JP2012197329A - Lubricant composition for metal processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant composition for metal processing that can achieve high level machining performance without increasing the addition amount of an extreme pressure agent.SOLUTION: The lubricant composition for metal processing includes: a hydrocarbon oil as a base oil; a compound having a perfluoroalkyl group; and an extreme pressure agent. The metal processing oil composition that can achieve high level machining performance is provided according to the lubricant composition for metal processing.

Description

  The present invention relates to a lubricating oil composition for metal processing, and more particularly, processing of metals such as aluminum, steel, stainless steel, copper, inconel, and alloys mainly thereof (cutting, grinding, plasticity, drawing, ironing, drawing). , Extrusion and rolling processes). In particular, it is suitably used for cutting and grinding.

  Metal working includes cutting, grinding, rolling, forging, pressing, drawing, rolling, and the like, and these processes are usually performed using a lubricant. For example, in cutting and grinding, productivity in machining, such as extending the life of tools such as drills, end mills, tools, and grindstones used in machining, improving the surface roughness of workpieces, and thereby improving machining efficiency For the purpose of improving the quality, oil for cutting and grinding is usually used.

  The cutting and grinding fluids are water-soluble cutting and grinding fluids that use diluted surfactant and lubricant components in water, and water-insoluble cutting and grinding fluids that use mineral oil as the main ingredient. There are roughly two types of processing oils.

  The most basic and important functions of the oil for cutting and grinding are lubrication and cooling. In general, water-insoluble cutting and grinding fluids are excellent in lubrication performance, and water-soluble cutting and grinding fluids are excellent in cooling performance. However, either type of lubrication performance or cooling performance is good. However, it is rare that only an oil agent is required, and both performances are required for an oil agent (for example, see Patent Documents 1 and 2). As a means for improving these performances, it is conceivable to increase the amount of the extreme pressure agent added in the oil agent. That is, the lubricity is improved by increasing the amount of the extreme pressure agent added, and the heat generation is reduced by the reduction in friction.

JP 2011-026517 A JP 2009-197183 A

  However, an increase in extreme pressure agents increases costs, shortens tool life, sulfur-based extreme pressure agents cause problems such as odor, and chlorinated extreme pressure agents generate dioxins when incinerated and discarded. It has various problems such as problems. In particular, a decrease in tool life can be a serious problem because it leads to a decrease in productivity. Therefore, there has been a demand for an oil agent that has high processing performance without increasing the amount of extreme pressure agent added and without reducing the tool life.

  The present invention has been made in view of such circumstances, and provides a lubricating oil composition for metal working capable of achieving a high level of processing performance without increasing the amount of extreme pressure agent added. For the purpose.

  As a result of intensive studies to achieve the above object, the present inventors use a lubricating oil composition for metal working containing an extreme pressure agent and a compound having a specific perfluoroalkyl group in a hydrocarbon oil. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

  That is, this invention provides the lubricating oil composition for metal processing containing the at least 1 sort (s) of base oil chosen from mineral oil and synthetic oil, the compound which has a perfluoroalkyl group, and an extreme pressure agent.

  According to the lubricating oil composition for metal working of the present invention, by having the above-described configuration, the machining performance can be sufficiently enhanced, so that the improvement of machining efficiency and the improvement of tool life can be achieved at a high level in a balanced manner. It becomes possible.

  The perfluoroalkyl group is preferably at least one selected from a perfluoroalkyl sulfonate group, a perfluoroalkylcarbonyl group, and a perfluorosulfonamide group.

［式（１）中、Ｒ^１は炭素数１〜１２のアルキル基又は炭素数２〜１２のアルケニル基を示し、Ａは炭素数１〜１８のパーフルオロアルキル基を示し、Ｂは水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、炭素数１〜１２のアルカノール基、炭素数６〜１２のアリール基、又は一般式（２）：

（式（２）中、Ｒ^２は水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基又は炭素数６〜１８のアリール基を示し、Ｒ^３は炭素数１〜１２のアルキレン基又は炭素数２〜１２のアルケニレン基を示す。）
で示される基を示す。］ Moreover, it is preferable that the lubricating oil composition for metal processing of this invention contains the compound which has a structure represented by following General formula (1) as a compound which has the said perfluoroalkyl group.

[In the formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, A represents a perfluoroalkyl group having 1 to 18 carbon atoms, B represents a hydrogen atom, A C1-C12 alkyl group, a C2-C12 alkenyl group, a C1-C12 alkanol group, a C6-C12 aryl group, or General formula (2):

(In the formula (2), ^{R 2} represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aryl group having 6 to 18 carbon atoms having 2 to 18 carbon atoms, ^{R 3} is 1 to 12 carbon atoms An alkylene group or an alkenylene group having 2 to 12 carbon atoms.)
The group shown by is shown. ]

  Moreover, it is preferable that the lubricating oil composition for metal processing of this invention further contains an oil-based agent and an organic acid salt.

  According to the present invention, a metal working oil composition capable of achieving a high level of processing performance is provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The metalworking oil composition according to this embodiment contains at least one base oil selected from mineral oil and synthetic oil, a compound having a perfluoroalkyl group, and an extreme pressure agent.

  The base oil may be mineral oil or synthetic oil, or a mixture thereof.

  As mineral oil, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, catalytic dewaxing, hydrogenation. Examples thereof include paraffinic mineral oil or naphthenic mineral oil that is refined by appropriately combining purification treatments such as purification, sulfuric acid washing, and clay treatment.

  Specific examples of the synthetic oil include propylene oligomer, polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, ethylene and propylene co-oligomer, ethylene and 1-octene co-oligomer, ethylene and 1- Poly α-olefins such as co-oligomers with decene or their hydrides; isoparaffins; alkylbenzenes such as monoalkylbenzenes, dialkylbenzenes and polyalkylbenzenes; alkylnaphthalenes such as monoalkylnaphthalenes, dialkylnaphthalenes and polyalkylnaphthalenes; dioctyl adipates, di Dibasic acid esters such as 2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, ditridecyl glutarate; Tribasic acid esters such as tutonic acid; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane oleate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate; polyethylene glycol, polypropylene glycol Polyglycols such as polyoxyethyleneoxypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, polyoxyethyleneoxypropylene glycol monoether, polyethylene glycol diether, polypropylene glycol diether, polyoxyethyleneoxypropylene glycol diether; Monoalkyl diphenyl ether, dialkyl diphenyl ether , Monoalkyl triphenyl ether, dialkyl triphenyl ether, tetraphenyl ether, monoalkyl tetraphenyl ether, dialkyl tetraphenyl ether, phenyl ether such as pentaphenyl ether; silicone oil; fluoro ether such as perfluoro ether, etc. These can be used alone or in combination of two or more.

