oil composition according to any one of the above [7] to

[11] , having a sulfur content of less than 0.01 mass % based on the total amount of the lubricating oil composition.

[13] A method for producing a lubricating oil composition, comprising the step of mixing a lubricating base oil (Z), the following component (X), and the following component (Y): Ingredient (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide EXAMPLES

[0063] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

[0064] [Methods for measuring various physical properties] The properties of the raw materials used in each Example and Comparative Example and the lubricating oil compositions in each Example and Comparative Example were measured according to the procedures described below.

[0065] (1) Kinematic viscosity and viscosity index at 100°C The kinetic viscosity at 100° C. was measured in accordance with JIS K2283:2000. The viscosity index was calculated in accordance with JIS K2283:2000 from the kinetic viscosity at 100° C. and the kinetic viscosity at 40° C. The kinetic viscosity at 40° C. was measured in accordance with JIS K2283:2000.

[0066] (2) Number average molecular weight (Mn) Columns (two columns of TSKgel GMH-XL and one column of G2000H-XL, both manufactured by Tosoh Corporation) were attached to a GPC apparatus (apparatus name: HLC-8220, manufactured by Tosoh Corporation), and measurements were performed under the following conditions: detector: refractive index detector, measurement temperature: 40°C, mobile phase: tetrahydrofuran, flow rate: 1.0 mL / min, concentration: 0.5 mg / mL, and the values ​​were calculated in terms of standard polystyrene.

[0067] [Example 1, Comparative Examples 1 to 8] Lubricant base oil (100℃ kinematic viscosity: 5.29mm 2 The lubricating oil compositions of Example 1 and Comparative Examples 1 to 8 were prepared by thoroughly mixing each of the raw materials described below in the amounts (unit: mass %) shown in Table 1 with a viscosity index of 104 / s and an API classification of Group II.

[0068] <Component (X)> Zirconium tetraacetylacetonate ("ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium content: 19% by mass), which is a compound corresponding to the zirconium chelate compound (X1), was used. Zirconium tetraacetylacetonate is a β-diketone-zirconium chelate compound in which, in the above general formula (x1), m=0, n=4, and L is a β-diketone.

[0069] <Component (Y)> Represented by the above general formula (y1), R 11 A compound obtained by boronizing polyolefin polyamine succinimide, in which the aryl group is a polyisobutenyl group (number average molecular weight (Mn): 950) with boric acid (boronized polyolefin polyamine succinimide) was used. The nitrogen content is 1.76% by mass and the boron content is 1.9% by mass.

[0070] <Component (Y')-1> A polyolefin polyamine succinimide polyol was used. The number average molecular weight (Mn) of the polyisobutenyl group in the polyolefin polyamine succinimide is 2,300.

[0071] <Component (Y')-2> Tributyl borate was used.

[0072] <Component (Y')-3> Zinc dialkyldithiophosphate (ZnDTP) was used. The ZnDTP is a secondary type ZnDTP having 3 and 6 alkyl carbon atoms.

[0073] [Evaluation method] The tests described below were carried out to evaluate the solubility in lubricating base oil (mineral oil) and the wear resistance.

[0074] <Evaluation of solubility in lubricating base oil (mineral oil)> The lubricating oil compositions of Example 1 and Comparative Examples 1 to 8 were heated to 80°C, stirred for 2 hours, and then allowed to stand until the temperature reached room temperature (25°C). The state of the oil when it reached room temperature was then visually evaluated, and the solubility of the blended components in the lubricating base oil was evaluated. The evaluation criteria were as follows: -Rating "A": Transparent. Rating "B": Sediment or cloudiness is observed.

[0075] <Wear resistance evaluation (ball-on-disk test)> Using a high-speed reciprocating friction tester TE77 (manufactured by Phoenix Tribology), the lubricating oil compositions of Example 1 and Comparative Examples 1 to 8 were introduced between the test plate and the test ball, and the test was performed by moving the test ball under the conditions described below. After the test, the wear scar diameters in the vertical direction and the horizontal direction of the test ball were measured, and the wear scar diameters were calculated using the following formula to perform an evaluation. Test plate Material: SUJ2, Shape: Length 58mm x Width 38mm x Thickness 3.9mm Test ball Material: SUJ2, diameter 10mm ·Lubricating conditions: oil bath, oil amount 3mL Load: 50N (5 min) → 100N (5 min) → 150N (5 min) → 200N (5 min) ·Temperature: 100℃ ·Amplitude: 10mm Frequency: 10Hz Wear scar diameter for evaluation = {(longitudinal wear scar diameter) + (lateral wear scar diameter)} / 2 The smaller the wear scar diameter, the more excellent the wear resistance of the lubricating oil composition. In this example, lubricating oil compositions with a wear scar diameter of 460 μm or less were judged to pass.

