JP2021138814A - Antiwear agent composition and fuel oil composition comprising the same - Google Patents

Abstract

To provide an antiwear agent composition which is excellent in handleability and exhibits high wear resistance, an antifungal property, and storage stability, and to provide a fuel oil composition comprising the same.SOLUTION: An antiwear agent composition according to the present invention comprises, as components: (A) a base oil; (B) a fatty acid, an acidic phosphate, or a mixture thereof; and (C) an isothiazoline compound. In the antiwear agent composition, a content ratio of the component (B) to the component (C) is 99:1 to 10:90 in a mass ratio.SELECTED DRAWING: None

Description

The present invention relates to an anti-wear composition which has excellent handleability and exhibits high abrasion resistance, antifungal property, and storage stability, and a fuel oil composition containing the same.

Lubricants, hydraulic oils, processing oils, and greases used in internal combustion engines such as automobiles and machinery such as machine tools, and fuel oils used in ships, vehicles, agricultural machinery, generators, etc. Various abrasion resistant agents are used to improve the properties. As conventional wear resistant agents, various phosphoric acid esters (Patent Document 1), fatty acids (Patent Document 2) and the like are known. However, although these wear-resistant agents have excellent wear-resistant properties, they have problems in terms of handleability, such as solidification and precipitation due to problems such as dissolution in base oil when applied to various applications.

Further, in the lubricating oil, an antibacterial agent or an antifungal agent may be used in combination so as to be suitable for the purpose of use and the environment of use. For example, Patent Document 3 describes an antibacterial lubricant composition containing a synthetic oil, a tertiary calcium phosphate, and a surfactant, and Patent Document 4 describes a specific anionic surfactant and a cationic surfactant. An antibacterial lubricant composition composed of a surfactant is proposed, and Patent Document 5 proposes a metal processing oil to which iodoacetate is added for the purpose of preventing the metal processing oil from spoiling and / or generating an offensive odor. ing.

Further, the fuel oil composition may also be required to have abrasion resistance and antifungal properties. For example, Patent Document 6 contains a specific cationic surfactant, a fatty acid, and an organic solvent, and is stable in storage. A composition having excellent properties and capable of improving the antifungal property and lubricity of the fuel oil by adding to the fuel oil is described. However, even in the composition of Patent Document 6, it is required to develop an anti-wear composition which has insufficient wear resistance and storage stability and is still excellent in various properties.

Japanese Unexamined Patent Publication No. 2012-107108 Special Table 2017-528588 Japanese Unexamined Patent Publication No. 2009-286957 Japanese Unexamined Patent Publication No. 08-333592 Japanese Unexamined Patent Publication No. 2000-109865 Japanese Unexamined Patent Publication No. 2016-0983030

Therefore, an object of the present invention is to provide an anti-wear composition having excellent handleability and exhibiting high abrasion resistance, antifungal property and storage stability, and a fuel oil composition containing the same. ..

As a result of diligent studies to solve the above problems, the present inventors have excellent handleability, and exhibit high wear resistance, antifungal property, and storage stability in an antiwear composition having a specific composition. We found that we did, and completed the present invention. That is, the present invention is an anti-wear composition containing a base oil as a component (A), a fatty acid as a component (B), an acidic phosphoric acid ester or a mixture thereof, and an isothiazoline-based compound as a component (C). The anti-wear composition is such that the ratio of the content of the component (B) to the content of the component (C) in the inhibitor composition is 99: 1 to 70:30 in terms of mass ratio.

According to the present invention, it is possible to provide an anti-wear composition having excellent handleability and exhibiting high abrasion resistance, antifungal property and storage stability, and a fuel oil composition containing the same.

The base oil used as the component (A) of the present invention includes mineral base oil, chemically synthesized base oil, animal and plant base oil, gasoline, light oil, heavy oil, kerosene, biofuel, and a mixture thereof, as appropriate according to the purpose of use and conditions. You can choose from base oil, etc. Here, examples of the mineral base oil include paraffin-based crude oil, naphthen-based crude oil, intermediate-based crude oil, and aromatic-based crude oil, and distillate oil obtained by atmospheric distillation of these, or usual There are distillate oils obtained by vacuum distillation of the residual oil of pressure distillation, and further refined oils obtained by refining these according to a conventional method, specifically solvent refined oils, hydrogenated refined oils, and dewazing treatments. Examples include oil and white clay treated oil.