  In the compound having a perfluoroalkyl group, the perfluoroalkyl group may be linear or branched, but is preferably linear, saturated or unsaturated, and has 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably Is from 1 to 6, most preferably from 1 to 4. When the number of carbon atoms is 19 or more, it is inferior in decomposability and may be an environmental burden when released to the outside.

  Examples of the compound having a perfluoroalkyl group include perfluoroalkylsulfonamide, perfluoroalkyl alkylene oxide adduct, perfluoroalkylamine, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, and salts and derivatives thereof. It is done.

［式（１）中、Ｒ^１は炭素数１〜１２のアルキル基又は炭素数２〜１２のアルケニル基を示し、Ａは炭素数１〜１８のパーフルオロアルキル基を示し、Ｂは水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数１〜１８のアルカノール基、炭素数６〜１８のアリール基、又は一般式（２）：

（式（２）中、Ｒ^２は水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基又は炭素数６〜１８のアリール基を示し、Ｒ^３は炭素数１〜１２のアルキレン基又は炭素数２〜１２のアルケニレン基を示す。）
で示される基を示す。］ As the perfluoroalkylsulfonamide, a compound having a structure represented by the following general formula (1) is preferable.

[In the formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, A represents a perfluoroalkyl group having 1 to 18 carbon atoms, B represents a hydrogen atom, C1-C18 alkyl group, C2-C18 alkenyl group, C1-C18 alkanol group, C6-C18 aryl group, or General formula (2):

(In the formula (2), ^{R 2} represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aryl group having 6 to 18 carbon atoms having 2 to 18 carbon atoms, ^{R 3} is 1 to 12 carbon atoms An alkylene group or an alkenylene group having 2 to 12 carbon atoms.)
The group shown by is shown. ]

A may be linear or branched, but is preferably linear. A may be saturated or unsaturated, but is preferably saturated. The carbon number of A is 1 or more and 18 or less, preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and most preferably 1 or more and 4 or less. When the number of carbon atoms is 19 or more, it is inferior in decomposability and may be an environmental burden when released to the outside. The carbon number of B is preferably 2-12, more preferably 3-8, and most preferably 4-6. B may be linear or branched, and may be saturated or unsaturated. R ¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 6, most preferably 1 to 4, and may be linear or branched, and may be saturated or unsaturated. R ² is preferably an alkyl group or alkenyl group having 6 to 18 carbon atoms, more preferably an alkyl group or alkenyl group having 8 to 18 carbon atoms, and most preferably an alkyl group or alkenyl group having 12 to 18 carbon atoms. preferable. The alkyl group or alkenyl group may be linear or branched, but is preferably branched. When used as a working fluid composition, an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms are preferable, an alkyl group having 1 to 4 carbon atoms and an alkenyl group having 2 to 4 carbon atoms are more preferable, and 2-3 The alkenyl group is most preferred. The alkyl group and alkenyl group may be linear or branched, and may be saturated or unsaturated. R ³ is preferably an alkylene group having 1 to 8 carbon atoms or an alkenylene group having 2 to 8 carbon atoms, and preferably an alkylene group having 1 to 4 carbon atoms.

  The perfluoroalkylsulfonamide may be a primary amide, a secondary amide, or a tertiary amide, but a tertiary amide is preferred.

As the alkylene oxide adduct of perfluoroalkyl, a compound represented by the following general formula (3) is suitable. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, and ethylene oxide and propylene oxide are preferable. The added mole number of alkylene oxide is 1 or more and 20 or less, preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and most preferably 1 or more and 6 or less. It may be an adduct of a single alkylene oxide or an adduct in which a plurality of alkylene oxides are mixed. In this case, the alkylene oxide polymerization portion may be a block polymer or a random polymer, but a random polymer is preferred.
_{^{R 4 -O- (R 5 O)}} a -A (3)
Wherein (3), A represents a perfluoroalkyl of 1 to 18 carbon atoms, ^{R 4} represents a hydrogen atom, an alkyl group or an acyl group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, ^{R 5} is A C2-C4 alkylene group is shown, a shows the integer of 1-20. ]

As the perfluoroalkylamine, a compound represented by the following general formula (4) is suitable. The number of perfluoroalkyl groups bonded to nitrogen may be 1 to 3, but is preferably one. Moreover, although 3-b R < ⁶ > couple | bonded with nitrogen may or may not contain a hydrogen atom, it is preferable that one is a hydrogen atom. Furthermore, R ⁶ other than a hydrogen atom that the compound may have is preferably an alkyl group or an alkanol group. The alkyl group and alkanol group represented by R ⁶ may be linear or branched, and may be saturated or unsaturated.
_{^{(R 6) (3-b}} ) -N-A b (4)
Wherein (4), A represents a perfluoroalkyl group having 1 to 18 carbon atoms, ^{R 6} is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 6 to an alkanol group or a carbon number of 1 to 18 carbon atoms 12 represents an aryl group having 7 to 12 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or an alkylcycloalkyl group having 7 to 12 carbon atoms, and b represents an integer of 1 to 3. ]

  Perfluoroalkyl sulfonic acid is a sulfonic acid having a C 1-18 perfluoroalkyl group. Examples of the salt include alkali metal salts, alkaline earth metal salts, and amine salts. Sodium, potassium are used as the alkali metal, and magnesium, calcium, and barium are used as the alkaline earth. Of these, sodium and potassium are preferable. Examples of amines include monoamines, polyamines, and alkanolamines.

  Monoamines include alkylamines having 1 to 3 alkyl groups having 1 to 22 carbon atoms, alkenylamines having alkenyl groups having 2 to 23 carbon atoms, two methyl groups and one alkenyl group having 2 to 23 carbon atoms. A monoamine having an aromatic group, an aromatic substituted alkylamine, a cycloalkylamine having a cycloalkyl group having 5 to 16 carbon atoms, a monoamine having two methyl groups and a cycloalkyl group, a cycloalkyl group substituted by a methyl group and / or an ethyl group And alkylcycloalkylamine having the following formula. The monoamine here includes monoamines such as beef tallow amine derived from fats and oils.

  Examples of the polyamine include alkylene polyamines having 1 to 5 alkylene groups having 2 to 4 carbon atoms, N-alkylethylenediamine having an alkyl group having 1 to 23 carbon atoms, and N-alkenylethylenediamine having an alkenyl group having 2 to 23 carbon atoms. , N-alkyl or N-alkenylalkylene polyamines. The polyamine here includes polyamines derived from fats and oils (such as beef tallow polyamine).

