JP6957145B2 - Metalworking oil composition - Google Patents

Description

The present invention relates to a metalworking oil composition.

Conventionally, in the field of metal processing, a metal processing oil composition has been used to lubricate a processed portion of a metal workpiece. The metalworking oil composition is required to have excellent workability such as suppressing seizure between the work piece and the tool. In order to improve such processability, metalworking oils are generally blended with extreme pressure agents such as chlorine compounds and sulfur compounds.

Chlorine compounds are excellent in workability when difficult to process stainless steel sheets. However, from the viewpoint of consideration for the global environment, the development of metalworking oil compositions containing no chlorine compounds has been promoted in recent years. For example, Patent Documents 1 and 2 disclose metalworking oil compositions containing zinc dialkyldithiophosphate.

Japanese Unexamined Patent Publication No. 2001-288490 Japanese Unexamined Patent Publication No. 2000-73083

However, according to the studies by the present inventors, there is still room for improvement in the conventional metalworking oil composition in terms of processability. In particular, in plastic working under difficult machining conditions such as drawing and ironing, heat generation due to friction and deformation is large, so further improvement in seizure resistance is required.

Therefore, an object of the present invention is to provide a metalworking oil composition having excellent processability.

［式（１）中、Ｘ^１及びＸ^２はそれぞれ独立に酸素原子又は硫黄原子を表し、Ｒ^１〜Ｒ^４はそれぞれ独立にアルキル基を表す。］ The present invention provides a metalworking oil composition containing a compound represented by the following formula (1) and a sulfur-based extreme pressure agent.

[In formula (1), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and R ^{1 to} R ⁴ each independently represent an alkyl group. ]

The metalworking oil composition may further contain a perbasic organic acid metal salt.

The sulfur-based extreme pressure agent is preferably an olefin sulfide.

According to the present invention, it is possible to provide a metalworking oil composition having excellent workability. This metalworking oil composition can particularly preferably suppress seizure between the workpiece and the tool in plastic working.

It is a schematic cross-sectional view which shows the structure of the burring tester used in an Example.

Hereinafter, embodiments of the present invention will be described.

The metalworking oil composition according to the present embodiment contains a compound represented by the following formula (1) and a sulfur-based extreme pressure agent.

In the above formula (1), X ¹ and X ² independently represent an oxygen atom or a sulfur atom, respectively. R ^{1 to} R ⁴ each independently represent an alkyl group.

［式（１−１）〜（１−３）中、Ｒ^１〜Ｒ^４は、それぞれ式（１）中のＲ^１〜Ｒ^４と同一の定義内容を示す。］ The compound represented by the formula (1) is a compound represented by any of the following formulas (1-1) to (1-3).

[In formulas (1-1) to (1-3), R ^{1 to} R ⁴ have the same definitions ^{as R 1 to} R ⁴ in formula (1), respectively. ]

The ^{alkyl groups represented by R 1 to} R ⁴ may be linear or branched. The alkyl group may have 1 or more, 2 or more or 3 or more carbon atoms, and may be 18 or less, 12 or less or 10 or less. The alkyl group may have 1-18, 1-12, 1-10, 2-18, 2-12, 2-10, 3-18, 3-12 or 3-10.

The content of the compound represented by the formula (1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further, based on the total amount of the metalworking oil composition, from the viewpoint of further improving workability. It is preferably 3% by mass or more. From the viewpoint of cost effectiveness, the content of the compound represented by the formula (1) is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less. The content of the compound represented by the formula (1) is preferably 0.1 to 60% by mass, 0. In 1-55% by mass, 0.1 to 50% by mass, 1 to 60% by mass, 1 to 55% by mass, 1 to 50% by mass, 3 to 60% by mass, 3 to 55% by mass or 3 to 50% by mass. be.

