TW202311512A - Heat-treatment oil composition - Google Patents

Abstract

The present invention addresses the problem of providing a heat-treatment oil composition that, even when using a sulfur compound which has poor effects for achieving good brightness in a metal material after a heat-treatment such as quenching, can achieve a good brightness, and that, moreover, has excellent oxidation stability. The problem was solved by providing a heat-treatment oil composition containing: one or more base oils (A) selected from the group consisting of a mineral oil (A1), a synthetic oil (A2), and a plant oil (A3); a sulfur compound (B); and a carboxylic acid compound (C). The sulfur compound (B) comprises a specific sulfide, and the carboxylic acid compound (C) is one or more selected from a compound having at least one carboxy group and an anhydride thereof.

Description

Heat Treatment Oil Composition

The present invention relates to a heat treatment oil composition.

Metal materials such as steel are sometimes subjected to heat treatments such as quenching, tempering, annealing, and normalizing in order to improve their properties. Among these heat treatments, quenching is a process of immersing the heated metal material in a coolant to transform it into a predetermined quenching structure. By quenching, metal materials will become very hard and their mechanical strength will increase.

Heat treatment oil compositions have been widely used as coolants for quenching. In addition to the performance as a coolant, from the viewpoint of improving the commercial value of the metal material after quenching, the heat treatment oil composition is also required to have the performance of enabling the metal material to maintain the surface gloss before quenching after quenching. That is, the heat treatment oil composition is required to have the property of improving the brightness of the metal material after quenching.

As the heat-treated oil composition, for example, a heat-treated oil composition using a base oil in which sulfur and sulfur compounds are mixed with at least one of mineral oil and synthetic oil with a sulfur content of 300 ppm or less has been proposed. At least one, and the total sulfur content is adjusted to 3~1,000ppm (for example, refer to Patent Document 1).

prior art literature patent documents Patent Document 1: Japanese Patent Laid-Open No. 7-70632

The problem to be solved by the invention However, as a result of the inventor's efforts in research, it is known that some of the sulfur compounds listed in Patent Document 1 (such as diphenyldisulfide) can improve the brightness of metal materials after quenching. not effectively. From the point of view that various sulfur compounds can be widely used, we think it is appropriate to establish a formulation of a heat treatment oil composition that even when using a sulfur compound that is not effective in improving the brightness of metal materials after quenching, Brightness can still be improved. Also, since the heat-treated oil composition is assumed to be in contact with air when used in an open oil tank, it is also expected to have excellent oxidation stability.

Therefore, the object of the present invention is to provide a heat treatment oil composition which can improve the brightness of the metal material after heat treatment such as quenching even when a sulfur compound which is not effective in improving the brightness of the metal material after heat treatment such as quenching is used. , and has excellent oxidation stability.

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²為至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] [2]一種熱處理油組成物之使用方法，係將如上述[1]之熱處理油組成物作為淬火油或回火油使用。 [3]一種熱處理油組成物之製造方法，包含一混合基油(A)、硫化合物(B)及羧酸系化合物(C)之步驟，該基油(A)係選自於由礦油(A1)、合成油(A2)及植物油(A3)所構成群組中之1種以上； 前述硫化合物(B)包含選自於由以下所構成群組中之1種以上：下述通式(b1)所示硫化物類(B1)、下述通式(b2)所示硫化物類(B2)、下述通式(b3)所示硫化物類(B3)及下述通式(b4)所示硫化物類(B4)；且 前述羧酸系化合物(C)係選自於由至少具有1個羧基之化合物及其酐所構成群組中之1種以上。 [化學式2]

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²表示至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] MEANS TO SOLVE THE PROBLEM According to this invention, following [1]-[3] can be provided. [1] A heat-treated oil composition comprising a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C), the base oil (A) being selected from mineral oil (A1), synthetic oil ( One or more of the group consisting of A2) and vegetable oil (A3); the aforementioned sulfur compound (B) includes one or more of the group consisting of: sulfide represented by the following general formula (b1) (B1), sulfides (B2) represented by the following general formula (b2), sulfides (B3) represented by the following general formula (b3), and sulfides represented by the following general formula (b4) ( B4); and the aforementioned carboxylic acid compound (C) is at least one selected from the group consisting of compounds having at least one carboxyl group and their anhydrides. [chemical formula 1]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² is an aryl with at least 6 to 15 carbons of hydroxyl; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with a carbon number of 6 to 15] [2] A method of using a heat-treated oil composition, which is to use the heat-treated oil composition as described in [1] above Used as quenching oil or tempering oil. [3] A method for producing a heat-treated oil composition, comprising a step of mixing a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C), the base oil (A) being selected from mineral oil (A1), synthetic oil (A2) and vegetable oil (A3) constitute one or more kinds; the aforementioned sulfur compound (B) contains one or more kinds selected from the group consisting of the following general formula: Sulfides (B1) represented by (b1), sulfides (B2) represented by the following general formula (b2), sulfides (B3) represented by the following general formula (b3), and the following general formula (b4) ) represented by sulfides (B4); and the aforementioned carboxylic acid compound (C) is at least one selected from the group consisting of compounds having at least one carboxyl group and their anhydrides. [chemical formula 2]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² represents an arylylene group with at least 6 to 15 carbons having a hydroxyl group; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms]

Invention effect According to the present invention, it is possible to provide a heat treatment oil composition which can improve the brilliance of a metal material after heat treatment such as quenching even when a sulfur compound which is not effective in improving the brilliance of the metal material after heat treatment such as quenching is used, and has Excellent oxidation stability.

form for carrying out the invention In this specification, the lower limit and upper limit of the preferable numerical range (for example, the range of content, etc.) described step by step can be combined independently. For example, from the description of "preferably 10~90, more preferably 30~60", you can also combine "preferably lower limit (10)" and "preferably upper limit (60)" to determine "10~ 60". In addition, the numerical range "lower limit to upper limit" described in this specification means more than the lower limit and less than the upper limit unless otherwise specified. In this specification, the numerical value of an Example is the numerical value which can be used as an upper limit or a lower limit. In this specification, the "dynamic viscosity at 40°C" is also referred to as "40°C dynamic viscosity".

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²表示至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] [Example of heat-treated oil composition] The heat-treated oil composition of this embodiment contains a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C). The base oil (A) is selected from One or more of the group consisting of oil (A1), synthetic oil (A2) and vegetable oil (A3). The aforementioned sulfur compound (B) includes at least one selected from the group consisting of: sulfides (B1) represented by the following general formula (b1), sulfides represented by the following general formula (b2) (B2), sulfides (B3) represented by the following general formula (b3), and sulfides (B4) represented by the following general formula (b4). Furthermore, the said carboxylic acid compound (C) is 1 or more types selected from the group which consists of the compound which has at least 1 carboxyl group, and its anhydride. [chemical formula 3]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² represents an arylylene group with at least 6 to 15 carbons having a hydroxyl group; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms]

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved by combining a sulfur compound (B) which is not effective in improving the brilliance of metal materials after heat treatment such as quenching, in combination with a carboxylic acid compound (C). According to the study of the inventors of the present application, the effect of improving brightness cannot be observed only by blending the carboxylic acid compound (C) into the base oil (A). It can be inferred from this that in the present invention, the sulfur compound (B) and the carboxylic acid compound (C) are used in combination, so some kind of interaction will occur between these compounds, and then lead to the sulfur compound (B). It has the brightness improvement effect, and exerts the effect of the present invention.

The heat-treated oil composition of this embodiment may be composed only of base oil (A), sulfur compound (B) and carboxylic acid compound (C), or may contain base oil (A) within the range that does not impair the effect of the present invention. ), sulfur compound (B) and other components other than carboxylic acid compound (C). In this embodiment, based on the total amount of the heat-treated oil composition, the total content of the base oil (A), sulfur compound (B) and carboxylic acid compound (C) is preferably 75% by mass to 100% by mass, More preferably, it is 80 mass %-100 mass %, More preferably, it is 85 mass %-100 mass %, More preferably, it is 90 mass %-100 mass %, More preferably, it is 95 mass %-100 mass %.

Each component contained in the heat-treated oil composition of the present invention will be described in detail below.

＜Base Oil (A)＞ The heat treatment oil composition of this embodiment contains a base oil (A). The base oil (A) is one or more types selected from the group consisting of mineral oil (A1), synthetic oil (A2) and vegetable oil (A3). Hereinafter, mineral oil (A1), synthetic oil (A2), and vegetable oil (A3) will be described in detail.

(mineral oil (A1)) Mineral oil (A1) can be used as a general substance of mineral oil used for a heat treatment oil composition, and it is not specifically limited. Specific examples of mineral oil (A1) include the following: atmospheric residual oil obtained by atmospheric distillation of crude oil such as paraffinic crude oil, intermediate crude oil, and naphthenic crude oil; Distillate oil obtained by vacuum distillation of residual oil at atmospheric pressure; obtained by subjecting the distillate oil to one or more of the treatments of solvent deasphalting, solvent extraction, hydrolysis, solvent dewaxing, contact dewaxing, and hydrofining The mineral oil; wax isomerization of mineral oil.

Also, the mineral oil (A1) is preferably a high-purity mineral oil obtained by reducing sulfur content by performing a refining process including at least one selected from hydrocracking and hydrorefining. Based on the total amount of high-purity mineral oil, the sulfur content of high-purity mineral oil is preferably less than 10 mass ppm, more preferably less than 5 mass ppm, more preferably less than 3 mass ppm.

In addition, the mineral oil (A1) may be a bright oil with a low sulfur content. In this specification, the so-called "bright oil" refers to high-viscosity mineral oil (kinematic viscosity at 40°C: about 350 mm ² /sec to 550 mm ² /sec) obtained by the following treatment: paraffinic crude oil, intermediate Atmospheric distillation of crude oil such as crude oil and naphthenic crude oil, and then vacuum distillation of the obtained atmospheric residual oil to obtain distillate oil, and then de-asphalting of the distillate oil to obtain de-asphalted oil, and then the de-asphalted oil The bituminous oil is subjected to one or more refining treatments selected from solvent refining, hydrorefining, and the like. The bright lubricating oil with low sulfur content is preferably a hydrogenated refined product, and based on the total amount of the bright lubricating oil, the sulfur content is preferably less than 10 mass ppm, more preferably less than 5 mass ppm, more preferably less than 3 mass ppm. In addition, the bright lubricating oil with low sulfur content should be classified as Group II in the API category.

Mineral oil (A1) may be used alone or in combination of two or more.