  Examples of the alkanolamine include mono-, di- and trialkanolamines of alcohols having 1 to 16 carbon atoms.

  The sulfonic acid which comprises a sulfonate can use the well-known thing manufactured by the conventional method. Specifically, from sulfonated alkyl aromatic compounds in the lubricating oil fraction of mineral oil, petroleum sulfonic acids such as mahogany acid produced as a by-product during white oil production, or from alkylbenzene production plants used as raw materials for detergents, etc. Synthetic sulfones such as those obtained by alkylating the by-produced polyolefin to benzene, sulfonated alkylbenzenes having linear or branched alkyl groups, and sulfonated alkylnaphthalenes such as dinonylnaphthalene Acid etc. are mentioned.

  Perfluoroalkyl carboxylic acids are compounds in which a carboxyl group is bonded to a C 1-18 perfluoroalkyl group. Specific examples of the salt include the same salts as those of perfluorosulfonic acid.

  The content of the compound having a perfluoroalkyl group is 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.08 to 2% by mass, based on the total amount of the working fluid composition. Most preferably, it is 0.10-1 mass%. If it exceeds 5% by mass, the coefficient of friction increases, which may adversely affect workability. If the amount is less than 0.01% by mass, it is difficult to obtain the effect.

  As the extreme pressure agent used as the extreme pressure agent in the present embodiment, a sulfur compound and / or a phosphorus compound can be preferably used.

  The sulfur compound is not particularly limited as long as it does not impair the characteristics of the lubricating oil composition for metal working, but dihydrocarbyl polysulfide, sulfurized ester (including sulfurized ester oil), sulfurized fatty acid, sulfide mineral oil, zinc dithiophosphate compound, Zinc dithiocarbamate compounds, molybdenum dithiophosphates and molybdenum dithiocarbamates are preferably used.

The dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin, and specifically means a compound represented by the following general formula (5).
_{^{R 7 -S c -R 8 (5}} )
[In Formula (5), R ⁷ and R ⁸ may be the same or different, and each has a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. It represents a 7-20 alkylaryl group or a C7-20 arylalkyl group, and c represents an integer of 2-6, preferably 2-5. ]

R ⁷ and R ⁸ in the general formula (5) are more preferably each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene, and is derived from ethylene or propylene. Particularly preferred is a branched alkyl group having 6 to 15 carbon atoms.

  Specific examples of the sulfurized ester include so-called sulfurized fats and oils obtained by sulfurizing animal and vegetable fats and oils such as beef tallow, pork tallow, fish fat, rapeseed oil, and soybean oil, and unsaturated fatty acids (oleic acid, linoleic acid, or the above). (Including fatty acids extracted from animal and vegetable fats and oils) and various alcohols obtained by sulfurizing unsaturated fatty acid esters obtained by any method and mixtures of animal and vegetable oils and unsaturated fatty acid esters by any method And sulfided with

Examples of the sulfurized fatty acid include oleic acid, linoleic acid, fatty acids extracted from animal and vegetable fats and oils, and those obtained by sulfurizing a mixture thereof.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil is not particularly limited. Specifically, the lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking. , Paraffinic mineral oils, naphthenic mineral oils, etc., which are refined by appropriately combining purification treatments such as solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. In addition, as the elemental sulfur, any form such as a lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled in a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in sulfur content in a sulfide mineral oil, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0.5 mass%. is there.

［式（６）〜（９）中、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は同一でも異なっていてもよく、それぞれ炭素数１以上の炭化水素基を表し、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４はそれぞれ酸素原子又は硫黄原子を表し、Ｘ^１とＸ^２、Ｘ^３とＸ^４はそれぞれ同一でも異なっていても良い。］ The zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate and the molybdenum dithiocarbamate mean compounds represented by the following general formulas (6) to (9), respectively.

[In the formulas (6) to (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms; X ¹ , X ² , X ³ and X ⁴ each represents an oxygen atom or a sulfur atom; X ¹ and X ² , X ³ and X ⁴ may be the same or different. ]

In the present embodiment, among the above sulfur compounds, at least one selected from the group consisting of dihydrocarbyl polysulfide, sulfurized ester and sulfurized fatty acid is preferable because the effect of improving machining efficiency and tool life can be obtained at a higher level. .
In addition, when a sulfur type extreme pressure agent mix | blends and prescribes | regulates, it may correspond to any of N2 type | species prescribed | regulated by JISK2241, N3 type | mold, and N4 type | mold, but the effect is especially in N3 type | mold and N4 type | mold. Can demonstrate.

  In addition, as the phosphorus compound used as the extreme pressure agent in the present embodiment, specifically, phosphate ester, acidic phosphate ester, amine salt of acidic phosphate ester, chlorinated phosphate ester, phosphite ester and phosphate Examples include thiothionate. Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof. In the present embodiment, a compound having both a phosphorus atom and a sulfur atom in one molecule is included in the phosphorus compound for convenience.

  In the present embodiment, among the above phosphorus compounds, higher processing efficiency and tool life improvement effect can be obtained, and therefore, phosphate esters, acidic phosphate esters, and amine salts of acidic phosphate esters are preferable.

  The lubricating oil composition for metal processing according to the present embodiment may contain only one of a sulfur compound and a phosphorus compound as an extreme pressure agent, and contains both a sulfur compound and a phosphorus compound. There may be. From the point that the effect of improving the machining efficiency and the tool life is further enhanced, it preferably contains a sulfur compound or both a sulfur compound and a phosphorus compound, and more preferably contains both a sulfur compound and a phosphorus compound.

  Although the content of the extreme pressure agent is arbitrary, it is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% on the basis of the total amount of the oil agent from the viewpoint of improving the processing efficiency and improving the tool life. It is at least mass%. Further, from the viewpoint of preventing abnormal wear and improving the tool life, the sulfur compound content is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably, based on the total amount of the lubricating oil composition. 30% by mass or less, particularly preferably 20% by mass or less.

［式（１０）中、Ｒ^２５は炭素数１〜３０の炭化水素基を表し、ｄは１〜６の整数を表し、ｅは０〜５の整数を表す。］

［式（１１）中、Ｒ^２６は炭素数１〜３０の炭化水素基を表し、ｆは１〜６の整数を表し、ｇは０〜５の整数を表す。］ Even if the lubricating oil composition for metal working according to the present embodiment comprises only at least one base oil selected from mineral oil and synthetic oil, a compound having a perfluoroalkyl group, and an extreme pressure agent. Although it is good, it is preferable to further contain an oily agent from the viewpoint of achieving higher working efficiency and an improvement effect of the tool life. As the oily agent, (C1) alcohol (excluding the following (C6)), (C2) carboxylic acid, (C3) sulfide of unsaturated carboxylic acid, (C4) represented by the following general formula (1) Compound, (C5) compound represented by the following general formula (2), (C6) polyoxyalkylene compound, (C7) ester (excluding ester as base oil), (C8) hydrocarbyl of polyhydric alcohol Examples include ruether and (C9) amine.