Examples of the chemically synthesized base oil include poly-α-olefin, polyisobutylene (polybutene), monoester, diester, polyol ester, silicic acid ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, alkylbenzene and GTL. Examples include base oil. Among these, poly-α-olefins, polyisobutylene (polybutene), diesters, polyol esters and the like can be used for general purposes. Examples of the poly-α-olefin include those obtained by polymerizing or oligomerizing 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, etc., or hydrogenating these. Can be mentioned. Examples of the diester include diesters of dibasic acids such as glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, and alcohol diesters such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol. Examples of the polyol ester include polyols such as neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and caproic acid, capric acid, lauric acid, capric acid, myristic acid and palmitic acid. , Esters with fatty acids such as stearic acid and oleic acid.

Animal and plant base oils include, for example, castor oil, olive oil, cacao butter, sesame oil, rice bran oil, saflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, cottonseed oil and palm. Examples thereof include vegetable fats and oils such as oils, beef fats, pork fats, milk fats, fish oils and animal fats and oils such as whale oil.

Among these, when the anti-wear composition of the present invention is used as fuel oil, the base oil used as the component (A) is one or more selected from gasoline, light oil, heavy oil, kerosene, and biofuel. It is preferable to use the base oil of No. 1, more specifically, No. 1 light oil, No. 1 light oil, No. 2 light oil, No. 3 light oil, No. 3 light oil, A heavy oil, B heavy oil, C heavy oil, No. 1 kerosene, No. 2 kerosene, MGO (Marine Gas oil), MDO (Marine Diesel Oil), VLSFO (Very Low Sulfur)
It is preferable to use one or more base oils selected from Fuel Oil) and ULSFO (Ultra Low Sulfur Fuel Oil).

When the anti-wear composition of the present invention is used as a fuel oil, the base oil used as the component (A) is preferably a base oil having a sulfur atom content of 0 to 5000 mass ppm in the base oil, preferably 100. A base oil of ~ 5000 mass ppm is more preferred.

The viscosity of the base oil used as component (A) of the present invention, from the viewpoint of handling of the antiwear agent composition preferably has a kinematic viscosity of 40 ° C. is 1~800mm ² / s, 2~500mm ² It is more preferably / s, and most preferably 5 to ^{400 mm 2 / s.} In the present invention, the kinematic viscosity is a value obtained by measuring by the method described in JIS K 2283.

The fatty acid used as the component (B) of the present invention is not particularly limited as long as it is a compound having a carboxylic acid group and a hydrocarbon group, and examples thereof include saturated fatty acids and unsaturated fatty acids. The acidic phosphoric acid ester is not particularly limited as long as it is a compound having an esterified structure of one or two of the P-OH bonds contained in the phosphoric acid group, but for example, a phosphoric acid monoester. Examples thereof include a phosphoric acid diester, a phosphoric acid monoester metal salt, a phosphoric acid diester metal salt, a phosphoric acid monoesteramine salt, and a phosphoric acid diesteramine salt. In the present invention, by including such a component (B), the component (B) functions as an abrasion resistant agent when used in combination with the component (A) and the component (C), and has excellent handleability. It is possible to obtain an anti-wear composition that exhibits high wear resistance, anti-mold property, and storage stability.

Here, as the fatty acid, a fatty acid having an alkyl group having 12 to 22 carbon atoms is preferable. Myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, baxenoic acid, linoleic acid, linolenic acid, eleostearic acid, gadrainic acid, eicosenoic acid, eikosazienoic acid, meadic acid, arachidonic acid, erucic acid, etc. Of these, oleic acid, stearic acid, and lauric acid are preferable.

