JP7675563B2 - Lubricating oil additive composition and lubricating oil composition - Google Patents

Description

The present invention relates to a lubricating oil additive composition and a lubricating oil composition containing the lubricating oil additive composition.

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).

Japanese Patent Application Publication No. 7-331270 JP 2020-026447 A

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 the elements sulfur and phosphorus. Therefore, there is a demand for the creation of new anti-wear agents that do not contain sulfur or phosphorus.

The present invention aims to provide a lubricating oil additive composition that does not contain sulfur or phosphorus, exhibits excellent solubility in lubricating base oils, and can impart excellent wear resistance to a lubricating oil composition, and a lubricating oil composition that contains the lubricating oil additive composition.

According to the present invention, the following [1] to [4] are provided.
[1] A lubricating oil additive composition comprising the following component (X) and component (Y):
Component (X): an organic zirconium compound; Component (Y): a boronized polyolefin polyamine succinimide; [2] A method of using the lubricating oil additive composition according to the above item [1] 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):
Component (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide

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 lubricating base oils, and can impart excellent wear resistance to a lubricating oil composition, and a lubricating oil composition that contains the lubricating oil additive composition.

The upper and lower limit values of the numerical ranges described in this specification can be combined in any manner. For example, when numerical ranges "A to B" and "C to D" are described, 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.

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

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 the present 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 the case where 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) Due to the interaction between the organic zirconium compound and the boronized polyolefin polyamine succinimide, a thin zirconium-based film is more effectively formed on the sliding surface than when the organic zirconium compound is used alone or when the boronized polyolefin polyamine succinimide is used alone, and an excellent effect of improving wear resistance is exhibited.
However, if non-boronized polyolefin polyamine succinimide is used in combination with boron-containing compound (e.g., tributyl borate, etc.) instead of boronized polyolefin polyamine succinimide, and these are used in combination with organic zirconium compound, 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 is used in combination with boron-containing compound, the formation of zirconium-based thin film on 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.

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 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%, based on the total amount of the lubricating oil additive composition.
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.).
The components (X) and (Y) will be described in detail below.

<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.

Examples of the zirconium chelate compound include compounds represented by the following general formula (x1).

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.
^R1 is a hydrogen atom or an alkyl group having a carbon number of 1 to 20. The alkyl group is preferably linear or branched.
When m is 2 or more, R ¹ may be the same or different.
L is a ligand.
When n is 2 or more, L may be the same or different.

As the ligand that can be selected as L, any ligand commonly used as a ligand for a chelating compound can be used without any 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. Moreover, when n is 2 or more, the ligands that can be selected as L are preferably the same.

In order to make it easier to achieve 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.

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 the alkanolamine-zirconium chelate compounds include zirconium tetrakis(diethanol aminate), isopropoxyzirconium tris(diethanol aminate), diisopropoxyzirconium bis(diethanol aminate), triisopropoxyzirconium mono(diethanol aminate), dibutoxyzirconium bis(diethanol aminate), zirconium tetrakis(triethanol aminate), dimethoxyzirconium bis(triethanol aminate), diethoxyzirconium bis(triethanol aminate), isopropoxyzirconium tris(triethanol aminate), diisopropoxyzirconium bis(triethanol aminate), triisopropoxyzirconium mono(triethanol aminate), and di-n-butoxyzirconium 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.

An example of the zirconium alkoxide compound is 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. In addition, the alkyl group constituting the alkoxy group may be linear or branched.
Specific examples of the zirconium alkoxide compound include zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, and the like.
The zirconium alkoxide compounds may be used alone or in combination of two or more.

The zirconium acylate compound may be a compound having one or more groups represented by the following general formula (x2).

In the above general formula (x2), ^R2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 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) tetrakis(2-ethylhexanoate).
The zirconium acylate compounds may be used alone or in combination of two or more.

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.

In this 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 component (X).

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

<Component (Y): Boronated Polyolefin Polyamine Succinimide>
The lubricating oil additive composition of this embodiment contains boronized polyolefin polyamine succinimide as component (Y).If the lubricating oil additive composition does not contain boronized polyolefin polyamine succinimide, the solubility of the organozirconium compound in the lubricating oil base oil is 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.