The content of the compound represented by the formula (1) is preferably 0.005% by mass or more, more preferably 0, in terms of phosphorus content, based on the total amount of the metalworking oil composition, from the viewpoint of further improving workability. It is 0.05% by mass or more, more preferably 0.15% by mass or more. From the viewpoint of cost effectiveness, the content of the compound represented by the formula (1) is preferably 12.5% by mass or less, more preferably 11.5% by mass or less, and further, based on the total amount of the metalworking oil composition. It is preferably 10.4% by mass or less. The content of the compound represented by the formula (1) is preferably 0.005 to 12 in terms of phosphorus content based on the total mass of the metal processing oil composition from the viewpoint of further improvement of processability and cost effectiveness. .5% by mass, 0.005 to 11.5% by mass, 0.005 to 10.4% by mass, 0.05 to 12.5% by mass, 0.05 to 11.5% by mass, 0.05 to 10% It is .4% by mass, 0.15 to 12.5% by mass, 0.15 to 11.5% by mass or 0.15 to 10.4% by mass.

Examples of the sulfur-based extreme pressure agent include olefin sulfide, sulfide ester (including sulfide oil and fat), and sulfide mineral oil. The sulfur-based extreme pressure agent is preferably an olefin sulfide from the viewpoint of further improving processability. It is assumed that the sulfur-based extreme pressure agent in this embodiment does not contain the compound represented by the formula (1).

The olefin sulfide is, for example, a compound represented by the following formula (2).

In formula (2), R ⁵ and R ⁶ are independently linear or branched alkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl having 7 to 20 carbon atoms, respectively. Represents an aryl group or an arylalkyl group having 7 to 20 carbon atoms. R ⁵ and R ⁶ are independent, preferably branched alkyl groups having 3 to 18 carbon atoms derived from ethylene or propylene, and more preferably 6 to 6 carbon atoms derived from ethylene or propylene. There are 15 branched alkyl groups. n represents an integer of 2 to 8, preferably an integer of 4 to 8.

Specific examples of the sulfide ester include so-called sulfide fats and oils obtained by sulphurizing animal and vegetable fats and oils such as beef fat, pork fat, fish fat, rapeseed oil, and soybean oil by any method, and unsaturated fatty acids (oleic acid, linoleic acid, or the above-mentioned sulphide ester. An unsaturated fatty acid ester obtained by reacting (including fatty acids extracted from animal and vegetable fats and oils) with various alcohols is sulfided by an arbitrary method, and a mixture of animal and vegetable fats and oils and an unsaturated fatty acid ester is used by any method. Examples include those sulphated with.

Sulfide mineral oil refers to mineral oil in which elemental sulfur is dissolved. The mineral oil is not particularly limited, but the lubricating oil distillate obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent desorption, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining. , Paraffin-based mineral oil refined by appropriately combining refining treatments such as sulfuric acid washing and white clay treatment, and naphthen-based mineral oil.

The content of the sulfur-based extreme pressure agent is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more, based on the total amount of the metalworking oil composition, from the viewpoint of further improving workability. It is 10% by mass or more. From the viewpoint of cost effectiveness, the content of the sulfur-based extreme pressure agent is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The content of the sulfur-based extreme pressure agent is preferably 2 to 70% by mass, 2 to 60% by mass, 2 to 2 based on the total amount of the metal processing oil composition from the viewpoint of further improvement of workability and cost effectiveness. It is 50% by mass, 5 to 70% by mass, 5 to 60% by mass, 5 to 50% by mass, 10 to 70% by mass, 10 to 60% by mass or 10 to 50% by mass.

From the viewpoint of further improving workability, the content of the sulfur-based extreme pressure agent is preferably 0.24% by mass or more, more preferably 0.6% by mass, in terms of the amount of sulfur, based on the total amount of the metalworking oil composition. Above, more preferably 1.2% by mass or more. From the viewpoint of cost effectiveness, the content of the compound represented by the formula (1) is preferably 27.5% by mass or less, more preferably 23.4% by mass or less, and further, based on the total amount of the metalworking oil composition. It is preferably 19.5% by mass or less. The content of the sulfur-based extreme pressure agent is preferably 0.24 to 27.5% by mass in terms of the amount of sulfur based on the total amount of the metal processing oil composition from the viewpoint of further improvement of workability and cost effectiveness. , 0.24 to 23.4% by mass, 0.24 to 19.5% by mass, 0.6 to 27.5% by mass, 0.6 to 23.4% by mass, 0.6 to 19.5% by mass. , 1.2 to 27.5% by mass, 1.2 to 23.4% by mass, or 1.2 to 19.5% by mass.