In addition, examples of the acidic phosphoric acid ester include those represented by the following general formula (1) or (2):

^{R 1} of the general formula (1) represents a monovalent hydrocarbon group having 4 to 30 carbon atoms. Examples of such a group include a linear alkyl group having 4 to 30 carbon atoms, a branched alkyl group having 4 to 30 carbon atoms, a linear alkenyl group having 4 to 30 carbon atoms, and a branched alkenyl group having 4 to 30 carbon atoms. , A monovalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. Among these, from the viewpoint of exhibiting high wear resistance, R ¹ is preferably a monovalent hydrocarbon group having 6 to 24 carbon atoms, a linear alkyl group having 6 to 18 carbon atoms, and 6 carbon atoms. It is more preferably any of a branched alkyl group of ~ 18 and a straight chain alkenyl group having 6 to 18 carbon atoms.

^{R 2} of the general formula (1) represents an alkylene group having 2 to 4 carbon atoms. Examples of such a group include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and the like. ^{Among these, R 2} is preferably an ethylene group or a propylene group from the viewpoint of exhibiting high wear resistance.

A in the general formula (1) represents a number from 0 to 10. Among these, a is preferably 0 to 6 from the viewpoint of exhibiting handleability and high wear resistance.

^{R 3} and R ⁵ of the general formula (2) independently represent monovalent hydrocarbon groups having 4 to 30 carbon atoms. Examples of such a group include a linear alkyl group having 4 to 30 carbon atoms, a branched alkyl group having 4 to 30 carbon atoms, a linear alkenyl group having 4 to 30 carbon atoms, and a branched alkenyl group having 4 to 30 carbon atoms. , A monovalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. Among these, from the viewpoint of exhibiting high wear resistance, R ³ and R ⁵ are preferably monovalent hydrocarbon groups having 6 to 24 carbon atoms, respectively, and are linear alkyl groups having 6 to 18 carbon atoms. , A branched alkyl group having 6 to 18 carbon atoms or a linear alkenyl group having 6 to 18 carbon atoms is more preferable.

^{R 4} and R ⁶ of the general formula (2) independently represent an alkylene group having 2 to 4 carbon atoms. Examples of such a group include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and the like. Among these, from the viewpoint of exhibiting high wear resistance ^{, it is preferable that R 4} and R ⁶ are ethylene groups or propylene groups, respectively.

B and c in the general formula (2) independently represent numbers 0 to 10. Among these, b and c are preferably 0 to 6, respectively, from the viewpoint of exhibiting handleability and high wear resistance.

Among these, the component (B) of the present invention is a fatty acid having an alkyl group having 12 to 22 carbon atoms from the viewpoint of exhibiting high wear resistance and storage stability, and the general formula (1) or the general formula (2). ) Is preferably contained, and at least one of the acidic phosphoric acid esters represented by the general formula (1) or the general formula (2) is more preferably contained, and the general formula (1) is more preferable. ) And the acidic phosphoric acid ester represented by the general formula (2) are further more preferably contained.

Further, as the isothiazolinone compound used as the component (C) of the present invention, for example, 2-methyl-4-isothiazolin-3-one, 2-methyl-4,5-trimethylone-4-isothiazolin-3-one, 5 −Chloro-2-methyl-4-isothiazolin-3-one, 2-n-octylisothiazolin-3-one, 4,5-dichloro-2-n-octylisothiazolin-3-one, 1,2-benzisothiazolin- Examples thereof include 3-one, Nn-butyl-1,2-benzisothiazolin-3-one and the like. Among these, from the viewpoint of storage stability and antifungal properties, it is preferable that the component (C) contains an alkylisothiazolinone compound having an alkyl group having 1 to 8 carbon atoms, and specifically, the component (C) It preferably contains at least 2-methyl-4-isothiazolin-3-one or 2-n-octylisothiazolin-3-one, and more preferably 2-n-octylisothiazolin-3-one. In the present invention, by including such an isothiazolin-based compound as the component (C), excellent wear resistance, antifungal property and storage stability can be exhibited.

In the anti-wear composition of the present invention, the ratio of the content of the component (B) to the content of the component (C) in the anti-wear composition is 99: 1 to 10:90 in terms of mass ratio. From the viewpoint of wear resistance, mold resistance and storage stability, the ratio of the content of the component (B) to the content of the component (C) is preferably 99: 1 to 50:50 in terms of mass ratio. It is more preferable that the mass ratio is 98: 2 to 70:30. In the present invention, by including the component (B) and the component (C) in such a content ratio, excellent wear resistance, antifungal property and storage stability can be exhibited.