(synthetic oil (A2)) Synthetic oil (A2) can be used as a general synthetic oil used for a heat treatment oil composition, and it is not specifically limited. To give specific examples of synthetic oil (A2), the following can be cited: poly-α-olefins, polyphenyl ethers, alkylbenzenes, alkylnaphthalenes, polyphenylene hydrocarbons, ester oils (for example, new fatty acid esters of polyhydric alcohols such as pentylene glycol, trimethylolpropane and neopentyl glycol), diol-based synthetic oils, and waxes produced from natural gas by the Fisher-Quebusch method (GTL GTL base oil obtained by isomerization of wax (Gas To Liquids WAX)). Among them, GTL base oil is preferred. Synthetic oil (A2) may be used individually by 1 type, and may use it in combination of 2 or more types.

(vegetable oil (A3)) Vegetable oil (A3) can be used as a general substance of vegetable oil used in heat-treated oil compositions, and is not particularly limited. Specific examples of vegetable oil (A3) include the following: linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil, sesame oil, olive oil, castor oil, peanut oil, coconut oil , palm kernel oil, palm oil, coconut oil, canola oil and rice bran oil. Vegetable oil (A3) may be used individually by 1 type, and may use it in combination of 2 or more types.

(A better form of base oil (A)) In this embodiment, as long as the base oil (A) is one or more selected from the group consisting of mineral oil (A1), synthetic oil (A2) and vegetable oil (A3), it is preferably selected from One or more species in the group consisting of mineral oil (A1) and synthetic oil (A2). Also, the base oil (A) preferably contains mineral oil (A1). When the base oil (A) contains mineral oil (A1), based on the total amount of the base oil (A), the content of the mineral oil (A1) is preferably 20% by mass to 100% by mass, more preferably 30% by mass ~100% by mass, more preferably 40% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, further preferably 70% by mass to 100% by mass , it is further preferably 80% by mass to 100% by mass, and further preferably 90% by mass to 100% by mass.

(Kinematic Viscosity of Base Oil (A) at 40°C) In this embodiment, the dynamic viscosity of base oil (A) at 40°C is preferably 5 mm ² /sec to 600 mm ² /sec, more preferably 6 mm ² /sec to 570 mm ² /sec, more preferably 7mm ² /sec to 540mm ² /sec, more preferably 8mm ² /sec to 520mm ² /sec, and more preferably 9mm ² /sec to 500mm ² /sec. If the 40°C kinematic viscosity of the base oil (A) is not less than 5 mm ² /sec, it is easy to produce a heat-treated oil composition in which the generation of oily smoke is suppressed. On the other hand, if the 40°C kinematic viscosity of the base oil (A) is 600 mm ² /sec or less, it is easy to produce a heat treatment oil composition with good cooling performance. In addition, in this specification, 40 degreeC dynamic viscosity is the value measured based on JISK2283:2000. In addition, considering the ease of adjustment of the 40°C kinematic viscosity of the base oil (A), the heat-treated oil composition of this embodiment should be used by mixing a plurality of base oils with different 40°C kinematic viscosities.

(Content of base oil (A)) In the heat-treated oil composition of this embodiment, based on the total amount of the heat-treated oil composition, the content of the base oil (A) is preferably at least 80.0% by mass, more preferably at least 82.0% by mass, more preferably at least 83.0% by mass %above. In addition, the content is preferably 98.99% by mass or less. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the content is preferably 80.0% by mass to 98.99% by mass, more preferably 82.00% by mass to 98.99% by mass, more preferably 83.0% by mass to 98.99% by mass.

＜Sulfur compound (B)＞ The heat-treated oil composition of this embodiment contains a sulfur compound (B). Regarding the sulfur compound (B), the effect of improving the brightness of the metal material after heat treatment such as quenching is not good. However, by using it in combination with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching can be improved. In this embodiment, the sulfur compound (B) includes 1 selected from the group consisting of sulfides (B1), sulfides (B2), sulfides (B3) and sulfides (B4). more than one species. In this embodiment, the sulfur compound (B) may only be selected from the group consisting of sulfides (B1), sulfides (B2), sulfides (B3) and sulfides (B4). One or more of them may contain sulfides (B1), sulfides (B2), sulfides (B3) and sulfides (B4) within the scope of not impairing the effect of the present invention. ) other than sulfur compounds. In this embodiment, one or more selected from the group consisting of sulfides (B1), sulfides (B2), sulfides (B3) and sulfides (B4) means Contains the following forms. Sulfides only (B1) Sulfides only (B2) Sulfides only (B3) Sulfides only (B4) Combination of Sulfides (B1) and Sulfides (B2) Combination of Sulfides (B1) and Sulfides (B3) Combination of Sulfides (B1) and Sulfides (B4) Combination of Sulfides (B2) and Sulfides (B3) Combination of Sulfides (B2) and Sulfides (B4) Combination of Sulfides (B3) and Sulfides (B4) Combination of sulfides (B1), sulfides (B2) and sulfides (B3) Combination of sulfides (B1), sulfides (B2) and sulfides (B4) Combination of sulfides (B1), sulfides (B3) and sulfides (B4) Combination of sulfides (B2), sulfides (B3) and sulfides (B4) Combinations of sulfur compounds (B1), sulfides (B2), sulfides (B3) and sulfides (B4) In this embodiment, based on the total amount of sulfur compounds (B), selected from sulfides (B1), sulfides (B2), sulfides (B3) and sulfides (B4) The content of one or more compounds in the group formed is preferably 70% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and more preferably 95% by mass %~100% by mass. Hereinafter, sulfides (B1), sulfides (B2), sulfides (B3), and sulfides (B4) will be described in detail.

(Sulfides (B1)) The sulfides (B1) are compounds represented by the following general formula (b1). [chemical formula 4]

In the aforementioned general formula (b1), Ar ¹¹ is an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group. When, for example, the compound represented by the aforementioned general formula (b1) has a structure in which a sulfur atom and an aryl group are bonded via a methylene group, it is not good in the effect of making the brightness of the metal material after heat treatment such as quenching become good. tendency. However, by using it in combination with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching can be improved. In addition, if the carbon number of the aryl group is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

In the aforementioned general formula (b1), the aryl group having 6 to 15 carbon atoms constituting Ar ¹¹ can be, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, fenyl, and anthracenyl. In addition, "6-15 carbon atoms" in "aryl group having 6-15 carbon atoms" means "6-15 ring-forming carbon atoms". The carbon number of the aryl group is preferably 6-10, more preferably 6, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C).

In the aforementioned general formula (b1), the aryl group having 6 to 15 carbon atoms constituting Ar ¹¹ has at least one hydroxyl group. If the aryl group does not have a hydroxyl group, the oxidation stability of the heat-treated oil composition may be insufficient. Here, the aryl group may further have a substituent other than a hydroxyl group, or may not have a substituent other than a hydroxyl group. Examples of such substituents include: monovalent aliphatic hydrocarbon groups with 1 to 10 carbons, alkoxy groups with 1 to 10 carbons, hydroxyl, amino, nitro, amido, benzamide, carboxyl, The residue obtained by removing a hydrogen atom from one hydroxyl group of a carboxylic acid, and a halogen atom. The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 3 to 10 carbons, more preferably a branched alkyl group having 3 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. In addition, the number of hydroxyl groups that the aryl group has may be one or plural, but one is preferred. Also, when the aryl group has a substituent other than a hydroxyl group, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

In the aforementioned general formula (b1), R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1). When the hydrocarbon group (X1) has a substituent, the substituent may include: a monovalent aliphatic hydrocarbon group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a hydroxyl group, an amino group, a nitro group, an amido group, A benzamide group, a carboxyl group, a residue obtained by removing a hydrogen atom from one hydroxyl group of a dicarboxylic acid, and a halogen atom. The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 3 to 10 carbons, more preferably a branched alkyl group having 3 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. When the hydrocarbon group (X1) has a substituent, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

In the aforementioned general formula (b1), the hydrocarbon group (X1) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, a cycloalkyl group with 3 to 15 carbons, and a cycloalkenyl group with 3 to 15 carbons , Cycloalkylalkyl with 4 to 15 carbons, cycloalkenylalkyl with 4 to 15 carbons, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons. The carbon number of the hydrocarbon group (X1) does not include the carbon number of the aforementioned substituents that the hydrocarbon group (X1) may have. In addition, if the number of carbon atoms that can be used as the hydrocarbon group (X1) is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

As an alkyl group with 1 to 15 carbon atoms that can be used as the hydrocarbon group (X1), for example, the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl , Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl and Pentadecyl. This alkyl group may be linear or branched.

Alkenyl groups having 2 to 15 carbon atoms that can be used as the hydrocarbon group (X1) include, for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl. , Nonenyl, Decenyl, Undecenyl, Dodecenyl, Tridecenyl, Tetradecenyl and Pentadecenyl. This alkenyl group may be linear or branched.

The cycloalkyl group having 3 to 15 carbon atoms that can be used as the hydrocarbon group (X1) includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. In addition, "carbon number 3-15" in "cycloalkyl group having 3-15 carbons" means "ring carbon number 3-15". The carbon number of the cycloalkyl group is preferably 5-10, more preferably 5-6, from the viewpoint that the effect brought about by the combination with the carboxylic acid compound (C) can be more easily exhibited.

Examples of the cycloalkenyl group having 3 to 15 carbon atoms that can be used as the hydrocarbon group (X1) include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. In addition, "carbon number 3-15" in "cycloalkenyl group having 3-15 carbons" means "ring carbon number 3-15". The carbon number of the cycloalkenyl group is preferably 5-10, more preferably 5-6, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C).

上述通式(c1)中，圓為環烷基，R ³¹為伸烷基。波浪線意指與上述通式(b1)中之碳原子鍵結的位置。 另外，「碳數4~15之環烷基烷基」的「碳數4~15」，意指環烷基之成環碳數與伸烷基(R ³¹)之碳數的合計碳數。 從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該環烷基烷基之環烷基的碳數(成環碳數)宜為5~10，較宜為5~6。 又，從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該環烷基烷基之伸烷基的碳數宜為1~6，較宜為1~4，更宜為1~2。 Cycloalkylalkyl groups with 4 to 15 carbon atoms that can be used as the hydrocarbon group (X1) include, for example, the following: cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl Cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl. In addition, cycloalkylalkyl is a group represented by the following general formula (c1), and is a group in which one hydrogen atom of the alkyl group is substituted with a cycloalkyl group. [chemical formula 5]

In the above general formula (c1), the circle is a cycloalkyl group, and ^R31 is an alkylene group. The wavy line means a bonded position to a carbon atom in the above general formula (b1). In addition, "carbon number 4-15" of "cycloalkylalkyl group having 4-15 carbons" means the total carbon number of the ring-forming carbon number of the cycloalkyl group and the carbon number of the alkylene group (R ³¹ ). From the point of view that it is easier to exert the effect brought by the combination with the carboxylic acid compound (C), the carbon number (ring carbon number) of the cycloalkyl group constituting the cycloalkylalkyl group is preferably 5 to 10, preferably 5~6. Also, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C), the carbon number of the alkylene group constituting the cycloalkylalkyl group is preferably 1 to 6, more preferably 1 to 4 , more preferably 1~2.