The metalworking oil composition may further contain a perbasic organic acid metal salt.

The hyperbasic organic acid metal salt is a compound in which the organic acid metal salt is superbasified with a carbonate, borate or the like. Examples of the organic acid metal salt include sulfonate, phenate or salicylate of an alkali metal or an alkaline earth metal.

The carbonate hyperbasic organic acid metal salt superbasified with a carbonate is, for example, a neutral (normal salt) sulfonate, phenate or salicylate in the presence of carbon dioxide gas, an alkali metal base or an alkaline earth metal. It is obtained by reacting with the base of. The borate hyperbasic organic acid metal salt superbasified with borate can be obtained, for example, by reacting the organic acid metal salt with calcium hydroxide or calcium oxide with boric acid or boric anhydride. Be done.

The alkali metal may be sodium, potassium or the like. The alkaline earth metal may be magnesium, calcium, barium or the like, preferably calcium. The hyperbasic organic acid metal salt is preferably a hyperbasic calcium sulfonate. When the metal component of the hyperbasic organic acid metal salt is calcium, higher processability tends to be obtained.

The total base value of the perbasic organic acid metal salt is preferably 20 mg / KOH or more, more preferably 100 mgKOH / g or more, still more preferably 150 mgKOH / g or more, from the viewpoint of further improving processability. The total base value of the perbasic organic acid metal salt is preferably 500 mgKOH / g or less, more preferably 470 mgKOH / g or less, still more preferably 410 mgKOH / g or less, from the viewpoint of easy availability. The total base value in the present specification is defined in JIS K 2501 “Petroleum products and lubricating oil-neutralization value test method”. It means the total base value [mgKOH / g] by the perchloric acid method measured according to.

The content of the perbasic organic acid metal salt is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1% by mass or more, based on the total amount of the metalworking oil composition, from the viewpoint of further improving the processability. 2% by mass or more. The content of the perbasic organic acid metal salt is 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less based on the total amount of the metalworking oil composition. , Or 10% or less by mass.
The content of the perbasic organic acid metal salt is 0.5 to 70% by mass, 0.5 to 60% by mass, 0.5 to 50% by mass, 0.5 to 40 based on the total amount of the metal processing oil composition. Mass%, 0.5-30% by mass, 0.5-20% by mass, 0.5-10% by mass, 1-70% by mass, 1-60% by mass, 1-50% by mass, 1-40% by mass , 1 to 30% by mass, 1 to 20% by mass, 1 to 10% by mass, 2 to 70% by mass, 2 to 60% by mass, 2 to 50% by mass, 2 to 40% by mass, 2 to 30% by mass, 2 It may be ~ 20% by mass, or 2-10% by mass.

The content of the perbasic organic acid metal salt is preferably 0.013% by mass or more in terms of the amount of metal constituting the organic acid metal salt based on the total amount of the metal processing oil composition from the viewpoint of further improving the processability. , More preferably 0.026% by mass or more, still more preferably 0.052% by mass or more. The content of the perbasic organic acid metal salt is 12.25% by mass or less, 10.5% by mass or less, or 8. It may be 75% by mass or less. The content of the perbasic organic acid metal salt is 0.013 to 12.25% by mass and 0.013 to 10.5 in terms of the amount of metal constituting the organic acid metal salt based on the total amount of the metal processing oil composition. Mass%, 0.013 to 8.75% by mass, 0.026 to 12.25% by mass, 0.026 to 10.5% by mass, 0.026 to 8.75% by mass, 0.052 to 12.25 It may be% by mass, 0.052 to 10.5% by mass, or 0.052 to 8.75% by mass.

If necessary, the metalworking oil composition may further contain a lubricating oil base oil from the viewpoints of viscosity adjustment, processing requirement difficulty, cost and the like. In this case, the content of the lubricating oil base oil is, for example, 59.9% by mass or less based on the total amount of the metalworking oil composition. The lubricating oil base oil may be either a mineral oil, a synthetic oil, or a mixture of both.