From the viewpoint of handleability, the anti-wear composition of the present invention preferably contains 1 to 1000 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), preferably 100 to 1000 parts by mass. It is more preferable to have 200 to 500 parts by mass, and even more preferably 200 to 500 parts by mass. The content of the component (C) with respect to 100 parts by mass of the component (A) is preferably 0.1 to 50 parts by mass, more preferably 1 to 20 parts by mass, and 2 to 10 parts by mass. It is even more preferable to have.

The anti-wear composition of the present invention may contain a solvent depending on the purpose and application. Examples of such a solvent include glycol-based solvents, ketone-based solvents, amide-based solvents, cyclic amide-based solvents, ester-based solvents, acetate-based solvents, and the like. Among these, diethylene glycol monoalkyl ethers and diethylene glycol dialkyl ethers. , Dipropylene glycol, 2-methyl-2,4-pentanediol, ethylene glycol, propylene glycol and other glycol-based solvents are preferable. The content of the solvent in the anti-wear composition is not particularly limited, but is preferably 0.01 to 40% by mass, more preferably 0.1 to 20% by mass, based on the total amount of the anti-wear composition.

In the method for producing the anti-wear composition of the present invention, the above-mentioned components (A), (B) and (C) may be mixed by a known method, for example, in an environment of room temperature to 100 ° C. It can be produced by adding the component (B) and the component (C) to the base oil which is the component (A) in the whole amount or in a plurality of times at a time, and stirring and mixing at room temperature to 150 ° C.

The use of the anti-wear agent composition of the present invention is not particularly limited as long as the anti-wear agent is used, for example, engine oil, gear oil, turbine oil, hydraulic oil, flame-retardant hydraulic fluid, refrigerating machine oil, and the like. Lubricating oils such as compressor oil, vacuum pump oil, bearing oil, insulating oil, sliding surface oil, rock drill oil, metal processing oil, plastic processing oil, heat treatment oil; bearing grease, gear grease, gear grease, joints Greases for automobiles, greases for bearings and the like; fuel oils for automobiles, fuel oils for ships, fuel oils for aircraft and the like can be mentioned, and among these, fuel oils can be suitably used. When the anti-wear composition of the present invention is used for these lubricating oils, greases and fuel oils, other base oils and additives may be used in combination depending on the application and purpose.

The fuel oil composition of the present invention is a fuel oil composition containing the above-mentioned anti-wear composition. The fuel oil composition of the present invention may further contain a fuel oil base oil or an additive depending on the purpose in addition to the above-mentioned anti-corrosion agent composition. Such an additive includes, for example, a surface. Ignition inhibitor, octane number improver, cetane number improver, bactericide / antibacterial agent [excluding component (C) of the present invention], rust preventive, deposit improver, antioxidant, metal inactivating agent, cleaning The total amount of one or more selected from agents / dispersants, fluidity improvers, antifreeze agents, antiknock agents, corrosion inhibitors, antistatic agents, combustion improvers, dyes, etc., in total fuel oil composition It may be contained in an amount of 0.001 to 50% by mass based on the amount of 0.001 to 50% by mass.