[In Formula (10), R ²⁵ represents a hydrocarbon group having 1 to 30 carbon atoms, d represents an integer of 1 to 6, and e represents an integer of 0 to 5. ]

[In Formula (11), R ²⁶ represents a hydrocarbon group having 1 to 30 carbon atoms, f represents an integer of 1 to 6, and g represents an integer of 0 to 5. ]

  (C1) Among the alcohols, the monohydric alcohol is a linear alcohol having 3 to 18 carbon atoms, a branched alcohol having 3 to 18 carbon atoms, a cycloalkyl alcohol having 5 to 10 carbon atoms, or an alkylcycloalkyl alcohol. Is mentioned. Specifically, linear or branched propanol (including n-propanol, 1-methylethanol, etc.), linear or branched butanol (n-butanol, 1-methylpropanol, 2-methyl) Propanol etc.), linear or branched pentanol (including n-pentanol, 1-methylbutanol, 2-methylbutanol, 3-methylbutanol, etc.), linear or branched hexanol (Including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, etc.), linear or branched heptanol (n-heptanol, 1-methylhexanol, 2-methylhexanol) , 3-methylhexanol, 4-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol, etc.), Chain or branched octanol (including n-octanol, 2-ethylhexanol, 1-methylheptanol, 2-methylheptanol, etc.), linear or branched nonanol (n-nonanol, 1- Methyl octanol, 3,5,5-trimethylhexanol, 1- (2′-methylpropyl) -3-methylbutanol, etc.), linear or branched decanol (n-decanol, iso-decanol, etc.) Linear) or branched undecanol (including n-undecanol, etc.), linear or branched dodecanol (including n-dodecanol, iso-dodecanol, etc.), linear or branched Tridecanol, linear or branched tetradecanol (including n-tetradecanol, iso-tetradecanol, etc.), linear or branched Pentadecanol, linear or branched hexadecanol (including n-hexadecanol, iso-hexadecanol, etc.), linear or branched heptadecanol, linear or branched And octadecanol (including n-octadecanol, iso-octadecanol, etc.), cyclopentanol, cyclohexanol, methylcyclohexanol, dimethylcyclohexanol, cycloheptanol and the like.

  Of the alcohols according to this embodiment, polyhydric alcohols having 2 to 8 hydroxyl groups are preferably used.

  Specific examples of the dihydric alcohol (diol) include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1 , 4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl- 2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanedi Lumpur, 1,9-nonanediol, 1,10-decanediol, 1,11-decanediol, 1,12-dodecane diol. Specific examples of trihydric or higher alcohols include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- ( Pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin, 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyvalent alcohols such as adonitol, arabitol, xylitol, mannitol, xylose, arabinose Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, genti North, sugars such as melezitose, and their partially etherified products and methyl glucosides (glycosides) and the like. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri- (penta Hindered alcohols such as erythritol are preferred.

  Among alcohols, a saturated monohydric alcohol having a branched chain is preferably used from the viewpoint of processability. Further, when a polyhydric alcohol is used, a so-called partial ester in which a part of the hydroxyl group is esterified may be used.

  (C2) The carboxylic acid may be a monobasic acid or a polybasic acid. A monovalent carboxylic acid having 1 to 40 carbon atoms is preferable, a carboxylic acid having 5 to 25 carbon atoms is more preferable, and a carbon number having 5 to 20 carbon atoms is most preferable because higher processing efficiency and tool life can be obtained. Carboxylic acid. These carboxylic acids may be linear or branched and may be saturated or unsaturated, but are preferably saturated carboxylic acids from the standpoint of stickiness prevention.

  Specifically, as the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used, and the fatty acid may be linear or branched, and may be saturated or unsaturated. Specifically, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptane Acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecane Acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecane Acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched Henicosanoic acid, linear or branched Saturated fatty acids such as cosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid, acrylic acid, linear or branched butenoic acid, linear or branched pentenoic acid, Linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, Linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecene Acid, linear or branched Unsaturated fatty acids such as cocenoic acid, linear or branched heicosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and the like And the like. Among these, from the viewpoint of improvement in processing efficiency and tool life, and handleability, a saturated fatty acid having 3 to 20 carbon atoms, an unsaturated fatty acid having 3 to 22 carbon atoms, and a mixture thereof are particularly preferable, and those having 4 to 18 carbon atoms. Saturated fatty acids, unsaturated fatty acids having 4 to 18 carbon atoms and mixtures thereof are more preferred, unsaturated fatty acids having 4 to 18 carbon atoms are more preferred, and saturated fatty acids having 4 to 18 carbon atoms are further preferred from the viewpoint of anti-stickiness. preferable.

  Examples of the polybasic acid include dibasic acids having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid Acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or Branched hexadecanedioic acid, linear or branched hexenedioic acid, linear or branched heptenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid , Linear or branched decenedioic acid, linear or branched undecenedioic acid, linear Is branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetradecenedioic acid, linear or branched heptadecenedioic acid, linear or branched hexadecene diacid Examples thereof include acids and mixtures thereof.

  (C3) Examples of the unsaturated carboxylic acid sulfide include unsaturated sulfides of the carboxylic acid (B). Specific examples include sulfides of oleic acid.

(C4) In the compound represented by the general formula (10), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁵ include, for example, a linear or branched alkyl group having 1 to 30 carbon atoms, A cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl having 7 to 30 carbon atoms Examples include an aryl group and an arylalkyl group having 7 to 30 carbon atoms. In these, it is preferable that it is a C1-C30 linear or branched alkyl group, More preferably, it is a C1-C20 linear or branched alkyl group, More preferably, it is a C1-C10. A linear or branched alkyl group, most preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group.

  The substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom. d is preferably an integer of 1 to 3, and more preferably 2. e is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (10) include p-tert-butylcatechol.