上述通式(c2)中，圓為環烯基，R ³²為伸烷基。波浪線意指與上述通式(b1)中之碳原子鍵結的位置。 另外，「碳數4~15之環烯基烷基」的「碳數4~15」，意指環烯基之成環碳數與伸烷基(R ³²)之碳數的合計碳數。 從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該環烯基烷基之環烯基的碳數(成環碳數)宜為5~10，較宜為5~6。 又，從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該環烯基烷基之伸烷基的碳數宜為1~6，較宜為1~4，更宜為1~2。 Cycloalkenylalkyl groups with 4 to 15 carbon atoms that can be used as the hydrocarbon group (X1) include, for example, the following: cyclopropenylmethyl, cyclopropenylethyl, cyclopropenylpropyl, cyclopropenylbutyl Cyclobutenylmethyl, cyclopentenylmethyl, cyclopentenylethyl, cyclopentenylpropyl, cyclohexenylmethyl, cyclohexenylethyl and cyclohexenylpropyl . In addition, the cycloalkenylalkyl group is a group represented by the following general formula (c2), and is a group in which one hydrogen atom of the alkyl group is substituted with a cycloalkenyl group. [chemical formula 6]

In the above general formula (c2), circle is a cycloalkenyl group, and ^R32 is an alkylene group. The wavy line means a bonded position to a carbon atom in the above general formula (b1). In addition, "carbon number 4-15" of "cycloalkenylalkyl group having 4-15 carbons" means the total carbon number of the ring-forming carbon number of the cycloalkenyl group and the carbon number of the alkylene group (R ³² ). From the point of view that it is easier to exert the effect brought by the combination with the carboxylic acid compound (C), the carbon number (ring carbon number) of the cycloalkenyl group constituting the cycloalkenylalkyl group is preferably 5 to 10, preferably 5~6. Also, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C), the carbon number of the alkylene group constituting the cycloalkenylalkyl group is preferably 1 to 6, more preferably 1 to 4 , more preferably 1~2.

The aryl group having 6 to 15 carbon atoms that can be used as the hydrocarbon group (X1) includes, for example, the following: phenyl, biphenyl, naphthyl, phenanthrenyl, fenyl, and anthracenyl. In addition, "6-15 carbon atoms" in "aryl group having 6-15 carbon atoms" means "6-15 ring-forming carbon atoms". The carbon number of the aryl group is preferably 6-10, more preferably 6, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C).

在上述通式(c3)中，雙重圓為芳基，R ³³為伸烷基。波浪線意指與上述通式(b1)中之碳原子鍵結的位置。 另外，「碳數7~15之芳烷基」的「碳數7~15」，意指芳基之成環碳數與伸烷基(R ³³)之碳數的合計碳數。 從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該芳烷基之芳基的碳數(成環碳數)宜為6~10，較宜為6。 又，從更容易發揮與羧酸系化合物(C)之組合所帶來之效果的觀點，構成該芳烷基之伸烷基的碳數宜為1~6，較宜為1~4，更宜為1~2。 Aralkyl groups with 7 to 15 carbon atoms that can be used as the hydrocarbon group (X1) include, for example, the following: phenylmethyl, phenylethyl, phenylpropyl, biphenylmethyl, biphenyl Ethyl, biphenylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl, phenanthrenylmethyl, fenylmethyl, fenylethyl and anthracenylmethyl. In addition, the aralkyl group is a group represented by the following general formula (c3), and is a group in which one hydrogen atom of the alkyl group is replaced by an aryl group. [chemical formula 7]

In the above general formula (c3), the double ring is an aryl group, and ^R33 is an alkylene group. The wavy line means a bonded position to a carbon atom in the above general formula (b1). In addition, the "7-15 carbon number" of "aralkyl group having 7-15 carbon atoms" means the total carbon number of the ring-forming carbon number of the aryl group and the carbon number of the alkylene group (R ³³ ). The number of carbons (number of ring-forming carbons) of the aryl group constituting the aralkyl group is preferably 6-10, more preferably 6, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C). Also, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C), the carbon number of the alkylene group constituting the aralkyl group is preferably 1 to 6, more preferably 1 to 4, and more preferably It should be 1~2.

Here, the hydrocarbon group (X1) is preferably an aryl group having at least 6 to 15 carbon atoms having a hydroxyl group. Specifically, the sulfides (B1) preferably contain a compound represented by the following general formula (b1-1). By combining the compound represented by the following general formula (b1-1) and the carboxylic acid compound (C), the brightness becomes more favorable easily. From the above point of view, based on the total amount of sulfides (B1), the content of the compound represented by the following general formula (b1-1) is preferably 70% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass.

[chemical formula 8]

In the aforementioned general formula (b1-1), R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 10 carbon atoms. From the point of view that it is easier to improve the oxidation stability of the heat-treated oil composition, the alkyl group is preferably a straight-chain or branched-chain alkyl group with 3-10 carbons, more preferably a branched-chain alkyl group with 3-10 carbons . The carbon number of the branched alkyl group is preferably 4-8, more preferably 4-6, more preferably 4.

In the aforementioned general formula (b1-1), m1 represents an integer of 0-4. m1 is preferably 1~3, more preferably 2. When m1 is 2 or more, the plurality of R ^15s present may be the same or different.

In the aforementioned general formula (b1-1), m2 represents an integer of 0-4. m2 is preferably 1~3, more preferably 2. When m2 is 2 or more, the plurality of R ¹⁶ present may be the same or different.

In addition, in the general formula (b1-1), the hydroxyl group is preferably located at the 4-position of the phenyl group. Also, m1 and m2 are each preferably 2, and two R ¹⁵ and two R ¹⁶ are preferably located at the 3-position and 5-position of the phenyl group, respectively. In addition, the two R ¹⁵ and the two R ¹⁶ are preferably branched chain alkyl groups with 3 to 10 carbon atoms. The carbon number of the branched alkyl group is preferably 4-8, more preferably 4-6, more preferably 4.

Specific examples of the sulfides (B1) include bis(3,5-ditertiary butyl-4-hydroxybenzyl) sulfide, 2-ethylthiomethylphenol, and the like. Among them, bis(3,5-ditert-butyl-4-hydroxybenzyl)sulfide is preferable.

The sulfides (B1) may be used alone or in combination of two or more.

<Sulfides (B2)> The sulfides (B2) are compounds represented by the following general formula (b2). [chemical formula 9]

In the aforementioned general formula (b2), Ar ¹² is an arylylene group having at least 6 to 15 carbon atoms of a hydroxyl group. When, for example, the compound represented by the aforementioned general formula (b2) has a structure in which a sulfur atom and an aryl group are bonded through a methylene group, it will be unfavorable in the effect of improving the brightness of the metal material after heat treatment such as quenching. Propensity. However, by using it in combination with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching can be improved. In addition, if the carbon number of the aryl group is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

In the aforementioned general formula (b2), the arylylene group having 6 to 15 carbon atoms constituting Ar ¹² can be exemplified as: phenylene, biphenylene, naphthyl, phenanthrylene, fluorenylene ) and anthracenyl, etc. In addition, "6-15 carbon atoms" in "arylylene group having 6-15 carbon atoms" means "6-15 ring-forming carbon atoms". The carbon number of the arylylene group is preferably 6-10, more preferably 6, from the viewpoint of making it easier to exert the effect brought by the combination with the carboxylic acid compound (C).

In the aforementioned general formula (b2), the arylylene group having 6 to 15 carbon atoms constituting Ar ¹² has at least one hydroxyl group. If the aryl group does not have a hydroxyl group, the oxidation stability of the heat-treated oil composition may be insufficient. Here, the aryl group may further have a substituent other than a hydroxyl group, or may not have a substituent other than a hydroxyl group. Examples of such substituents include monovalent aliphatic hydrocarbon groups with 1 to 10 carbons, alkoxy groups with 1 to 10 carbons, hydroxyl groups, amino groups, nitro groups, carboxyl groups, and halogen atoms. The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 1 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. In addition, the number of hydroxyl groups in the aryl group may be one or plural, but one is preferred. Also, when the aryl group has a substituent other than a hydroxyl group, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

In the aforementioned general formula (b2), R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2). When the hydrocarbon group (X2) has a substituent, the substituent can include: a monovalent aliphatic hydrocarbon group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a hydroxyl group, an amino group, a nitro group, a carboxyl group, and a halogen atom . The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 3 to 10 carbons, more preferably a branched alkyl group having 3 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. When the hydrocarbon group (X2) has a substituent, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

In the aforementioned general formula (b2), the hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, a cycloalkyl group with 3 to 15 carbons, and a cycloalkenyl group with 3 to 15 carbons , Cycloalkylalkyl with 4 to 15 carbons, cycloalkenylalkyl with 4 to 15 carbons, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons. The carbon number of the hydrocarbon group (X2) does not include the carbon number of the aforementioned substituents that the hydrocarbon group (X2) may have. In addition, if the carbon number that can be used as the base of the hydrocarbon group (X2) is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

Alkyl with 1 to 15 carbons, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkenyl with 4 to 15 carbons can be used as the hydrocarbon group (X2). Cycloalkylalkyl with 15 carbons, cycloalkenylalkyl with 4 to 15 carbons, aryl with 6 to 15 carbons, and aralkyl with 7 to 15 carbons. Examples of such groups include the following hydrocarbon groups ( X1) Alkyl with 1 to 15 carbons, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, ring with 4 to 15 carbons Alkylalkyl, cycloalkenylalkyl with 4 to 15 carbons, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons. The preferable range of each group is also the same as that of the above-mentioned hydrocarbon group (X1).

Here, the sulfides (B2) preferably contain compounds represented by the following general formula (b2-1). By combining the compound represented by the following general formula (b2-1) and the carboxylic acid-based compound (C), brightness becomes more favorable easily. From this point of view, based on the total amount of sulfides (B2), the content of the compound represented by the following general formula (b2-1) is preferably 70% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass.

[chemical formula 10]

In the aforementioned general formula (b2-1), R ¹⁷ each independently represent a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms. From the point of view that it is easier to improve the oxidation stability of the heat-treated oil composition, the alkyl group is preferably a straight-chain or branched-chain alkyl group with 1-6 carbons, more preferably a straight-chained alkyl group with 1-3 carbons .

In the aforementioned general formula (b2-1), m3 represents an integer of 0 to 3. m3 is preferably 1~2, more preferably 1. When m3 is 2 or more, the plurality of R ^15s present may be the same or different.

In the aforementioned general formula (b2-1), R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2). As the hydrocarbon group (X2), there can be mentioned the same groups as those listed in the description of the aforementioned general formula (b2), and among them, an unsubstituted hydrocarbon group (X2) is preferred, with 1 to 15 carbon atoms The unsubstituted alkyl group is preferred. The carbon number of the alkyl group is preferably 6-15, more preferably 6-14. The alkyl group may be linear or branched, but is preferably linear.