Examples of the surface ignition inhibitor include organic phosphorus compounds such as tributyl phosphate, trimethyl phosphate, tricresyl phosphate, tricyclohexyl phosphate, cresyldiphenyl phosphate, trimethyl phosphate, and methylphenyl phosphate; 2-ethylhexyl boronate and Examples thereof include organic boron compounds such as butyldiisobutylboronate, and one or more of these can be used. The content of the surface ignition inhibitor is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the octane number improver include methanol, ethanol, butanol, butyl acetate, methyl-tert-butyl ether, ethyl-tert-butyl ether, methyl-tert-amyl ether, N-methylaniline, methylcyclopentadienyl manganese tricarbonyl, and the like. Examples thereof include tetraethyl lead, and one or more of these can be used. The content of the octane number improver is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the cetan value improver include aliphatic nitrates such as ethyl nitrate, methoxyethyl nitrate, isopropyl nitrate, amyl nitrate, hexyl nitrate, heptyl nitrate, octyl nitrate, 2-ethylhexyl nitrate and cyclohexyl nitrate; di-tert-butyl peroxide. Peroxides and the like can be mentioned, and one or more of these can be used. The content of the cetane number improver is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the bactericidal agent / antibacterial agent include inorganic bactericides such as silver sulfate, silver nitrate, zinc sulfate, zinc nitrate, copper sulfate, and ethylenediamine-4 copper acetate; hexahydro-1,3,5-tris (2-hydroxyethyl). Organic nitrogen-based antibacterial agents such as -S-triazine; organic copper-based antibacterial agents such as 2,2-dibromo-3-nitrilopropionamide, 1,4-bis (bromoacetoxy) -2-ethane, and bistribromomethylsulfone. , And one or more of these can be used. The content of the bactericidal agent / antibacterial agent is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the rust preventive include aliphatic amines and salts thereof, organic phosphoric acid esters, organic sulfonates, and the like, and one or more of these can be used. The content of the rust preventive is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the deposit improver include tricresyl phosphate, trimethyl phosphate, tris (chloroethyl) phosphate, polypropylene, polybutene, polyisobutyleneamine, polyetheramine, polyalkylamine, polyoxyalkyleneamine, polyalkylphenoxyaminoalkanol, and the like. Examples thereof include polyalkylene succinimide, and one or more of these can be used. The content of the deposit improver is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the antioxidant include diphenylamine, nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, N, N'-diisopropyl-p-phenylenediamine, N, N'-dibutyl-p-phenylenediamine, N, N. Amines such as'-dioctyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-ditril-p-phenylenediamine, N-tolyl-N'-xylenyl-p-phenylenediamine Antioxidants; 2-t-butylphenol, 2,6-diamine-butylphenol, 2,6-diamine-butyl-4-methylphenol, 2,4-dimethyl-6-tershaributylphenol, 2,4,6-tri Examples thereof include phenolic antioxidants such as -t-butylphenol, and one or more of these can be used. The content of the antioxidant is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the metal inactivating agent include amino compounds such as ethylenediamine; N, N'-disalicylidene-1,2-diaminopropane, N, N'-disalicylidene-2-cyclohexanediamine, N, N'-disalicyli. Denethylenediamine, N, N'-bis (dimethylsalicylidene) Ethylenediamine, N, N'-bis (dimethylsalicylidene) Salicylidene compounds such as ethylenetetramine, salicylaldoxime; 1- [bis (2-ethylhexyl) Aminomethyl-1,2,4-triazole, 1- (1-butoxyethyl) -1,2,4-triazole, 4,4'-methylenebis (2-undecyl-5-methylimidazole), bis [(N-N- Triazole compounds such as methyl) imidazol-2-yl] carbinol octyl ether; 4-alkylbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole, 1- [bis Bentriazoles such as (2-ethylhexyl) aminomethyl) triazole, 1- [bis (2-ethylhexyl) aminomethyl) benzotriazole, 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole, etc. Examples thereof include compounds, and one or more of these can be used. The content of the metal inactivating agent is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

Examples of the cleaning agent / dispersant include phosphate amide, aminoalkane, alkylamine phosphate ester, polyetheramine, polybutenylamine, alkenyl succinate imide, alkenyl succinate ester, sulfonic acid metal salt, and metal carboxylate. Examples thereof include salts, salicylate metal salts, phosphonic acid metal salts and the like, and one or more of these can be used. The content of the cleaning agent / dispersant is not particularly limited, but is preferably 0.001 to 10% by mass with respect to the total amount of the fuel oil composition, for example.

The content of the above-mentioned anti-wear agent composition in the fuel oil composition of the present invention is not particularly limited, but from the viewpoint of wear-resistant properties, antifungal properties and storage stability of the fuel oil composition, the anti-wear agent composition The content of the component (B) in the fuel oil composition is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, based on the total amount of the fuel oil composition. The amount is preferably 0.01 to 1% by mass, and even more preferably. Further, from the viewpoint of wear resistance, mold resistance and storage stability of the fuel oil composition, the content of the component (C) in the fuel oil composition is 0.0001 to 1 with respect to the total amount of the fuel oil composition. The amount is preferably 0.0003 to 0.5% by mass, more preferably 0.0005 to 0.1% by mass, and even more preferably 0.0005 to 0.1% by mass.