[0076] The results are shown in Table 1. In Table 1, "Zirconium content derived from component (X) (X Zr ) is a value calculated from the zirconium content of component (X) and the content of component (X) (based on the total amount of the lubricating oil composition). In Table 1, the boron content derived from component (Y) (Y N ) is a value calculated from the boron content of component (Y) and the content of component (Y) (based on the total amount of the lubricating oil composition). In Table 1, "Nitrogen content derived from component (Y) (Y N ) is a value calculated from the nitrogen content of component (Y) and the content of component (Y) (based on the total amount of the lubricating oil composition).

[0077] [Table 1]

[0078] From Table 1, we can see the following: The results shown in Example 1 show that the lubricating oil composition containing component (X) and component (Y) has good solubility of the blended components in the lubricating base oil and also has excellent wear resistance. In contrast, the results shown in Comparative Example 2 show that a lubricating oil composition containing component (X) but not component (Y) has poor solubility of the blended components (specifically, component (X)) in the lubricating base oil and also poor wear resistance. The results shown in Comparative Example 3 show that the lubricating oil composition containing component (Y) but not component (X) has good solubility of the blended components in the lubricating base oil, but has poor wear resistance. The results shown in Comparative Example 4 show that when component (X) is contained and a polyol of polyolefin polyamine succinimide (a non-boronated polyolefin polyamine succinimide) is used instead of component (Y), the solubility of the blended components in the lubricating base oil is good, but the wear resistance is poor. The results shown in Comparative Example 5 show that a lubricating oil composition that uses a polyol of polyolefin polyamine succinimide (a non-boronated polyolefin polyamine succinimide) instead of component (Y) and does not contain component (X) has good solubility of the blended components in the lubricating oil base oil, but has poor wear resistance. The results shown in Comparative Example 6 show that the lubricating oil composition of Example 1 has significantly better wear resistance than the lubricating oil composition containing ZnDTP as an anti-wear agent.

[0079] In addition, from the results shown in Comparative Examples 7 and 8, it can be seen that when a non-boronated polyolefin polyamine succinimide is used in combination with a boron-containing compound instead of a boronated polyolefin polyamine succinimide, the solubility of the blended components in the lubricating base oil is good, but the wear resistance is significantly reduced.

Claims

1. Contains the following component (X) and the following component (Y), Component (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide The lubricating oil additive composition used as an anti-wear agent, wherein the component (X) comprises at least one compound selected from the group consisting of zirconium chelate compounds, zirconium alkoxide compounds, and zirconium acylate compounds.

2. Boron (Y Ｂ ) and nitrogen (Y Ｎ ) and the content ratio [(Y Ｂ ) / (Y Ｎ 2. The lubricating oil additive composition according to claim 1, wherein the mass ratio of each of the components (a) to (c) is 0.33 to 2.

0.

3. Nitrogen (Y Ｎ ) and zirconium (X) derived from the component (X) Ｚｒ ) and the content ratio [(Y Ｎ ) / (X Ｚｒ 3. The lubricating oil additive composition according to claim 1 or 2, wherein the mass ratio of each of the above components is 3.5 or more.

4. A method for using the lubricating oil additive composition according to any one of claims 1 to 3 as an anti-wear agent.

5. A lubricating oil composition comprising a lubricating base oil (Z) and the lubricating oil additive composition according to any one of claims 1 to 3.

6. Zirconium (X) derived from the component (X) Ｚｒ 6. The lubricating oil composition according to claim 5, wherein the content of said component (I) is 100 ppm by mass or more based on the total amount of said lubricating oil composition.

7. Boron (Y Ｂ 7. The lubricating oil composition according to claim 5, wherein the content of said component (I) is 350 ppm by mass or more based on the total amount of said lubricating oil composition.

8. Nitrogen (Y Ｎ The lubricating oil composition according to any one of claims 5 to 7, wherein the content of said component (I) is 340 ppm by mass or more based on the total amount of said lubricating oil composition.

9. The lubricating oil composition according to any one of claims 5 to 8, having a phosphorus content of less than 0.01 mass %, based on the total amount of the lubricating oil composition.

10. The lubricating oil composition according to any one of claims 5 to 9, having a sulfur content of less than 0.01 mass %, based on the total amount of the lubricating oil composition.

11. The method includes a step of mixing a lubricating base oil (Z), the following component (X), and the following component (Y), Component (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide The method for producing a lubricating oil composition comprising a lubricating oil additive composition used as an anti-wear agent, wherein the component (X) comprises one or more compounds selected from the group consisting of zirconium chelate compounds, zirconium alkoxide compounds, and zirconium acylate compounds.

Images