In addition, in the general formula (b2-1), the hydroxyl group is preferably located at the 1-position of the phenylene group. Also, m3 is preferably 1, and R ¹⁷ is preferably located at the 2-position of the phenylene group. In addition, ^R17 is preferably a linear alkyl group having 1 to 3 carbon atoms.

If specific examples of sulfides (B2) include: 2-methyl-4,6-bis[(n-dodecylthio)methyl]phenol, 2-methyl-4,6-bis[( n-octylthio)methyl]phenol, etc.

Sulfides (B2) may be used alone or in combination of two or more.

<Sulfides (B3)> The sulfides (B3) are compounds represented by the following general formula (b3). [chemical formula 11]

In the aforementioned general formula (b3), Ar ¹³ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group. Ar ¹⁴ represents a substituted or unsubstituted aryl group having 6 to 15 carbon atoms. When, for example, the compound represented by the aforementioned general formula (b3) has a structure in which a sulfur atom is directly bonded to an aryl group and two sulfur atoms are bonded via a carbon atom, the brightness of the metal material after heat treatment such as quenching changes. Good effects tend to be bad. However, by using it in combination with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching can be improved. In addition, if the carbon number of the aryl group is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

In the aforementioned general formula (b3), Ar ¹³ may be the same group as Ar ¹¹ described in the aforementioned general formula (b1), and the preferred range is also the same as that of Ar ¹¹ .

In the aforementioned general formula (b3), the aryl group having 6 to 15 carbon atoms constituting Ar ¹⁴ can be, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, fenyl, and anthracenyl. In addition, "6-15 carbon atoms" in "aryl group having 6-15 carbon atoms" means "6-15 ring-forming carbon atoms". From the viewpoint of making the effect of the combination of the compound and the carboxylic acid compound (C) more likely to be exerted, the carbon number of the aryl group is preferably 6-10, more preferably 6.

When the aryl group has a substituent, the substituent can include: a monovalent aliphatic hydrocarbon group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a hydroxyl group, an amino group, a nitro group, an amido group, a benzene A formamide group, a carboxyl group, a residue obtained by removing a hydrogen atom from one hydroxyl group of a dicarboxylic acid, and a halogen atom. The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 3 to 10 carbons, more preferably a branched alkyl group having 3 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. When the aryl group has a substituent, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

Here, the sulfides (B3) preferably contain compounds represented by the following general formula (b3-1). By combining the compound represented by the following general formula (b3-1) and the carboxylic acid type compound (C), the luminance becomes more favorable easily. From this point of view, based on the total amount of sulfides (B3), the content of the compound represented by the following general formula (b3-1) is preferably 70% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass. [chemical formula 12]

In the aforementioned general formula (b3-1), R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms. From the point of view that it is easier to improve the oxidation stability of the heat-treated oil composition, the alkyl group is preferably a straight-chain or branched-chain alkyl group with 3-10 carbons, more preferably a branched-chain alkyl group with 3-10 carbons . The carbon number of the branched alkyl group is preferably 4-8, more preferably 4-6, more preferably 4.

In the aforementioned general formula (b3-1), m4 represents an integer of 0-4. m4 is preferably 1~3, more preferably 2. When m4 is 2 or more, the plurality of R ¹⁸ present may be the same or different.

In the aforementioned general formula (b3-1), m5 represents an integer of 0-4. m5 is preferably 1~3, more preferably 2. When m5 is 2 or more, the plurality of R ¹⁹ present may be the same or different.

In addition, in the general formula (b3-1), the hydroxyl group is preferably located at the 4-position of the phenyl group. Also, m4 and m5 are each preferably 2, and two R ¹⁸ and two R ¹⁹ are preferably located at the 3-position and 5-position of the phenyl group, respectively. In addition, the two R ¹⁸ and the two R ¹⁹ are preferably branched chain alkyl groups with 3 to 10 carbon atoms. The carbon number of the branched alkyl group is preferably 4-8, more preferably 4-6, more preferably 4.

If specific examples of sulfides (B3) include the following: 4,4'-[propane-2,2-diylbis(sulfanediyl)]bis[2,6-bis(1,1 -Dimethylethyl)phenol] (Probucol (Probucol)), 4-[4-[2-(4-hydroxy-3,5-ditertiary butyl-phenyl) mercaptoprop-2 -Hydroxy]-2,6-ditertiary-butyl-phenoxy]-4-oxobutanoic acid (Succinobucol). Among them, 4,4'-[propane-2,2-diylbis(sulfandiyl)]bis[2,6-bis(1,1-dimethylethyl)phenol]( Probucol) is preferred.

Sulfides (B3) may be used alone or in combination of two or more.

<Sulfides (B4)> The sulfides (B4) are compounds represented by the following general formula (b4). [chemical formula 13]

In the aforementioned general formula (b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group having 6 to 15 carbon atoms. When, for example, the compound represented by the aforementioned general formula (b4) has a structure in which a sulfur atom is directly bonded to an aryl group and two sulfur atoms are directly bonded, it will be effective in improving the brightness of the metal material after heat treatment such as quenching. Has bad tendencies. However, by using it in combination with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching can be improved. In addition, if the carbon number of the aryl group is greater than 15, even if it is combined with the carboxylic acid compound (C), the brightness of the metal material after heat treatment such as quenching may not be improved.

In the aforementioned general formula (b4), the aryl groups having 6 to 15 carbon atoms constituting Ar ¹⁵ and Ar ¹⁶ include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, fenyl, and anthracenyl. In addition, "6-15 carbon atoms" in "aryl group having 6-15 carbon atoms" means "6-15 ring-forming carbon atoms". From the viewpoint of making the effect of the combination of the compound and the carboxylic acid compound (C) more likely to be exerted, the carbon number of the aryl group is preferably 6-10, more preferably 6.

When the aryl group has a substituent, the substituent can include: a monovalent aliphatic hydrocarbon group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a hydroxyl group, an amino group, a nitro group, an amido group, a benzene A formamide group, a carboxyl group, a residue obtained by removing a hydrogen atom from one hydroxyl group of a dicarboxylic acid, and a halogen atom. The monovalent aliphatic hydrocarbon group having 1 to 10 carbons is preferably a linear or branched alkyl group having 3 to 10 carbons, more preferably a branched alkyl group having 3 to 10 carbons. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. When the aryl group has a substituent, the number of the substituent may be one or plural. And, when the substituents are plural, the plural substituents may be the same or different.

In the above-mentioned general formula (b4), Ar ¹⁵ and Ar ¹⁶ should each be independently an unsubstituted aryl group with 6 to 15 carbons or an aryl group with at least 1 or more hydroxyl groups with 6 to 15 carbons, preferably the carbon number 6-10 unsubstituted aryl groups or 6-10 aryl groups having at least one hydroxyl group, preferably unsubstituted aryl groups having 6 carbon atoms or 6-carbon aryl groups having at least one hydroxyl group The aryl group is more preferably an unsubstituted aryl group having 6 carbon atoms.

If specific examples of sulfides (B4) include the following: diphenyl disulfide, di-p-tolyl disulfide, 4,4'-dithiodiphenylamine, 2,2'-disulfide Diphenylamine, 2,2'-dithiodibenzoic acid, bis(2-benzamidophenyl) disulfide, bis(4-hydroxyphenyl) disulfide. Among them, diphenyl disulfide is preferable.

Sulfides (B4) may be used alone or in combination of two or more.

(Preferable form of sulfur compound (B)) In the heat-treated oil composition of this embodiment, the sulfur compound (B) preferably contains One or more selected from the group consisting of: sulfides (B1) represented by the above general formula (b1), sulfides (B2) represented by the above general formula (b2), and the above general formula ( The sulfides (B3) represented by b3) preferably include at least one selected from the group consisting of: the sulfides (B1) represented by the above general formula (b1), and the above general formula (b2 ) sulfides (B2). In the present embodiment, one or more selected from the group consisting of: sulfides (B1) represented by the above general formula (b1), sulfides (B1) represented by the above general formula (b2) B2), and the sulfides (B3) represented by the above general formula (b3) include the following aspects. Only sulfides (B1) represented by the above general formula (b1) Only sulfides (B2) represented by the above general formula (b2) Only sulfides (B3) represented by the above general formula (b3) Combination of sulfides (B1) represented by the above general formula (b1) and sulfides (B2) represented by the above general formula (b2) A combination of sulfides (B1) represented by the above general formula (b1) and sulfides (B3) represented by the above general formula (b3) Combination of sulfides (B2) represented by the above general formula (b2) and sulfides (B3) represented by the above general formula (b3) Combinations of sulfides (B1) represented by the above general formula (b1), sulfides (B2) represented by the above general formula (b2) and sulfides (B3) represented by the above general formula (b3) In the embodiment, one or more selected from the group consisting of: the sulfides (B1) represented by the above general formula (b1) and the sulfides (B2) represented by the above general formula (b2) ), which includes the following forms. Only sulfides (B1) represented by the above general formula (b1) Only sulfides (B2) represented by the above general formula (b2) Combination of sulfides (B1) represented by the above general formula (b1) and sulfides (B2) represented by the above general formula (b2) In addition, from the viewpoint that it is easier to further improve the oxidation stability and further exert the effect brought by the combination with the carboxylic acid compound (C), the sulfur compound (B) preferably contains a compound selected from the group consisting of One or more of the group: sulfides (B1) containing the compound represented by the above general formula (b1-1), sulfides (B2) containing the compound represented by the above general formula (b2-1), and the above Sulfides (B3) of the compound represented by the general formula (b3-1). Also, among these, from the viewpoint of further improving oxidation stability, the sulfur compound (B) preferably contains at least one selected from the group consisting of the above-mentioned general formula (b1-1) Sulfides (B1) of the compound shown, and sulfides (B2) including the compound represented by the above general formula (b2-1). In this embodiment, one or more selected from the group consisting of: sulfides (B1) including the compound represented by the above general formula (b1-1); 1) The sulfides (B2) of the compound represented by the above formula (b3-1) include the following aspects. Sulfides (B1) containing only compounds represented by the above general formula (b1-1) Sulfides (B2) containing only the compound represented by the above general formula (b2-1) Sulfides (B3) containing only compounds represented by the above general formula (b3-1) Combination of sulfides (B1) comprising the compound represented by the above general formula (b1-1) and sulfides (B2) comprising the compound represented by the above general formula (b2-1) Combination of sulfides (B1) comprising the compound represented by the above general formula (b1-1) and sulfides (B3) comprising the compound represented by the above general formula (b3-1) Combination of sulfides (B2) comprising the compound represented by the above general formula (b2-1) and sulfides (B3) comprising the compound represented by the above general formula (b3-1) Combination of sulfides (B2) comprising the compound represented by the above general formula (b2-1) and sulfides (B3) comprising the compound represented by the above general formula (b3-1) Sulfides (B1) comprising the compound represented by the above general formula (b1-1), sulfides (B2) comprising the compound represented by the above general formula (b2-1), and sulfides (B2) comprising the compound represented by the above general formula (b3-1) Combinations of sulfides (B3) of the indicated compounds Also, in this embodiment, one or more selected from the group consisting of: sulfides (B1) including the compound represented by the above general formula (b1-1), and The sulfides (B2) of the compound represented by (b2-1) include the following aspects. Sulfides (B1) containing only compounds represented by the above general formula (b1-1) Sulfides (B2) containing only the compound represented by the above general formula (b2-1) Combination of sulfides (B1) comprising the compound represented by the above general formula (b1-1) and sulfides (B2) comprising the compound represented by the above general formula (b2-1)

(Content of sulfur compound (B)) From the viewpoint of making it easier to exert the effect of the present invention, in the heat-treated oil composition of this embodiment, based on the total amount of the heat-treated oil composition, the content of the sulfur compound (B) is preferably 0.01% by mass or more, more preferably 0.02% by mass, more preferably 0.05% by mass or more. In addition, from the viewpoint of easily suppressing the generation of sludge caused by adding too much sulfur compound and easily suppressing the life of the heat-treated oil composition, the content of the sulfur compound (B) is preferably 2.0% by mass or less, more preferably 1.0% by mass or less , more preferably 0.5% by mass or less. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the content is preferably 0.01% by mass to 2.0% by mass, more preferably 0.02% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass.