(C5) In the compound represented by the general formula (11), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁶ are represented by R ²⁵ in the general formula (10). The same thing as the example of a C1-C30 hydrocarbon group can be mentioned, and the example of a preferable thing is also the same. The substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom. f is preferably an integer of 1 to 3, and more preferably 2. g is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (11) include 2,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

Examples of the (C6) polyoxyalkylene compound include compounds represented by the following general formula (12) or (13).
_{^{R 27 O- (R 28 O)}} h -R 29 (12)
[In Formula (12), R ²⁷ and R ²⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ²⁸ represents an alkylene group having 2 to 4 carbon atoms, and h is a number average molecular weight. Represents an integer such that 100 is 3500. ]
_{^{X - [(R 30 O)}} i -R 31] j (13)
Wherein (13), X represents a polyvalent residue which is obtained by removing some or all of the hydrogen atoms of the hydroxyl groups of an alcohol having 3-8 hydroxyl groups, R ³⁰ represents an alkylene group having 2 to 4 carbon atoms R ³¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, i represents an integer having a number average molecular weight of 100 to 3500, and j represents the number of hydrogen atoms removed from the hydroxyl group of X. Represents the same number. ]

In the general formula (12), at least one of R ²⁷ and R ²⁸ is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁷ and ^{R 28,} for example, the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by ^{R 25} in formula (10) Examples of preferred ones are also the same. Specific examples of the alkylene group having 2 to 4 carbon atoms represented by R ²⁸ include an ethylene group, a propylene group (methylethylene group), and a butylene group (ethylethylene group). h is preferably an integer such that the number average molecular weight is 300 to 2,000, more preferably an integer such that the number average molecular weight is 500 to 1,500.

  In the general formula (13), specific examples of the polyhydric alcohol having 3 to 8 hydroxyl groups constituting X include the polyhydric alcohols exemplified in the description of (C1) alcohol.

  (C7) The constituent alcohol of the ester may be a monohydric alcohol or a polyhydric alcohol. In addition, the carboxylic acid constituting the (C7) ester may be a monobasic acid or a polybasic acid.

  Examples of the monohydric alcohol and polyhydric alcohol constituting the ester include the same monohydric alcohol and polyhydric alcohol as exemplified in the description of (C1) alcohol.

  As described above, the alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol, but it is possible to achieve better processing efficiency and tool life, and a low pour point. Polyhydric alcohols are preferred from the standpoints that products are easier to obtain and handleability in winter and cold regions is improved. Further, when an ester of polyhydric alcohol is used, in the cutting / grinding process, the accuracy of the finished surface of the workpiece is improved and the effect of preventing wear of the tool edge is further increased.

  The acid constituting the ester oily agent may be a monobasic acid as the (C2) carboxylic acid shown as the oily agent, or a polybasic acid.

  When a polyhydric alcohol is used as the alcohol component, it may be a complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified, or a partial ester in which some of the hydroxyl groups are not esterified and remain as hydroxyl groups. Good. Further, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, or a part of the carboxyl group is not esterified and remains as a carboxyl group. It may be a partial ester.

  The total number of carbon atoms of the ester oil-based agent is not particularly limited, but from the viewpoint of improving processing efficiency and tool life, an ester having a total carbon number of 7 or more is preferable, an ester of 9 or more is more preferable, and an ester of 11 or more is preferable. Most preferred. Further, from the viewpoint of not increasing the occurrence of stain and corrosion, and compatibility with organic materials, an ester having a total carbon number of 60 or less is preferred, an ester of 45 or less is more preferred, an ester of 26 or less is more preferred, 24 or less esters are more preferred, and 22 or less esters are most preferred.

  (C8) The polyhydric alcohol constituting the hydrocarbyl ether of the polyhydric alcohol is the same as the polyhydric alcohol of the alcohol compound according to the present invention.

  Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylol Methylol butane and the like, and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol , 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols and mixtures thereof, such as mannitol and the like are preferable. Even more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof. Among these, glycerin is most preferable from the viewpoint of improving the processing efficiency and the tool life.

  As the hydrocarbyl ether of the polyhydric alcohol, one obtained by converting a part or all of the hydroxyl groups of the polyhydric alcohol into a hydrocarbyl ether can be used. From the viewpoint of improving processing efficiency and tool life, a product obtained by hydrocarbyl etherifying a part of hydroxyl groups of a polyhydric alcohol (partially etherified product) is preferable. Here, the hydrocarbyl group is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 11 carbon atoms, carbon A hydrocarbon group having 1 to 24 carbon atoms such as an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms is represented.

  Among these, from the viewpoint of improvement in machining efficiency and tool life, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and the number of carbon atoms 3-12 linear or branched alkyl groups and oleyl groups (residues obtained by removing hydroxyl groups from oleyl alcohol) are more preferred.

  (C9) Monoamine is preferably used as the amine. The carbon number of the monoamine is preferably 6 to 24, more preferably 12 to 24. The carbon number here means the total number of carbon atoms contained in the moamine, and when the monoamine has two or more hydrocarbon groups, it represents the total number of carbon atoms.

  As the monoamine used in the present embodiment, any of a primary monoamine, a secondary monoamine, and a tertiary monoamine can be used. From the viewpoint of improving processing efficiency and tool life, the primary monoamine is preferable.

  As the hydrocarbon group bonded to the nitrogen atom of the monoamine, any of an alkyl group, alkenyl group, cycloalkyl group, alkylcycloalkyl group, aryl group, alkylaryl group, arylalkyl group, etc. can be used. From the viewpoint of improving efficiency and tool life, an alkyl group or an alkenyl group is preferable. The alkyl group and alkenyl group may be linear or branched, but are preferably linear from the viewpoint of improving processing efficiency and tool life.

  Preferable monoamines used in this embodiment are, for example, hexylamine (including all isomers), heptylamine (including all isomers), octylamine (including all isomers). ), Nonylamine (including all isomers), decylamine (including all isomers), undecylamine (including all isomers), dodecylamine (including all isomers), tridecylamine (all ), Tetradecylamine (including all isomers), pentadecylamine (including all isomers), hexadecylamine (including all isomers), heptadecylamine (including all isomers) ), Octadecylamine (including all isomers), nonadecylamine (including all isomers), icosylamine (including all isomers), Nicosylamine (including all isomers), docosylamine (including all isomers), tricosylamine (including all isomers), tetracosylamine (including all isomers), octadecenylamine (all (Including isomers) (including oleylamine and the like) and mixtures of two or more thereof. Among these, from the viewpoint of improvement in machining efficiency and tool life, primary monoamines having 12 to 24 carbon atoms are preferable, primary monoamines having 14 to 20 carbon atoms are more preferable, and primary monoamines having 16 to 18 carbon atoms are preferable. Grade monoamines are more preferred.