From the viewpoint of storage stability, abrasion resistance, etc. of the fuel oil composition, the fuel oil composition of the present invention preferably has a sulfur atom content of 0 to 5000 mass ppm, preferably 100 to 5000 mass ppm. Is preferable.

The use of the fuel oil composition of the present invention is not limited as long as it uses liquid fuel oil. For example, fuel oil for automobiles such as passenger cars and trucks, fuel oil for ships such as passenger ships and freight ships, and airplanes. It can be used as fuel oil for aircraft such as helicopters and helicopters, fuel oil for railway vehicles such as diesel locomotives, fuel oil for agricultural machinery, fuel oil for construction machinery, etc. Among these, it is used as fuel oil for ships. Is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples. In the following examples, "%" is based on mass unless otherwise specified. The components (A) to (C) used in the examples are shown below.

<Each ingredient used>
(A) Ingredients Base oil 1: Naften-based mineral oil (sulfur atom content: 200 mass ppm, 40 ° C kinematic viscosity: 9.1 mm ² / s)
Base oil 2: Paraffinic mineral oil (sulfur atom content: less than 10 mass ppm, 40 ° C dynamic viscosity: 20 mm ² / s)
Base oil 3: Kerosene (sulfur atom content: less than 10 mass ppm, 40 ° C kinematic viscosity: 2.0
mm ² / s)
(B) Component Abrasion resistant agent 1: Oleic acid Abrasion resistant agent 2: ^{A compound in which R 1} is a 2-ethylhexyl group and a is 0 in the general formula (1), and R ^{3 in the general formula (2).} , R ⁵ are 2-ethylhexyl groups, respectively, and b and c are 0, respectively. Acidic phosphate ester with a compound having a molar ratio of 1: 1. Abrasion resistant agent 3: In the general formula (1). , R ¹ is an oleyl group, R ² is an ethylene group, a is 1 to 6 (average value is 4), and in the general formula (2), R ³ and R ⁵ are oleyl, respectively. Acidic phosphoric acid consisting of a mixture of compounds in which R ⁴ and R ⁶ are ester groups and b and c are 1 to 6 (average value is 4), respectively, in a molar ratio of 1: 1. Ester Abrasion Resistant 4: In the general formula (1), R ¹ is an octyl group and a is 0, and in the general formula (2), R ³ and R ⁵ are octyl groups, respectively. Acidic phosphate ester (C) component consisting of a mixture of compounds having 0 and c in a molar ratio of 1: 1 Isothiazolin-based compound 1: Octylisothiazolin Other components Abrasion resistant agent A (comparative component): The following general formula Neutral Ester Abrasion Resistant B (Comparative Component): Oleyl Alcohol Abrasion Resistant C (Comparative Component): Octyl Oleate Bactericide A (Comparative Component): Dihydroxyethyl Lauryl Amin solvent 1: butyl diglycol

（式中、ｎは１〜３の数を表し、ｎの平均値は１．２である）

(In the formula, n represents a number from 1 to 3, and the average value of n is 1.2)

<Preparation of anti-wear composition>
In the flask, the component (A), the component (B), the component (C) and other components are mixed at the content ratio shown in Table 1 (“%” in the table represents mass%), and 1 at 100 ° C. By stirring for a time, the anti-wear composition of Examples 1 and 2 and Comparative Examples 1 to 3 was prepared.

<Evaluation of handleability>
Regarding the handleability of the anti-wear agent compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3, 20 g of each was put into a glass container and allowed to stand at room temperature for 1 month, and the state after that was used as the following evaluation criteria. Evaluated based on. The evaluation results are shown in Table 1.
Handling evaluation criteria ○: Liquid state and fluidity were maintained ×: Solidified or almost no fluidity

<Preparation of fuel oil composition>
In the flask, the components (A), (B), (C) and other components are mixed with the compositions shown in Tables 2 to 5 (% in the table represents mass%), and the mixture is stirred at 50 ° C. for 1 hour. The fuel oil compositions of Examples 3 to 9 and Comparative Examples 4 to 17 were prepared.