(Molecular weight of sulfur compound (B)) In the heat-treated oil composition of this embodiment, the molecular weight of the sulfur compound (B) is preferably 100 or more, more preferably 150 or more, and more preferably 180 or more, from the viewpoint of making it easier to exhibit the effects of the present invention. In addition, the molecular weight is preferably not more than 1,500, more preferably not more than 1,200, more preferably not more than 1,000. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the molecular weight is preferably 100-1,500, more preferably 150-1,200, more preferably 180-1,000.

＜Carboxylic acid compound (C)＞ The heat-treated oil composition of this embodiment contains a carboxylic acid compound (C). As explained above, regarding the sulfur compound (B), the effect of improving the brightness of the metal material after heat treatment such as quenching is not good. However, by using it in combination with the carboxylic acid-based compound (C), the sulfur compound (B) and the carboxylic acid-based compound (C) interact to improve the brightness of the metal material after heat treatment such as quenching.

The carboxylic acid compound (C) is one or more types selected from the group consisting of compounds having at least one carboxyl group and their anhydrides. The compound having at least one carboxyl group may be a monovalent carboxylic acid or a divalent or higher polyvalent carboxylic acid. Moreover, the partial ester which esterified a part of polyhydric carboxylic acid may be sufficient. Among them, the compound having at least one carboxyl group is preferably a bivalent or higher polycarboxylic acid, more preferably a divalent carboxylic acid, from the viewpoint of more easily exhibiting the effect of combining with the sulfur compound (B). That is, the carboxylic acid compound (C) is preferably one or more types selected from the group consisting of divalent carboxylic acids and their anhydrides. Furthermore, among these, divalent carboxylic acids are preferable. A carboxylic acid type compound (C) may be used individually by 1 type, and may use it in combination of 2 or more types.

As preferable carboxylic acid type compound (C), 1 or more types chosen from divalent carboxylic acids, such as alkylsuccinic acid and alkenylsuccinic acid, and anhydrides thereof, etc. are mentioned. Among them, one or more divalent carboxylic acids selected from alkyl succinic acid and alkenyl succinic acid are preferred from the viewpoint of more easily exhibiting the effect of combination with the sulfur compound (B), And alkenyl succinic acid is preferred. Moreover, it is preferable that the carbon number of the alkyl group which the alkyl succinic acid has and the alkenyl group which the alkenyl succinic acid has are 10-20.

Divalent carboxylic acids such as alkyl succinic acid and alkenyl succinic acid (preferably alkenyl ^succinic acid) are suitable for use as carboxylic acid compounds (C). 15 mm ² /sec or more, more preferably 20 mm ² /sec or more. Furthermore, the 40°C kinematic viscosity is preferably not more than 50 mm ² /sec, more preferably not more than 40 mm ² /sec, more preferably not more than 30 mm ² /sec. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the kinematic viscosity at 40°C is preferably 10 mm ² /sec to 50 mm ² /sec, more preferably 15 mm ² /sec to 40 mm ² /sec, more preferably 20 mm ² /sec to 30 mm ² /sec. In this specification, the 40 degreeC kinematic viscosity of divalent carboxylic acid (preferably alkenyl succinic acid), such as an alkyl succinic acid and an alkenyl succinic acid, means the value measured based on JISK2283:2000. Also, divalent carboxylic acids (preferably alkenyl succinic acid) such as alkyl succinic acid and alkenyl succinic acid suitable for use as the carboxylic acid compound (C) have an acid value of 50 mgKOH/g or more, preferably 100 mgKOH /g or more, more preferably 150mgKOH/g or more. In addition, the acid value is preferably not more than 400 mgKOH/g, more preferably not more than 300 mgKOH/g, more preferably not more than 250 mgKOH/g. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the acid value is preferably 50 mgKOH/g-400 mgKOH/g, more preferably 100 mgKOH/g-300 mgKOH/g, more preferably 150 mgKOH/g-250 mgKOH/g. In this specification, the acid value of divalent carboxylic acids such as alkyl succinic acid and alkenyl succinic acid (preferably alkenyl succinic acid) refers to the acid value measured by the indicator titration method according to JIS K 2501:2003-5 value.

(Content of carboxylic acid compound (C)) From the viewpoint of making it easier to exert the effects of the present invention, in the heat-treated oil composition of the present embodiment, based on the total amount of the heat-treated oil composition, the content of the carboxylic acid compound (C) is preferably 0.1% by mass or more. Preferably it is 0.15 mass %, More preferably, it is 0.2 mass % or more. Furthermore, the content of the carboxylic acid compound (C) is preferably at most 5.0% by mass, more preferably at most 3.0% by mass, more preferably at most 2.0% by mass. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the content is preferably 0.1% by mass to 5.0% by mass, more preferably 0.15% by mass to 3.0% by mass, more preferably 0.2% by mass to 2.0% by mass.

<Content ratio of sulfur compound (B) to carboxylic acid compound (C) [(B)/(C)]> From the viewpoint of making it easier to exhibit the effects of the present invention, in the heat-treated oil composition of the present embodiment, the content ratio [(B)/(C)] of the sulfur compound (B) to the carboxylic acid compound (C) is expressed as a mass ratio It is preferably at least 0.002, more preferably at least 0.02, and more preferably at least 0.1. In addition, the content ratio is preferably 0.8 or less, more preferably 0.5 or less, more preferably 0.3 or less. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the content ratio is preferably 0.002 to 0.8, more preferably 0.02 to 0.5, more preferably 0.1 to 0.3.

＜Additives＞ The heat treatment oil composition of this embodiment is prepared by mixing base oil (A), sulfur compound (B) and carboxylic acid compound (C), and additives commonly used in heat treatment oil compositions can also be blended as desired . As said additive, a steam film breaking agent, a luminance improving agent, a cooling property improving agent, and an antioxidant are mentioned, for example. These additives may be used alone or in combination of two or more.

(vapor film breaker) As the vapor film breaking agent, the following can be cited: ethylene-α-olefin copolymers such as ethylene-propylene copolymers (the carbon number of the α-olefin is 3 to 20); hydrogenation of the ethylene-α-olefin copolymers 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and other α-olefins with 5 to 20 carbon atoms Polymers; hydrogenated products of such α-olefin polymers; olefin polymers with 3 or 4 carbon atoms such as polypropylene, polybutene and polyisobutene; hydrogenated products of such olefin polymers; polymethacrylates, poly Polymer compounds such as methacrylate, polystyrene and petroleum resin; asphalt. These vapor film breakers may be used alone or in combination of two or more. The number average molecular weight (Mn) of the vapor film breaking agent is generally preferably 800~100,000. The number average molecular weight (Mn) of the vapor film breaking agent is a value in terms of polystyrene measured by gel permeation chromatography (GPC). Based on the total amount of the heat-treated oil composition, the content of the vapor film breaking agent is preferably 0.5% by mass to 18% by mass, more preferably 1.0% by mass to 16% by mass, more preferably 2.0% by mass to 15% by mass.

(brightness improver) As brightness improving agents, for example: fats and oils; complete esters of alkyl succinic acids, alkyl succinimides, and derivatives thereof; complete esters of alkenyl succinic acids, alkenyl succinimides, and their derivatives; Derivatives such as substituted hydroxyaromatic carboxylic acid esters (full esters) and their derivatives, etc. These luminance improvers may be used alone or in combination of two or more. Based on the total amount of the heat-treated oil composition, the content of the brightness improver is preferably 0.1% by mass to 5.0% by mass, more preferably 0.3% by mass to 3.0% by mass, more preferably 0.4% by mass to 2.0% by mass.

(cooling enhancer) As a cooling property improvement agent, metal-based cleaning agents, such as a metal sulfonate, a metal salicylate, and a metal phenate, are mentioned, for example. Examples of the metal constituting the metal-based cleaning agent include alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium, calcium, and barium. In addition, as the cooling performance improving agent, the following can also be mentioned: imide-based dispersants such as boron-containing alkenyl succinimides, valent or divalent carboxamides represented by fatty acids or succinic acid wait. These cooling property improving agents may be used individually by 1 type, and may use it in combination of 2 or more types. Here, from the viewpoint that the effects of the present invention are more likely to be exhibited, the less the content of the cooling property improving agent, the better. Specifically, based on the total amount of the heat-treated oil composition, the content of the cooling enhancer is preferably less than 0.20% by mass, more preferably less than 0.10% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. Even better without cooling enhancers.