  In this embodiment, only 1 type chosen from the said oil-based agent (C1)-(C9) may be used, and 2 or more types of mixtures may be used. Among these, one or a mixture of two or more selected from (C1) alcohol, (C2) carboxylic acid, (C6) polyoxyalkylene compound, and (C9) amine from the viewpoint of improving machining efficiency and tool life. It is preferable that

  The content of the oily agent is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the lubricating oil composition, from the viewpoint of improvement in processing efficiency and tool life. More preferably, it is 1% by mass or more. From the viewpoint of stability, the content of the oily agent is preferably 40% by mass or less, more preferably 45% by mass or less, and still more preferably 30% by mass or less, based on the total amount of the lubricating oil composition. If the amount is too large, the effect corresponding to the added amount cannot be obtained, and if the amount is too small, the effect cannot be obtained.

  In addition, the lubricating oil composition for metal working according to the present embodiment provides a hydrocarbon oil as a base oil, a compound having a perfluoroalkyl group, and an extreme pressure from the viewpoint of obtaining better working efficiency and tool life. In addition to the agent, it is preferable to further contain an organic acid salt. Furthermore, an organic acid salt can be used in combination with the above oil agent.

  As the organic acid salt, sulfonate, phenate, salicylate, and a mixture thereof are preferably used. The positive components of these organic acid salts include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; ammonia and alkylamines having 1 to 3 carbon atoms (monomethylamine, dimethyl). Amines, trimethylamines, monoethylamines, diethylamines, triethylamines, monopropylamines, dipropylamines, tripropylamines, etc.), alkanolamines having an alkanol group having 1 to 3 carbon atoms (monomethanolamine, dimethanolamine, trimethanolamine, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine etc.) such as amine, zinc, etc. But an alkali metal or alkaline earth metals are preferred, calcium is particularly preferred. When the positive component of the organic acid salt is an alkali metal or alkaline earth metal, higher lubricity tends to be obtained.

  The total base number of the organic acid salt is preferably 50 to 500 mgKOH / g, more preferably 100 to 450 mgKOH / g. When the total base number of the organic acid salt is less than 100 mgKOH / g, the lubricity improving effect due to the addition of the organic acid salt tends to be insufficient. On the other hand, the organic acid salt having a total base number exceeding 500 mgKOH / g is Usually, since manufacture is very difficult and acquisition is difficult, it is unpreferable respectively. The total base number referred to here is JIS K 2501 “Petroleum products and lubricants—Test method for neutralization number”. The total base number [mgKOH / g] by the perchloric acid method measured according to the above.

  Further, the content of the organic acid salt is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and further preferably 1 to 20% by mass based on the total amount of the lubricating oil composition. It is. When the content of the organic acid salt is less than the lower limit value, the effect of improving the processing efficiency and tool life due to the addition of the organic acid salt tends to be insufficient. On the other hand, when the content exceeds the upper limit value, the metal working oil composition There is a tendency that precipitates are likely to be produced due to a decrease in the stability of.

  As the sulfonate, one produced by any method can be used. For example, alkali metal salts, alkaline earth metal salts, amine salts and mixtures of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700 are used. it can. As the alkyl aromatic sulfonic acid here, generally, a sulfonated alkyl aromatic compound of a lubricating oil fraction of mineral oil, a petroleum sulfonic acid such as so-called mahogany acid, which is produced as a by-product during production of white oil, and a detergent. Alkylbenzene having a linear or branched alkyl group obtained by by-production from a raw material alkylbenzene production plant or alkylating polyolefin to benzene, or alkylnaphthalene such as dinonylnaphthalene Synthetic sulfonic acids such as those obtained by sulfonating and the like. In addition, the above alkyl aromatic sulfonic acid and an alkali metal base (such as an alkali metal oxide or hydroxide), an alkaline earth metal base (such as an alkaline earth metal oxide or hydroxide), or the above-mentioned So-called neutral (normal salt) sulfonates obtained by reacting with amines (ammonia, alkylamines, alkanolamines, etc.); neutral (normal salt) sulfonates, excess alkali metal bases, alkaline earth metal bases Or so-called basic sulfonates obtained by heating an amine in the presence of water; reacting a neutral (normal salt) sulfonate with an alkali metal base, an alkaline earth metal base or an amine in the presence of carbon dioxide. So-called carbonate overbased (superbasic) sulfonates obtained by: neutral (normal salt) sulfonates with alkaline gold Bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased sulfonates and boric acids such as boric acid or boric anhydride. And so-called borate overbased (superbasic) sulfonates produced by reacting acid compounds; and mixtures thereof.

  Further, as the phenate, specifically, in the presence or absence of elemental sulfur, an alkylphenol having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide or Hydroxides), alkaline earth metal bases (alkaline earth metal oxides, hydroxides, etc.) or neutrals obtained by reacting with the amines mentioned above (ammonia, alkylamines, alkanolamines, etc.). Phenates; neutral phenates and excess alkali metal bases, alkaline earth metal bases or amines obtained by heating in the presence of water, so-called basic phenates; neutral phenates in the presence of carbon dioxide So-called carbonate overbased (superbase) obtained by reacting with metal bases, alkaline earth metal bases or amines ) Phenates; neutral phenates are reacted with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) phenates And so-called borate overbased (superbasic) phenates produced by reacting boric acid compounds such as boric acid or boric anhydride; and mixtures thereof.

  Further, as the salicylate, specifically, an alkyl salicylic acid having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide) in the presence or absence of elemental sulfur. And hydroxides), alkaline earth metal bases (such as alkaline earth metal oxides and hydroxides) or the above-described amines (such as ammonia, alkylamines and alkanolamines). So-called basic salicylate obtained by heating neutral salicylate and excess alkali metal base, alkaline earth metal base or amine in the presence of water; neutral salicylate in the presence of carbon dioxide gas So-called carbonate overbases obtained by reacting with alkali metal bases, alkaline earth metal bases or amines (Superbasic) salicylates; neutral salicylates react with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbases) A so-called borate overbased (superbasic) salicylate produced by reacting a metal salicylate with a boric acid compound such as boric acid or anhydrous boric acid; and a mixture thereof.

  In the present embodiment, it is particularly preferable to use a combination of three types of sulfur compounds, phosphorus compounds, and organic acid salts when organic acid salts are blended from the viewpoint of further improving machining efficiency and tool life. The blending amount of the organic metal salt is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and most preferably 2% by mass or more and 25% by mass or less. If the amount is too large, an effect commensurate with the amount added cannot be obtained, and if it is too small, the effect cannot be obtained.

  Moreover, it is preferable that the lubricating oil composition for metal working which concerns on this embodiment further contains antioxidant. By adding an antioxidant, it is possible to prevent stickiness due to alteration of the constituent components, and to improve thermal and oxidation stability.