<Abrasion resistance test>
For each of the fuel oil compositions prepared in Examples 3 to 9 and Comparative Examples 4 to 17, the wear mark diameter was measured using a ball-on-disk type high frequency reciprocating device (HFRR). Specifically, the SUJ2 test plate and the SUJ2 test ball are set at predetermined positions, and the test balls are moved under the following test conditions while being lubricated with the fuel oil composition, and then the wear mark diameter of the test balls is measured. It was measured. The smaller the value of the wear mark diameter, the better the wear resistance, and from the viewpoint of practicality, the wear mark diameter is required to be 460 μm or less. The measurement results of the wear mark diameter (μm) are shown in Tables 2 to 5, respectively.
Test conditions Load: 890 kgf
Amplitude: 10 mm
Frequency: 1Hz
Temperature: 60 ° C

<Mold resistance test>
The antifungal properties of each of the fuel oil compositions prepared in Examples 3 to 9 and Comparative Examples 4 to 17 were evaluated by an antifungal test. Specifically, five types of molds (Aspergillus nigel, Penicillium) prepared in accordance with JIS Z 2911: 2018 by placing a glucose-peptone liquid medium in a petri dish with a diameter of 90 mm and pasting a 55 mm diameter sterile filter paper on the medium. After adding 0.50 ml of a spore suspension containing citrinum, resorps oryzae, cladosporium sphaerospermum, ketomium globosum), inject 15 ml of each fuel oil composition and incubate in a thermostat kept at 29 ° C for 4 weeks. bottom. Observe the growth state of the mold after culturing, and if the area of the growth part of the mold observed in the contacted part of the spore suspension does not exceed 1/3, the evaluation result is "○", which exceeds 1/3. In the case, it was evaluated as an evaluation result “x”. The evaluation results are shown in Tables 2 to 5, respectively.

<Storage stability test>
With respect to the fuel oil compositions prepared in Examples 3 to 9 and Comparative Examples 4 to 17, 20 g of each was put into a glass container and allowed to stand at room temperature for 1 day, and then the state was evaluated based on the following criteria. The evaluation results are shown in Tables 2 to 5, respectively.
Evaluation Criteria for Storage Stability ○: Overall transparent state ×: Retained matter was observed at the bottom

From the above results, the anti-wear composition of the present invention is excellent in handleability, and by using this anti-wear composition, excellent wear resistance, antifungal property and storage stability are exhibited. It can be seen that a fuel oil composition can be obtained.

Claims (7)

An anti-wear composition containing a base oil as a component (A), a fatty acid as a component (B), an acidic phosphoric acid ester or a mixture thereof, and an isothiazoline-based compound as a component (C) in the anti-wear composition. An anti-wear composition in which the ratio of the content of the component (B) to the content of the component (C) is 99: 1 to 10:90 in terms of mass ratio. The anti-wear composition according to claim 1, further comprising an alkylisothiazolin having an alkyl group having 1 to 8 carbon atoms as a component (C). Claim 1 includes, as the component (B), a fatty acid having an alkyl group having 12 to 22 carbon atoms, an acidic phosphoric acid ester represented by the following general formula (1) or general formula (2), or a mixture thereof. Or the anti-wear composition according to 2.

(In the formula, R ¹ , R ³ , and R ⁵ each independently represent a monovalent hydrocarbon group having 4 to 30 carbon atoms, and R ² , R ⁴ , and R ⁶ independently represent 2 to 4 carbon atoms, respectively. Represents the alkylene group of, and a, b, and c each independently represent a number from 0 to 10.) Any of claims 1 to 3, wherein the content of the component (B) is 0.01 to 90% by mass and the content of the component (C) is 0.01 to 40% by mass with respect to the total amount of the anti-wear composition. The anti-wear composition according to item 1. The anti-wear composition according to any one of claims 1 to 4, wherein the base oil of the component (A) has a sulfur atom content of 0 to 5000 mass ppm. A fuel oil composition containing the anti-wear composition according to any one of claims 1 to 5. The fuel oil composition according to claim 6, wherein the fuel oil composition has a sulfur atom content of 0 to 5000 mass ppm.