Examples of the polyolefin polyamine succinimide constituting the boronized polyolefin polyamine succinimide include compounds represented by the following general formulas (y1) and (y2).

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 the present 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, for example, by 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 of TSKgel GMH-XL and one column of 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.

Examples of the alkenyl group that can be selected as R ¹¹ , R ¹³ , and R ¹⁶ 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.

In the above general formulas (y1) and (y2), R ¹² , R ¹⁴ , and R ¹⁵ each independently represent an alkylene group having 2 to 5 carbon atoms.
In the above general formulae (y1) and (y2), A ¹ and A ² each independently represent -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.

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.

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 polyamine 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.

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.

(Boron Content (Y _B ) Derived from Component (Y))
From the viewpoint of making it easier to exert the effects of the present invention, the boron content (Y _B ) derived from 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), and 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 %.

(Nitrogen Content ( _YN ) Derived from Component (Y))
From the viewpoint of making it easier to exert the effects of the present invention, the nitrogen content ( _YN ) derived from 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), and 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 %.

(Content ratio [(Y _B )/(Y _N )])
From the viewpoint of making it easier to exert the effects of the present invention, the content ratio of the boron content ( _YB ) derived from component (Y) to the nitrogen content ( _YN ) derived from component (Y) [( _YB )/( _YN )] is, in mass ratio, 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.

<Content ratio [(Y _N )/(X _Zr )]>
In the lubricating oil additive composition of this embodiment, the content ratio [( _YN )/ ₍ XZr)] of the nitrogen content (YN) derived from component (Y) to the zirconium content ( _XZr ) derived from component ( _X ) is preferably 3.5 or more, more preferably 4.0 or more, even more preferably 4.5 or more, even more preferably 5.0 or more, even more preferably 5.5 or more, and even more preferably 6.0 or more, in terms of solubility in lubricating base oil. Also, from the viewpoint of improving wear resistance, it 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 still more preferably 6.0 to 10.0.

<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.

(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 phenol-based antioxidants 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).

(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.

(Detergent/Dispersant)
Detergent-dispersants include metal sulfonates, metal salicylates, and metal phenates.

(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., styrene-diene hydrogenated copolymers, etc.).

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

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

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

<Dilution 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.

<Uses of the 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.

[Lubricating oil composition]
The lubricating oil composition of this embodiment contains the lubricating oil additive containing component (X) and component (Y), and a 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).
Component (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide

In the lubricating oil composition of this embodiment, the "preferred compounds for component (X) and component (Y)", "zirconium content ( _XZr ) derived from component (X) (based on the total amount of component (X))", "boron content ( _YB ) derived from component (Y) (based on the total amount of component (Y))", "nitrogen content ( _YN ) derived from component (Y) (based on the total amount of component (Y))", "content ratio [( _YB )/( _YN )]", and "content ratio [( _YN )/( _XZr )]" are as explained in the above aspect of the lubricating oil additive.

<Lubricant base oil (Z)>
As the lubricating base oil (Z), any general base oil used in lubricating oil compositions can be used without particular limitation.Specific examples thereof include one or more types selected from the group consisting of mineral oils and synthetic oils.
The kinematic viscosity of the lubricating base oil (Z) at 100° C. is preferably in the range of 1 mm ² /s to 50 mm ² /s, more preferably in the range of 2 mm ² /s to 30 mm ² /s, and even more preferably in the range of 3 mm ² /s to 20 mm ² /s. 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.

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 the synthetic oil, 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.

<Content of zirconium (X _Zr ) derived from component (X)>
In the lubricating oil composition of this embodiment, from the viewpoint of making it easier to improve wear resistance, the content of zirconium ( _XZr ) derived from component (X) is preferably 100 mass ppm or more, more preferably 150 mass ppm or more, and even more preferably 180 mass ppm or more based on the total amount of the lubricating oil composition. Also, from the viewpoint of the solubility of component (X) in the lubricating base oil, it is preferably 1,000 mass ppm or less, more preferably 800 mass ppm or less, and even more preferably 500 mass ppm 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.
When the lubricating oil composition does not contain any zirconium-containing compound other than component (X), the content of zirconium (X _Zr ) derived from component (X) is equal to the content of zirconium 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) may be adjusted to satisfy the content of zirconium (X _Zr ) derived from component (X). 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% by mass to 0.50% by mass, more preferably 0.08% by mass to 0.40% by mass, and even more preferably 0.09% by mass to 0.25% by mass.