  Antioxidants that can be used include phenolic antioxidants, amine-based antioxidants, and those used as other food additives. Furthermore, the zinc dithiophosphate compound represented by the general formula (6) can also be used as an antioxidant.

  As the phenol-based antioxidant, any phenol-based compound used as an antioxidant for lubricating oils can be used, and is not particularly limited. For example, an alkylphenol compound is preferable.

  As the amine-based antioxidant, any amine-based compound used as an antioxidant for lubricating oils can be used, and is not particularly limited. For example, phenyl-α-naphthylamine, Np-alkyl Preferred examples include phenyl-α-naphthylamine and p, p′-dialkyldiphenylamine, and specifically include 4-butyl-4′-octyldiphenylamine, phenyl-α-naphthylamine, octylphenyl-α-naphthylamine, dodecylphenyl. -Α-naphthylamine and mixtures thereof.

  Moreover, the antioxidant currently used as a food additive can also be used, and although it overlaps with the phenolic antioxidant mentioned above partially, for example, for example, 2,6-di-tert-butyl-p-cresol (DBPC), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-thiobis (6-tert) -Butyl-o-cresol), ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4- Hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trime Rukinorin (ethoxyquin), 2- (1,1-dimethyl) -1,4-benzenediol (TBHQ), can be mentioned 2,4,5-hydroxybutyronitrile phenone (THBP).

  Among these antioxidants, those used as phenolic antioxidants, amine antioxidants, and food additives are preferred. Furthermore, when importance is attached to biodegradability, what is used as the said food additive is more preferable, and among them, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 2,6- Di-tert-butyl-p-cresol (DBPC), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin), 2- (1,1-dimethyl) -1,4-benzenediol (TBHQ), or 2,4,5-tri Hydroxybutyrophenone (THBP) is preferred, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid Ether, tocopherol (vitamin E), 2,6-di -tert- butyl -p- cresol (DBPC), or 3,5-di -tert- butyl-4-hydroxyanisole are more preferred.

  The content of the antioxidant is not particularly limited, but the content is preferably 0.01% by mass or more based on the total amount of the lubricating oil composition, more preferably 0 in order to maintain good thermal / oxidative stability. 0.05% by mass or more, and most preferably 0.1% by mass or more. On the other hand, since the effect cannot be expected even if it is added more, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.

  The lubricating oil composition for metal working according to this embodiment may contain conventionally known additives other than those described above. Examples of such additives include extreme pressure agents other than the above-described phosphorus compounds and sulfur compounds (including chlorine-based extreme pressure agents); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, microwax, slack wax Film forming agents such as polyolefin waxes; water displacement agents such as fatty acid amine salts; solid lubricants such as graphite, graphite fluoride, molybdenum disulfide, boron nitride, polyethylene powder; amines, alkanolamines, amides, carboxylic acids, carboxylic acids Corrosion inhibitors such as acid salts, sulfonates, phosphoric acid, phosphates, partial esters of polyhydric alcohols; metal deactivators such as benzotriazoles and thiadiazoles; antifoams such as methylsilicones, fluorosilicones, and polyacrylates Agents: alkenyl succinimide, benzyl Min, ashless dispersants such as polyalkenyl amines polyaminoamide; and the like. The content when these known additives are used in combination is not particularly limited, but the amount is such that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the lubricating oil composition. It is common to add.

  Although the lubricating oil composition for metal working according to the present embodiment may contain a chlorine-based additive such as a chlorine-based extreme pressure agent as described above, it improves safety and reduces the burden on the environment. From the viewpoint, it is preferable that no chlorine-based additive is contained. The chlorine concentration is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, still more preferably 200 ppm by mass or less, and 100 ppm by mass or less, based on the total amount of the lubricating oil composition. It is particularly preferred that

Although the kinematic viscosity of the lubricating oil composition for metal working according to the present embodiment is not particularly limited, the kinematic viscosity at 40 ° C. is preferably 200 mm ² / s or less from the viewpoint of easy supply to the machined part. It is preferably 100 mm ² / s or less, more preferably 75 mm ² / s or less, and most preferably 50 mm ² / s or less. Further, the kinematic viscosity at 40 ° C. of the composition is preferably 1 mm ² / s or more, more preferably 3 mm ² / s or more, and most preferably 5 mm ² / s or more.

  The lubricating oil composition for metal working according to the present embodiment having the above-described configuration is excellent in processing performance such as processing efficiency, tool life, and handleability, and is therefore suitably used in a wide range of applications in the metal processing field. can do. The metal processing here is not limited to cutting / grinding, but broadly means general metal processing. Moreover, the lubricating oil composition for metal working according to the present embodiment can be applied not only to metal processing by a normal oil supply method but also to cutting / grinding processing (MQL processing) with a very small amount of oil supply.

  Specific examples of metal processing include cutting, grinding, rolling, forging, pressing, drawing, rolling, and the like. Among these, the lubricating oil composition for metal working according to the present embodiment is very useful for applications such as cutting, grinding, and rolling.

  The metalworking oil composition according to the present embodiment can be used either in an aqueous system that does not intentionally contain water or in an aqueous system that is diluted with water.

  When the lubricating oil composition according to the present embodiment contains water, the composition comprises water as a continuous layer, in which the oil component is finely dispersed to form an emulsion, where water dissolves in the oil component. It can take any form of a solubilized state or a suspended state in which water and an oil agent are mixed by vigorous stirring.

  In the case of diluting with water, the dilution ratio is arbitrarily selected depending on the use conditions, but in general, the stock solution is diluted with water to a weight ratio of 2 to 100 times, preferably 3 to 70 times, and practical metalworking fluid. It is customary to obtain In this case, for example, tap water, industrial water, ion exchange water, or distilled water can be used as the dilution water, and it does not matter whether it is hard water or soft water.