As the mineral oil, for example, the lubricating oil distillate obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, solvent removal, contact removal, contact removal, and hydrogenation. Examples thereof include paraffin-based mineral oil or naphthen-based mineral oil refined by appropriately combining refining treatments such as purification, sulfuric acid washing, and white clay treatment.

The% Cp of the mineral oil is preferably 40 or more, more preferably 45 or more, still more preferably 50 or more, preferably 80 or less, more preferably 75 or less, still more preferably 70 or less. % Cp in the present specification means% Cp measured in accordance with the "Standard Test Method for Calculation Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method" defined in ASTM D-3238.

Specific examples of the synthetic oil include propylene oligomers, polybutenes, polyisobutylenes, 1-octene oligomers, 1-decene oligomers, co-oligomers of ethylene and propylene, co-oligomers of ethylene and 1-octene, and ethylene and 1-. Examples thereof include poly-α-olefins such as co-oligoene with decene or hydrides thereof; isoparaffin; alkylbenzenes such as monoalkylbenzenes, dialkylbenzenes and polyalkylbenzenes; alkylnaphthalene such as monoalkylnaphthalene, dialkylnaphthalene and polyalkylnaphthalene. These can be used individually by 1 type or in combination of 2 or more types.

The kinematic viscosity of the lubricating oil base oil at 40 ° C. is preferably 6 mm ² / s or more, more preferably 10 mm ² / s or more, preferably 1000 mm ² / s or less, and more preferably 500 mm ² / s or less. The kinematic viscosity in the present specification means the kinematic viscosity measured according to JIS K 2283.

The metalworking oil composition may further contain other additives in addition to the above components. Examples of other additives include extreme pressure agents other than the above-mentioned sulfur-based extreme pressure agents; wetting agents such as diethylene glycol monoalkyl ethers; film-forming agents such as acrylic polymers, paraffin waxes, microwaxes, slack waxes, and polyolefin waxes. Water substituents such as fatty acid amine salts; _{Solid lubricants such as ceramic nanoparticles (SiO 2} , ZrO ₂ , Al ₂ O _3, etc.), graphite, graphite fluoride, molybdenum disulfide, boron nitride, polyethylene powder; amines, Corrosion inhibitors such as alkanolamines, amides, carboxylic acids, carboxylates, sulfonates, phosphates, phosphates, partial esters of polyhydric alcohols; metal inactivating agents such as benzotriazole, thiadiazol; methylsilicone, Defoaming agents such as fluorosilicone and polyacrylate; ashless dispersants such as alkenyl succinimide, benzylamine and polyalkenylamine aminoamide; oily agents such as sulfides of alcohols, carboxylic acids and unsaturated carboxylic acids; phenolic oxidation Examples thereof include antioxidants such as antioxidants and amine-based antioxidants. The total content of the other additives is not particularly limited, but may be 0.1 to 10% by mass based on the total amount of the metalworking oil composition.

Kinematic viscosity at 40 ° C. metalworking oil composition is preferably 20 mm ² / s or more, more preferably 40 mm ² / s or more, more preferably 50 mm ² / s or more, particularly preferably 60 mm ² / s or more, It is preferably 700 mm ² / s or less, more preferably 600 mm ² / s or less, ^{still more preferably 500 mm 2} / s or less, and particularly preferably 400 mm ² / s or less.

The metalworking oil composition according to this embodiment is used for metalworking such as plastic working, cutting and grinding. Examples of plastic working include drawing, ironing, drawing, pressing, rolling, forging, and rolling. The metalworking oil composition is preferably used for plastic working, and is particularly preferably used for plastic working under difficult working conditions such as drawing and ironing. The workpiece may be a difficult-to-process material such as a steel plate, a stainless steel plate, a surface-treated steel plate, an aluminum alloy plate, or a titanium alloy.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

In Examples and Comparative Examples, metalworking oil compositions having the compositions shown in Tables 1 and 2 (mass% based on the total amount of the metalworking oil composition) were prepared using the following components, respectively. Tables 1 and 2 also show the phosphorus content, the sulfur content derived from the sulfur-based extreme pressure agent, and the calcium content in the metalworking oil composition (all by mass% based on the total amount of the metalworking oil composition). Shown.