(Antioxidants) As an antioxidant, a phenolic antioxidant, an amine antioxidant, etc. are mentioned, for example. As the phenolic antioxidant, the following can be cited, for example: 2,6-ditertiary butyl-p-cresol, 2,6-ditertiary butyl-4-ethylphenol, 2,4,6-tri Tertiary butylphenol, 2,6-ditertiary butyl-4-hydroxymethylphenol, 2,6-ditertiary butylphenol, 2,4-dimethyl-6-tertiary butylphenol, 2,6-ditertiary butyl-4-(N,N-dimethylaminomethyl)phenol, 2,6-ditertiary pentyl-4-methylphenol, n-octadecyl-3- Monocyclic phenols such as (4-hydroxy-3,5-ditertiary butylphenyl) propionate; 4,4'-methylene bis(2,6-ditertiary butylphenol), 4, 4'-isopropylidene bis(2,6-ditertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), 4,4'- Bis(2,6-ditertiary butylphenol), 4,4'-bis(2-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-ethyl- 6-tertiary butylphenol), 4,4'-butylene bis(3-methyl-6-tertiary butylphenol) and other polycyclic phenols. As an amine antioxidant, a diphenylamine antioxidant, a naphthylamine antioxidant, etc. are mentioned, for example. As diphenylamine-based antioxidants, for example: alkylated diphenylamine having an alkyl group with a carbon number of 3 to 20, etc., specifically the following: diphenylamine, monooctyldiphenylamine, monononyldiphenylamine , 4,4'-dibutyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, tetrabutyldiphenylamine, Tetrahexyldiphenylamine, tetraoctyldiphenylamine and tetranonyldiphenylamine. As naphthylamine-based antioxidants, for example: alkyl-substituted phenyl-α-naphthylamines with 3 to 20 carbon atoms, etc., specifically the following: α-naphthylamine, phenyl-α-naphthylamine, Butylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, and nonylphenyl-α-naphthylamine. These antioxidants may be used alone or in combination of two or more. Based on the total amount of the heat-treated oil composition, the content of the antioxidant is preferably 0.01% by mass to 5.0% by mass, more preferably 0.02% by mass to 3.0% by mass, more preferably 0.05% by mass to 2.0% by mass.

[Physical properties of the heat-treated oil composition of the present invention] ＜Sulfur content＞ In the heat-treated oil composition of this embodiment, based on the total amount of the heat-treated oil composition, the sulfur content is preferably at least 10 mass ppm, more preferably at least 20 mass ppm, more preferably at least 25 mass ppm. In addition, the sulfur content is preferably not more than 10,000 mass ppm, more preferably not more than 7,000 mass ppm, more preferably not more than 5,000 mass ppm, and more preferably not more than 3,000 mass ppm. The upper limit and lower limit of these numerical ranges can be combined arbitrarily. Specifically, the sulfur content is preferably 10 mass ppm to 10,000 mass ppm, more preferably 20 mass ppm to 7,000 mass ppm, more preferably 25 mass ppm to 5,000 mass ppm, and more preferably 25 mass ppm to 3,000 mass ppm . In this specification, regarding the sulfur content in the heat-treated oil composition, when measuring the mass ppm level, it means the value measured according to the ultraviolet fluorescence method of JIS K 2541-6:2013, and when measuring the mass % level, it means Refers to the value measured by the wavelength dispersive fluorescent X-ray method in accordance with JIS K 2541-7:2013.

＜Amount of Phosphorus, Molybdenum and Zinc＞ In the heat-treated oil composition of this embodiment, the amount of phosphorus, molybdenum, and zinc is preferably independently less than 0.01% by mass based on the total amount of the heat-treated oil composition, more preferably less than 0.001% by mass, and more preferably free of phosphorus, molybdenum, and zinc. Molybdenum and Zinc. In this specification, the amount of phosphorus, molybdenum, and zinc in the heat-treated oil composition can be measured in accordance with JPI-5S-38-03.

<Kinematic Viscosity at 40°C> The composition of the heat treatment oil in this embodiment has a dynamic viscosity at 40°C depending on the desired oil temperature during heat treatment such as quenching. The heat treatment oil composition is divided into: cold oil used at low oil temperature, hot oil used at high oil temperature, and semi-hot oil used at an oil temperature in the middle of these oil temperatures. Cold oil is classified into one type of JIS K2242:2012, and semi-thermal oil and hot oil are classified into two types of JIS K2242:2012. When the heat-treated oil composition of this embodiment is used as cooling oil, the kinematic viscosity at 40°C is preferably not less than 5 mm ² /sec and less than 40 mm ² /sec. When the heat-treated oil composition of this embodiment is used as semi-thermal oil or hot oil, the kinematic viscosity at 40°C is preferably not less than 40 mm ² /sec and not more than 500 mm ² /sec. In this specification, the 40 degreeC kinematic viscosity of a heat-treated oil composition means the value measured based on JIS K2283:2000.

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²表示至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] [Method for producing heat-treated oil composition] The method for producing the heat-treated oil composition of this embodiment is not particularly limited. For example, the production method of the heat-treated oil composition of this embodiment includes a step of mixing a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C). The base oil (A) is selected from One or more of the group consisting of oil (A1), synthetic oil (A2) and vegetable oil (A3). The aforementioned sulfur compound (B) includes at least one selected from the group consisting of: sulfides (B1) represented by the following general formula (b1), sulfides represented by the following general formula (b2) (B2), sulfides (B3) represented by the following general formula (b3), and sulfides (B4) represented by the following general formula (b4). Furthermore, the said carboxylic acid compound (C) is 1 or more types selected from the group which consists of the compound which has at least 1 carboxyl group, and its anhydride. [chemical formula 14]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² represents an arylylene group with at least 6 to 15 carbons having a hydroxyl group; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms]

The method for mixing the above components is not particularly limited, and examples include a method comprising the steps of mixing the sulfur compound (B) and the carboxylic acid compound (C) into the base oil (A). The sulfur compound (B) and the carboxylic acid compound (C) may be blended in the base oil (A) at the same time, or may be blended separately. When the heat-treated oil composition further contains other components (the above-mentioned additives) other than the base oil (A), the sulfur compound (B) and the carboxylic acid-based compound (C), the other components can be mixed with the sulfur compound (B) and the carboxylic acid-based compound (C). The compound (C) may be blended together in the base oil (A), or may be blended individually. In addition, each component may be blended after adding diluent oil or the like to form a solution (dispersion). After mixing the ingredients, it is preferable to stir them by a known method to disperse them uniformly. In addition, preferred aspects of the base oil (A), the sulfur compound (B) and the carboxylic acid compound (C) are as described above.

[Use of heat treatment oil composition] When the heat treatment oil composition of this embodiment is used during heat treatment such as quenching of metal materials, the brightness of the metal material after heat treatment such as quenching can be improved. For example, it is suitable as a heat treatment oil composition for quenching and other heat treatments of various alloy steels such as carbon steel, nickel-manganese steel, chromium-molybdenum steel, and manganese steel. In addition, the heat-treated oil composition of this embodiment also has excellent oxidation stability. Therefore, the heat treatment oil composition of this embodiment is suitably used as a heat treatment oil (preferably quenching oil or tempering oil) required for quenching metal materials. In addition, this embodiment provides a method of using the heat treatment oil composition, which uses the heat treatment oil composition of this embodiment as heat treatment oil (preferably quenching oil or tempering oil) for quenching metal materials. When the heat treatment is quenching, the oil temperature of the heat treatment oil should be set at 40°C~280°C, more preferably at 50°C~200°C, more preferably at 60°C~150°C. When the heat treatment is tempering, the oil temperature can be further increased, for example, the upper limit can be 300°C. In addition, the quenching temperature of the metal material may be not less than 800°C and not more than 900°C, or may be higher than 900°C and not more than 1100°C.

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²為至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] [2]如上述[1]之熱處理油組成物，其中在前述通式(b1)中，前述烴基(X1)為至少具有羥基之碳數6~15之芳基。 [3]如上述[1]或[2]之熱處理油組成物，其中前述硫化合物(B)包含選自於由以下所構成群組中之1種以上：前述通式(b1)所示硫化物類(B1)、前述通式(b2)所示硫化物類(B2)及前述通式(b3)所示硫化物類(B3)。 [4]如上述[1]至[3]中任一項之熱處理油組成物，其中以前述熱處理油組成物之總量為基準計，硫份為10質量ppm~10,000質量ppm。 [5]如上述[1]至[4]中任一項之熱處理油組成物，其中以前述熱處理油組成物之總量為基準計，前述硫化合物(B)之含量為0.01質量%~2.0質量%。 [6]如上述[1]至[5]中任一項之熱處理油組成物，其中以前述熱處理油組成物之總量為基準計，前述羧酸系化合物(C)之含量為0.1質量%~5.0質量%。 [7]如上述[1]至[6]中任一項之熱處理油組成物，其中硫化合物(B)與羧酸系化合物(C)之含有比率[(B)/(C)]以質量比計為0.002~0.8。 [8]如上述[1]至[7]中任一項之熱處理油組成物，其進一步含有選自於由蒸氣膜破裂劑、抗氧化劑、輝度改良劑及冷卻性提升劑所構成群組中之1種以上。 [9]如上述[1]至[8]中任一項之熱處理油組成物，其可用作淬火油或回火油。 [10]一種熱處理油組成物之使用方法，係將如上述[1]至[9]中任一項之熱處理油組成物作為淬火油或回火油使用。 [11]一種熱處理油組成物之製造方法，包含一混合基油(A)、硫化合物(B)及羧酸系化合物(C)之步驟，該基油(A)係選自於由礦油(A1)、合成油(A2)及植物油(A3)所構成群組中之1種以上； 前述硫化合物(B)包含選自於由以下所構成群組中之1種以上：下述通式(b1)所示硫化物類(B1)、下述通式(b2)所示硫化物類(B2)、下述通式(b3)所示硫化物類(B3)及下述通式(b4)所示硫化物類(B4)；且 前述羧酸系化合物(C)係選自於由至少具有1個羧基之化合物及其酐所構成群組中之1種以上。 [化學式16]