  In the case of the emulsion type, when the lubricating oil composition according to the present embodiment is diluted with water, an emulsion in which water is used as a continuous phase and oil components are finely dispersed therein is obtained. In this case, the average particle diameter of the oil droplets dispersed in water is preferably 300 nm or less, particularly preferably 100 nm or less. If the average particle size of the dispersed oil droplets is large, not only oil pits are easily generated and the surface gloss of the processed product is impaired, but there is a possibility that a fine filter cannot be used for cleaning the metalworking fluid.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

（極圧剤）
Ｂ１：ジ−ｔ−ノニルポリサルファイド（ｔ−ノニル基はプロピレンの３量体から誘導されたもの；１分子中の平均硫黄原子数４．６；硫黄含有量３８質量％）
Ｂ２：硫化ラード（硫黄含有量１１％）
Ｂ３：トリメチロールプロパンのトリオレートの硫化物（硫黄含有量１３質量％）
Ｂ４：トリクレジルホスフェート
Ｂ５：硫化オレイン酸（硫黄含有量１１質量％）
（油性剤）
Ｃ１：オレイルアルコール
Ｃ２：オレイン酸
Ｃ３：ポリエチレンオキサイドモノオレート（エチレンオキサイド部の平均重合度：４．５）
Ｃ４：オクタデシルアミン
（その他の添加剤）
Ｄ１：炭酸カルシウム含有過塩基性カルシウムスルフォネート（平均分子量４５０の石油スルホン酸の過塩基性カルシウム塩；塩基価（過塩素酸法）４００ｍｇＫＯＨ／ｇ）
Ｄ２：２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール [Examples 1-41 and Comparative Examples 1-10]
In Comparative Examples 1-41 and Comparative Examples 1-10, the following base oils a to c, compounds A1 to A6 having a perfluoroalkyl group, extreme pressure agents B1 to B4, oil agents C1 to C4, and other Lubricating oil compositions for metal working having the compositions shown in Tables 1 to 8 were prepared using the additives D1 and D2.
(Base oil)
Base oil a: mineral oil (kinematic viscosity at 40 ° C .: 42 mm ² / s)
Base oil b: trioleate of trimethylolpropane (kinematic viscosity at 40 ° C .: 49.3 mm ² / s)
Base oil c: poly α-olefin (kinematic viscosity at 40 ° C. 47 mm ² / s)
(Compound having a perfluoroalkyl group)
A1: Perfluorobutylethylene oxide adduct (average addition number 5)
A2: perfluoroalkyl amine _{(C 3} F 7 _-NH 2)
A3: perfluorobutyl sulfonate sodium salt _{(C 4 F 9 -SO 3 Na} )
A4: perfluorobutyl potassium carboxylate salt _{(C 4} F 9 -COOK)
A5: perfluorobutyl sulphonamide _{(C 4 F 9 -SO 2 NH} 2)
A6: Perfluoroalkylsulfonamide represented by the following formula

(Extreme pressure agent)
B1: Di-t-nonyl polysulfide (t-nonyl group is derived from propylene trimer; average number of sulfur atoms in one molecule is 4.6; sulfur content is 38% by mass)
B2: Sulfurized lard (sulfur content 11%)
B3: Trimethylolpropane trioleate sulfide (sulfur content 13% by mass)
B4: tricresyl phosphate B5: sulfurized oleic acid (sulfur content 11% by mass)
(Oil-based agent)
C1: oleyl alcohol C2: oleic acid C3: polyethylene oxide monooleate (average degree of polymerization of ethylene oxide part: 4.5)
C4: Octadecylamine (other additives)
D1: Calcium carbonate-containing overbased calcium sulfonate (overbased calcium salt of petroleum sulfonic acid having an average molecular weight of 450; base number (perchloric acid method) 400 mgKOH / g)
D2: 2,6-di-tert-butyl-p-cresol

(Tapping test)
With respect to the metal processing oil compositions of Examples 1 to 41 and Comparative Examples 1 to 10, the processing performance was evaluated using di2-ethylhexyl adipate as a comparative standard oil. Specifically, a tapping test was performed under the following conditions using each of the metalworking fluid compositions of Examples 1 to 40 or Comparative Examples 1 to 10 and di-2-ethylhexyl adipate alternately. When supplying the metal processing oil composition to the processing site, it was sprayed directly onto the processing site under the condition of 6 L / hr.
When diluting the oil agent with water, a homogenizer was used, and the test was performed while homogenizing.
Tapping condition:
Work material: JIS AC8A (aluminum material)
Tool diameter: 8mm
Tap pitch: 1.25mm
Tap rake angle: 1.5 degrees Tap bite angle: 10 degrees Tap pilot hole diameter: 7.4 mm
Rotation speed: 400rpm
Standard oil: Di-2-ethylhexyl adipate The tapping energy in the above test was measured, and the tapping energy efficiency (%) was calculated using the following formula.
Tapping energy efficiency (%) = (tapping energy when using comparative standard oil) / (tapping energy when using metalworking oil composition)
The obtained results are shown in Tables 1-8. In the table, the higher the value of tapping energy efficiency, the higher the lubricity.

(Abrasion resistance evaluation test)
About the lubricating oil composition for metal working of Examples 1-41 and Comparative Examples 1-10, the performance with respect to tool wear was evaluated. Specifically, the tapping energy efficiency with respect to the standard oil after processing 10 holes and 150 holes under the following conditions was measured, and the decrease rate of the 150th value with respect to the 10th hole was obtained. The degree of decrease in tapping energy efficiency with the number of machining was judged to be due to tool wear. In addition, it tested by removing the aluminum adhering to a tool for every 10 holes with a 10% sodium hydroxide solution. The obtained results are shown in Tables 1-8.
Tapping condition:
Work material: JIS AC8A (aluminum material)
Tool diameter: 8mm
Tap pitch: 1.25mm
Tap rake angle: 1.5 degrees Tap bite angle: 10 degrees Tap pilot hole diameter: 7.4 mm
Rotation speed: 360rpm
Number of processing: 10, 150 holes Standard oil: Di-2-ethylhexyl adipate

Claims (4)

Hydrocarbon oil as base oil,
A compound having a perfluoroalkyl group;
A lubricating oil composition for metalworking containing an extreme pressure agent.   The lubricating oil composition for metal working according to claim 1, wherein the perfluoroalkyl group is at least one selected from a perfluoroalkyl sulfonate group, a perfluoroalkylcarbonyl group, and a perfluorosulfonamide group. The lubricating oil composition for metal working according to claim 1 or 2, comprising a compound having a structure represented by the following general formula (1) as the compound having a perfluoroalkyl group.

[In the formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, A represents a perfluoroalkyl group having 1 to 18 carbon atoms, B represents a hydrogen atom, A C1-C12 alkyl group, a C2-C12 alkenyl group, a C1-C12 alkanol group, a C6-C12 aryl group, or General formula (2):

(In the formula (2), ^{R 2} represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aryl group having 6 to 18 carbon atoms having 2 to 18 carbon atoms, ^{R 3} is 1 to 12 carbon atoms An alkylene group or an alkenylene group having 2 to 12 carbon atoms.)
The group shown by is shown. ]   The lubricating oil composition for metalworking according to any one of claims 1 to 3, further comprising an oily agent and an organic acid salt.