<Content of boron (Y _B ) derived from component (Y)>
In the lubricating oil composition of this embodiment, from the viewpoint of making it easier to exert the effects of the present invention, the content of boron ( _YB ) derived from component (Y) 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.
When the lubricating oil composition does not contain any boron-containing compound other than component (Y), the content of boron (Y _B ) derived from component (Y) is equal to the content of boron in the lubricating oil composition.
The boron content can be measured by inductively coupled plasma (ICP) optical emission spectroscopy.

<Content of Nitrogen ( _YN ) Derived from Component (Y)>
In the lubricating oil composition of this embodiment, from the viewpoint of making it easier to exert the effects of the present invention, the content of nitrogen ( _YN ) derived from component (Y) 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) may be adjusted so as to satisfy the content of nitrogen ( _YN ) derived from component (Y). 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 range is preferably 1.9% by mass to 13% by mass, more preferably 2.8% by mass to 11% by mass, and even more preferably 3.9% by mass to 10% by mass.

<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 other 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.

[Method of producing 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).
Component (X): an organic zirconium compound Component (Y): a boronized polyolefin polyamine succinimide The production method may further include a step of blending one or more types selected from the other additives described above, as necessary.
The method for mixing the components is not particularly limited, and examples thereof include 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 (i.e., 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 the components together and disperse them uniformly by stirring using a known method.
In addition, in the method for producing the lubricating oil composition of this embodiment, the "preferred compounds for component (X) and component (Y)", "zirconium content ( _XZr ) derived from component (X) (based on the total amount of component (X))", "boron content ( _YB ) derived from component (Y) (based on the total amount of component (Y))", "nitrogen content ( _YN ) derived from component (Y) (based on the total amount of component (Y))", "content ratio [( _YB )/( _YN )]", and "content ratio [( _YN )/( _XZr )]" are as explained in the above aspect of the lubricating oil additive.
In addition, the "zirconium content ( _XZr ) derived from component (X) (based on the total amount of the lubricating oil composition)", "boron content ( _YB ) derived from component (Y) (based on the total amount of the lubricating oil composition)", and "nitrogen content ( _YN ) derived from component (Y) (based on the total amount of the lubricating oil composition)" are also as explained in the above embodiments of the lubricating oil composition.

[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.

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

(Phosphorus content)
The lubricating oil composition of the present 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 the lubricating oil composition means the value measured in accordance with JIS-5S-38-03.

(Sulfur content)
The lubricating oil composition of the present embodiment preferably has a low sulfur content, more 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 a value measured in accordance with JIS K2541-6:2013 (ultraviolet fluorescence method).

(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.

[Uses of the 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, for example, 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.

[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.

[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 component (Y):
Component (X): an organic zirconium compound; Component (Y): a boronized polyolefin polyamine succinimide. [2] The lubricating oil additive composition according to the above item [1], wherein the component (X) comprises one or more compounds selected from the group consisting of a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound.
[3] The lubricating oil _{additive composition according to the above [1] or [2], wherein the content ratio [(Y B ) /} (Y _N )] of boron (Y B ) derived from component (Y) to nitrogen (Y N ) derived from component (Y) is 0.33 to 2.0 in mass ratio.
[4] The lubricating oil additive composition according to any one of the above [ ₁ ] to [3], wherein the content ratio [( _YN )/( _XZr )] of nitrogen (YN) derived from the component (Y) to zirconium ( _XZr ) derived from the component (X) is 3.5 or more in mass ratio.
[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 [1] to [5] above.
[8] The lubricating oil composition according to the above [7], wherein the content of zirconium (X _Zr ) derived from the component (X) is 100 ppm by mass or more based on the total amount of the lubricating oil composition.
[9] The lubricating oil composition according to the above [7] or [8], wherein the content of boron (Y _B ) derived from the component (Y) is 350 ppm by mass or more based on the total amount of the lubricating oil composition.
[10] The lubricating oil composition according to any one of the above [7] to [9], wherein the content of nitrogen (Y _N ) derived from the component (Y) is 340 ppm by mass or more based on the total amount of the 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):
Component (X): Organic zirconium compound Component (Y): Boronized polyolefin polyamine succinimide

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

[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.