[前述通式(b1)中，Ar ¹¹表示至少具有羥基之碳數6~15之芳基；R ¹¹表示取代或未取代之烴基(X1)；前述烴基(X1)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b2)中，Ar ¹²表示至少具有羥基之碳數6~15之伸芳基；R ¹²及R ¹³各自獨立表示取代或未取代之烴基(X2)；前述烴基(X2)表示碳數1~15之烷基、碳數1~15之烯基、碳數3~15之環烷基、碳數3~15之環烯基、碳數4~15之環烷基烷基、碳數4~15之環烯基烷基、碳數6~15之芳基、碳數7~15之芳烷基； 前述通式(b3)中，Ar ¹³表示至少具有羥基之碳數6~15之芳基；Ar ¹⁴表示取代或未取代之碳數6~15之芳基； 前述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自獨立表示取代或未取代之碳數6~15之芳基] [An aspect of the present invention that can be provided] According to an aspect of the present invention, the following [1] to [11] are provided. [1] A heat-treated oil composition comprising a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C), the base oil (A) being selected from mineral oil (A1), synthetic oil ( One or more of the group consisting of A2) and vegetable oil (A3); the aforementioned sulfur compound (B) includes one or more of the group consisting of: sulfide represented by the following general formula (b1) (B1), sulfides (B2) represented by the following general formula (b2), sulfides (B3) represented by the following general formula (b3), and sulfides represented by the following general formula (b4) ( B4); and the aforementioned carboxylic acid compound (C) is at least one selected from the group consisting of compounds having at least one carboxyl group and their anhydrides. [chemical formula 15]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² is an aryl with at least 6 to 15 carbons of hydroxyl; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms] [2] The heat-treated oil composition as described in [1] above, wherein in the aforementioned general formula (b1), The aforementioned hydrocarbon group (X1) is an aryl group having at least 6 to 15 carbon atoms having a hydroxyl group. [3] The heat-treated oil composition according to the above-mentioned [1] or [2], wherein the aforementioned sulfur compound (B) contains at least one selected from the group consisting of: the sulfur compound represented by the aforementioned general formula (b1) Species (B1), sulfides (B2) represented by the aforementioned general formula (b2), and sulfides (B3) represented by the aforementioned general formula (b3). [4] The heat-treated oil composition according to any one of [1] to [3] above, wherein the sulfur content is 10 mass ppm to 10,000 mass ppm based on the total amount of the heat-treated oil composition. [5] The heat-treated oil composition according to any one of the above-mentioned [1] to [4], wherein the content of the aforementioned sulfur compound (B) is 0.01% by mass to 2.0% by mass based on the total amount of the aforementioned heat-treated oil composition. quality%. [6] The heat-treated oil composition according to any one of the above-mentioned [1] to [5], wherein the content of the carboxylic acid-based compound (C) is 0.1% by mass based on the total amount of the heat-treated oil composition ~5.0% by mass. [7] The heat-treated oil composition according to any one of the above-mentioned [1] to [6], wherein the content ratio [(B)/(C)] of the sulfur compound (B) to the carboxylic acid compound (C) is expressed by mass The ratio is 0.002~0.8. [8] The heat-treated oil composition according to any one of the above-mentioned [1] to [7], which further contains a vapor film breaking agent, an antioxidant, a brightness improving agent, and a cooling enhancer selected from the group consisting of One or more of them. [9] The heat treatment oil composition according to any one of [1] to [8] above, which can be used as a quenching oil or a tempering oil. [10] A method of using a heat treatment oil composition, comprising using the heat treatment oil composition according to any one of the above [1] to [9] as quenching oil or tempering oil. [11] A method for producing a heat-treated oil composition, comprising a step of mixing a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C), the base oil (A) being selected from mineral oil (A1), synthetic oil (A2) and vegetable oil (A3) constitute one or more kinds; the aforementioned sulfur compound (B) contains one or more kinds selected from the group consisting of the following general formula: Sulfides (B1) represented by (b1), sulfides (B2) represented by the following general formula (b2), sulfides (B3) represented by the following general formula (b3), and the following general formula (b4) ) represented by sulfides (B4); and the aforementioned carboxylic acid compound (C) is at least one selected from the group consisting of compounds having at least one carboxyl group and their anhydrides. [chemical formula 16]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² represents an arylylene group with at least 6 to 15 carbons having a hydroxyl group; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms]

Example The present invention will be described more specifically by the following examples, but the present invention is not limited by the following examples.

[Measuring methods of various physical properties] (1) 40°C kinematic viscosity of base oil (A), carboxylic acid compound (C) and heat-treated oil composition The base oil (A) and carboxylic acid compound (C) used in each example and each comparative example, as well as the heat-treated oil composition prepared in each example and each comparative example, their 40°C dynamic viscosities are based on JIS K2283 : 2000 to measure. (2) Sulfur content The base oil (A) used in each example and each comparative example, and the heat-treated oil composition prepared by each example and each comparative example, the sulfur content of which is based on the ultraviolet fluorescence of JIS K 2541-6:2013 method to measure.

[Examples 1-8, Comparative Examples 1-9] The raw materials used to prepare the heat-treated oil compositions of Examples 1-8 and Comparative Examples 1-9 are listed below.

(1) Base oil (A) ・"Mineral oil (A1)-1": High-viscosity mineral oil classified as Group II in the API category (equivalent to bright lubricating oil with low sulfur content), sulfur content: less than 3 Mass ppm, dynamic viscosity at 40°C: 396.7mm ² /sec ・"Mineral oil (A1)-2": Mineral oil classified as Group II in the API category, sulfur content: less than 3 mass ppm, dynamic viscosity at 40°C: 7.573mm ² /sec ・"Mineral oil (A1)-3": Mineral oil classified as Group III in the API category, sulfur content: less than 3 mass ppm, dynamic viscosity at 40°C: 20.57mm ² /sec ・"Mineral oil Oil (A1)-4": Mineral oil classified as Group II in the API category, sulfur content: less than 3 mass ppm, dynamic viscosity at 40°C: 31.49 mm ² /sec

上述化學式(b1-1-1)所示化合物在前述通式(b1-1)中，m1及m2為2，且2個R ¹⁵及2個R ¹⁶皆為三級丁基。羥基位於苯基之4-位置。三級丁基位於苯基之3-位置及5-位置。 (2) Sulfur compounds (B) ・"Sulphides (B1)-1": bis(3,5-ditertiary butyl-4-hydroxybenzyl) sulfide (molecular weight: 470.75) A chemical formula ( The compound shown in b1-1-1). [chemical formula 17]

In the compound represented by the above chemical formula (b1-1-1), in the above general formula (b1-1), m1 and m2 are 2, and two R ¹⁵ and two R ¹⁶ are all tertiary butyl groups. The hydroxyl group is at the 4-position of the phenyl group. The tertiary butyl group is located at the 3-position and 5-position of the phenyl group.

上述化學式(b2-1-1)所示化合物在上述通式(b2-1)中，m3為1，且R ¹⁷為甲基。羥基位於苯基之1-位置。甲基位於苯基之2-位置。 ・"Sulfides (B2)-1": 2-methyl-4,6-bis[(dodecylthio)methyl]phenol (molecular weight: 536.96) One of the following chemical formula (b2-1-1) Compounds shown. [chemical formula 18]

In the compound represented by the above chemical formula (b2-1-1), in the above general formula (b2-1), m3 is 1, and ^R17 is a methyl group. The hydroxyl group is at the 1-position of the phenyl group. The methyl group is at the 2-position of the phenyl group.

上述化學式(b3-1-1)所示化合物在上述通式(b3-1)中，m4及m5為2，且2個R ¹⁸及2個R ¹⁹皆為三級丁基。羥基位於苯基之4-位置，三級丁基位於苯基之3-位置及5-位置。 ・「Sulfides (B3)-1」: Probucol (4,4'-[propane-2,2-diylbis(sulfanediyl)]bis[2,6-bis(1,1- Dimethylethyl)phenol], molecular weight: 516.84) A compound represented by the following chemical formula (b3-1-1). [chemical formula 19]

In the compound represented by the above chemical formula (b3-1-1), in the above general formula (b3-1), m4 and m5 are 2, and two R ¹⁸ and two R ¹⁹ are all tertiary butyl groups. The hydroxyl group is located at the 4-position of the phenyl group, and the tertiary butyl group is located at the 3-position and the 5-position of the phenyl group.

上述化學式(b4-1-1)所示化合物在上述通式(b4)中，Ar ¹⁵及Ar ¹⁶各自為未取代之苯基。 ・"Sulfides (B4)-1": Diphenyl disulfide (molecular weight: 218.33) A compound represented by the following chemical formula (b4-1-1). [chemical formula 20]

In the compound represented by the above chemical formula (b4-1-1), in the above general formula (b4), each of Ar ¹⁵ and Ar ¹⁶ is an unsubstituted phenyl group.

(3) Comparative example Sulfur compound (B') - "Dibenzothiophene": thiophenes represented by the following chemical formula (b'). [chemical formula 21]

(4) Carboxylic acid compound (C) ・"Alkenyl succinic acid": Divalent carboxylic acid. The carbon number of alkenyl is 10~20. Dynamic viscosity at 40°C: 26.0 mm ² /sec Acid value: 195 mgKOH/g In addition, the acid value is a value measured by an indicator titration method in accordance with JIS K 2501:2003-5.

(5) Non-carboxylic acid compound (C') ・"Calcium sulfonate": alkali value 300mgKOH/g In addition, the base value of calcium sulfonate is the value measured by the potentiometric titration method (base value-perchloric acid method) according to JIS K 2501:2003-9.

(6) Additives ・Vapor film breaker: Polymer

The above-mentioned raw materials were fully mixed according to the blending amounts (mass %) shown in Table 1-Table 2, and the heat-treated oil compositions of Examples 1-8 and Comparative Examples 1-9 were respectively prepared.

[Evaluation method] (1) The evaluation method of brightness refers to "The influence of oxygen in the heat treatment oil tank on brightness (Idemitsu tribo review, No.31, pp.1963~1966, issued on September 30, 2008)", and evaluated the quenching After the steel brightness. Specifically, the test piece was made by combining dumbbell-shaped steel material S45C (diameter: 16mm, length: 30mm, hardness _HRC : 16) and cylindrical steel material SUJ2 (diameter: 10mm, length: 30mm, hardness _HRC : 15) . Specifically, SUS303 metal wire is used to bind the central part of the dumbbell-shaped steel S45C and the cylindrical steel SUJ2, and the dumbbell-shaped steel S45C and the cylindrical steel SUJ2 are fastened (see Figure 1). In addition, "steel material S45C" is carbon steel described in JIS G 4051. "Steel material SUJ2" is a high-carbon chromium bearing steel material described in JIS G 4805. "Metal wire made of SUS303" is a stainless steel wire described in JIS G 4309. Then, after heating the test piece in a furnace made into a nitrogen-hydrogen mixed gas atmosphere, the test piece was put into the heat treatment oil composition and quenched, and a quenching test was performed. The conditions of the quenching test were set to the following two conditions.

(Quenching test condition 1: hot oil hypothetical test, Table 1) Test objects: Examples 1~4, Comparative Examples 1~7 Furnace temperature: 850°C Test piece retention time in the furnace: 40 minutes after the temperature in the furnace reaches 850°C Heat treatment oil composition temperature: 120°C The immersion time (quenching time) of the test piece immersed in the heat treatment oil composition: 10 minutes

(Quenching test condition 2: hypothetical cold oil test, Table 2) Test objects: Examples 5-8, Comparative Examples 8-9 Furnace temperature: 850°C Test piece retention time in the furnace: 40 minutes after the temperature in the furnace reaches 850°C Heat treatment oil composition temperature: 80°C The immersion time (quenching time) of the test piece immersed in the heat treatment oil composition: 10 minutes

Regarding the test piece after quenching, focus on "brightness", "coloring at the edge" and "coloring at the contact part", and evaluate brightness according to the following criteria. In addition, the brightness of the test piece was comprehensively evaluated according to the following criteria based on the evaluation results of "brightness", "coloring at the edge" and "coloring at the contact part". (brightness) Make the appearance sample after predetermined coloring, and compare it with the color of the quenched test piece to evaluate with naked eyes. The degree of coloring of the appearance samples is represented by the values shown below. 0: No coloring at all. 1: There is slight coloring. 2: There is dark brown to black coloring. (coloring at the end) Observe the end of the test piece with the naked eye (see Figure 1), and evaluate according to the following criteria. 0: No coloring at all or almost no coloring. 1: Slight coloring can be confirmed. 2: Dark brown to black coloring can be confirmed. (coloring of contact part) Observe the contact portion of the test piece with the naked eye (the contact portion between the dumbbell-shaped steel material and the cylindrical steel material, refer to Figure 1), and evaluate according to the following criteria. 0: No coloring at all or almost no coloring. 1: Slight coloring can be confirmed. 2: Dark brown to black coloring can be confirmed.