Ｂ１：下記式（４）で表され、ｎが３〜８の整数である硫化オレフィンの混合物（硫黄含有量：３９質量％）

Ｃ１：過塩基性カルシウムサリシレート（カルシウム含有量：１２質量％、全塩基価３５０ｍｇＫＯＨ／ｇ）
Ｃ２：過塩基性カルシウムスルホネート（カルシウム含有量：１５質量％、全塩基価４００ｍｇＫＯＨ／ｇ）
Ｄ１：グループＩ鉱油（４０℃動粘度：１００．４ｍｍ^２／ｓ、飽和分：６２．２質量％、粘度指数：９６） A1: A compound represented by the formula (1-1) in which R ^{1 to} R ⁴ are linear alkyl groups having 8 carbon atoms (phosphorus content: 8.8% by mass).
A2: A compound represented by the formula (1-2) in which R ^{1 to} R ⁴ are linear alkyl groups having 8 carbon atoms (phosphorus content: 8.4% by mass).
a1: A compound represented by the following formula (3) in which R ^{7 to} R ¹⁰ are linear alkyl groups having 8 carbon atoms (phosphorus content: 8.0% by mass).

B1: A mixture of olefin sulfides represented by the following formula (4) and n being an integer of 3 to 8 (sulfur content: 39% by mass).

C1: Hyperbasic calcium salicylate (calcium content: 12% by mass, total base value 350 mgKOH / g)
C2: Hyperbasic calcium sulfonate (calcium content: 15% by mass, total base value 400 mgKOH / g)
D1: Group I mineral oil (40 ° C. kinematic viscosity: 100.4 mm ² / s, saturation: 62.2% by mass, viscosity index: 96)

In order to evaluate the processability of each metalworking oil composition of Examples and Comparative Examples, the following burring test was carried out. The results are shown in Tables 1 and 2.

FIG. 1 is a schematic cross-sectional view showing the configuration of the burring tester used in this test. The burring tester shown in FIG. 1 has a support 1 having a hollow inside, a die 2 arranged on the support 1, a die cushion 3 provided in the hollow portion of the support 1, and a die. A wrinkle pressing member 4 arranged above the die 2 and a punch 5 provided above the die 2 are provided.

In the test, first, using a waste cloth impregnated with the metalworking oil composition, 1 to 2 g / m on both sides of the test piece 6 (material SUS304 material, outer diameter 80 mm, inner diameter 4.2 mm, thickness 2 mm). ^The metalworking oil composition was applied so as to be 2. Next, the test piece 6 and the steel ball 7 (material SUJ2, diameter 15 mm) are arranged on the die 2, and while holding them by the wrinkle pressing member 4, the steel ball 7 is pressed from above by the punch 5 and the die cushion is pressed. 3 was raised and the test piece 6 was squeezed. The test temperature at this time was 100 ° C., and the ironing rate ((thickness of test piece 6 before deformation-thickness of deformed part after ironing) / thickness of test piece 6 before test) was 58.5%. The processing speed was 10 mm / s. The degree of damage to the steel balls after the test was visually confirmed, and the workability was evaluated according to the following criteria.
S: Almost no scratches A: Slight scratches B: Slight cloudy scratches on the surface C: Adhesion or seizure D: Large adhesion or seizure E: Ball penetrates Before, the test piece 6 is torn (broken)

1 ... Support, 2 ... Die, 3 ... Die cushion, 4 ... Wrinkle holding member, 5 ... Punch, 6 ... Test piece, 7 ... Steel ball.

Claims (2)

Contains a compound represented by the following formula (1-2), a sulfur-based extreme pressure agent (however, the compound represented by the above formula (1-2) is not included), and a hyperbasic calcium sulfonate. death,
A metalworking oil composition used for cutting, grinding, drawing, ironing, drawing, pressing, rolling, or forging.

[In formula (1-2), R ^{1 to} R ⁴ each independently represent an alkyl group. ] The metalworking oil composition according to claim 1, wherein the sulfur-based extreme pressure agent is an olefin sulfide.

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