(1) Kinematic Viscosity and Viscosity Index at 100° C. The kinematic 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.

(2) Number average molecular weight (Mn)
Columns (two columns, product name: TSKgel GMH-XL, and one column, product name: G2000H-XL, 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.

[Example 1, Comparative Examples 1 to 8]
A lubricating base oil (100°C kinematic viscosity: 5.29 ^mm2 /s, viscosity index: 104, API classification: Group II) and each of the raw materials described below were thoroughly mixed in the amounts (unit: mass%) shown in Table 1 to prepare the lubricating oil compositions of Example 1 and Comparative Examples 1 to 8.

<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.

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

<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.

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

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

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

<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": Precipitation or cloudiness is observed.

<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 ball was moved under the conditions described below to perform the test. After the test, the wear scar diameters in the vertical direction and the horizontal direction of the test ball were measured, and the evaluation was performed based on the wear scar diameter calculated by the following formula.
Test plate: Material: SUJ2, Shape: Length 58 mm x Width 38 mm x Thickness 3.9 mm
Test ball: Material: SUJ2, diameter 10 mm
・Lubrication conditions: oil bath, oil amount 3mL
Load: 50N (5 minutes) → 100N (5 minutes) → 150N (5 minutes) → 200N (5 minutes)
・Temperature: 100℃
・Amplitude: 10mm
・Frequency: 10Hz
Wear scar diameter for evaluation = {(wear scar diameter in the vertical direction) + (wear scar diameter in the horizontal direction)} / 2
The smaller the wear scar diameter, the more excellent the wear resistance of the lubricating oil composition.
In this example, lubricating oil compositions having a wear scar diameter of 460 μm or less were judged to pass.

The results are shown in Table 1.
In Table 1, the "zirconium content (X _Zr ) derived from component (X)" 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, "boron content (Y _N ) derived from component (Y)" 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 (Y _N ) derived from component (Y)" 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).

From Table 1, the following can be seen:
From the results shown in Example 1, it can be seen 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 the 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 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.
From the results shown in Comparative Example 4, it can be seen 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 in which a polyol of polyolefin polyamine succinimide (a non-boronated polyolefin polyamine succinimide) is used instead of component (Y) and does not contain 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 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.

The results shown in Comparative Examples 7 and 8 show 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 (11)

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 . The lubricating oil additive composition according to claim 1, wherein the content ratio [(Y _B )/(Y _N )] of boron (Y _B ) derived from component (Y) to nitrogen (Y _N ) derived from component ( Y) is 0.33 to 2.0 in mass ratio. The lubricating oil additive composition according to claim 1 or 2, wherein a content ratio [( _YN )/( _XZr )] of nitrogen (YN) derived from the component ( _Y ) to zirconium ( _XZr ) derived from the component (X) is 3.5 or more in mass ratio. A method for using the lubricating oil additive composition according to any one of claims 1 to 3 as an anti-wear agent. 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 . The lubricating oil composition according to claim 5 , wherein the content of zirconium (X _Zr ) derived from the component (X) is 100 ppm by mass or more based on the total amount of the lubricating oil composition. The lubricating oil composition according to claim 5 or 6 , wherein the content of boron (Y _B ) derived from the component (Y) is 350 ppm by mass or more based on the total amount of the lubricating oil composition. The lubricating oil composition according to any one of claims 5 to 7 , wherein the content of nitrogen (Y _N ) derived from the component (Y) is 340 ppm by mass or more based on the total amount of the lubricating oil composition. 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. 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. 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.