(Comprehensive evaluation of brightness) Using the evaluation results of "Brightness", "Coloring at Edges" and "Coloring at Contacts", comprehensive evaluation was performed based on the following criteria. Evaluation S: The sum of the evaluation results of "brightness", "coloring at the edge" and "coloring at the contact part" is 0 Evaluation A: The sum of the evaluation results of "brightness", "coloring at the edge" and "coloring at the contact part" is 1 Evaluation B: The sum of the evaluation results of "brightness", "coloring at the edge" and "coloring at the contact part" is 2 Evaluation C: The sum of the evaluation results of "brightness", "coloring at the edge" and "coloring at the contact part" is 3 or more However, if the evaluation result of any one of "brightness", "coloring at the edge", and "coloring at the contact part" is 2 or more, the evaluation is C. The brilliance of the heat-treated oil composition of evaluation S is extremely excellent. The heat-treated oil composition of Evaluation A was excellent in brilliance. On the other hand, the brilliance of the heat-treated oil composition of Evaluation B was slightly poor. The brilliance of the heat-treated oil composition of evaluation C is not good.

(2) Oxidation degradation test Referring to "6.3 Stability Test Method" of JIS K2242:2012, the heat-treated oil composition is oxidized and degraded by the following method. In a container with a capacity of 730mL (φ45mm×length 500mm), feed 400mL of heat treatment oil without catalyst, and make it oxidize and deteriorate for 24 hours at a temperature of 170°C and an air flow rate of 10L/hour. Then, measure the 40°C kinematic viscosity of the non-oxidatively deteriorated heat-treated oil composition (hereinafter also referred to as "fresh oil") and the oxidatively deteriorated heat-treated oil composition, and calculate the 40°C dynamic viscosity after oxidatively deteriorated according to the following formula Increase rate (increase rate of kinematic viscosity at 40°C from new oil). (Increase rate of dynamic viscosity at 40°C from new oil)=[(Kinematic viscosity of oil after oxidative deterioration at 40°C)-(Kinematic viscosity of new oil at 40°C)]/(Kinematic viscosity of new oil at 40°C) The greater the 40°C kinematic viscosity increase rate from the new oil, the easier it is to advance the oxidation degradation of the heat-treated oil composition. In other words, it means that the oxidation stability of the heat-treated oil composition is low. Conversely, the smaller the rate of increase in kinematic viscosity at 40°C from the new oil, the less likely it is to advance the oxidative deterioration of the heat-treated oil composition. In other words, it means that the oxidation stability of the heat-treated oil composition is high.

Regarding the heat-treated oil compositions of Examples 1 to 4 and Comparative Examples 1 to 7, Table 1 shows the results of brightness evaluation. 2 shows the state of the test piece after the quenching test using the heat-treated oil compositions of Examples 1-4 and Comparative Examples 1-7. Regarding the heat-treated oil compositions of Examples 5 to 8 and Comparative Examples 8 to 9, Table 2 shows the results of measuring the dynamic viscosity at 40°C. In addition, regarding these heat-treated oil compositions, the results of the fresh oil and the oil after the 24-hour oxidation degradation test are shown in Table 2. Moreover, FIG. 3 shows the state of the test piece after the quenching test using the heat-treated oil composition (new oil) of Examples 5-8 and Comparative Examples 8-9. In addition, in Tables 1-2, ">" means "less than".

[表2]

[Table 1]

[Table 2]

From Table 1 we can see the following things. From the results shown in Examples 1 to 4, it can be seen that by using the sulfides (B1), (B2), (B3) or (B4) in combination with the carboxylic acid compound (C), it is possible to make the quenched A heat-treated oil composition with excellent brilliance of the test piece. On the other hand, it can be seen that when the carboxylic acid-based compound (C) is used alone such as Comparative Example 2, or when the sulfides (B1) and (B2) are used alone such as Comparative Examples 3 to 6 , (B3) or (B4), it becomes a heat treatment oil composition that makes the brightness of the test piece after quenching poor. In addition, it can be seen that in Comparative Example 7, in which calcium sulfonate was used instead of the carboxylic acid compound (C), the heat-treated oil composition caused the brightness of the test piece after quenching to be poor.

From Table 2 we can see the following things. From the results shown in Examples 5 to 8, it can be seen that by using the sulfides (B1), (B2), (B3) or (B4) in combination with the carboxylic acid compound (C), the quenched test piece The brilliance is excellent, and the oxidative deterioration of the heat-treated oil composition is not easy to proceed, and the oxidation stability of the heat-treated oil composition can be improved. On the other hand, it can be seen that in the case of using thiophenes as the sulfur compound such as Comparative Example 9, the combined use of the carboxylic acid compound (C) makes the brilliance of the test piece after quenching excellent, but the oxidation of the heat-treated oil composition deteriorates. It is easy to carry out, but the oxidation stability of the heat-treated oil composition cannot be sufficient.

(none)

FIG. 1 is a diagram showing positions of "ends" and "contacts" when visually observing test pieces used in Examples. Fig. 2 is a photograph for replacing the drawing, which shows the state of the test piece after the quenching test was carried out using the heat-treated oil compositions of Examples 1-4 and Comparative Examples 1-7. Fig. 3 is a photograph for replacing the drawing, showing the state of the test piece after the quenching test was performed using the heat-treated oil composition (fresh oil) of Examples 5-8 and Comparative Examples 8-9.

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Claims (11)

A heat treatment oil composition, containing base oil (A), sulfur compound (B) and carboxylic acid compound (C), the base oil (A) is selected from mineral oil (A1), synthetic oil (A2) and One or more of the group consisting of vegetable oil (A3); the aforementioned sulfur compound (B) includes one or more of the group consisting of: sulfides (B1) represented by the following general formula (b1) ), sulfides (B2) represented by the following general formula (b2), sulfides (B3) represented by the following general formula (b3) and sulfides (B4) represented by the following general formula (b4); And the aforementioned carboxylic acid compound (C) is one or more selected from the group consisting of compounds having at least one carboxyl group and their anhydrides; [Chemical Formula 1]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² is an aryl with at least 6 to 15 carbons of hydroxyl; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms]. The heat-treated oil composition according to claim 1, wherein in the aforementioned general formula (b1), the aforementioned hydrocarbon group (X1) is an aryl group having at least 6 to 15 carbon atoms having a hydroxyl group. The heat-treated oil composition according to claim 1 or 2, wherein the aforementioned sulfur compound (B) contains at least one selected from the group consisting of: the aforementioned sulfides (B1) represented by the general formula (b1), Sulfides (B2) represented by the aforementioned general formula (b2) and sulfides (B3) represented by the aforementioned general formula (b3). The heat-treated oil composition according to any one of Claims 1 to 3, wherein the sulfur content is 10 mass ppm to 10,000 mass ppm based on the total amount of the heat-treated oil composition. The heat-treated oil composition according to any one of claims 1 to 4, wherein based on the total amount of the heat-treated oil composition, the content of the aforementioned sulfur compound (B) is 0.01% by mass to 2.0% by mass. The heat-treated oil composition according to any one of claims 1 to 5, wherein based on the total amount of the heat-treated oil composition, the content of the aforementioned carboxylic acid compound (C) is 0.1% by mass to 5.0% by mass. The heat-treated oil composition according to any one of Claims 1 to 6, wherein the content ratio [(B)/(C)] of the sulfur compound (B) to the carboxylic acid compound (C) is 0.002 to 0.8 in terms of mass ratio . The heat treatment oil composition according to any one of Claims 1 to 7, which further contains one or more selected from the group consisting of a vapor film breaking agent, an antioxidant, a brightness improving agent, and a cooling improvement agent. The heat treatment oil composition according to any one of claims 1 to 8, which can be used as quenching oil or tempering oil. A method of using a heat treatment oil composition is to use the heat treatment oil composition according to any one of Claims 1 to 9 as quenching oil or tempering oil. A method for producing a heat-treated oil composition, comprising a step of mixing a base oil (A), a sulfur compound (B) and a carboxylic acid compound (C), the base oil (A) being selected from mineral oil (A1) , at least one type selected from the group consisting of synthetic oil (A2) and vegetable oil (A3); the aforementioned sulfur compound (B) contains at least one type selected from the group consisting of: the following general formula (b1) The sulfides (B1), the sulfides (B2) represented by the following general formula (b2), the sulfides (B3) represented by the following general formula (b3), and the following general formula (b4) Sulfides (B4); and the aforementioned carboxylic acid compound (C) is one or more selected from the group consisting of compounds having at least one carboxyl group and their anhydrides; [Chemical Formula 2]

[In the aforementioned general formula (b1), Ar ¹¹ represents an aryl group having at least 6 to 15 carbon atoms of a hydroxyl group; R ¹¹ represents a substituted or unsubstituted hydrocarbon group (X1); the aforementioned hydrocarbon group (X1) represents an aryl group with 1 to 15 carbon atoms Alkyl, alkenyl with 1 to 15 carbons, cycloalkyl with 3 to 15 carbons, cycloalkenyl with 3 to 15 carbons, cycloalkylalkyl with 4 to 15 carbons, cycloalkyl with 4 to 15 carbons Cycloalkenylalkyl, aryl with 6 to 15 carbons, aralkyl with 7 to 15 carbons; In the aforementioned general formula (b2), Ar ¹² represents an arylylene group with at least 6 to 15 carbons having a hydroxyl group; R ¹² and R ¹³ each independently represent a substituted or unsubstituted hydrocarbon group (X2); the aforementioned hydrocarbon group (X2) represents an alkyl group with 1 to 15 carbons, an alkenyl group with 1 to 15 carbons, and a cycloalkane with 3 to 15 carbons Group, cycloalkenyl with 3~15 carbons, cycloalkylalkyl with 4~15 carbons, cycloalkenylalkyl with 4~15 carbons, aryl with 6~15 carbons, 7~15 carbons Aralkyl; In the aforementioned general formula (b3), Ar ¹³ represents an aryl group with at least 6 to 15 carbon atoms of a hydroxyl group; Ar ¹⁴ represents a substituted or unsubstituted aryl group with 6 to 15 carbon atoms; the aforementioned general formula ( In b4), Ar ¹⁵ and Ar ¹⁶ each independently represent a substituted or unsubstituted aryl group with 6 to 15 carbon atoms].

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